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QuingdaoQuingdao
09.05.09.05.--15.05.201115.05.2011
Werner Werner ObrechtObrecht
TheThe attachedattached filesfiles of of mymy lecturelecture areare mymy personal personal propertyproperty. For . For thethe exclusiveexclusive
personal personal useuse, an , an elctronicelctronic copycopy of of thethe filesfiles will will bebe mademade availableavailable to to thethe
participantsparticipants of of thethe lecturelecture. . ItIt isis prohibitedprohibited to to makemake copiescopies oror multiplymultiply thethe filesfiles
forfor commercialcommercial useuse. .
““Chemistry and Technology of RubbersChemistry and Technology of Rubbers””
1. Overview on Rubbers, Definitions, Market, Properties, Production and Applications
2.1. Natural Rubber2.2. Synthetic Polyisoprene
3. Overview on Emulsion Rubbers3.1. Emulsion-Styrene/Butadiene-Rubber3.2. Polychloroprene3.3. Nitrile Rubber
4. Overview on Solution Rubbers 4.1. Overview on Polybutadiene4.2. Li-Polybutadiene and Solution-Styrene/Butadiene-Rubber with an Emphasis on
Integral Rubber4.3. Chemistry and Production Technology of High cis-1,4-BR with a Special Emphasis on
Nd-BR4.4. Ethylene/Propene-Co- und Terpolymers4.5. Butyl- and Halobutyl Rubber
5. High Performance Rubbers5.1. Fluoro Rubber5.2. Silicon Rubber 5.3. Hydrogenated Nitrile Rubber 5.4. Ethylene/Vinylacetate-Copolymers
6. Thermoplastic Elastomers
7. Test Questions
ChemistryChemistry and Technology of Rubbersand Technology of Rubbers
1. 1. OverviewOverview on Rubbers, on Rubbers, DefinitionsDefinitions, Market, , Market, PropertiesProperties, , ProductionProduction, and , and ApplicationsApplications
• Definition of the Terms “Rubber“, “Elastomer“ and “Thermoplastic Elastomer“
• Nomenclature
• Market
• Important Rubbers and Property Profiles
• Rubber Producers
• Production Technologies
• Producers of Synthetic Rubber and Production Capacities
• Available Vulcanization Methods and Network Properties
Standard Standard TerminologyTerminology RelatingRelating to Rubberto Rubber(ASTM D 1566 (ASTM D 1566 -- 98 )98 )
DISCUSSION - A rubber in itsmodified state, free of diluents, retracts within 1 min to less than 1,5 times its original length after beingstretched at room temperature (18 to 29°C) to twice its length and held for 1 min before release. Elongation [%]
100
Str
ess [
MP
a]
0 50
5
0
10
15
20
25
301 min
rubber, n-a material that is capable of recovering from large deformationsquickly and forcibly, and can be, oralready is modified to a state in whichit is essentially insoluble (but canswell) in boiling solvent, such as benzene, methyl ethyl ketone, orethanol toluene azeotrope.
rubber
1 min
ε =ε residual
ComparisonComparison of Materials of Materials AccordingAccording to ASTM D 1566to ASTM D 1566
NR/BR based tyre treadNR gum stock
Elongation (εεεε) [%]
300
Resid
ual
Elo
ng
ati
on
[%]
0 100 2000
100
200
300
Definition of „Rubber“according to ASTM D 1566 - 98
SBS
TPO
TPV Thermoplastic
Elastomers
In English, the term „Rubber“ is ambiguous as this term refers to unvulcanizedas well as to vulcanized rubber:
• rubber tree• natural rubber
• rubber boot
My personal Definition of My personal Definition of ““UnvulcanizedUnvulcanized RubberRubber““, , ““Vulcanized RubberVulcanized Rubber““, , ““ElastomerElastomer““, and , and ““TPETPE““
Unvulcanized Rubber is an uncrosslinked, amorphous or partiallycrystalline polymer (synthetic or natural) with a Tg < temperature of use
Vulcanized Rubber (or: „Crosslinked Rubber“ or „Elastomer“) is obtainedby chemically crosslinking (vulcanization) of unvulcanized rubber
Thermoplastic Elastomers (TPE) are physically crosslinked rubbers
Thermoplasts are unvulcanized polymers (synthetic or natural) with a softeningtemperature (Tg oder Tm) > temperature of use
Thermoset resins (or duroplasts) are highly crosslinked polymers which do not soften withincreasing temperature, but will deteriorate at high temperatures
unvulcanized (=uncrosslinked) rubber
vulcanized (=crosslinked) rubber
TgsTgs of Polymers of Polymers withwith a a SaturatedSaturated CC--C Main ChainC Main Chain
O
O
CH3
O
CH3
OO
O
CH3
O
CH3
O
O
CH3
O
O
CH3
O
O
CH3
O
O
CH3
SiO
SiO
SiO
SiO
SiO
SiO
SiO
Polyethylene
Polypropylene(atactic / amorphous)
Polyvinylacetate
Polystyrene(ataktisch / amorph)
Silicon Rubber
~ -130°C
-18°C
+30°C
+100°C
-120°C
TgsTgs of Polymers of Polymers withwith an an UnsaturatedUnsaturated C=C Main ChainC=C Main Chain
Cl
Cl
Cl
Cl
CN
CN
Polybutadiene
Polyisoprene
Polychloroprene
Nitrile Rubber
-115°C (100% 1,4-cis)
-75°C (100% 1,4-cis)
-45°C (100% 1,4-trans)
-50°C bis -5°C (depending on ACN-content)
InfluenceInfluence of of TgTg on Rebound of on Rebound of VulcanizedVulcanized Rubbers Rubbers ((50 50 phrphr carboncarbon blackblack, , withoutwithout plasticizerplasticizer))
• With increasing temperature rebound elasticity passes throug a minimum• The temperature at the rebound minimum correlates with Tg, except for butyl rubber• The temperature at the rebound minimum is significantly higher than the Tg of the respective rubber• In this respect, butyl rubber performs different from the other rubbers
Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA
20
40
0
60
80
IIR
EPDM
NBRSBR
NR
1,4-cis BR
Reb
ou
nd
[%
]
-75 -50 -25 0 25 50 75 100
Temperature [°C]
0,1
1
10
100
1000
10000
-150 -100 -50 0 50 100 150 200
Temperature [°C]
Sh
ear
Mo
du
lus [
MP
a]
NR (raw rubber)
NR/5 phr DCP
Polystyrene
SchematicSchematic PresentationPresentation of of thethe DependenceDependence of of thetheShearShear ModulusModulus on on TemperatureTemperature
Class- Chemical Description ExamplesDesignation
M Rubbers with fully saturated main chain CM, CSM, EAM, ACM, (polymethylene type rubbers) EPM, EPDM,
N Nitrogen containing rubbers NBR, HNBR
O Rubbers with oxygen in the main chain CO, ECO, GPO(Polyether type rubbers)
Q rubbers with a polysiloxane main chain MQ, MVQ, PMVQ, FMQ
R Rubbers with an unsaturated main chain NR, SBR, BR, NBR, (double bond containing rubbers) CR, IIR
T Rubbers with sulfur in the main chain OT, EOT(Polythioether type rubbers)
U Rubbers which contain carbon, nitrogen AU, EUand oxygen in the main chain(polyurethane type rubbers)
Z Rubbers with phosphorus and oxygen in FZthe main chain (polyphosphazenes)
Designation of Rubbers (DIN/ISO 1629)Designation of Rubbers (DIN/ISO 1629)
Butadiene-Rubber
Chloroprene Rubber
Chlorinated Polyethylene
Chlorosufonated Polyethylene
Ethylene/Propylene-Rubber
Ethylene/Propylene/Diene-Rubber
Epoxidised Natural Rubber
Synthetic Polyisoprene
Butyl rubber
Natural Rubber
Nitrile-Butadiene-Rubber
Styrene-Butadiene-Rubber (E-SBR und S-SBR)
Fluoro Rubber (DIN / ISO 1629)
Fluoro Rubber (ASTM D-1418)
AbbreviationsAbbreviations (DIN / ISO 1629) and (DIN / ISO 1629) and ExamplesExamples
BR
CR
CM
CSM
EPM
EPDM
ENR
IR
IIR
NR
NBR
SBR
FPM
FKM
AnnualAnnual ConsumptionConsumption of NR and of NR and SyntheticSynthetic RubberRubber
0
2000
4000
6000
8000
10000
12000
14000
1920 1930 1940 1950 1960 1970 1980 1990 2000 2010 2020
An
nu
al C
on
su
mp
tio
n [
10
00
me
tric
to
ns
] Natural Rubber
Synthetic Rubber (Solid + Latex)
Sources:•IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions•Outlook for Elastomers 1996-97 (Wembley 1998)•Rubber World, 21916 (1999) 13-14•European Rubber Journal (Quotation of IISRP Statistics), various editions•LMC International Ltd, Rubber March 2005: Verbrauch 2001-2005
ApplicationApplication AreasAreas of Solid Rubber of Solid Rubber ((rubberrubber latexlatex notnot includedincluded))
Modification
of Plastics
14%
Automotive
15%
Others
15%
Machine
building
5%
Construction
3%
Tyres
45%
Cable and
Wire
3%
Price and Price and VolumeVolume of Rubbers (of Rubbers (withoutwithout Latex) Latex)
CR (0.3 Mio t)
NBR (0.32 Mio t)
IIR/X-IIR (0.5 Mio t)
EPM/EPDM (0.9 Mio t)
FZ
FQ
FKM
HNBR Q
AU/EU EVM
Volume
Pri
ce
General PurposeRubbers
High Performance Rubbers
SpecialRubbers
BR (2,8 Mio t)
SBR (2,7 Mio t)
NR (6.7 Mio t)
Source: Rubber World, 21916 (1999) 13-14
Special Rubbers
17%
High Performance Rubbers 1%
General Purpose Rubbers: 82%
Volume Shares
Special Rubbers 30%
High Performance Rubbers 10%
General Purpose Rubbers: 60%
Shares in Turnover
Oil Oil –– and and TemperatureTemperature ResistanceResistance of of VulcanizatesVulcanizates AccordingAccording to ASTM D 2000to ASTM D 2000
0 20 40 60 80 100 120 140
Degree of Swelling in ASTM-Oil Nr. 3 [Vol %]
ma
x. se
rvic
ete
mp
era
ture
[°C
]
100
125
150
175
200
225
250
75
50
FKM
FMVQ
FZ
EU
CMCSM
no requirement
NRAU
CR SBR BR
EPDM(H)IIR
EVM
MVQ
CO/ECO
ACMHNBR
40 % VAc
18 % ACN
44 % ACN NBR
80 % VAc
AEM
General Purpose RubbersSpecial RubbersHigh Performance Rubbers
General Purpose RubbersSpecial RubbersHigh Performance Rubbers
Evaluation of Evaluation of VulcanizateVulcanizate PropertiesProperties
Criteria of Evaluation:
• Maximal Service Temperature
• Low Temperature Flexibility
• Oil Swell
• Mechanical Properties
• Ozone Resistance
Improvement
1 2 3 4 5 6 7 8 9 10
Evaluation of Evaluation of VulcanizateVulcanizate Performance*Performance*
Rubber Low
temperature
performance
Max. Service
Temperature
Mechanical
Properties
Oil Swell
(ASTM 2000-90)
Ozone
Resistance
Price Performance
Index
Tg Rating T max. Rating Tear
Resistance
Rating Rating Rating Rating
[°C] [°C] [MPa] [Vol.%] [€/kg]
NR -72 8 80 1 25 10 >140 (70) 1 1 1,1 21
SBR ca. -40 6 95 3 22 7 130 2 1 1,1 19
BR -120 10 85 2 20 6 >140 1 1 1,3 20
EPDM -60 5 145 6 24 8 >140 1 8 2,2 28
IIR -60 6 135 5 15 3 >140 1 6 2,7 21
NBR -40 5 125 5 22 7 20 bis 50 7 6 2,5 30
CR -39 4 115 4 22 7 55 bis 65 3 2 3,4 20
CM -25 3 140 6 15 4 80 4 5 3,1 22
CSM -25 3 135 5 16 4 80 4 9 3,8 25
EVM -35 4 170 8 14 3 20 bis 100 6 9 3,8 30
AEM -35 4 170 8 15 4 50 5 9 6,9 30
ECO -50 5 130 5 15 4 30 6 8 6,9 28
AU -30 4 80 1 25 10 3 bis 25 7 9 7,5 31
VMQ -120 8 250 10 10 1 30 bis 50 6 10 7,5 35
ACM -35 4 170 8 14 3 20 bis 40 7 9 9,4 31
HNBR -26 3 160 6 25 10 15 bis 40 8 9 28,1 36
FKM -20 2 250 10 14 3 5 9 10 43,8 34
FMVQ -70 8 215 9 10 1 10 9 10 125 37
FZ -65 8 180 8 16 4 10 9 10 500 39
*Ullmann‘s Encyclopedia of Industrial Chemistry, VCH Weinheim 1993, Vol. A23, Rubber 3. Synthetic; W. Obrecht „Introduction“
E-SBR and S-SBR may not be evaluated according to these criteria as SBR is designed for high Tgs (improvement of wet skid)
CorrelationCorrelation of Rubber Price and of Rubber Price and VulcanizateVulcanizatePerformancePerformance
0
5
10
15
20
25
30
35
40
45
0,1 1 10 100 1000
Price of Rubber [€/kg]
Perf
orm
an
ce In
dex
NRBRSBR
EVM AUNBR
ECO
CMIIR
CR
EPDMAEM
CSM
HNBRMVQ FKM
FZFMVQ
ACM
Ranking of Top 10 Tyre Ranking of Top 10 Tyre ProducersProducers
Source: European Rubber Journal, vol. 184, no. 10, Oktober 2002, S. 28-30
Rank Company Sales of Tyres Share
of
Tyres
Return
on
Sales
[%]
Market
Shares
in
Tyres
[Mio US $] [%] [%] [%]
1 Michelin 13.425,0 95,0 6,6 19,6
2 Bridgestone 12.950,0 74,0 5,5 18,9
3 Goodyear * 12.470,0 86,7 2,4 18,2
4 Continental 4.901,0 49,0 -4,2 7,2
5 Sumitomo** 2.598,2 72,7 7,7 3,8
6 Pirelli 2.534,5 39,0 6,1 3,7
7 Yokohama 2.272,2 71,0 5,7 3,3
8 Cooper Tire 1.705,3 54,0 3,4 2,5
9 Toyo 1.247,6 61,5 2,1 1,8
10 Kumho 1.246,5 60,3 -13,1 1,8
11 Hankook 118,9 88,9 8,5 0,2
Sums: 81,0
Total Sales: 100,0
55.469,2
68.500,0 * Dunlop is not included** Goodyear und Sumitomo operate in NA und WE in 75/25 joint ventures (Dunlop)
Bri
dg
es
ton
e
Mic
he
lin
Go
od
ye
ar
Co
nti
ne
nta
l
0
5
10
15
20
Capitalization of SharesSales
Source: FAZ 18.08.2003
Ranking of Top 22 Ranking of Top 22 ProducersProducers of of TechnicalTechnical Rubber Rubber ProductsProducts((withoutwithout TyresTyres))
Rank Company Company Sales 2001 Return on Sales
Site [Mio US$] [%]
1 Hutchinson SA France 2156 *)
2 Bridgestone Corp. Japan 2065 0,8
3 Freudenberg Group Germany 2060 3,7
4 Tomkins plc. UK 1855 5,7
5 Parker Hannifin US 1500 5,7
6 Cooper Tire & Rubber US 1477 2
7 Trelleborg AB Sweden 1446 2,9
8 Continental AG Germany 1270 *)
9 Federal Mogul Corp. US 1160 *)
10 Goodyear Tire & Rubber US 1122 *)
11 NOK Inc. Japan 1120 *)
12 Tokai Rubber Industries Ltd. Japan 987 2,7
13 Metzeler Automotive Profile Syst. Germany 900 *)
14 Toyoda Gosei Co. Ltd. Japan 897 1,3
15 Mark IV Automotive US 812 *)
16 GenCorp. Inc. US 808 8,6
17 Ansell Ltd. Australia 759 *)
18 Sumitomo Rubber Ind. Japan 750 *)
19 Yokohama Rubber Co Ltd. Japan 703 1,8
20 Dana Corp. US 695 *)
21 Toyo Tire Rubber Co. Ltd. Japan 670 1,3
22 Phoenix AG Germany 662 *)
*) not availableSource: European Rubber Journal 184,9 September 2002
Lanxess 8.7%
Exxon Mobil 5.7%
Goodyear 5.3%
JSR Corporation 5.2%
Sinopec 5.2%
Sibur 5.1%
Korea Kumho 4.8%
Dow 4.5%Polimeri 4.2%
Petro-China3.6%
Michelin 3.3%Petroflex 3.3%
Zeon Corporation 3.2%
Nizhnekamskneftekhim Inc. 3.1
Bridgestone/Firestone 2.8%ISP Elastomers 2.2%
Others30%
Total:
12,097 KMT
Source:
R. J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008„Globalization of Synthetic Rubber Industry“
ProducersProducers of of SyntheticSynthetic Rubber and Rubber and CapacitiesCapacities
Chemical and Chemical and TechnologicalTechnological Features of Features of Rubber Rubber ManufacturingManufacturing ProcessesProcesses
Chemical Aspects
RadicalPolymerization
Ziegler/Natta-Polymerization
AnionicPolymerization
Cationicolymerization
Polyaddition and Polycondensation
Polymer Modification
Technological Features
Emulsion Solution Dispersion Bulk Gas-Phase
E-SBR, CR, NBR, E-BR, ACM, FKM, EVM
EVM EVMAEMEVM
G-EPMG-EPDM
G-BR**
BR, EPM, EPDM
BR, L-SBR. IR
CIIR, BIIR, CM, CSM, H-NBR, FZ
ECO, CO
AU, EU
IIR
EU
CM, CSM,
H-NBR*
EPM, EPDM
Q
Q
AU Q
BR*
* Technology not established (only patents for the hydrogenation of NBR-latex)** Technology not established (only patents for the gas phase polymerization of butadiene)
FlowFlow Diagram of an EPDM Solution Diagram of an EPDM Solution ProcessProcess
Purification
Modifier
VOCl3
Wrapper
EASC
Reactivator
External
cooler
Baler
Waste Water
Waste
water
Abwasser
Waste Air
steam
PH-
Control
Stripping
aid
Antioxydant
Oil
Stripper
Reactor
Dewatering
screw
Expeller
Air bed
Dryer
Settler
Azeotropic-
Destillation
Water
Temperature: 35-65°C
Pressure: 5-10 bar
Residence Time: 30 min
Solids Content: 10 -12 wt.%
Moisture Content: < 3 ppm
Temperature: 35-65°C
Pressure: 5-10 bar
Residence Time: 30 min
Solids Content: 10 -12 wt.%
Moisture Content: < 3 ppm
Condenser
Condenser
Hexane
Flash
Vessel
Propene
Dryer
Ethene
ENBHexane
Purification/
Drying
Dryer
Purification
Purification/
Drying
Evaluation of Rubber Evaluation of Rubber ManufacturingManufacturing ProcessesProcesses
Aspect
Viscosity
Heat Removal
max. Solids Cont.
Stereoregularität
Waste Water
Waste Air
Sum
Polymerization Process
Emulsion Solution Dispersion Bulk Gas-Phase
Slurry
8
10
5
0
0
5
28
2
3
2
10
5
5
27
8
8
5
10
5
5
41
1
3
9
8
10
8
39
10
5
5
10
10
5
45
Ranking: (Gas-Phase) > Dispersion > Bulk >> Emulsion > SolutionPrerequistes: comparable running times
AvailableAvailable VulcanizationVulcanization MethodsMethods forfor thetheDifferent Different TypesTypes of Rubber of Rubber
Example Method of Vulcanization
Sulfur Peroxide Resin Other
“R“- Rubbers
“M“-Rubbers
Other
Rubbers
NR BR CRSBRNBRHNBRIIRXIIR
EPDMEPM FKM CM
MVQ
XX--X
(X)
XXXXXXX X
XX
X--
X
(X)
(X)-
XXX
XX
XXXXXXXX
XXXXXXXXXXXXX
-X -
(X)X
XX-
XX
X(X) (X)(X)(X)(X)XXXX
(X) (X)XX(X)(X)(X)(X)XX
Ten
sil
eS
tren
gth
[MP
a]
Reciprocal chain length 1/Mc x 10-4
0,2
0
10
30
20
0,4 0,6 0,8 1,0 1,2 1,4
InfluenceInfluence of of VulcanizationVulcanization MethodMethod and and CrosslinkingCrosslinkingDensityDensity on on TensileTensile StrengthStrength ((unfilledunfilled NRNR--VulcanisatesVulcanisates))
• For high moduli and high tensile strength the vulcanization method and the length of rubberchains between two crosslinking sites are decisive factors
• There is an optimum in tensile strength for Mc ~10.000 g/mol• The tensile strength of rubber vulcanizates is only 1/100 - 1/1000 of the theoretical values
Sx accelerated sulfur cureS1 TMTD-cure
C C peroxide cureC C high energy radiation cure
Sources: R. Houwink, H. K. de Dekker „Elasticity, Plasticity and Structure of Matter“ University Press, Oxford 3. Auflage (1971)K. Dinges, Kautschuk und Gummi. Kapitel 2 in H. Batzer „Polymere Werkstoffe“Georg Thieme Verlag Stuttgart, New York (1984)
SchematicSchematic PresentationPresentation of of thethe Deformation of a Deformation of a Rubber Rubber NetworkNetwork
TSexpt. = 1/100 - 1/1000 TStheor.
Type of Bond BondEnergy[ KJ/Mol]
C-C 350
C-O 350
C-N 282
C-S-C 272
C-S-S-C 266
-S-S-S-S- < 266
Type of Bond BondEnergy[KJ/Mol]
covalent 260 - 350
physical 10 - 20
•Oil Resistance•Low temperature flexibility•Resistance to heat- and ageing•Adhesion to cord, fibres and fabrics•Covulcanisation of layers•Tensile Strength•Elongation at break•Static and dynamic moduli•Shore A Hardness•Abrasion Resistance•Compression Set •Cut growth Resistance during dynamic stress•Heat-buid-up•Electical conductivity• …….•……..•……..•…….
InfluenceInfluence of Compound of Compound IngredientsIngredients on on VulcanizateVulcanizatePerformancePerformance
Rubber
Filler
VulcanizationMethod
2.1. 2.1. NaturalNatural RubberRubber
• Microstructure and Property Profile• NR-Market
–Designation of Grades and Glossary–Development of Market and Price–NR-Production, Areas of Application and Important Grades
• NR-Production–NR-Latex and Latex Finishing–General Features of NR and Hevea brasiliensis–NR Grades and Specifications
• Chemical and Physical Properties of NR–Solution Fractionation of NR–Mastication of NR–Crystallization (Spontaneous-and Strain induced)
• Chemically Modified NR-Grades–CV-Grades–SP-Grades–ENR-Grades
• Vulcanization of NR
NR: NR: MicrostructureMicrostructure and Property Profileand Property Profile
C CH
CH2
CH3
CH2
1
2 3
4
5
Physical Properties:Tg: -72°C1,4-cis-content ~ 97%Tm (equilibrium): + 30 °Cmax. rate of crystallization: -25°Cmax. degree of crystallinity: ~ 30 %Strain induced crystallization
Positive:• Low price and good ratio of price versus performance• Standardized NR-grades• High level of mechanical properties
(Tensile Strength, Modulus Abrasion)• Good Dispersability of Fillers
(due to high viscosities at the start of the mixing cycle)• Low rolling resistance (truck tyres)• High abrasion resistance (truck tyres)• Slow spontaneous crystallization• Significant strain induced crystallization
Negative:• Poor resistance to swelling with hydrocarbons
(fuels, oils and grease)• Need for mastication prior to compounding• bad wet skid performance• Poor resistance to heat ageing
NR: Designation of Grades and NR: Designation of Grades and GlossaryGlossary
General Purpose Grades:TSR Technically Specified Rubber (TSR 10, TSR 20, TSR 50)SMR Standard Malysian Rubber (SMR 5, SMR 10, SMR 20, SMR 50)SCR Standard Chinese Rubber (SCR 5, SCR 10, SCR 20, SCR 50) GP General Purpose GradeADS Air Dried SheetRSS Ribbed Smoked Sheet
Special Grades:OENR Oil Extended NRL-Grades „Light“ Grades (with colour specification) produced by the
selection of latices and removal of carotinoids by latex creaming,addition of Na-HSO3, and intenisve wash etc.
SP-Grades „Superior Processing“ (Sol/Gel-Blends)CV-Grades „Constant Viscosity“ NR
obtained by the addition of hydroxyl amin prior to latex finishingENR Epoxidized NR
NR: NR: AnnualAnnual ConsumptionConsumption (incl. Latex)(incl. Latex)
Source:• IRSG (International Rubber Study Group, Rubber Statistical Bulletin, Wembley, different editions• Outlook for Elastomers 1996-97 (Wembley 1998)• Rubber World, 21916 (1999) 13-14• European Rubber Journal (Quotation of IISRP Statistics), different editions• Consumption 2001-2005: LMC international Ltd. „Rubber, March 2005“
0
2
4
6
8
10
12
14
1880 1900 1920 1940 1960 1980 2000 2020
Mio
to
ns
Naturkautschuk
Synthesekautschuk (Fest + Latex)
Source: European Rubber Journal, January/February 2011, 16
NR: NR: ProductionProduction
0
500
1000
1500
2000
2500
3000
3500
1980 1985 1990 1995 2000 2005
x 1
000 m
etr
ic t
on
s
MalaysiaIndonesiaThailandothers
Sources:• K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591• LMC International Ltd; Rubber April 2005
Thailand 1.934 31,90% 2.988 34,50% India 570 9,40% 741 8,60% Ivory coast 87 1,40%
Indonesia 1.530 25,20% 1.942 22,40% China 400 6,60% 585 6,70% Philippines 60 1,00%
Malysia 1.070 17,60% 1.175 13,58% Sri Lanka 113 1,90% 92 1,10% Camerun 56 0,90%
Vietnam 110 1,80% 423 4,90% Cambodsha 49 0,80%
Brasil 35 0,60%
Liberia 25 0,40%
Burma 21 0,40%
Nigeria 13 0,20%
Total 4.534 75% 6.105 70% 1.193 20% 1.841 21% 346 5,7%
19971997 2004 1997 2004
Source: Römpp Lexikon Chemie; Version 1.5; Stuttgart/New York Thieme-Verlag 1998LMC International Ltd; Rubber April 2005
NR: NR: ApplicationApplication AreasAreas
None automotive
5%
Shoes
4%
Automotive
(other than tyre)
2%
Others
7%
Latex-Products
11%
Tyres
71%
Source:K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-OthmerEncyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
UseUse of NR in Truck of NR in Truck TyresTyres
Year Tread [wt.%] Side Wall [wt.%] Carcass [wt.%]NR SBR BR NR SBR BR NR SBR BR
1974 45 21 34 48 37 15 71 20 9
1981 60 12 28 44 19 37 84 11 4
1983 77 7 16 58 6 36 100
1985 86 5 9 62 38 100
1990 86 5 9 75 25 100
1994 100 60 40 100
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-OthmerEncyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
The major application of NR is in truck tyres
NR: NR: ProductionProduction
As of today, only Bridgestone, Michelin und Goodyear run NR-plantations
NR-Production by smallholders:Area cultivated per smallholder: 1,25 ha;Number of trees: 625 trees in total; 520 trees under tapAnnual tappings per tree: 180/aTotal number of tappings per year: 95.000 tappings for 625 trees/aAnnual yield: 850 kg/aAnnual earnings: ca. 250 €/a (0,30 €/kg)Earnings/different source*: 1020 €/a (1,2 €/kg)
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591*Broadcast in German TV (ZDF) “Mission“ about Charles Goodyear on 17.10.2004
Share of smallholdersin rubber production:Thailand 95%Indonesia 83% India 83%Malaysia 81%Brasil 70%Sri Lanka 33%Ivory Coast 29%Source: International Rubber Study Group
Source: http://www.therubbereconomist.com
Features of Features of thethe Rubber Rubber TreeTree ((HeveaHevea BrasiliensisBrasiliensis))
• Botanical Family: Euphorbiaceae• Habitat: Equator + 15°
–Height: < 300 m–Temperature: 25-30°C–Humidity: > 70%–Rain fall: 1800-2000 mm/year–Soil: good drainage (not at the bottom of vallleys)
• max. age of tree: 30-40 Jahre (plantation), 100 Jahre (rain forest)• Height of tree: 20 m (plantation), 40 m (rain forest)• tapping age of tree: 5-7 years•Tappings: every 2nd day = 180 days/year• Yield per tree: 1-2 kg/a• Yield per tap: 5-11g• density of trees: 500/ha• Rubber yields: 400-1.200 kg/ha
–Plantation: 1.000 kg/ha –Maximum yield: 3.000 kg/ha –Smallholder: 850 kg/ha
• Fungal infection: Dothidella Ulei (Yellow leaf blythe) • Spread of fungus: so far, endemic and restricted to Brasil
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer, Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591
Features of NRFeatures of NR--LatexLatex• Total solids concentration:(25) 30-40 wt. % (dependent on many parameters) • Rubber content: 90 - 95 wt. % of total solids• Particle diameter: 150-3000 nm (dependent on many parameters)• Gel content: dependent on many parameters (latex age, finishing method)• Molar mass: 105-107 g/mol (not constant, dependent on many parmaters) • Latex stability without the addition of additives (NH3, formaldehyde, boric acid,
phenolates, Na2SO3 (0,05 Gew.%), etc.) latex coagulation occursas a consequence of encymatic decay
• Dilution of the latex to 15-20 wt. % solids• Removal of heavy impurities such as sand by sedimentation• Removal of impurities such as wood, leafs, insects, etc. by filtration• Latex fractionation for the removal of carotinoids for „L“ (light = colourless) grades• Addition of:
• Na2SO3 (0,15 wt.%) for pale-crepe-grades
• [HONH3]2 SO4 for CV- grades (“Constant Viscosity“)
• Discontinuous latex coagulation with formic or acetic acid (5 wt. %) in pH-range 5,0 - 5,2• Completion of coagulation by maturing for 12-16 h• Mechanical water removal by riffle mills (6-9 passes)• Drying in smoke at 60°C/1 week for RSS-production (“RSS” = Ribbed Smoked Sheet)• Drying in air at 40°C/2 months (“ADS“ = Air Dried Sheet)
Latex Latex FinishingFinishing
Latex- Acid Coagulation Acid Coagulation Naturalconcentration (factory) (Plantation/Smallholder Coagulation of latex
„Cup lump“
„Smallholder‘slump“
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
SMR 5
60% 40%
Sales latex SMR L SMR CV 50 SMR GP SMR 10 SMR 20 (60 wt. % solids) SMR CV 60
centrifugation, creaming,
evaporation of water
Sheet-Material(RSS, ADS)
Baled or Crumb wet and dry field gradesRubber blending processes
Comminution Process: multi-stage wet blending process with mechanical generation of
crumbs, crumb blending and washing with subsequent crumb drying at 100-120°C/4-5 h is
used for the homogenization and purification of cup lumps
NR: Range of GradesNR: Range of Grades
NR: NR: SMRSMR--GradesGrades und und SpecificationsSpecifications
Besides NR purity, price is also an important factor for the selection of an appropriate NR grade. As a consequence of price and quality, theranking of NR grades for tyre building is as follows:
SMR 20 > SMR 10 > SMR GP > SMR 5 > RSS
0,500,200,100,100,05Strainer Residue [wt.%]
(mesh width: 45 mm)
SMR 50SMR 20SMR 10SMR GPSMR 5NR Grade
• The content of none rubber like residues is an important qualitycriterium for NR
• As a consequence, the content of impurities is a feature in thedesignation of NR grades
NR: NR: VulcaniaztionVulcaniaztion of Different of Different SMRSMR--GradesGrades
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical
Technology, vol 21, 4th ed., 562-591 (ISO 1658: Natural Rubber - Test Recipes and Vulcanization Characteristics,
International Organization for Standardization, Geneva, Switzerland, 1973
ACS 1- CompoundNR 100 phrStearic Acid 0,5 phrZnO 6,0 phrSulfur: 3,5 phrMBT 0,5 phr
Typ Monsanto-Rheometer (160°C)Delta F [J/cm2] TS 2 [min] t90 [min]
SMR CV 29,4 2,2 11,6
SMR L 33,9 1,8 9,7
SMR 5 37,2 1,5 7,8
SMR 10 40 1,3 6,8
SMR 20 41,1 1,2 6,8Imp
uri
tyL
eve
l
With increasing impurity level, the followingfeatures are observed:• reduction of scorch time• reduction of vulcanization time• Increase of crosslinking density
The impurities in NR perform like a vulcanization accelerator
FractionNr.:
bale123456
Soluble portion
Chemical and Chemical and PhysicalPhysical CompositionComposition of NRof NR
Solution fractionation of NR by sequential coagulation:1. Preparation of a NR solution in toluene2. Incremental addition of methanol
share
[wt.%]10024,419,715,58,0
12,912,86,7
1,2-content
[%]0,60,60,50,50,70,60,5-
• NR has a broad distribution of molar masses (“polydispersity“ or “physical inhomogenity“)• The polydispersity increases with the age of the tree• NR fractions with a low molar mass have a higher content of 1,4-trans moietiesthan the fractions with a higher molar mass (“chemical inhomogenity“)
Source: Rubber Chem. Technol. 57, 104 (1984)
Viscosity(toluene/25°C)
[dl/g]11,57,73,91,91,160,620,3-
1,4-transcontent
[%]2,22,02,02,03,44,05,0-
Source: Rubber Chem. Technol. 82, 283-314
NR (TSR 5, Defo 700) [phr] Carbon black/Corax N 2200 [phr]Stearic Acid [phr]Zinc oxide [phr]Antilux 654 [phr]IPPD (Vulkanox® 4010 NA) [phr]TMQ (Vulkanox® HS/LG) [phr]Mineral oil/Enerthene 1849 [phr]Sulfur [phr]TBBS (Vulkacit® NZ) [phr] Desmodur® TT [phr]
100-33
1,5113
1,610
100-33
1,5113
1,610
100-33
1,5113
1,6115
100-33
1,5113
1,6125
1005033
1,5113
1,610
1005033
1,5113
1,6110
NNNNNNNN
OOOO
OOOO NNNN CCCC OOOO
CCCC HHHH3333
OOOO CCCC NNNN
CCCCHHHH3333NNNN HHHH CCCC HHHH
CCCC HHHH3333
CCCC HHHH3333
NNNN HHHHSSSS
NNNNSSSS NNNN HHHH
CCCC HHHH3333
CCCC HHHH3333
CCCC HHHH3333
NR: NR: VulcanizationVulcanization withwith MultifunctinalMultifunctinal IsocyantesIsocyantes
First Hint on NR-Vulcanization with Diisocyanates from O. Bayer, Angew. Chemie 59 (1947) 9, 257-272
IPPD (Vulkanox® 4010 NA) TBBS (Vulkanox® NZ) Desmodur® TT (TDI Uretdione)
1005010
1,7836,260,347,479,07
25,24801,93,18,0
14,4
75-
--
133
NR (masticated TSR 5)Carbon black (Corax N 220)Desmodur TT
Fmin [dNm]Fmax-Fmin [dNm]t10 [min]t80 [min]t90 [min]
Tensile Strength [MPa]Elongation at break [%]M50 [MPa]M100 [MPa]M200 [MPa]M300 [MPa]
Shore A Härte/23°CShore A Härte/70°C
Rebound/23°C [%]Rebound/70°C [%]
DIN-Abrasion [mm3]
NR: NR: VulcanizationVulcanization withwith MultifunctionalMultifunctional IsocyantesIsocyantes
10000
0,307,414,346,217,53
17,86050,60,91,42,2
4345
7481
183
10000
0,186,304,826,778,24
15,36500,40,60,71,2
4038
6978
327
1000
15
0,5424,200,74
15,2317,60
25,76351,52,02,95,0
66-
59-
155
1000
25
0,9620,060,71
15,5619,08
21,85651,82,43,76,0
6865
5560
123
100500
1,0615,941,964,224,99
27,85401,52,77,3
13,4
66-
--
102
NR contains polymer bound functional groups (-NH2, -COOH, -OH, -CONH2) which react with isocyanates
MasticationMastication of NRof NR
• At low temperatures (<120°C) mechanical chainscission prevails
• At temperatures >120°C thermo-oxidative chainscission prevails
• In the temperature range 100-130°C the masticationeffect shows a minimum
C**C
184 kJ/mol 343 kJ/mol
C* *C
Cl
Cl
Cl
Cl
Cl
SH
NH
O
S S
NH
O
Pentachlorothiophenol 2,2'-Dibenzamidodiphenyl-Disulfide (DBD)
• By the use of mastication additives the mastication of NR is accelerated (oxidation catalysts and radical scavengers)
• Pentachlorothiophenol is an effective mastication aid; it isbanned in WE
• Today, disulfides as well as Fe-complexes are used for theacceleration of NR mastication
Deg
ree
of
Masti
cati
on
Temperature [°C]0 100 200
Source:
C. Clarke, M. Hensel, Rubber World, November 2009, 28-31
„Improved natural rubber processing and physical properties
by use of selected compounding additives“
NR: NR: CrystallizationCrystallization at at --2525°°CC
0
5
10
15
20
25
30
35
0 5 10 15 20 25 30
time [h]
Cry
sta
llin
ity
[%
]
Pale Crepe
pale crepe after acetone extraction
• The Shore A Hardness of NR increases due to crystallization during storage at low temperatures• NR can only be processed in the uncrystallized state• Decrystallization can be achieved by storage at elevated temperatures (40°C-50°C)• The decrystallization in the interior of bales needs 2 weeks at 30°C• The maximum degree of crystallinity of unvulcanized NR is ~ 30%• NR contains impurities which accelerate the speed of crystallization• The crystallization accelerators can be removed by acetone extraction (e.g. stearic acid)
NR: NR: DependenceDependence of of CrystallizationCrystallization Rate and Rate and CrystalliteCrystallite Melting Melting TemperatureTemperature on on StorageStorage TemperatureTemperature
1
10
100
1000
-50 -30 -10 10
storage temperature [°C]
ha
lf t
ime
[h
]
Source:U. Eisele Intorduction to Polymer Physics, Springer-Verlag 1990
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Naturalin Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 21, 4th ed., 562-591
-40
-30
-20
-10
0
10
20
30
40
-50 -30 -10 10 30
storage temperature [°C]
me
ltin
g t
em
pe
ratu
re [
°C]
Stress/StrainStress/Strain--PerformancePerformance of of UnfilledUnfilled NRNR-- and and SBRSBR--VulcanizatesVulcanizates ((gumgum stocksstocks))
0
5
10
15
20
25
30
0 200 400 600 800 1000
strain [%]
str
es
s [
MP
a]
NR
SBRStrain induced crystallization
DependenceDependence of Tack on of Tack on TestingTesting TemperatureTemperature((UnvulcanizedUnvulcanized NRNR-- and and SBRSBR--CompoundsCompounds))
0
5
10
15
20
25
0 20 40 60 80 100 120
temperature [°C]
Ta
ck
-In
de
x
NR
SBR
ChemicallyChemically ModifiedModified NRNR--Grades Grades
Source:
K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
Improved oil resistance
Improved wet skid
Improved silica interaction
Epoxydation (ENR)
Improved processability of NR-compoundsBlend with NR-gel (“SP”-Grades)
improved compounding, no mastication required
Hydroxyl amine (“CV”-Grades)
ApplicationModification
NR: CVNR: CV--GradesGrades
• During storage at ambient and elevated temperatures, the viscosity of NR increases to
a greater extent than for synthetic IR (storge hardening)
• It is assumed that the viscosity increase of NR is caused by the chemical reaction of
polymer bound –NH2 and polymer bound –CH=O groups
• By the addition of hydroxylamine to the NR latex prior to latex coagulation –CH=O
groups are chemically eliminated
•CV-Grades (“Constant Viscosity“) exhibit an improved storage stability
0
1
2
3
4
5
6
7
8
9
10
0 5 10 15 20
storage time [days]
Mo
on
ey
- In
cre
as
e [
MU
]
SMR 20
IR/Natsyn 2200 (IR / Ti)
O
HH
N
HH
H
NH2
H
- H2O
+
NR: CVNR: CV--GradesGrades
50
60
70
80
90
100
110
120
130
140
0 0,02 0,04 0,06 0,08
Hexanediamine [mol/kg]
Mo
on
ey-V
isco
sit
y M
L1+4
(100°C
)
before hot air ageingafter hot air ageing
Grade Ml 1+4 (100°C)
CV 50CV 60CV 70LV 50
Minimum45556554
Maximum55657555
Specification of CV-Grades
O
HH NH
2
NH2
O
HH
NN
HH
HH
- 2 H2O
+ +
0
10
20
30
40
50
60
70
0 0,05 0,1 0,15 0,2
hydroxyl amine [wt. %]
Inc
rea
se
of
Mo
on
ey
Vis
co
sit
y [
%]
NR CV-Grades (“Constant Viscosity“) are obtained by the addition of hydroxylammonium chloride to the latex prior to latex finishing
C
O
H
H NH2OH
C
N
H
H
OH
+
- H2O
NR: CVNR: CV--GradesGrades
ENR: ENR: DependenceDependence of of PropertiesProperties on on thethe DegreeDegree of of EpoxidationEpoxidation
Source: Ullmann‘s Encyclopedia of technical Chemistry
O
O
O
Epoxidation with peracids in the latex stage
-80
-60
-40
-20
0
20
40
0 20 40 60 80 100
Degree of Epoxidation [%]
Tg
[°C
]
Epoxydation of NR has the following effects:
• Increase of polarity (Reduction of the swelling in oil)
• Increase of Tg (Improvement of wet skid and reduction of gas permeation)
• Resistance to ageing is unchanged (as bad as for unmodified NR)
• Processability is reduced (supposedly this problem has been solved)
NR [phr]ENR 25 (Degree of Epoxidation: 25%) [phr]ENR 50 (Degree of Epoxidation: 50%) [phr]Carbon black (N 220) [phr]
Shore A Härte/23°C M300 [MPa]Tensile Strength [MPa]Elongation at break [%]Elasticity/23°C [%]Goodrich HBU [°C]CS/24h/70°C [%]
Volume Swell (70h/70°C)ASTM-Oil No. 1 [%]ASTM-Oil No. 2 [%]ASTM Oil No. 3 [%]
Air permeability/23°C [1018 x m4/s.N]
ENR: ENR: DependenceDependence of of VulcanizateVulcanizate PropertiesProperties on on thetheDegreeDegree of of EpxidationEpxidation
100--
30
597,8
27,1550784417
66114191
27,0
-100
-30
566,9
25,9590256046
7328
108
8,0
--
10030
598,8
27,8560155217
-56
21
2,0
NR: SPNR: SP--GradesGrades
Grade Precrosslinked
NR
Uncrosslinked
NR
Oil
[wt.%] [wt.%] [phr]
SP 20 20 80 0
SP 21 40 60 0
SP 22 50 50 0
SP 23 80 20 40
SP 24 80 20 0
• SP-Grades (“Superior Processing“) are obained by blending crosslinked NR with uncrosslinked NR in the latex stage.
• The crosslinked NR-latex (NR-gel) is obtained by sulfur cure in the latex
• The SP-series of grades comprises different blend ratios of ucrosslinkedand unrosslinked NR as well as oil extended grades
Source: BP 880739; Natural Rubber Producers‘ Association, Appl.: 28.03.1957, Inv.: B. C. Sekhar „Improvement in the Preparation of Superior Processing Rubbers“
SP-grades have the following advantageous properties:• reduced die-swell• Increased extrusion out-put• Reduced roughness on surface and edges
NR (SMR 5) [phr]N 330 [phr]Oil [phr]ZnO [phr]Stearic Acid [phr]Sulfur [phr]TBBS [phr] CBS [phr]TMTD [phr]Santoflex 13 [phr]TMQ [phr]DCP [phr]Novor 924 [phr] Caloxol [phr]ZDMC [phr]ZMBT [phr]
NR: Impact of NR: Impact of VulcanizationVulcanization Systems on Systems on VulcanizateVulcanizatePropertiesProperties
Schwefel(conv.)
10050,04,05,03,02,50,5--
2,0------
Sulfur(Semi EV)
10050,04,03,52,51,2-
0,80,42,0------
Sulfur(EV)
10050,04,05,02,0
0,33-
0,80,42,0------
Peroxide
10050,03,05,0------
2,02,5----
CappedDi-Iso-
Cyanate
10050,03,05,0------
2,0-
6,75,02,02,0
Source: K. Baranwal, R. Ohm, R. R. Fell, B. Rodgers, Rubber, Natural in Kirk-Othmer Encyclopedia of Chemical Technology, vol 21, 4th ed., 562-591
NR: NR: VulcanizationVulcanization withwith A A CappedCapped DiisocyanateDiisocyanate ((NovorNovor 924)924)
O N ON
N
NH NH
N
O
O
O
O
O
O
O N O H ONOH
N
N N
N
O
OC CO O
O N OHONO H
N O N
N
NH NH
N
O
O
O O
O
HH
Thermal Cleavage
Tautomerization Tautomerization
- H2O- H2O
•F. Barlow „Rubber Compounding“ 2nd edition, Marcel Dekker, Inc. Chapter 7, page 96-98
• Vulcanization with Novor 924, NR Technical Bulletin, MRPRA, Brickendonbury, England
• Novor Application Data Sheet, Solid Tyres, ADS-5H, Rubber Consultants, Brickendonbury, England
• C. S. L. Baker, Novor Vulcanizing Systems: Their Technical Development and Application Areas, Rubber Manufacture and Technology Seminar, P. R. I.
(Malaysian Section), Kuala Lumpur, July 21-23-1981
Novor 924: TDI based diisocyanate
Novor 950: MDI based diisocyanate
Due to health and safety reasons Novor
924 has been replaced by Novor 950
Sources:
Shore A Hardness/23°C M100 [MPa]Tensile Strength [MPa]Elongation at break [%]Rebound/23°C [%]Fatigue to Failure [kZ]Goodrich HBU [°C]CS/24h/70°C [%]∆ ∆ ∆ ∆ TS (7d/100°C) [%]
NR: NR: DependenceDependence of of VulcanizateVulcanizate PropertiesProperties on on VulcanizationVulcanization SystemSystem
Sulfur(konv.)
652,0828,851570
223292773
Sulfur(Semi EV)
652,2230,148577
106321454
Sulfur(EV)
672,3424,23906768361024
Peroxide
612,2821,43107251341149
CappedDi-Iso-
cyanate
702,6024,04606690--
30
2.2. 2.2. SyntheticSynthetic PolyisoprenePolyisoprene (IR)(IR)
Contents:• Differences between IR and NR• IR-Grades, Catalysts and Microstructures• Price, Producers, and Production Capacities• Comparison of Unvulcanized NR- and IR- Properties• Vulcanizate properties of NR and IR• Compound and Vulcanizate Properties of Poly-3,4-Isoprene
Li Ti Nd
cis-1,4-content [mol %] 98 93 97 99
Need for Mooney adjustment before use yes
Gel yes - - -
functional groups yes - - -
IR
no mastication needed
NR
IR grades and chemical differences between NR und IR:
2.2. 2.2. SyntheticSynthetic PolyisoprenePolyisoprene (IR)(IR)
C2
C3
C1
C4
CH3
Poly-3,4-Isoprene
Poly-cis-1,4-Isoprene Poly-trans-1,4-Isoprene
Isoprene
Type of IR Catalyst Solvent Microstructure
Trade Name cis-1,4 trans-1,4 1,2- 3,4-
Cariflex IR-3091)
Li unpolar (benzene) 93 0 0 7
Natsyn 2001)
Ti unpolar hydrocarbon 97 0 0 3
Vestogrip2)
Li Hexane/Additive 60
IR3)
Nd unpolar hydrocarbon 99 - - -
Sources:1) E. Schoenberg, H. A. Marsh, S. J. Walters, W. M. Saltman, Polyisoprene, Rubber Chemistry and Technology, Vol 52, S. 526-6042) Data sheet of Hüls AG: “Vestogrip“ (Production by Karbochem / South Africa: ca. 3.000t)3) WO 02/38635 A1 (Michelin), Erf.: P. Laubry, Prior.: 13.11.20003) WO 02/48218 A1 (Michelin), Erf.: P. Laubry, Prior.: 28.11.2001
IR: IR: DevelopmentDevelopment of Prices, of Prices, ProducersProducers and and ProductionProductionCapacitiesCapacities
Source: R.J. Chang; SRI Consulting; IISRP 49th AGM Moscow 2008 „Globalization of Synthetic Rubber Industry“
Company Plant Location Capacity [kt]
Goodyear Beaumont/Texas/USA 90
Kraton Polymers Rotterdam-Pernis/Nederland 25
Kauchuk Sterlitamak Sterlitamak/Russia 100
Nishnekamskneftekhim Nishnekamsk /Russia 200
Togliattikauchuk Togliatti 130
JSR Corporation Kashima / Ibaraki Pref. 36
Zeon Corporation Mitzushima / Okayama Pref. 40
Karbochem Newcastle / Natal /South Africa 3
Total Capacity [kt] 624
0
0,5
1
1,5
2
2,5
3
1980 1985 1990 1995 2000 2005 2010
Pri
ce [
US
$ /
kg
]IR
NR (RSS)
ComparisonComparison of NR and IR: of NR and IR: Stress/StrainStress/Strain--CurvesCurves of of UnvulcanizedUnvulcanizedPolyisoprenePolyisoprene CompoundsCompounds
0
1
2
3
4
5
6
7
8
9
0 100 200 300 400 500
Strain [%]
Str
ess [
MP
a]
NR (SMR 5)High cis-IR/Ti (97%)Low cis-IR/Li (93%)
Evaluation of CompoundEvaluation of Compound-- and and VulcanizateVulcanizate PropertiesProperties of of NR and IRNR and IR
Li Ti Nd
Mastication - + + +
Mixing cycle - + + +
Die swell - + + +
Tack + - - +
Green strength + - - +
IR NR
Li Ti Nd
Modulus + - - +
Tensile Strength + - - +
Cut growth resistance + - - +
Rebound Elastivity + - - +
Abrasion resistance + - - +
IR NR
Compound Properties
Vulcanizate Properties
Compound PropertiesML 1+4(100°C) [MU]t10/150°C [min]t90/150°C [min]
Vulcanization (30 min/150°C)Shore A Härte (22°C)Shore A Härte (75°C)M 100 [MPa]M 300 [MPa]TS [MPa]εεεεb [%]
Cut growth resistance [N/mm]Residual elongation [%]
Rebound / 22°C [%]Rebound / 75°C [%]
tan δδδδ/25°Ctan δδδδ/75°C
7713,827,5
67522,18,414,7510
2520
244
0,260,11
PolyPoly--3,43,4--Isoprene: Compound and Isoprene: Compound and VulcanizateVulcanizate PropertiesProperties
Source: Data sheet of Hüls AG
„Vestogrip
(3,4-Polyisopren-Kautschuk)“
3,4-Polyisoprene 100 phr
CB (Corax N 330) 50 phr
HAR-oil 10 phr
Zinc oxide 3 phr
Stearic acid 2 phr
CBS 1 phr
Sulfur 2 phr
3,4-content (NMR): ca. 60 %
ML 1+4 (100°C): 65 MU
Tg -8°C
Source: P. Roch (Goodyear) KGK 48,6 (1995) 430-434“Compounding for Wet Grip“
3.0. 3.0. OverviewOverview on on EmulsionsEmulsions RubbersRubbers
• Emulsion Rubbers and Features of the Emulsion Process
• Essentials of the Emulsion Polymerization
• Mechanism of Emulsion Polymerization
• Kinetic Aspects of the Emulsion Polymerization
• Flow Diagram of Continuous Emulsion Polymerization
• Flow Diagram of Latex Finishing
• Finishing of CR-Latex
• Legal Aspects of Water Usage
Emulsion Rubbers and Features of Emulsion Rubbers and Features of thethe ProcessProcess
Application Areas for Rubber Latices:• Carpet backing, paper-, textile- and leather finishing (X-SBR)
• Latex dipping process for improvement of cord adhesion
• Manufacture of dipped articles such as protection gloves etc. (NR, NBR, CR)
Features of the Emulsion Process
Advantages:• high reactor output• good heat removal• low viscosities• high solids• high molar masses• high reproducibility
Disadvantages:• Waste water• Product impurities (residuals from
emulsifier and coagulants)• no water resistant catalysts
available (Stereospecifity)
Emulsion- Latex rubber Coagulation
E-SBR electrolyteNBR electrolyteCR freezingACM electrolyteFKM electrolyte
Wasser
Polymerization
Monomer emulsion Polymer dispersion(Latex or rubber latex)
Initiator
PrinciplesPrinciples of Emulsion of Emulsion PolymerizationPolymerization
Emulsifier
Monomer
MechanismMechanism of of EmulsionsEmulsions PolymerizationPolymerization
Monomer containing emulsifier micelleDiameter: 5-10 nm concentration: 1021 lw
-1
M
M
M
Monomer dropletDiameter: 0,1-10*10 -6 mconcentration: 1013 lw
-1
MMM
MM M
Polymerization occurs only inmonomer loaded micelles andnot in monomer droplets
Literature:• P. E. Lovell, M. S. El-Aasser, Emulsion Polymerization, Wiley 1998• Blackley, Emulsion Polymerization, 1975• H. Gerrens, Advances in Polymer Science, volume 1
M
Latex particleParticle diameter: 10-500 nmconcentration: 1017 lw
-1
M
M
PhasesPhases in Emulsion in Emulsion PolymerizationPolymerization
Literature: P. E. Lovell, M. S. El-Aasser, Emulsion Polymerisation, Wiley 1998Blackley, Emulsion Polymerisation, 1975H. Gerrens, Fortschritte der Hochpolymerforschung
0
10
20
30
40
50
60
70
80
0 20 40 60 80 100
Monomer Conversion [%]
Arb
itra
ry U
nit
s
Surface tenisonpressurepolymerization rate
Phase I Phase II Phase III
KineticKinetic AspectsAspects of Emulsion of Emulsion PolymerizationPolymerization
Number of latex particles formed:
NL = k * (E-CMC)x
* I y
Polymerization rate in Phase II:
VBr = NL * kw* [n]* [M]
NL: number of latex particles [lw-1]
E-CMC: effective emulsifier concentration [lw-1]
I: Initiator concentration [lw-1]
kw: propagation rate constant [l * mol-1 * sec-1][n]: average concentration of radicals per particle [without dimension][M]: monomer concentration in latex particle [Mol * l-1]
Phase I: NL and Vbr increase„free“ emulsifier reduces surface tension
Phase II: NL und Vbr remain constantthe monomer concentration in latex particles remains constantthe latex particles grow and soap coverage decreasessurface tenison increases
Phase III: the monomer droplets have disappearedthe monomer contained in latex particles is consumedthe number of latex particles remains constant
Prediction by the Smith Ewart Theory: x = 0,4; y = 0,6
[n]= 0,5
FlowFlow Diagram of a Diagram of a ContinuousContinuous Emulsion Emulsion PolymerizationPolymerization (E(E--SBR)SBR)
Po
lym
eris
a-t
ion
skess
el
Flash evaporation
Bu
tad
ien
e
Sty
ren
e
Aq
ueo
us
em
uls
ifie
rso
luti
on
Hy
dro
pero
xid
e
Aq
ueo
us
cata
lyst
solu
tio
n
Po
lym
eris
a-t
ion
skess
el
Po
lym
eris
a-t
ion
skess
el
Po
lym
eris
a-t
ion
skess
el
Po
lym
eris
a-t
ion
skess
el
Sh
ort
sto
p
Abstopp-kessel
Strippingcolumn
Brüdenkondensation
Vapourcondensation
Mixer/Settler
Wate watertreatment
Recovered butadiene
Mixer/Settler
Waste water treatment
Recovered styrene
Latex-storage
Va
po
ur
Puffertank
FlowFlow Diagram of Latex Diagram of Latex FinishingFinishing(E(E--SBR, NBR)SBR, NBR)
Dewateringscrew
Mass Balance:
Latex volume : 400.000 tRubber (25%): 100.000 tWater serum (75%): 300.000 tWash water: 100.000 tWaste water: 400.000 t
Baler and packaging
dryer
Wash-tank
Coagulationtank
Co
ag
ula
nts
Ad
dit
ives
(oil
, etc
)
La
tex
AO
Wa
shw
ate
r
Waste water treatment
FinishingFinishing of CRof CR--LatexLatex
packaging
dryer
Acidic acid
strippedLatex
Waste water treatment
dewatering rolls
Powdering Chopper
Latex-surge
tank
Freezingroll
Wasserhaushaltsgesetz (WHG)“Legislation on the regulation of the water household"
of September 23rd, 1986, BGB1. I, S. 1654
Abwasserabgabegesetz (AbwAG)“Legislation on Charges for the emission of polluted water“
of November 6th, 1990, BGB1. I, S. 2432
Abwasserherkunftsverordnung (AbwHerkV)“Legislation on the provinence of waste water"
Of July 3rd, 1987, BGB1.I, S. 1578
Trinkwasserverordnung (TrinkwV)“Legislation on the quality of drinking water and on water which is used in
food production”
of December, 5th, 1990, BGB1. I, S. 2612
Legal Legal AspectsAspects of Water of Water SurveillanceSurveillance in Germanyin Germany
Source:
W. Guhl und U. Werner; Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH,
D-69469 Weinheim, 1997
“Legislation on the regulation of the water household“of September 23rd, 1986, BGB1. I, S. 1654
Water is a natural ressource. It has to be used in a sustainablemanner for the benefit of the community as well as for the benefitof individuals. Negative impacts have to be avoided.
Everybody who uses water is obliged under the necessarycircumstances to act in a careful and responsible manner in order to avoid water pollution and negative impacts on the properties of water.
Legal Legal AspectsAspects of Water of Water SurveillanceSurveillance in Germanyin Germany
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
Legal Legal AspectsAspects of Water of Water SurveillanceSurveillance in in GermanyGermany
“Legislation on Charges for the emission of polluted water“of November 6th, 1990, BGB1. I, S. 2432
By law, in 1990 one “pollution unit“ was fixed at 70 DM. According tothis law, one pollution unit was defined to correspond to:
Source: Nachr. Chem. Tech. Lab. 45 (1997) Supplement; Wiley-VCH Verlag GmbH, D-69469 Weinheim, 1997
• 50 kg O2 (COD) • 3 kg Phosphorous• 25 kg Nitrogen• 2 g organic halides• 20 g Hg• 100 g Cd• 500 g Cr• 500 g Ni• 500 g Pb• 1 kg Cu• etc.
1. COD = 0
2. BOD = 0
3. COD = BOD
4. COD < BOD
5. BOD < COD
Which equation does not make sense?
Legal Legal AspectsAspects of Water of Water SurveillanceSurveillance in Germanyin Germany
COD: Chemical Oxygen Demand
BOD: Biological Oxygen Demand
Explanation:
COD = 0 no impurities present which can be chemically
oxidized (very pure water)
BOD = 0 no biologically degradable substances present
(substances which are not biodegradable might
be present)
COD = BOD all impurities are biodegradable
COD < BOD this is not possible
BOD < COD The impurities are only partially biodegradable
Legal Legal AspectsAspects of Water of Water SurveillanceSurveillance in Germanyin Germany
3.1. 3.1. EmulsionEmulsion--SBRSBR (E(E--SBR)SBR)
• Overview–Microstructure and Property Profile
–Market
–Application Areas, Market, Products and Important Grades
–Producers and Production Capacities
• Polymerisation –Polymerization Recipe („Cold Rubber“)
–Ingredients of a Polymerization Recipe
–Sequence of Reaction Steps
–Copolymerisation of Styrene und Butadiene
–Influence of Chain Modification Agents
• Product Properties–Tg
–Influence of None Polymeric Residues on Compound and
Vulcanizate Properties
MicrostructureMicrostructure of Eof E--SBRSBR
CH3
CH2
CH21
CH2
4
CH2
1
CH2
CH3
CH24
CH2
CH21
CH2 CH
21
CH3
CH
2
4
1,4-cis 1,4-trans Vinyl Styrene
Tyres
72%
mechanical
parts
8%
Others
2%Buildings
5%Shoes
5%Automotive
8%
EE--SBR: Property Profile and SBR: Property Profile and ApplicationApplication AreasAreas
Positive:• good mechanical properties of filled vulcanizates (TS, Modulus, Abrasion
Resistance)• Good wet skid properties (dependent on amount of incorported styrene/Tg)• short sequences of incorportated styrene (low hysteresis losses and low
rolling resistance)• Availability of high Mooney-grades which allow for high loadings of mineral
oil (oil extended grades with reduced price)• Great variety of standardized grades• Many competitors/low price (commodity)
Negative:• poor ageing resistance• poor resistance to swelling in oils• no variation of microstructure• low / no profits / no R&D-activities
Application Areas in Western Europe
EE--SBR: SBR: ProducersProducers and and ProductionProduction CapacitiesCapacitiesProduer Site Country CapacityCopolymer (DSM) Baton Rouge USA 150.000
Goodyear Houston USA 267.000
Ameripol Synpol Port Arthur/Odessa USA 336.000
Bayer Sarnia Can. 20.000
Petroquimica Argentina Pto. Gral, San Martin Argentinia 53.500
Petroflex/Coperbo Duque de Caxias/Triunfo Brasil 255.000
Negromex Altamira Mexico 74.500
Bayer France La Wantzenau France 90.000
Dow Schkopau Germany 120.000
Enichem. Ravenna Italy 295.000
Shell Pernis Netherlands 120.000
Dwory Oswiecim Poland 104.000
Chemopetrol Kralupy Czech Rep. 76.000
HIP Petrohemija Zrenjanin Crotia 40.000
Combinatul Petrochimic Onesti Rumania 100.000
Neftochim Burgas Bulgaria 20.000
JSR Kawasaki Japan 195.000
Mitsubishi Kasei Corp. Yokkaichi Japan 65.000
Zeon Corp. Tokuyama/Kawasaki Japan 200.000
Sumitomo Chemical Comp. Chiba Japan 50.000
Korea Kumho Ulsan Korea 190.000
Hyundai Daesan Korea 60.000
Taiwan Synthetic Kaohsiung Taiwan 105.000
BST Elastomers Mab Ta Phut, Rayong Thailand 60.000
Gadjha Tunggal Indonesia 60.000
Quenos Altona Australia 35.000
Apar und Synthetics &Chemicals Bombay/Bareilly India 75.000
V/O Raznoimport Omsk/Sterlitamak/Togliatti/Voronezh USSR 486.000
SINOPEC und Petro China Lanzhou/JiLin China 200.000
Sum 3.902.000
Market: 2,0 Mio tCapacity: 3,9 Mio tCapacity utilization: 51%
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
EE--SBR: SBR: ProducersProducers and and CapacitiesCapacities in Europe in Europe ((withoutwithout Latex Latex CapacitiesCapacities): ):
Company Site Country CapacityLanxess France La Wantzenau France 45.000
Dow Schkopau Germany 120.000
Enichem. Ravenna Italy 295.000
Dow (prior owner: Shell) Pernis Netherlands 120.000
Sum 580.000
415.000Dwory Oswiecim Poland 104.000
Chemopetrol Kralupy Czech Republic 76.000
HIP Petrohemija Zrenjanin Croatia 40.000
Combinatul Petrochimic Onesti Rumania 100.000
Neftochim Burgas Bulgaria 20.000
Sum 340.000
0
100
200
300
400
500
600
700
1990 1992 1994 1996 1998 2000 2002
Pro
du
cti
on
[t]
Market Volume in WE: 666 k tCapacities in WE: 415 ktFormal Capacity Utilization in WE: 160 %
Source: Worldwide Rubber Statistics 2001, IISRP, International Institute of Synthetic Rubber Producers, Inc.
Dow Chemical shuts down ESBR-Plant in Pernis/ end of March 2004 (Chemical Week of 24.03.2004)
Lanxess shuts down E-SBR production in La ‚Wantzenau effective by July 2008
Range of ERange of E--SBR Grades SBR Grades
Source: The Synthetic Rubber Manual, 14th edition IISRP (International Institute of Synthetic Rubber Producers, Houston (1999)
Cold Rubber
Hot Rubber
High Styrene Rubber
without
additives
Carbon Black-
Masterbatch
Oil-extension
(<14 phr)
Oil extension
(>14 phr)
1000 - - - - X -
1500 X - - - - -
1600 - X X - - -
1700 - - - X - -
1800 - X - X - -
1900 - - - - - X
Cold Rubbernumber of
grade
assignation
Hot
Rubber
High
styrene
rubber
EE--SBR: SBR: SelectedSelected GradesGrades
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
E-SBR
grade
Styrene-
content
[wt.%]
ML 1+4
(100°C)
[MU]
Antioxydant
System
Remarks & Application
Areas
1500 23,5 50-52 S - - - -
General purpose rubber for
tyre treads and for technical
rubber goods
1502 23,5 50-52 NS - - - - uncoloured technical goods
1507 23,5 30-35 NS - - - -
Compounds with good
processability
(calandered and injection
moulded products)
1509 23,5 30-35 NS - - - -
E-SBR with low ash content
and low water swell (cables
and electronic industry)
1707 23,5 49-55 NS NAPH 37,5 - -lught colourd rubber goods
(hoses and profiles)
1712 23,5 49-56 S HAR 37,5 - -
1721 40 50-55 S HAR 37,5 - -
1609 23,5 61-68 S HAR 5 N 110 4Abrasion resistant
compounds für retreading
1808 23,5 48-58 S HAR 47,5 N 330 76tyre treads, dark colured
technical rubber goods
Mineral Oil
grade loading
- [phr]
Carbon Black
grade loading
- [phr]
Tyre treads, transportation
belts, dark colured technical
S: staining
NS: none staining
NAPH: naphthenic oil
HAR: highly aromatic
EE--SBR: SBR: RecipeRecipe forfor Cold Rubber Cold Rubber ProductionProduction
Monomers:
Butadiene
Styrene
Modifier: t-DDM
Reaction medium:
Water
Emulsifier System:
K-salt of disproportionated rosin
Na-salt of methylen-bis-naphthalinsulfonic acid
Initiator-System:
p-Menthylhydroperoxide
FeSO4 * 7 H20
Di-sodium salt of ethylenediaminotetraacetic acid
Na-salt of Formaldehydesulfoxylate
Na3PO4*12 H2O
23,2 wt.%
9,5 wt.%
0,07 wt.%
65,4 wt.%
1,5 wt.%
0,03 wt.%
0,04 wt.%
0,01 wt.%
0,02 wt.%
0,03 wt.%
0,16 wt.%
EE--SBR: SBR: IngredientsIngredients of of PolymerizationPolymerization RecipeRecipe II((EmulsifiersEmulsifiers))
CH3
CH3
COOHH
CH3
CH3
COOHH
CH3
CH3
COOH
H
CH3
CH3
COOH
H
+ +
Abietic Acid
Dehydroabietic Acid Dihydroabietic Acid Tetrahydroabietic Acid
Pd
Disproportionation of Abietic Acid
Na-Salt of Methylene-bis(Naphthalin-sulfonic Acid) (Baykanol PQ(R))
CH2
-SO3
Na
-SO3
Na
2 Na +
EE--SBR: SBR: IngredientsIngredients of of PolymerizationPolymerization RecipeRecipe IIII
CH2
CH2
CH
CH2
CH2
CHCH3
CH3
CH3
O O H
N CH2
CH2
N
CH2
CH2
CH2
CH2
OH
OH
OH
OH
O
OO
O
S
O
O
H
O
H
H Na+
p-Menthanehydroperoxide (p-MHP)
Na-FormaldehydesulfoxylateNa-Hydroxymethanesulfinate
Ethylenedinitrilotetraacetic Acid (EDTA)
Oil soluble hydroperoxide
Reducing agent
Sequestering agent
for Fe-Ions
EE--SBR: SBR: SequenceSequence of of ReactionReaction StepsSteps
Redox Initiation:R-OOH + Fe2+ R-O* + OH- + Fe3+
Fe3+ + Reducing agent Fe2+ + oxydized reducing agentR-O* + Monomer R-O-Mon*
Growth Reaction:R-O-Mon* + n Monomer P*
Regulation of Molar Mass with Mercaptanes:P* + HS - R P - H + R - S*R - S* + n Monomer R - S - Mn*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Transfer Reaction:P* + R - H R - H + P*
Termination Reaction:P* + P* P - P
EE--SBR: SBR: InfluenceInfluence of of ThiolsThiols
Tert-dodecylmercaptane [phm] Tert-dodecylmercaptane [phm]
Gel
con
ten
t[w
t.%
]
100
80
60
40
20
0
(ML
1+
4 (
100°C
)[M
E]
175
140
105
70
35
0
0 0,2 0,4 0 0,2 0,4
EE--SBR: SBR: Styrene/ButadieneStyrene/Butadiene--CopolymerizationCopolymerization (Differential (Differential StyreneStyrene Incorporation)Incorporation)
0 10 20 30 40 50 60 70 80 90 100
Styrene Content of Monomer Feed [wt. %]
Sty
ren
eC
on
ten
tof
Po
lym
er [
wt.
%]
100
90
80
70
60
50
40
30
20
10
0
Copolymerization Parameters
(Styrene = M1; Butadiene = M2)
r1 = 0,7
r2 = 1,4
As a Consequence of these
copolymerization parameters
there is no azeotropic composition
k11r1 =k12
k22r2 =k21
EE--SBR: SBR: CopolymerizationCopolymerization of of ButadieneButadiene and and StyreneStyrene(Integral (Integral StyreneStyrene Incorporation)Incorporation)
Inte
gra
l S
tyre
ne
Co
nte
nt
[wt.
%]
0 20 40 60 80 100
Monomer Conversion [%]
100
80
60
40
20
0
Polymerization Temperature:
+ 50°C Hot Polymerisation
- 20°C (Cold Polymerisation)
Monomer Feed
Styrene/Butadiene:
30/70
Ideal (random) Copolymerization forMonomer Feed Styrene/Butadiene: 30/70
Copolymerization Parameter:
r1 (Styrene) = 0,78
r2 (Butadiene) = 1,39
EE--SBR: Distribution of SBR: Distribution of StyreneStyrene SequencesSequencesin Ein E--SBR 1502SBR 1502
0
10
20
30
40
50
60
70
80
1 2 3 4 5 6 7 8 9 10 11 12
Number of Styrene Units
Pro
ba
bil
ity
[%
]
k11r1 =k12
k22r2 =k21
Copolymerization-
parameter
Styrol = M1
Butadien= M2
r1 = 0,7
r2 = 1,4
EE--SBR: SBR: MicrostructureMicrostructure
Source: The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Polymerization-
temperature
[°C]
-20
5
50
100
BR-Microstructure
1,4-cis 1,4-trans Vinyl
[%] [%] [%]
0,8 79,6 19,6
7,7 71,5 20,8
14,8 62,0 23,2
27,6 51,4 21,0
EE--SBR: SBR: DependenceDependence of of TgTg on on StyreneStyrene ContentContent
-100
-80
-60
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Styrene Content [Gew.%]
Tg [
°C]
expt. data
Fox-Flory-equation
Fox-Flory-Equation
1 w1 w2= + Tg Tg1 Tg2
Tg: Tg of copolymers in KTg1: Tg of homopolymer 1 in KTg2: Tg of homopolymer 2 in Kwn: weight fraction of copolymers 1 und 2Tg of
E-BR
Source: T. G. Fox, P. J. J. Flory; Appl. Sci., 21,581 (1950)
Tg of atacticpolystyrene
InfluenceInfluence of of NoneNone PolymericPolymeric ResiduesResidues on Compound and on Compound and VulcanizateVulcanizate PropertiesProperties: : AnalyticalAnalytical DataData
Product
Krylene 1500
mod.* Krylene 1500
Krynol 1712
mod.* Krynol 1712
Al
[ppm]
-
-
655
1
water-
extract
[wt.%]
0,33
0,23
0,41
0,20
Ash cont.
(850°C)
[wt.%]
0,33
0,23
0,41
0,20
chloride
[ppm]
0,110
0,079
0,230
0,045
Na
[ppm]
1105
910
1502
355
acetone-
extract
[wt.%]
6,9
2,4
32,3
30,1
Product
Krylene 1500
mod. Krylene 1500*
Krylene 1712
mod. Krynol 1712*
Mw
[g/mol]
424.280
429.210
740.170
716.760
Mw/Mn
3,46
3,51
3,69
3,74
ML 1+4
(100°C)
[ME]
45
51
52
54
Tg
[°C]
-51
-53
-50
-50
137,5 phr
of Krynol 1712 contains
37,5 phr oil
==>
27,27 wt.% oil
* Modification of latex finishing (coagulation and crumb wash) in order to obtaina rubber with a reduced content of residues with low molar mass
Krylene 1712 [phr]Krylene 1500 [phr]mod. Krylene 1712* [phr]mod. Krylene 1500* [phr]Carbon black N 339 [phr]Carbon black N 234 [phr]Mineral oil [phr]TMQ [phr]IPPD [phr]DTBD [phr]Stearic acid [phr]Zinc oxide [phr]Sulfur [phr]CBS [phr]DPG [phr]
InfluenceInfluence of of NoneNone PolymericPolymeric ResiduesResidues on Compound and on Compound and VulcanizateVulcanizate PropertiesProperties: Compound : Compound CompositionComposition
68,7550---
8020,00,5
0,750,752,02,51,91,20,3
--
68,7550-
8020,00,50,750,752,02,51,91,20,3
103,1325,0
--
80,0-
10,00,5
0,750,752,52,51,91,1
0,55
--
103,1325,080,0
-10,00,50,750,752,52,51,91,10,55
* Modification of latex finishing (coagulation and crumb wash) in order to obtaina rubber with a reduced content of residues with low molar mass
Krylene 1712 [phr]Krylene 1500 [phr]mod. Krylene 1712* [phr]mod. Krylene 1500* [phr[
Compound-Mooney ML1+4 (100°C) [MU]
Rheometer (160°C)ΜΜΜΜL [dNm]∆∆∆∆ F [dNm]ts1 [min]t50 [min]t90 [min]
Vulcanizate Properties:Tensile Strength [MPa]Elongation at break [%]M100 [MPa]M300 [MPa]Shore A Hardness/23°CShore A Hardness/70°CRebound/23°C [%]Rebound/70°C [%]
InfluenceInfluence of of NoneNone PolymericPolymeric ResiduesResidues on on Compound on Compound on VulcanizateVulcanizate PropertiesProperties
103,1325,0
--
67,0
8,335,34,87,511,2
17,34252,512,669632538
68,7550--
73,5
9,137,34,78,2
12,6
17,94802,3
10,972642233
--
68,7550
77,0
10,139,24,57,9
11,1
18,94702,3
11,871642536
--
103,1325,0
71,0
8,838,24,36,89,3
18,54102,714,371642742
• Overview
– Property Profile and Application Areas
– Producers and Poroduction Capacities
– Grades and Application Areas
• Manufacturing
– CR-Microstructure
– Monomer Manufacturing Processes
– Basic Features of Polymerization Recipes
• Influence of CR-Microstructure on Chemical and Physical Properties
– Crystallization, Glass Transition Temperature, CR-Vulkanization
• Rubber Grades
– Standard Grades
– Sulfur Grades
– Precrosslinked Grades
• CR-Vulcanization
– Mechanism
• Substitution of CR
3.2. 3.2. PolychloroprenePolychloroprene (CR)(CR)
Sources:- W. Obrecht, Houben Weyl-Müller Makromolekulare Stoffe (1987), volume E20/Teil 2, S. 842-859- P. R. Johnson, Rubber Chem. Technol. 49 (1976) 650-702
CR: Property Profile and CR: Property Profile and ApplicationApplication AreasAreas
Positive Aspects:• High loadability
• gute Vulkanisationsfähigkeit
• Adjustable crystallization rate
• Good vulcanizate properties
• Good dynamic properties
• High weather an ozone resistance
• Good adhesion to metals
• Good resistance against fungi, mould and bacteria
• Fair insulation properties
• Excellent fire resistance
• Low gas permeability
• Broad range of grades
Negative Aspects:• High density (2,5 g/cm3)
• High compound price
• Modest resistance against chemicals and oils
• Crystallization at low temperatures
• poor ageing resistance at elevated temperatures
Source: Various Press Releases
CR: CR: ProducersProducers and and ProductionProduction CapacitiesCapacities (2010)(2010)
X-Chongquing/China28Chonquin Changshou Chemicals
X-Yerewan/Armenia10Nairit Scientific Industrial
360Total
X
X
-
X
X
X
-
Butadiene
-
-
X
-
-
-
X
Acetylene
Kawasaki/Japan20Showa Denko KK
India25Pidilite
Datong/China25Shanxi Syntheic Rubber Co
Nanyo/Japan32Tosoh
Pontchartrin/USA45DuPont
Dormagen/Germany75Lanxess
Omi/Japan100Denki Kagaku Kogyo KK
SiteCapacityProducer
Grenoble/France
Houston/USA
Maydown/N.-Ireland
Louisville/USA
Site
25Polimeri (BP)
25Bayer
30
50
DuPont
CapacityProducer
Plant ClosuresStagnant CR-Consumption in WE and USA
Growing Consumption in South-East Asia
CH CH
CH CH CH2
CH CH CH2
CH2
CHCHCH2 CH
2
Cl Cl
CH CH CH2
CH2
ClCl
CH2
CH
ClCl
CH CH2
CH CH2
Cl
CH2 CH CH CH
2CH
Cl
HCl/CuCl(30-60°C)
2
CuCl/NH4Cl/HCl
Nieuwland
Acetylene Route (1930) Butadiene Route (Gas phase chlorination / 1956)
+
+
+ NaOH - HCl (85°C)
Cl2
CuCl
(ca. 40 %)
Side products: chlorinated C8-Compounds Tetrachlorobutane
(ca. 60 %)
1-Chloroprene (impurity)2-Chloroprene
+
+
DE 1149001; Knapsack AG, Prior.:10.07.1961Erf.: W. Vogt, K. Kaiser, H. Weiden
GB 804254; Distillers Co. Ltd. , Prior.:21.03.1956;Erf.: F. J. Bellringer
Monomer Monomer ManufacturingManufacturing ProcessesProcesses
C CH CH2
Cl
CH2
C C CH2
Cl
CH2
Cl
C CH CH2
Cl
CH2
Cl Cl
+
+ NaOH/85°C - HCl
Cl2
2-Chlorobutadiene-1,3 (Chloroprene)
Only DuPont, Lanxess und Denki
produce DCB
2,3-Dichlorobutadiene 1,3
(DCB)
CR: Grades and CR: Grades and AplicationAplication AreasAreas
DCB-Content of Monomer Feed [phm]
Po
lym
eriz
ati
on
Tem
pera
ture
[°C
]
0 1 2 3 4 5 6 7
Latex Grades Rubber Grades
(Standard Grades, precrosslinked grades
and sulfur grades)
AdhesiveGrades
50
45
40
35
30
25
20
15
10
0
CR Application Areas (2006)
Rubber
Applications
60%
Latex
applications
5%Latex based
adhesives
5%
Solvent
based
adhesives
30%
Application Areas of Rubber Grades
Profiles
11%Hoses
44%
Belts
12%
Cables
21%
Conveyor
Belts
12%
CR: CR: InfluenceInfluence of of PolymerizationPolymerization TemperatureTemperature on on MicrostructureMicrostructure
Polymerization Temperature [°C]
1,4
-tra
ns
-Co
nte
nt
[Mo
l %
]
0 10 20 30 40 50 60 70
Rubber- and Latex GradesAdhesivegrades
95
90
85 80
CH2
C2
C3
CH2
Cl
H
CH2
C2
C3
CH2
Cl
H1,2 3,4
CH2
C C
CH2
Cl
H
CH2
C C
CH2
Cl H
1,4-trans
1,4-cis
Polymerization 1,4-trans- 1,4-cis 1,2 3,4temperature [°C] [%] [%] [%] [%]
+12 94,5 3,8 1,0 0,8+30 93,5 4,5 1,2 1,0+42 93,5 4,5 1,2 1,1+57 91,5 5,8 1,4 1,3+75 88,5 8,4 1,5 1,4
For commercially available CR-grades small differences in thepolymerization temperature and in the 1,4-trans content are an important
factor
Tg [°C] -45 -20
Tm [ °C] 105 70
trans-1,4
> 89%
Microstructure cis-1,4
> 95%
CR: Basic Features of CR: Basic Features of CRCR--PolymerizationPolymerization RecipesRecipes
CH3
CH3
COOHH
CH3
CH3
COOHH
CH3
CH3
COOHH
+ +
Dehydroabietic Acid Dihydroabietic Acid Tetrahydroabietic Acid Na-Methylene-Bis(Naphthalinsulfonate)
(Baykanol PQ R)
CH2
-SO3
Na
-SO3
Na
2 Na +
60 - 85
20-50
-
-
0,0125
0,2-1,0
0,05-0,5
0,3-0,7
0,5-1,0
2,5-5,0
100-200
-
100
Latex grade
70 - 85
30-50
0,1-0,3
-
0,0125
0,2-1,0
0,05-0,5
0,3-0,7
0,5-1,0
2,5-5,0
100-200
-
100
Precrosslinkedgrades
60 - 85
30-50
-
0,3-0,7
0,0125
0,2-1,0
0,05-0,5
0,3-0,7
0,5-1,0
2,5-5,0
100-200
0 - 10
90-100
Sulfurgrades
60 - 85
30-50
-
-
0,0125
0,2-1,0
0,05-0,5
0,3-0,7
0,5-1,0
2,5-5,0
100-200
0 - 10
90-100
Standard grades
-Sulfur
-Dimethacrylates of alkanediols
5 - 20Polymerization temperature [°C]
60 - 85Monomer conversion [%]
0,0125Na-Anthrachinon-2-Sulfonate
0,2-1,0Potassiumpersulfate
0,05-0,5n-dodecylmercaptane
0,3-0,7Na-methylene-bis(naphthalinsulfonate)
0,5-1,0NaOH or KOH
2,5-5,0Disproportionated abietic acid
100-200Water
-2,3-Dichlorobutadiene
100Chloroprene
Adhesivegrade
Recipe Ingredients [wt.-parts]
Dependence of Shore A Hardnesson Crystallization Rate
Sh
ore
A H
ard
ne
ss
Storage time [h]
0,1 1 10 100 1000 10000
Hi
He-Hi
He
t1/2
1/2(He- Hi)
CR: Determination of CR: Determination of CrystallizationCrystallization RateRate
Source: U. Eisele: Internal Bayer-Reporting System
Mercury dilatometry for the determinationof crystallization rate
(Tc =-5°C pretreatment: 30 min at 80°C)
Storage time [h]
0,1 1 10 100 1000
80
60
70
50
40
30
20
10
0
Vo
lum
e[m
m3]
30
Dependence of t1/2 on StorageTemperature
(Baypren 210; Pretreatment: 1 h / 60°C)
Storage Temperature [°C]
5
10
15
25
20
t 1/2
[h
]
0
-20 -15 -10 -5 0 5 10 15 20
CR: CR: CrystallizationCrystallization Rate and Rate and CrystalliteCrystallite Melting Melting TemperatureTemperature
Source: U. Eisele „Introduction to Polymer Physics“ Springer Verlag
0
10
20
30
40
50
60
70
80
-60 -10 40
Polymerization temperature [°C]
Cry
sta
llit
e m
elt
ing
te
mp
era
ture
[°C
]
lowest figures
highest figures
Dependence of Crystallite Melting Temperatures on Polymerization
Temperature
DCB-Content of Monomer Feed [%]
Tg
[°C
]
DependenceDependence of of TgTg and and CrystallizationCrystallization Rate at Rate at --1010°°C on C on Monomer Monomer FeedFeed and and PolymerizationPolymerization TemperatureTemperature
- 31
0 3 12 1596
- 38
- 37
- 36
- 35
- 33
- 34
Sym-bol
T[°C]453525155
t 1
/2[h
]
10-1
100
102
101
103
0 3 9 12 156
DCB-Content of Monomer Feed [%]
45 35 25 15 5
Polymerization-temperature [°C]
CrystalliaztionCrystalliaztion Rates of Rates of UnvulcanizedUnvulcanized CR, CR, UnvulcanizedUnvulcanized CRCR--CompoundsCompounds and and CRCR--VulcanizatesVulcanizates at at -- 1010°°CC
t1/2 [h] (unvulcanized CR)
500
400
300
200
100
0
0 100 200 300 400 500 600 700 800
B. 210
B. 112
KA 8418
B. 110
B. 110 VSC
t 1/2
[h]
Unvulcanized CR-compounds
CR
-base
svu
lcan
izate
s
Unvu
lcan
ized
CR
CR 100,0 phr
Carbon black (N 762) 75,0 phr
Polyetherthioether 10,0 phr
Vulkanox DDA 2,0 phr
Vulkanox 4010 NA 0,5 phr
Stearic acid 0,5 phr
Magnesium oxide 4,0 phr
Zinc oxide 5,0 phr
25
20
15
10
5
0
DependenceDependence of of CrystallizationCrystallization Rate on Rate on BlendingBlending Ratio of Ratio of TwoTwoCRCR--GradesGrades and on Type of and on Type of PlasticizerPlasticizer
t 1/2
[h
]
Baypren 110 VSC (slowly crystallizing)
Baypren 210 (normally crystallizing) 0 20 40 60 80 100
100 80 60 40 20 0
Unvulcanized ISO- 2475-1975 Compounds; Measurements at - 10°C
CR 100 phrStearic acid 0,5 phrMagnesium oxide 0,5 phrPhenyl-2-Naphthylamin 2,0 phrCarbon black (N 772) 30 phrZinc oxide (active) 5,0 phrVulkacit® NP 0,5 phr
300
Influence of Plasticizers(CR-grade: Neoprene® W (~ Baypre® 210)
Temperature [°C]
50
100
150
250
200
t 1/2
[h
]
0
-20 -15 -10 -5 0 5 10 15 20
Source:R. M. Murray, J. D. Detenber Rubber Chem . Technol. 34 (1961) 668-685 “First and Second Order Transitions in Neoprene“
Neoprene® W + mineral oil
Neoprene® W + Butyloleate
DependenceDependence of of CompressionCompression Set (CS) of Different Set (CS) of Different CRCR--GradesGrades on on StorageStorage TemperatureTemperature
Temperature [°C]
-60 -40 -20 0 20 40 60 80 100 120 140 160 180
100
90
80
70
60
50
40
30
20
10
0
DCB-containing rubber grade (Baypren® 110) DCB-free rubber grade (Baypren® 210)CR Adhesive grade (Baypren® 320)
Bayer-Brouchure: „Chloropren-Kautschuk von Bayer: Der vielseitig einsetzbare Werkstoff“
CS
(1
68
h / v
ari
ab
le t
em
pe
ratu
res)
RecipeRecipe Features Features whichwhich areare specificspecific forfor Different Different CRCR--RubberRubber GradesGrades
CH2
CH CH2
Cl
CH2
CH2
Cl Cl
CH2
CH3
O
OCH2
CH3
O
O CH2
n
S
SS
S
SS
S
S
2 - Chloro - 1,3 - Butadiene
2,3 - Dichloro - 1,3 - Butadiene
Dimethacrylate
Sulfur
• Standard CR-Grade
• Sulfur Grade
• Precrosslinked CR-Grade
Molar Molar MassMass ControlControl byby MercaptanesMercaptanes and and bybyXanthogendisulfidesXanthogendisulfides
Molar mass control by Xanthogendisulfides results in the formation of polymer molecules withtwo identical (xanthate) end groups. Xanthate end groups participate in vulcanization. As a consequence, vulcanizates based on xanthate modified CR exhibit better mechanical propertiesthan mercaptane modified CR
Molar mass control by mercaptanes
P* + HS - R P - H + R - S*
R - S* + nM R - S - Mn*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Molar mass control by Xanthogendisulfides
P* + (RO - CS - S -)2 P - S - CS - OR + RO - CS - S*
RO - CS - S* + Mn RO - CS - S - Mn*
RO - CS - S - Mn* + (RO - CS - S -)2 RO - CS - S - Mn - S - CS - OR + RO - CS - S*
CR: CR: InfluenceInfluence of End of End GroupsGroups on on VulcanizateVulcanizatePropertiesProperties
30 40 50 60 70 80 90 100 110
ML 1+4 (100°C)
16
15
14
13
12
11
10
Modulus M300 [MPa]
Ten
sile
Str
ength
[MP
a]
22
21
20
19
18
10 11 12 13 14 15
ISO-Compound 2475CR 100,0 phrCarbon black N 762 30,0 phrStearic Acid 0,5 phrMgO 4,0 phrPhenyl-2-Naphthylamine 2,0 phrZnO active 5,0 phrVulkacit NPV/C 0,5 phr
Vulcanization: 40 min/150°C
CR-grade with xanthate end groups
Mercaptan modified CR-grade
M300
[MP
a]
DynamicDynamic ResistanceResistance of of CRCR--StandardStandard Grades (Grades (MonsantoMonsanto Test)Test)
52 54 60 62 64 665856
Strain Amplitude[%]
0
50
100
150
250
200
Cy
cles
un
til
fail
ure
[kcy
cles
]
Source: R. Musch presented at the 140th ACS Rubber Division Meeting, Detroit October 8-11, 1991
68
Xanthate modified CR-Grade (Baypren 121) unaged
7 days / 100°C
Mercaptane modfied CR-grade (Baypren 110 VSC) unaged
7 days / 100°C
ISO-Compound 2475CR 100,0 phrCarbon black N 762 30,0 phrStearic Acid 0,5 phrMgO 4,0 phrPhenyl-2-Naphthylamine 2,0 phrZnO active 5,0 phrVulkacit NPV/C 0,5 phr
Vulcanization: 40 min/150°C
CRCR--SulfurSulfur GradesGrades
NR2 C S CH
2
S
C
Cl
CH CH2
S CH2
C
Cl
CH CH2
S C NR2
S
u v w x y( )()
Application:Vulcanizates which are based on CR sulfur grades perform particularly well in dynamicapplications. As a consequence, belts which meet the requirements of different applications area major application area (conveyor belts, V-belts, poly-v-belts, timing belts)Production:CR-Sulfur Grades are obtained by two consecutive production steps (1. Polymerization and 2. Chemical break down of high molar masses)In the 1st production step chloroprene and sulfur are copolymerized. The copolymers obtainedhave a high molar mass and long sulfur bridges. In the 2nd production step, the molar mass of the copolymers is reduced by a break down of sulfur bridges (peptization). As a consequence of the chemical breakt down of the sulfur bridges dithiocarbamate end groups are incorporated. These end group participate in vulcanization.. As a consequence, the number of dangling chainends is reduced and vulcanizate properties are improved. Compounding and Vulcanization:During compounding residual sulfur bridges are broken down "Mastication". Sulfur grades can be vulcanized by the addition of ZnO and/or MgO (without the addition of accelerators).Critical Aspects:During storage, the Mooney viscosity of sulfur modified CR can increase or decrease. Heatresistance of vulcanizates based on sulfur modified CR is inerior to that of standard CR.
ProductionProduction of of CRCR--SulfurSulfur GradesGrades
S CH2
Cl
CH CH2
S S CH2
Cl
CH CH2
S S
S
NR2
S
NR2
S
S
NR2
S CH2
CH CH2S CH
2
Cl
CH CH2
S S
S
NR2
v x( )()
a w
x)(
v( )
a n
n
w
CH2
C
Cl
CH CH2
S8+
1) Copolymerization of Chloroprene and Sulfur
2) Chemical break down of high molar masses by the use of disulfides, particularly Thiuramdisulfides
Impact of Impact of thethe AmountAmount of Incorporated of Incorporated SulfurSulfur on on MasticationMasticationand and AgeingAgeing PerformancePerformance
30
32
34
36
38
40
42
44
46
48
50
0 2 4 6 8 10
Mastication time [min]
ML
1+
4 (
10
0°C
) [M
E]
Baypren 510
Baypren 610
Inco
rpora
ted
Su
lfu
r
Mastication:
Mill size: 200 x 400 mmFriction: 1:1,2Revolutions: 20 min-1
Width: 1,2 mmAmount: 600 mg
0
10
20
30
40
50
60
70
80
0 0,2 0,4 0,6
Sulfur [phm]
Ch
an
ge o
f M
10
0 (
7d
/10
0°C
) [%
]
Compound Ingredients:
CR 100 phrRuß (N 762) 75 phrPolyetherthioether 10 phrVulkanox DDA 2,0 phrVulkanox 4010 NA 0,5 phrStearic acid 0,5 phrMagnesium oxide 4,0 phrZinc oxide 5,0 phr
VulcanizationVulcanization of of CRCR--SulfurSulfur GradesGradesH
CH
H
N
S
N
S Sx
S
S
S
N
H
S
Sx
S
S
H
C
H
N
S
N
SH
CR-Sulfur grades (which are fullycommercially available) containdithiocarbamate end groups which areattached via sulfur bridges. These end groups are active in vulcaniaztion.
CR-Sulfur grades can be considered as "rubber bound intermediates“ which areknown from theoretical considerationson the mechanism of sulfur cure.
As a consequence, CR sulfur grades arevulcanized by the use of ZnO and MgO(+ Stearinsäure) without usingaccelerators.
CR sulfur grades exhibit a criticalstability of Mooney viscosities duringstorage particularly at elevatedtemperatures.
PrecrosslinkedPrecrosslinked CRCR--GradesGrades
CR-Gel
Ungelled
(soluble)
CR
Application:
Unvulcanized CR compounds whichcontain CR gel exhibit good processingfeatures, particularly a low die swell.
Major application areas are extrudedarticles (wiper blades as well as windowand door seals In these applications CR is being substituted by EPDM and TPEs.
Production:
Precrosslinked CR-rades are blends of gelled CR and ungelled (soluble) CR. Thetwo blend components are producedseparately by emulsion polymerization. Prior to finishing, the two latices areblended. By the latex blending process a good dispersion of the gelled CR pariclesin the soluble CR phase is achieved.
ded0
Rubber Compound
Die swell = x 100de
do
PropertiesProperties of of PrecrosslinkedPrecrosslinked CRCR--GradesGradesD
ie S
well
[%]
26
38
42
46
34
30
50
10
16
18
20
14
12
Gel content [wt.% %]
Ten
sil
eS
tren
gth
[MP
a]
0 10 20 30 40 50 60 70
Gel content [wt.% %]
0 10 20 30 40 50 60 70
VulcanizationVulcanization of CRof CR
CH2
CH2
NHNH
S
CH2
Cl
CH
CH2
CH2
CH2
NHNH
S+
CH2
CH
CH2
CH2
CH2
NHNH
Cl S
CH2
CH
CH2
CH2
CH2
NHNH
O S
CH2
CH
CH2
CH2
CH2
NHNH
O S
CH2
CH
CH2
CH2
CH2
NHNH
O
S
CH2
CH
CH2
S
CH2
CH
CH2
CH2
Cl
CH
CH2
CH2
CH
CH2
S
CH2
CH
CH2
- ZnCl2
Cl
+
+ ZnO
- ZnCl +
-
Mechanism of CR-Vulcanization according to Pariser/Du Pont
+ ZnCl ++
CH2CH
2
NHNH
S
CH2CH
2
NS
S
CH3
Ethylenethiourea(ETU/Vulkacit(R) NPV)
"cyclic Dithiocarbamate" (Vulkacit(R) CRV)
Chemicals for CR-Vulcanization
OS
S
R
NR2
S
S
Sx
Xanthate end groups are presentin in xanthate modified CR
Dithiocarbamate end groups arepresent in sulfur modified CR
End groups which participate inCR-Vulcanization
Substitution of CRSubstitution of CR
0 20 40 60 80 100 120 140
max. Volume Swell in ASTM-Öl Nr. 3 [Vol %]
ma
x.
se
rvic
ete
mp
era
ture
[°C
]
100
125
150
175
200
225
250
75
50
FKM
FMVQ
FZ
EU
CMCSM
norequirements
NRAU
NBR
CR SBR BR
EPDM(H)IIR
EVM
MVQ
AEMACMHNBR
80 % VAcResistance to high temperatures
Resistance to dynamic stress
Price
Resistance to high temperatures, flame resistance
• Overview– NBR-Microstructure
– Basic Features of NBR and Range of NBR Grades
– Application Areas of NBR and Market
– Producers and Production Capacities
– Range of NBR Grades
– Dependence of Properties on Acrylonitrile Content
• Polymerisation– Emulsifiers
– Initiator systems
– Molar mass regulation
– Copolymerization
• Product groups and Properties– Standard grades
– Carboxylated grades
– Precrosslinked grades
• Vulcanization and Vulcanizate Properties
NitrileNitrile Rubber (NBR)Rubber (NBR)
NBR: NBR: MicrostructureMicrostructure
CH3
CH2
CH21
CH2
4
CH2
CH CH
CH2
CH2 CH
21
CH3
CH
2
4
1,4-cis 1,4-trans Vinyl Acrylonitrile
CN
CH2CH
21
δ +δ +δ +δ +
δ δ δ δ −−−−
C
N
CN
DependenceDependence of of thethe MicrostructureMicrostructure of Incorporated of Incorporated ButadieneButadiene MoietiesMoieties on on PolymerizationPolymerization TemperatureTemperature
Source:The Synthetic Rubber Manual (International Institute of Synthetic Rubber Producers, Houston (1989)
Polymerization-
temperature
[°C]
-20
5
50
100
Microstructure of Butadiene Sequences
1,4-cis 1,4-trans Vinyl
[%] [%] [%]
0,8 79,6 19,6
7,7 71,5 20,8
14,8 62,0 23,2
27,6 51,4 21,0
Basic Features of NBRBasic Features of NBR
Positive:• Low degree of swelling in oil, fuels, greases and fats
•High kevel of mechanical properties•High abrasion resistance especiall for carboxalatedgrades
• Broad range of grades• Low gas permeability• Low price level / high competition
Negative:• Maximal service temperature: < 110 °C
(Criterium: 1000 h / εεεεb=0,5*εεεεb0)• Standard grades are not applicable for outdoor use
(contrary to NBR/PVC-Blends)
slow cure
peroxide cure
Fast curing / Low mouldfouling
(Injection moulding)
liquid NBR-HO-terminated-COO-terminated-NH2-terminated
NBR-powder grades
NBR/PVC-Blends
NBRmit bound antioxydant
X-NBR Special grades
Standard
grades
Precrosslinked NBR
NBRNBR--ApplicationApplication AreasAreas in Western Europein Western Europe
Others
4%
Adhesives
1%
Cable and
wiring
5%
shoes
5% building
5%
Rubber
modification of
Thermoplastic
and
duroplastic
polymers
11%
Automotive
35%Rubber Goods
(without
automotive)
34%
time in ASTM-ÖL3 [days]0 7 14 21
0
50
100
150
200
250
300
NBRCR
SBR
NR
Vo
lum
esw
ell
[%]
NBR:MarketNBR:Market-- und und DevelopmentDevelopment
0
50
100
150
200
250
300
350
400
450
1985
1990
1995
2000
2005
2010
Co
ns
um
pti
on
[j/
y]
NBR: NBR: ProductionProduction CapacitiesCapacities(European Rubber Journal 181, n(European Rubber Journal 181, noo 4, April, S. 10 1999; 4, April, S. 10 1999; updatedupdated in in JulyJuly 2010)2010)
Zeon Tokuyama / JP 45 NipolKawasaki /JP 20 NipolLouisville / USA Goodrich 35 HycarHouston / USA Goodyear 28 ChemigumBarry/Wales / GB BP 15 Breon(Baton Rouge / USA) (Copolymer) 15 (Nysin)
Lanxess La Wantzenau / FR Polysar 100 Perbunan / KrynacLeverkusen / DE Bayer 35 PerbunanSarnia / CAN Polysar 25 Perbunan / KrynacTriunfo / BRA Petroflex 30 Perbunan
JSR Yokkaichi / JP 35 JSR NBRPolimeri Porto Torres / IT 30 EuropreneParatec Altamira / Mexico Negromex/Uniroyal 25 ParatecKorean Kumho Ulsan 20 Kumho NBRLucky Gold Hyundai 16President Kaoshing / Taiwan 15Eliokem Sandouville / FR Goodyear 11 Chemigum (Powder)
Valia /Gujarat - Indien Goodyear 25 Chemigum (bales)Nitriflex Duque de Caxais / BRA 10 Nitriflex/NitricleanPASA Santa Fe 5S&C Bareilly 2Sibur Omsk
Total: 424
NBRNBR--StandardStandard GradesGrades
Mooney Viscosity ML 1+ 4 (100°C)
Acr
ylo
nit
rile
con
ten
t[w
t. %
]
without pretreatment (DIN 53523)
15
20
25
30
35
40
20 30 40 50 60 70 80 90 100 125
45
50
NBR: NBR: DependenceDependence of of TgTg on on AcrylonitrileAcrylonitrile ContentContent
Tg
[°C
]100
80
60
40
20
+0
-20
-40
-60
-80
-100
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile content [wt.%]
E-BR
PAN
Gordon-Taylor-Equation*
TgCopolymer = w1*Tg1 + w2*Tg2
TgE-BR = - 80°C
TgPAN = + 100°CRange of C
omm
ercia
l gra
des
*Gordon M., Taylor J. S., J. Appl. Sci., 21, 581 (1950)
NBR: NBR: DependenceDependence of of VolumeVolume SwellingSwelling on on AcrylonitrileAcrylonitrile ContentContent
vvvv
vW
eig
ht
Ch
an
ge[
%]
90
80
70
60
50
40
30
20
10
0
-10
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile content [wt.%]
Fuel C (Isooctan/Toluene: 50/50)Fuel B (Isooctan/Toluene: 70/30)
ASTM Öl Nr. 3 (aromatic/naphthenic)ASTM Öl Nr. 1 (paraffinic)
Expt. Conditions:
14 days
Fuel B and C: 20°C
ASTM-Oils: 140°C
DependenceDependence of of ShoreShore AA--HardnessHardness and Rebound on and Rebound on AcrylonitrileAcrylonitrile ContentContent
Reb
ou
nd
[%
]
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile [wt.%]
75°C
20°C
Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)
Sh
ore
A H
ard
nes
s
90
80
70
60
50
400 5 10 15 20 25 30 35 40 45 50
Acrylonitrile content [wt.%]
75°C
20°C
DependenceDependence of of CompressionCompression Set on Set on AcrylonitrileAcrylonitrileContentContent
Co
mp
ress
ion
Set
(70
h/1
00°C
) [%
]
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
Acrylonitrile-content [wt.%]
Source: Rubber, 3 Synthetic Ullmann‘ s Encyclopedia of Technical Chemistry, Vol A 23 (1993)
NBRNBR--PolymerizationPolymerization: : ActivationActivation of of PolymerizationPolymerization, , Molar Molar MassMass Regulation and Regulation and DeactivationDeactivation
Redox Initiation:R-OOH + Fe2+ R-O* + OH- + Fe3+
Fe3+ + Reducing agent Fe2+ + oxydized Reducing agentR-O* + Monomer R-O-Mon*
Growth reaction:R-O-Mon* + n Monomer P*
Molar Mass Regulation by Mercaptanes:P* + HS - R P - H + R - S*R - S* + n Monomer R - S - Mn*
R - S - Mn* + HS - R R - S - Mn - H + R - S*
Transfer Reaction:P* + R - H R - H + P*
Deactivation:P* + P* P - P
EmulsifiersEmulsifiers forfor NBRNBR--PolymerizationPolymerization
CH3
CH3
COOHH
CH3
CH3
COOHH
CH3
CH3
COOHH
CH3
CH3
COOHH
+ +
Abietic Acid Dehydro abietic acid Dihydro abietic acid Tetrahydro abietic acid
Pd
Disproportionated Abietic Acid
Methylen-Bis (Naphthalin- sulfonsäure), Na-Salz (Baykanol PQ(R))
CH2
-SO3
Na
-SO3
Na
2 Na +
Partially hydrogenated tallow fatty acids
Producer Brand name C14 ges. C14 ges. C18 ges. C18 unges.BAX AG IS/1 3,1 32,5 33,5 31
Holm THT 1618W 0,4 27,5 34,8 37,3
Oleon Radiacid 40 3,5 35,1 24,8 36,6
Unichema Prifac 5910 2,6 37,7 31,5 28,3
Cognis Edenor C1618 1,2 40,3 26,4 32,1
Sulfates- und Sulfonates (Examples)Na-Laurylsulfate (Texapon)
Na-Alkylarylsufonate (Marlon)
Na-Alkylsufonate (Mersolat)
ActivatatorActivatator Systems Systems forfor NBRNBR--PolymerizationPolymerization
CH2
CH2
CH
CH2
CH2
CHCH3
CH3
CH3
O O H
N CH2
CH2
N
CH2
CH2
CH2
CH2
OH
OH
OH
OH
O
OO
O
S
O
O
H
O
H
H Na+
Fe SO4
p-Menthylhydroperoxide (p-MHP)
Na-FormaldehydesulfoxylateNa-Hydroxymethanesulfinate
Ethylenedinitrilotetraacetic acid (EDTA)
Ion-(II) sulfate
(NH4)2 S
2O
8
N
CH2
CH2
CH2
CH2
CH2
CH2
OH OH
OH
Ammoniumperoxodisulfate
Triethanolamine
“Organic“ Activation System“Inorganic“
Activation System
CopolymerizationCopolymerization Diagram Diagram forfor thethe CopolymerisationCopolymerisation of of Butadiene/ACNButadiene/ACN-- ((forfor incrementalincremental conversionsconversions))
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile content of monomer feed [wt.%]
Acr
ylo
nit
rile
con
ten
tof
poly
mer
[w
t. %
] 100
90
80
70
60
50
40
30
20
10
0
Copolymerization Parameters
(ACN = M1; Butadiene = M2)
5°C: r1 = 0,02; r2 = 0,28
50°C: r1 = 0,04; r2 = 0,42
Azeotropic composition:
(calculated for 5°C)
Acrylonitrile: ca. 38+5 Gew.%
Butadiene: ca. 62+ 5 Gew.%
k11r1 =k12
k22r2 =k21
Source: W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
AzeotropicComposition
Ideal Copolymerisation
NBR: NBR: DependenceDependence of Integral of Integral CopolymerCopolymerCompositionComposition on Monomer on Monomer ConversionConversion
Acr
ylo
nit
rile
Con
ten
tof
Poly
mer
[G
ew. %
]100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Monomer Conversion [%]
Acrylonitrile content
of monomer feed:
60 wt.%
50 wt.%
38 wt.%33 wt.%28 wt.%
20 wt.%
10 wt.%5 wt.%
Modellierungsparameter
(ACN = M1; Butadien = M2):
r1 = 0,02; r2 = 0,28
W. Hofmann, Nitrilkautschuk, Berliner Union Verlag
NBR: NBR: DependenceDependence of of IncrementalIncremental and Integral and Integral AcrylonitrileAcrylonitrile ContentContent on Monomer on Monomer ConversionConversion
Acr
yln
itri
lon
itri
leco
nte
nt
of
poly
mer
[w
t. %
]
100
90
80
70
60
50
40
30
20
10
0
0 10 20 30 40 50 60 70 80 90 100
Monomer conversion [%]
Monomer Feed:
Acrylonitrile: 73,7 wt.%
Butadiene: 26,3 Gew.%
Copolymerizatin parameters:
r1 = 0,023; r2 = 0,30
Incremental composition
Integral composition
Incorporation of ACN during batch-polymerization
For the production of a NBR-grade with
a high chemical homogenity one or both
of the two monomers (ACN respectively
butadiene) have to be incrementally added
during the course of the polymerization in
order to compensate for changes in the
composition of the monomer feed, unless
polymerization is performed in the azeo-
tropic monomer composition
NBR: NBR: DependenceDependence of of TgTg on on PolymerizationPolymerization ParametersParameters((BatchBatch--PolymerizationPolymerization))
Lower Tg Upper Tg
[wt.%] [°C] - [%] [°C] [°C]
A 38,9 5 - >57 -19
B 32,8 5 - >57 -22
C 25,8 5 - >57 -61 -33
D 44,8 50 - >57 -13
E 34 50 - >57 -26
F 29,2 50 - >57 -46 -32
G 28,5 50 - >57 -49 -33
H 23 50 - >57 -64 -40
I 21,1 50 + >57 -53
K 31,4 50 - 57 -31
TgMonomer
Conversion
Sample Bound
ACN
Polymerization
temperature
ACN-addition
during
polymerization
Source:V. R. Landi (Uniroyal) Presented at a meeting of the Divison of Rubber Chemistry of the American Chemical Society, Cleveland, Ohio, October 12-15 (1971)
Rubber Chemistry and Technology
Batchwise NBR-Polymerization may result in chemically
inhomogenous blends which exhibit two separate Tg-peaks
InfluenceInfluence of of TDMTDM--QualityQuality on on thethe EfficiencyEfficiency of of Molar Molar MassMass RegulationRegulation
• For NBR-Production C12-Mercaptans are efficient molar mass modifiers
• Tert.-Dodecylmercaptane (TDM) is specifically important
• TDM by Chevron Phillips is based on propene-tetramers
• TDM by Lanxess is based on isobutene-trimers
0
20
40
60
80
100
120
140
160
0 0,1 0,2 0,3 0,4 0,5 0,6 0,7
Amount of TDM [phm]
Mo
on
ey V
isco
sit
y
ML
1+
4 (
100°C
)
TDM / Lanxess
TDM / Phillips Chevron
Molar Molar MassMass Regulation Regulation byby TDM TDM BasedBased on TIBon TIB
H+
H+
SH
++
Wagner- Meerwein- Rearrangement
+
-
+
"Triisobutene (TIB)"
1. TIB- Production by Isobutene-Oligomerisation
2
+
2. TDM-Production by the Addition of H2S to TIB
H2S / Cat.
2,2',4,6,6'-Pentmethylheptanthiol-4
+
"Triisobutene (TIB)"
TDM-Mischung: Herstellung und Anwendung22.05.2007LanxessDE 102007024009
Zeon
Zeon
Zeon
Company
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol27.12.1994Jp 07 316 128
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol27.12.1994Jp 07 316 127
Preparation of 2,2,4,6,6-pentamethylheptan-4-thiol27.12.1994Jp 07 316 126
Patent TitlePriorityPatent No.
ReactionReaction of Incorporated of Incorporated TDMTDM--EndEnd GroupsGroups DuringDuringVulcanizationVulcanization
CH3
C CH2 C CH C CH
3
CH3
CH3
CH3
CH3
CH3
CH3
C
CH2
C
CH2
C
CH3
CH3
CH3
S CH3
CH3
CH3
CH2
CHCHCH2
SHCH2
CHCHCH2
3. Thermal Decomposition of TDM-End Groups
+Vulcanization
TDM derived end groups result in:• Acceleration of speed of cure
• Reduction of free (dangling) chain ends / Improvement of mechanical properties
• During vulcanization TIB is released which causes odour
29.08.1994 (Jp)ZeonEP 0779300
Zeon
Zeon
Company
29.08.1994 (Jp)EP 0779301
Unsatuarated Nitrile/Conjugated Diene copolymer, process for Producing the same, and Rubber Composition
30.03.1993 (Jp)EP 0692496
Patent TitlePriorityPatent No.
DependenceDependence of of NBRNBR--PropertiesProperties on on ContentContent of of Metal IonsMetal Ions
_
Ion-Number = 3 40
cCa cNa cK
23 39++
cMg
24 Atomic weightweight
ppm
Nitrile Rubber with Specific Ion Number22.05.2007LanxessDE 102007024011
Nitrile Rubber with Specific Ion Number22.05.2007LanxessDE 102007014010
Nitrile Rubber with Specific Ion Number22.05.2007LanxessDE 102007024010
Company Patent TitlePriorityPatent No.
Influence of Ions on Speed of Cure:accelerating: Na-, K- Ionsretarding: Mg-, Ca- Ions
DependenceDependence of of NBRNBR--PropertiesProperties on on ContentContent of of Metal IonsMetal Ions
0
10
20
30
40
50
60
70
0,00 20,00 40,00 60,00 80,00 100,00 120,00
Ion-Number (IN)
Mo
on
ey
sc
orc
h M
S5
(1
20
°C)
[min
]
_
Ion-Number = 3 40
cCa cNa cK
23 39++
cMg
24 Atomic Weight
ppm
DependenceDependence of of NBRNBR--PropertiesProperties on Metal Ion on Metal Ion ContentContent
0
1
2
3
4
5
6
7
8
9
10
-20 0 20 40 60 80 100 120
Ion-Number (IN)
M3
00
[M
Pa
]
_
Ion-Number = 3 40
cCa cNa cK
23 39++
cMg
24 Atomic Weight
ppm
NBR: Peroxyde NBR: Peroxyde CurableCurable GradesGrades
Crosslinkingefficiency
1,0
Type of Rubber Theoretical X-linkingefficiency
M - Rubber 1
R - Rubber > 1
Degradating rubbers < 1
NumberNumber of of xx--linkslinksXX--linkinglinking efficiencyefficiency = =
PeroxidePeroxide--functionsfunctions
Rubber
NBRO O O
O C
C
C
C
2
2 +
(R*)
+ 2 R-H
OH
OH
OH
OH
S
OH
Avoidance of phenol-and amine based antioxydants
(=radical scavengers)
IngredientsNBR (18 wt.% ACN)* [phr]Zinc oxide [phr]Stearic acidVulkanox OCDTMQVulkanox MB-2Carbon black (N 550)Carbon black (N 772)Dioctylphthalat (Vestinol/Hüls)Etherthioether (Vulkanol OT)Vulkalent ESulfur (Rhenocure IS-60-50)Vulkacit CZVulkazit NZVulkacit ThiuramPerkadox BC 40 (Akzo)Vulcanization t [min]/T [°C]
Peroxide100
---
1,0-
40-
5,0------
4,012/180
EV 21005,01,0-
1,51,53050-
6,01,00,3-
1,52,0-
16/160
EV 11005,00,5-
1,0-
50-
5,0--
0,42,0-
2,0-
25/160
EV 31005,00,52,5-
2,580--
201,00,31,5-
2,5-
25/160
* Perbunan NT 1845 (ACN; 18 Gew. %; ML 1+4 (100°C): 50 ME; MR: 14%)
VulcanizationVulcanization of NBR: Compound of NBR: Compound StudyStudy
Vulcanization System
ML1+4 (100°C) [ME]ts [min]t90 [min]
Shore A TS [MPa]εεεεb [%]M100 [MPa]M300 [MPa]
CS (70h/100°C) [%]CS (70h/120°C) [%]CS (70h/125°C) [%]
Brittleness Point [°C]Tg [°C]CS (24h/-20°C) [%]
Peroxide
770,64,9
70 18,32604,2
13,0
--
14
---
EV 2
871,82,6
7219,53654,417,3
20-
31
-62-53,5
17
EV 1
783,27,2
7116,93104,316,3
12--
-60-49-
EV 3
673,47,0
7115,83104,715,4
16--
-62-6020
VulcanizationVulcanization of NBR: of NBR: ResultsResults of Compound of Compound StudyStudy
C
N
CN
COOH
CarboxylatedCarboxylated NBR (XNBR (X--NBR)NBR)
Application Areas:• Spinning Cods und spinning hoses• high performance shoe soles• pump stators / Pump seals• belts• Hydraulic hoses
Application Areas:• Spinning Cods und spinning hoses• high performance shoe soles• pump stators / Pump seals• belts• Hydraulic hoses
Advantages:• High tensile strength• High moduli• Good dynamic performance (cut growth resistance)• High abrasion resistance
Disadvantages:• Scorchiness of Compounds• Cost of ZnO2 in relation to ZnO• high Compression Set• high heat-built-up bei dyn. Beanspruchung• Reduced ageing resistance
Carboxl-containing monomers:
• Methacrylic acid
• Itaconic acid
• Maleic Acid
C
CH2
OOC
CH3
CH2
COOC
CH3
C
CH2
OOC
CH3
CH2
CCOO
CH3
CH2
C COO
CH3
CCH
2
COO
CH3
C
CH2
COO
CH3
CH2
COOC
CH3
ZnO
Zn
Zn
2+_
2+
2+
Zn
ZnOH+
_
ZnO
_
ZnOH+
_
_
__
_
_
_
CH2
C
COOH
CH3
8
+ ZnO
ChemistryChemistry of of VulcanizationVulcanization withwith Metal Metal oxidesoxides
- H2O
• Vulcanization with metal oxides is used for X-NBR and CSM.
• The following metal oxides are used: CaO, MgO, ZnO and ZnO2
• For scorch safety ZnO2 is superior over ZnO
• Usually, vulcanization with metal oxides is combined with sulfur cure
• Dual vulcanization results in a „hybride-network-structure“
• In a hybride network chemical as well as physical networks are present.
Sources: Eisenberg, A. Macromolecules, Vol 3, 2 (1974) 147 „Clustering of Ions in Organic Polymers - A Theoretical Approach“
Ibarra, L., Alzorriz, M. Polym. Int. 48: 580-586 (1999)
Naskar, N., Debnath, S. C., Basu, D. K.; J. Appl. Pol. Sc., Vol 80, 1725-1736 (2001)
Brown, H. P. Rubber Chemistry and Technol, 30 (1957) 1347 Crosslinking Reactions of Carboxylated Elastomers“
CompoundCompound-- and and VulcanizateVulcanizate PropertiesProperties of NBR and Xof NBR and X--NBRNBR
X - NBR
NBR
CB (N 660)
Dibutylphthalate
Stearic acid
Wingstay 29
Sulfur
TMTD
MBS
Zinc oxide
100
0
40
5
2
1
0,5
2
1
5
50
50
40
5
2
1
0,5
2
1
5
0
100
40
5
2
1
0,5
2
1
5
X-NBR
NBR
Fmin. [Nm]
Fmax.
ts [min]
t90 [min]
t95 [min]
Shore A
M100 [MPa]
M200 [MPa]
M300 [MPa]
TS [MPa]
εεεεb [%]
Abrasion Index
Ageing at 70h/121°C
∆ elongation [%]
CS [%]
100,0
0
9,0
86,3
3,0
10,0
21,5
83
5,2
11,0
18,6
25,5
430
493
- 42
34,1
50,0
50,0
10,2
78,7
2,7
7,0
11,0
80
4,5
10,0
15,5
21,0
415
159
- 35
27,1
0
100,0
8,0
60,0
2,8
6,8
8,3
67
1,7
4,8
11,0
18,2
500
73
- 30
14,7
PrecrosslinkedPrecrosslinked NBRNBR
Properties:• Reduction of die swell
• Increased dimension stability after extrusion
• Improvement of surface quality of extruded/calendered articles
• Increase of Moduli
• Improvement of CS
• Reduction of TS
• Reduction of elongation at break
Properties:• Reduction of die swell
• Increased dimension stability after extrusion
• Improvement of surface quality of extruded/calendered articles
• Increase of Moduli
• Improvement of CS
• Reduction of TS
• Reduction of elongation at break
Precrosslinked NBR High Mooney NBRKrynac 34.80
Precrosslinked NBR-grades provide for high dimensional stability after extrusion which is
only matched by standard NBR-grades with considerably increased Mooney viscosities
NBR* (34 Gew.% ACN)
NBR (34 Gew.% ACN)
Zincoxide
Stearic acid
TMQ (Vulkanox HS)
Zincmethylmercaptobenzimidazol
Carbon black (Corax N 550)
Vulkanol 81
Sulfur
TBBS (Vulkacit NZ)
TMTD (Vulkacit Thiuram)
10
90
3,0
1,0
1,5
1,5
30
10
0,3
1,5
1,5
Krynac VP KA 8769
Krynac 34.50
Lanxess
Henkel KGaA
Lanxess
Lanxess
Degussa
Lanxess
Kali Chemie
Lanxess
Lanxess
Source: Bayer AG, Marinelli/Welle, KALIS-Nr.: 9588 vom 05. 10. 2000
PrecrosslinkedPrecrosslinked NBR: Compound NBR: Compound StudyStudy
phr
phr
phr
phr
phr
phr
phr
phr
phr
phr
phr
20
80
3,0
1,0
1,5
1,5
30
10
0,3
1,5
1,5
30
70
3,0
1,0
1,5
1,5
30
10
0,3
1,5
1,5
40
60
3,0
1,0
1,5
1,5
30
10
0,3
1,5
1,5
* Precrosslinked NBR
NBR* (34 Gew.% ACN)NBR (34 Gew.% ACN)
Compound-ML [ME]Mooney-Relax. [%]Die swell /linear [%]Fmin. [dNm]Fmax. [dNm]ts1 [min]t90 [min]t95 [min]Shore A/23°CShore A/70°CM100 [MPa]M200 [MPa]M300 [MPa]Tensile Strength [MPa]Elongation at break [%]Rebound/23°C [%]
Rebound/70°C [%]CS (70h/23°C) [%]CS (70h/100°C) [%]
1090425,8
42,90,7710,631,855,316,6151491,22,44,5
19,867740541334
PrecrosslinkedPrecrosslinked NBR: NBR: ResultsResults of Compound of Compound StudyStudy
2080445,6
31,70,9511,311,774,765,8453501,42,95,2
16,456339561332
3070475,5
31,21,1512,11,684,585,5755521,53,25,8
15,556039571330
4060515,7
16,81,4413
1,644,5
5,4857541,73,66,4
14,148839611228
4. 4. OverviewOverview on Solution Rubberson Solution Rubbers• Features of the Solution Process
• Definition of “Solution Rubbers“
• Isolation of Rubbers from their Solutions– Dry Finishing with Extruders
– Dry Finishing with Heated Mills (under vacuum)
– Solvent Removal by „Steam Striping“
– Expeller Screw for Mechanical Water Removal from Rubber
Advantages:• Use of water sensitive catalyst systems (Z/N, anionic, cationic)• evaporation cooling• low cooling costs if semi- or total adiabatic processses are applied
Disadvantages:• low content of solids• high viscosities• reactor fouling• waste air• waste water (depending on finishing technology)• high drying costs for recycled solvents (depending on finishing technology)
Definition of Solution Rubbers and Definition of Solution Rubbers and ExamplesExamples
Rubber
Ti-BRNi-BRCo-BRNd-BR
Li-BR
L-SBREPM/EPDM
CM/CSMHNBR
IIR
So
lutio
n R
ub
bers
So
lutio
n-B
R
ReactionMedium
solvent solvent solventsolvent
solvent
solvent solvent
solventsolvent
solvent
Catalyst/Process
Z/N*Z/N*Z/N*Z/N*
anionic
anionicZ/N*
polymer modif.polymer modif.
cationic
Hig
h-cis-
1,4
-BR
* Z/N = Ziegler-Natta Catalysis
A “solution rubber” is prepared in the presence of an organic solvent
in which the rubber is either dissolved or dispersed.
Examples
DryDry FinishingFinishing withwith ExtrudersExtruders ((UnderUnder VacuumVacuum))
US 4124306 (French Oil Mill Machinery)Prior.: 30.11.1977Inv.: D. K. Bredesen, G. C. Craig, W. W. Gilius, C. R. Johnson
Dry Finishing: Recovery of rubbers from their solutions by direct evaporationwith extruders without the use of steam
Vent for Devolatilizing Srew press
DryDry FinishingFinishing withwith Hot Mills (Hot Mills (UnderUnder VacuumVacuum))
Dry Finishing: Recovery of rubbers from their solutions by direct evaporationunder vacuum with „heated mills“without the use of steam
Source:
DE 4032598 (Bayer AG)
Prior.: 16.04.1992
Inv.: B. von der Linden, K. Goth
Solvent Removal Solvent Removal byby SteamSteam StrippingStripping
US 2,592,814(Du Pont)Prior.: 20.12.1947Inventor: J. L. LudlowPH-
Control
Steam
Strippingaid
Antioxydant
oil
Stripping
unit Dewatering(expeller)
screw
Expanderscrew
Steam
Waste water
Isolation of CSM from Solution
US 5266211Bunawerke Huels GmbHPrior.: 13.06.19990Inventor: W. Breuker, H. Wagner, E. Moeller, B. Schleimer
Process for Precipitating Polymers
ExpellerExpeller ScrewScrew forfor MechanicalMechanical Removal of Removal of Water Water fromfrom RubbersRubbers
Source:US 2003007709 (Bayer AG) Prior.: 05.07.2001Inv.: N. Schweigler H. Goebel, T.-O. Neuner
After steam stripping a dispersion of rubber crumbs in water isotained. Before thermal drying water is removed mechanically
Source:US 3672641 (French Oil Mill Machinery)Prior.: 14.09.1970Inv.: R. K. Slaby
In order to obtain rubber crumbs a cutting deviceis often attached at the end of a dewatering screw
4.1. 4.1. OverviewOverview on on PolybutadienePolybutadiene Rubbers (BR):Rubbers (BR):
• BR: Overview– Property Profile and Areas of Application
– Microstructure, Glass Transition Temperature and Crystallization
– Producers and Production Capacities
– Market- und Market Development
• Application of BR for Tyres and for Impact Modification (HIPS/ABS)– Comparison of BR grades in Tyre Performance
• Unvulcanized Compound Properties (Green Strength and Tac)
• Vulcanizate Performance (Dynamic Performance and Abrasion Resistance)
– Comparison of BR-Grades for the Impact Modification of Thermoplastics(HIPS/ABS)
• Principle of Rubber Toughening
• BR Branching and Viscosity of Solutions
• Correlation of Mooney- and Solution Viscosities
• Performance Requirements for Tyres and Impact Modification
• Comparison of Production Technologies for High-cis-BR
• Summary
CH2
CH CH
CH2
CH2
CH CH
CH2
CH2
CH CH
CH2
CH2
CH
CH
CH2
1,4-cis 1,4-trans 1,2- bzw. Vinyl
Property Profile and Property Profile and AreasAreas of of ApplicationApplication
Positive:• Low price and good performance/price-ratio
• Broad range of BR-grades with different molar masses, oil extenison, Tgs etc.
• Brod spectrum of applications(tyres, modification of thermoplastics, TRP, golf balls)
• Dependence of strain induced crystallization on 1,4-cis content
• Low glass transition temperature
Negative:• Poor resistance to heat and ageing
• High degreee of swelling in fuels, oils and greases
• high gas permeability
•Spontaneous crystallization
Golf ball cores
1%
Technical
Rubber
Products
5%
Rubber
Toughening
23%
Tyres
71%
Application Areas
Catalyst Li* Co Ni Ti Nd E-BR**
Tg -93 -106 -107 -103 -109 -80
Microstructure (according to manufacturer‘s product specifications) [%]
1,4-cis 36-38 97 97 93 98 12,9
1,4-trans 52 1 2 3 1 68,3
Vinyl 10-11 2 1 3-4 <1 18,8
Microstructure (according to Thorn-Csanyi et al.) [%]Vinyl/1H-NMR*** 10,4 1,9 4,0 <1 18,1
Vinyl/FT-IR*** 11,4 1,0 5,4 0,6 17,7
Vinyl/Metathese*** 10,7 1,7 4,6 0,7 17,8
BR: BR: MicrostucturesMicrostuctures and Glass and Glass TransitionTransitionTemperaturesTemperatures
* aliphatic, cycloaliphatic aromatic solvents without polar additives
CH2
1
CH2
CH3
CH2
4
CH2
1
CH2
CH3
CH24
CH21
CH2
CH3
CH24
1,4-cis 1,4-trans
*** E. Thorn-Csanyi, H.-D. Luginsland, Rubber Chem. Technol. (1977) 222-230
** Polymer Handbook/Polymerisation temperature: 25°C
1,2- bzw. Vinyl
CrystallizationCrystallization Rate of Rate of UnvulcanizedUnvulcanized and and VulcanizedVulcanized BR BR (Nd (Nd catalyzedcatalyzed BR) BR)
0,1
1
10
100
-100 -80 -60 -40 -20 0
Temperature [°C]
t 1/2
[m
in]
Raw Rubber
Vulcanizate
Source: U. Eisele Introduction to Polymer Physics, Springer-Verlag 1990
BR: Impact of 1,4BR: Impact of 1,4--ciscis--Content on Content on CrystalizationCrystalization Rate and Rate and Melting Melting TemperatureTemperature of of CrystallitesCrystallites
0
50
100
150
200
250
90 92,5 95 97,5 100
1,4-cis-content [%]
t 1
/2 (
-20
°C)
[min
]
Nd
Ni
Co
Ti
-25
-20
-15
-10
-5
0
90 92,5 95 97,5 100
1,4-cis-content [%]
Me
ltin
g t
em
pe
ratu
re o
f c
rys
tallit
es
[°C
]
Nd NiCo Ti
BR: BR: ProducersProducers and and ProductionProduction CapacitiesCapacities
0
50
100
150
200
250
300
350
400
450
500
Lanxe
ss
Goodye
ar
Mic
helin
Sin
opec
BS/F
S
Kum
ho
Sib
ur
Pol
imer
i
Dow
Thaila
nd
Nizhnek
amsk
nefte
chim
TSRC
Ube
JSR
Asa
hi
Zeon
other
s
Cap
acity [kt]
Source: IISRP Worldwide Rubber Statistics 2001 / Amendments 2011
SelectedSelected BRBR--ProducersProducers and BRand BR--GradesGrades
0 50 100 150 200 250 300 350 400
Goodyear Tyre&Rubber Co., Beaumont, Tx
ASRC (Michelin), Louisville, Ky
Sinopec, GaoQiao, Caojing
Lanxess, Orange, Texas
BS/FS, Lake Charles, La
Korea Kumho, Yeochin, Yeosu
Lanxess, Port Jérôme, FR
Petroflex, Cabo, BR
Dow, Schkopau, DE
Michelin, Bassens, FR
Nizhnekamskneftechim
Ube, Chiba, JP
Chemizna Dwory, SA, Kralupy, CZ
Lanxess, Dormagen, DE
Polimeri, Ravenna, IT
Capacity [kt]
Li
Ni
Ti
Co
Nd
Li/Co/Nd
Ni/Nd
BR: BR: ApplicationApplication AreasAreas
Tyre Market (2.2 Mio t)Ni-BR
38%
Nd-BR
8%
Li-BR
7%
Ti-BR
18%Co-BR
22%
not
assigned
7%
HIPS/ABS-Market (0,68 Mio t)
Li-BR
48%
Co-BR
52%
Application Areas of BR
Tyres
71%
HIPS/ABS
23%
Technical
Rubber
Goods
5%
Golf balls
1%
Anatomy of a Passenger Tire and Use of BRAnatomy of a Passenger Tire and Use of BR
SidewallNR/BR: 60/40
TreadSBR/BR: 70/30
Sub TreadNR/BR: 80/20
CarcassNR/BR: 90/10
Rim CushionNR/BR: 80/20
ApexNR/BR: 80/20 Source:
ComparisonComparison of BRof BR--Grades Grades forfor thethe ApplicationApplicationin in TyresTyres ((ASTMASTM--CompoundCompound 3189 3189 –– 90)90)
Source:Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
ASTM Designation: D 3189 - 90 „Standard Test Methods for Rubber-Evaluation of Solution BR
BR (Nd-, Co-, Ti-, Li-) 100,0 phr
Zinc oxide 3,0 phr
Sulfur 1,5 phr
Stearic acid 2,0 phr
Carbon black (NBS 378) 60,0 phr
TBBS 0,9 phr
Oil (ASTM Type 103) 15,0 phr
Vulcanization: 145°C/35 min
Green Green StrengthStrength of of BRBR--CompoundsCompounds
0 250 500 750 1000
5
4
3
2
1
0
Str
ess
[MP
a]
Strain [%]
Nd-BRLi-BR Ti-BR Co-BR
Source:
Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
Tack of Tack of UnvulcaniuzedUnvulcaniuzed BRBR--CompoundsCompounds
0
50
100
150
200
250
300
350
100 1000 10000
critical load for separation [g]
tim
e u
nti
l sep
ara
tio
n [
sec]
Li-BR
Ti-BR
Co-BR
Nd-BR
Imp
rov
emen
t
Source:„Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
VulcanizateVulcanizate PropertiesProperties of BR Gradesof BR Grades
Source:“Butadiene Rubber for the rubber industry“ Bayer AG Rubber Business Group, Order No.: KA 34287e. Edition 10.98
BR Grade
Vulcanizate properties
Tensile Strength [MPa]
Elongation at break [%]
M300 [MPa]
Shore A-Hardness
Rebound [%]
DIN-Abrasion [mm3]
Pendulum -Skid
Asphalt, dry
Asphalt, wet
Dynamic properties
Goodrich-HBU [°C]
De-Mattia crack growth [mm/kc]
Monsonto-FTF/εεεε =100% [cycles]
Nd
15,3
400
9,4
65
49
23
85
33
27
1,9
460
Co
14,5
525
8,6
63
47
27
85
33
32
6,0
50
Ti
13,4
510
8,1
64
45
33
85
33
36
1,5
115
Li
13,0
480
8,0
66
47
52
89
35
18
5,6
63
1,41,4--cis BR: cis BR: DynamicDynamic Performance of Performance of BRBR--VulcanizatesVulcanizates ((MonsantoMonsanto FatigueFatigue to to FailureFailure Test)Test)
0
5
10
15
20
25
30
35
40
Nu
mb
er o
f K
ilo
cy
cle
s u
nti
l F
ail
ure
Ti Ni Co Nd
Imp
rov
emen
t
Source: D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“
Makromol. Chem., Macromol. Symp. 66, 273-288 (1993)
1,41,4--cis BR: cis BR: AbrasionAbrasion ResistanceResistance of of BRBR--VulcanizatesVulcanizates((DINDIN--AbrasionAbrasion))
20
25
30
35
40
45
50
0 5 10 15Modulus at 300% elongation [MPa]
Ab
rasi
on
[m
m3
]
Ti-BR
Ni-BR
Co-BR
Nd-BR
Imp
rov
emen
t
Source:D. J. Wilson „Recent Advances in the Neodymium Catalysed Polymerisation of 1,3-Dienes“ Makromol. Chem.,
Macromol. Symp. 66, 273-288 (1993)
Phase Phase MorphologyMorphology of Rubber of Rubber ModifiedModifiedThermoplasticsThermoplastics and Thermoset and Thermoset ResinsResins
Soft Phase
BRBREPDMEPMNBR
Hard Phase
SANPSSANPPPP
Examples
ABSHIPSAESEPM/PPNBR/PP
Rubber Modified Thermoplastics
Soft (dispersed) Phase
Grafted Shell„Compatibilizer“Hard Phase (coherent phaseor matrix)
Source:C. Schade, H.-J Renner, W. Heckmann
(BASF)
„Predictive property Adjustment“
Kunststoffe international 7/2010, 36-39
The impact resistance of hard and brittle thermoplasticand duroplastic polymers is improved by rubber particles
Prerequisites for an efficient impact modification are:
1) good dispersion of the rubber phase in the matrix
2) good mechanical bonding across the phase boundaries
3) x-linking of the rubber phase
InfluenceInfluence of Rubber of Rubber ContentContent on on NotchedNotched Impact Impact ResistanceResistance of of EPM/PPEPM/PP--BlendsBlends
Source:H. Schwager (BASF); Kunststoffe 82, 499 (1992)T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“
Temperature [°C]
No
tch
ed
imp
act
resis
tan
ce
[kJ/m
2]
0 20-20-400
80
60
40
2020
25
3347 37
ho
he
52
Rubber content[wt.%]
Impact of Impact of BranchingBranching on Solution on Solution ViscositiyViscositiyof Liof Li--BR in BR in StyreneStyrene
1
10
100
1000
10000
100000
5 7 9
Solid Contents of BR solution [wt.%]
Vis
co
sit
y [
mP
a*s
]
HX 565 Mooney: 65 Degree of Branching: 50-55
HX 501 Mooney: 40 Degree of Branching: ca. 18
HX 530 Mooney: 65 Degree of Branching: ca. 10
Source: Rubbers as Impact Modifiers for Plastics Bayer AG Rubber Business Group Order No.: KA 34271e
CorrelationCorrelation of Solution and of Solution and MooneyMooney ViscositiesViscosities of of Different BRDifferent BR--Grades Grades
0 10 20 30 40 50 60 70 80
Mooney-Viscosity (ML1+4/100°C) [MU]
260
240
220
200
180
160
140
120
100
80
60
40
20
0Solu
tion
Vis
cosi
ty(5
,43 w
t.%
in
tolu
ene)
[m
Pa*s]
Source: „Rubbers as Impact Modifiers for Plastics“ Bayer AG, Rubber Business Group, Order No.: KA 34271e
Li-BR (commercial grades)
Co-BR (commercial grades)
Star shaped BR
Lin
ear an
d slig
htly
branch
edBR
gra
des
Performance Performance RequirementsRequirements forfor thetheApplicationApplication of BR in of BR in TyresTyres and HIPS/ABSand HIPS/ABS
The performance profiles for HIPS/ABS und for tyresdiffer significantly
Property Performance Requirements
for tyres for HIPS/ABS
Tg as low as possible as low as possible
Vinyl content - > 1 Mol%
Gel content not crical <500 ppm
Solution viscosity - <21 mPas (5,2% / toluene)
colour - colourless
Tack yes -
Green strength yes -
Strain induced crystallization yes -
dynamic resistance yes -
Abrasion resistance yes -
Butadiene 4-Vinylcyclohexene (4-VCH)
Formation of 4-VCH bya Diels-Alder-Reaction
Positivefeature
[ppm]
[%]
[min]
lowVeryhigh
highhighFormation of 4-VCH
100-200200-25050-10010-50Transition metal content
fullyadiabatic
partiallyadiabatic
partiallyadiabatic
partiallyadiabatic
Heat removal
18-2211-1215-1614-22Solids Content
nonoyesyesMolar MassControl agents
Very lowlowhighhighTendency towardsgel formation
<100<95<8555-80Conversion
100-120120120150Residence time
HexaneAliphatics
BenzeneToluene
BenzeneTolueneHexane
Benzene, Toluene(Aliphatics)
Solvent
NdTiNiCoTransition Metal
HighHigh--ciscis--BRBR ProductionProduction TechnologiesTechnologies
SummarySummary
From the different BR grades, Nd-BR is advantageous from two points of view:
• Tyre applications (particularly tyre treads)
• Production technology
For the impact modification of thermoplatics (HIPS and ABS)
• Li-BR and Co-BR are superior
• for Nd-BR a highly branched grade with a low solution viscosity is required
• Selected Milestones in Rubber History
• Capacities of Multi-Purpose Solution Plants
• Origins of S-SBR Technology and Basic Features
• Chemical Aspects of the Anionic Polymerization and Consequences
– Reaction Mechanism and Catalyst Costs
– Vinyl-Content and Impact on Tg
– Branching and Impact on Processability
– Styrene/Butadiene-Copolymers, Preparation and Properties
– Integral Rubber
• Green Tyre Technology
• Recent Developments in S-SBR Technology Towards Improving Tyre Performance
–Functionalisation of S-SBR
4.2. 4.2. LiBRLiBR and Sand S--SBRSBRWithWith a Special a Special EmphasisEmphasis on Integral Rubberon Integral Rubber
SelectedSelected MilestonesMilestones in Rubber in Rubber HistoryHistory withwith a a Special Special EmphasisEmphasis on on AnionicAnionic PolymerizationPolymerization
1839 Charles Goodyear discovers the vulcanization by sulfur
1888 John Dunlop patents pneumatic tire
1929 First laboratory scale E-SBR by Tschunkur & Bock (Buna S)
1938 Invention of redox activation by Bock (“cold E-SBR“)
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Consequences, Marcel Dekker Inc. New. York, Basel 1996
1910 Matthews, Strange (England), Harries (Germany) and Schlenk
(Germany) discover sodium as a catalyst for polymerization
1914-18 Start-up of Methyl-Rubber production in Germany
(2,3-dimethylbutadiene/Na-catalyst)
1929 Ziegler discovers BuLi to be a polymerization catalyst
1936 Ziegler describes the features of the anionic polymerization
1939-45 BR-production in Russia (catalysts based on Na and K)
1952 Start-up of R&D into diene base rubbers/Li-metal by Firestone
1960ies Start- up of commercial productions using anionic initiators by
Firestone, Shell and by Phillips Petroleum
1926 Butadiene rubber developed in Germany (Buna)
Plant Location Capacity [kt] RemarksWestern EuropeEniChem Ravenna 100.000 incl. TPE‘s
Grangemouth 80.000Bayer Lillebonne 120.000Michelin Bassens 85.000Repsol Qimica Santander 80.000 incl. TPE‘sFina Polymers Antwerp 80.000 incl. TPE‘sDow Schkopau 60.000
AmericasASR Louisville, Ky 110.000Bridgestone/Firestone Lake Charles 180.000
Orange 125.000 incl. TPE‘sBayer Orange 30.000Goodyear Beaumont, Tx 360.000Petroflex Cabo 35.000 incl. TPE‘sNegromex Salamanca 30.000
Altamira 10.000
JapanAsahiJapan Elastomer Oita 48.000 incl. TPE‘sNippon Zeon Tokuyama 296.500 incl. E-SBRJSR Yokkaichi 30.000 incl. Hydrogenated polymers
OthersKorean Kumho Yeochon 145.000Taiwan Synthetic Kaohsiung 210.000 incl. TPE‘sDow (Carbochem) Newcastle 30.000
Total Capacity 2.274.500
CapacitiesCapacities of of MultiMulti--PurposePurpose Solution Solution PlantsPlants* * (BR/S(BR/S--SBRSBR--SBSSBS--TPETPE‘‘s)s)
* Source: IISRP Worldwide Rubber Statistics 2001
Origin of basic technology
Firestone/Asahi
Phillips-Petroleum
technology origin not assigned
OriginOrigin of of SS--SBRSBR--TechnologiesTechnologies and Basic Features and Basic Features
Initiator
Solvent
Randomizer
branching agent/chain end coupling
short stop
process
temperature control
sequential monomer addition
Vinyl content of BR-moieties
molar mass distribution of base polymer
Firestone/Asahin-Bu-Li
n-hexane
none
DVB
water
continuous
adiabatic
butadiene
~ 10%
broader
Phillipssec.-Bu-Li
cyclohexane
glymes
DVB, SiCl4, SnCl4
stearic acid
discontinuous, batch
isotherm
one shot
> 20%
narrower
Until today, the technologies have merged and there are onlysmall differencies in the technologies of the leading companies
Feature Technology
Basic Patents:Firestone: US 3317918, CA 966949, US 3205211, FR 1546396, FR 1539429, FR 1539427, BE 718549,
US 3681304, OS 2134656, US 3558575, US 3726844, US 3726844, US 3787377Phillips: US 3458490, US 3438952, US 3502746Bridgestone: JP 75-015271
MechanismMechanism of of thethe AnionicAnionic PolymerizationPolymerization
Li+
R
CH2
n
R
CH2 Li
+ Li+
Li+
R R
CH2
+
+
Initiation:
Chain growth:
n
Transfer reactions: ideally none
Termination reactions: ideally none
• Under ideal polymerization conditions, there is neither chain transfer nor
termination reactions and the active species are truly living.
• All polymer chains are initiated at the start of the polymerization and all
chains grow up to total monomer consumption.
• The resulting polymer molecules have a narrow molar mass distribution
and a high chemical homogeinity
Features of a Features of a ““LivingLiving PolymerizationPolymerization““
Living Polymerization: Rational for Uniform Terminology T.r. Darling, T. P. Davis, M. Fryd, A. A. Gridnev, D. M.
Haddleton, S. D. Ittel, R. R. Matheson, jr., G. Moad, E. Rizzardo, Journal of Polym. Chemistry, Vol 38, 1706-1708 (2000)
0 0,5 1,0
Monomer Conversion X
Mola
r M
ass
(Mn
) [g
/mo
l]
nInitiator = u
nInitiator = v
nInitiator = w
u < v < w
DP: degree of po0lymerization
Mn: number average of molar mass
X: monomer conversion
nMonomer : amount of monomer [moles]
MWMonomer: molar mass of monomer
nInitiator : amount of initiator [moles]
f: functionality of initiator
u, v, w: amounts of initiator
nMonomer
DP = X nInitiator * f
nMonomer * MWMonomer
Mn = XnInitiator * f
Mn = m * X + C
C = 0
n Monomer * MGMonomerm = nInitiator * f
0
5
10
15
20
25
0 50000 100000 150000 200000 250000 300000 350000 400000
Molar mass [g/mol]
Co
sts
fo
r B
uL
i [[
Pf/
kg
]
Consequences from the living nature of the polymerization:• Catalyst costs increase with decreasing molar masses.• Star shaped polymers are obtained by the coupling of low molar mass
polymers. Therefore star shaped polymers are bound to be more expensivethan standard rubbers at the same molar mass.
Basis of calculation:
• 65 DM/kg BuLi (4 DM/mol BuLi; MwBuLi: 61 g/mol)
• Ideally “Living Polymerization“
Impact of Initiator Impact of Initiator ConcentrationConcentration on Molar on Molar MassesMasses and on and on CatalystCatalyst CostsCosts
Co
sts
for
Bu
-Li
[Pf/
kg
ru
bb
er]
Molar mass [g/mol]
Impact of the Impact of the GegenionGegenion and of the Solvent and of the Solvent on the Vinylon the Vinyl--ContentContent
Gegen- Microstructure
ion (Benzene)
cis-1,4 trans-1,4 1,2-
[%] [%] [%]
Li 35 55 10
Na 10 25 65
K 15 40 45
Cs 6 35 59
Solvent Microstructure
cis-1,4 trans-1,4 1,2-
[%] [%] [%]
Hexane 35 55 10
Toluene 35 52 13
THF 0 9 91
Sources:R. Casper in Ullmann‘s Encyclopedia of Technical Chemistry
G. Sylvester u. P. Müller in Houben Weyl, Methoden der organischen Chemie,
Band E 20/Teil2, Makromolekulare Stoffe, S. 801
PP
LiLi
P
P
X X
LiLi
+
+
+
+
-
-
-
X X
-
X XEther with two coordination sites
1,4-insertion:
1,2-insertion:
Dependence of the VinylDependence of the Vinyl--Content on Polymerization Content on Polymerization Temperature and Modifier (Type and Concentration)Temperature and Modifier (Type and Concentration)
0,1 1,0 10 100
Ether [mol/mol Li]
90
80
70
60
50
40
30
20
10
0
Vin
yl-
Co
nte
nt
[mo
l%]
DME30°C
DME50°C
DME70°C
THF30°C
THF50°C
THF70°C
Source: Ullmann‘s Encyclopedia of Technical Chemistry
Modifier:DME: DimethoxyethaneTHF: Tetrahydrofuran
Impact of Impact of thethe Vinyl Vinyl ContentContent of Liof Li--BR on BR on TgTg
Tg
[°C
]
+ 0
-10
-20
-30
-40
-50
-60
-70
-80
-90
-100
0 10 20 30 40 50 60 70 80 90 100
Vinyl-Content [%]
VI-BR
Standard-Li-BR (without modifiers)
S. L. Aggarwal, T. G. Hargis, R. A. Livigni, H. J. Fabris, L. F. Marker, „Advances in
Elastomers & Rubber Elasticity, J. Lal a. J. E. Mark, Eds., Plenum Press, New York, 1986, p. 17
Range of commercialVinyl-BR grades
LiLi--BR: BR: DependenceDependence of of WetWet SkidSkid and and AbrasionAbrasion ResistanceResistance
on Vinyl on Vinyl ContentContent
Vinyl-BR SBR
1712
Vinyl Content 10 47 64 66 88 18
1,4-cis 40 26 21 18 7 8
1,4-trans 50 27 15 16 5 74
Wet Skid Performance (Laboratory)
Portable Test Device* - 84 109 104 120 100
Retreaded Tyre
Concrete 70 95 92 93 - 100
Asphalt 70 90 92 93 - 100
Abrasion Resistance 140 100 80 100
* Road Research Laboratory Instrument, on wet Syenite-Glass Surface
BranchingBranching byby thethe CopolymerizationCopolymerization withwithDivinylbenzeneDivinylbenzene
Li+
CH2R
n
R CH
CH
n
R
n
Li+
Li+Li
+
CH2
R
n
+
Copolymerization with multifunctional monomers (DVB):
Li+
SiCl4
Li+
Cl
C
Si
4
+ 4
Chain end coupling with SiCl4, SnCl4 etc.:
(SnCl4 as alternative)
BranchingBranching byby Chain End Chain End CouplingCoupling
Coupling with SiCl4:• Reduction of Cold-Flow
• low viscosity of BR-solutions
• Application for HIPS and Bulk-ABS
• Highly filler loaded rubber compounds
with good processability and high Shore-
A Hardness (roll covers, tyre beads etc.)
Coupling with SnCl4:exclusive úse is for tyres; during compound
preparation the Sn-C bonds seems to break
and the bound rubber content is increased.
As a consequence hysteresis of vulcanizates
is reduced.
Many patents in this area, for example:
US 6271317 (Goodyear) Prior.: 19.01.1998,
Inv.: A. F. Halasa, S. Futamura, W. L. Hsu,
B. A. Matrana „Asymmetrical Tin-Coupled
Rubbery Polymers and Method of Making“
(Star shaped rubbers with at least 3
brances; 1 branch with MW <40.000 g/mol
and 1 branch with MW>80.000 g/mol)
Impact of Chain Impact of Chain BranchingBranching on on ProcessabilityProcessability
Shear rate [sec-1]
Source: U. Eisele, Introduction to Polymer Physics, Springer Verlag 1990
Vis
cosi
ty
Highly branched
(Star shaped)
Broad molar mass
distribution
Narrow molar
mass distribution
100 101 102 103 104 105 106
Cold Mooney- Com- Calan- Ex- Injection Spin-
flow measure- pression dering trusion moulding drawing
ment moul-
ding
Imp
rovem
ent
Imp
rovem
ent
LiLi--BR: BR: InfluenceInfluence of of BranchingBranching on Cold on Cold FlowFlow
Co
ld F
low
[mg
/min
]
0 20 40 60 80 100
Mooney-Viscosity ML 1+4 (100°C) [MU]
14
12
10
8
6
4
2
0
Divinylbenzene
[phm]
0,03
0,06
Linear Chain
Star shaped
polymer with
3 branches
Linear BR has an extremely high cold flow which results in the instability of
rubber bales. BR has to be branched in order to improve the stability of bales.
Li-BR linear star branched
Coupling agent without SiCl4
Mw [g/Mol] 256.000 310.000
Mn [g/Mol] 188.000 158.000
Mw/Mn 1,4 2,0
Cold flow [mg/min] 16 0
ML 1+4(100°C) 53 54
Compound-Mooney ML 1+4 (100°C) 98 80
Shore A Hardness 64 61
S300 [Mpa] 8,0 8,1
Tensile Strength [Mpa] 16,5 16,2
heat-build-up [°C] 32 40
Rebound [%] 77 71
Compound Preparation:
BR: 100 phr, Ruß (IRB Nr. 2): 50 phr, Zink oxide: 3 phr, Mineral oil : 10 phr, Stearic acid: 2 phr,
Sulfur: 1,75 phr, Accelerator: 0,8 phr; Vulcanization: 135 °C/35 min
PropertiesProperties of Linear and Star of Linear and Star BranchedBranched LiLi--BRBR
S-SBR: Solution-SBR
LL--SBR: Market and Market SBR: Market and Market DevelopmentDevelopment
Source: IISRP; Evaluation by Bayer AG (Wachholz/BPO-IIS-BPSC-SP)
0
100
200
300
400
500
600
700
1989 1991 1993 1995 1997 1999 2001
Co
ns
um
pti
on
[t]
Introduction of “Green Tyre Technology by Michelin“
CopolymerizationCopolymerization of of StyreneStyrene and and ButadieneButadiene at at Differential Monomer Differential Monomer ConversionsConversions
0 10 20 30 40 50 60 70 80 90 100
Styrene-content of monomer feed [wt. %]
Sty
ren
eco
nte
nt
of
po
lym
er [
wt.
%]
100
90
80
70
60
50
40
30
20
10
0
Parameters of copolymerization
(styrene = M1; butadiene = M2)
Radical copolymerization
(emulsion)
r1 = 0,7
r2 = 1,4
Anionic colymerisation in
hexane
(Bu-Li/no randomizers/50°C)
r1 = 0,04
r2 = 11,8
E-SBR
S-SBRin hexane
CopolymerizationCopolymerization of of StyreneStyrene and and ButadieneButadiene
The anionic copolymerization of styrene and butadiene in an unpolar
solvent (hexane) yields a block copolymer with the following features:• high chemical homogeinity
• narrow molar mass distribution
• tapered intermediate sequence
Butadiene block tapered sequence styrene block
Course of the copolymerization in hexane (full batch process):
start up of the reaction
For For tyretyre applicationsapplications block block styrenestyrene blocksblocks havehave to to bebeavoidedavoided as as theythey cause high cause high hysteresishysteresis losseslosses. .
0 10 20 30 40 50 60 70 80 90 100
Styrene content in the monomer feed [wt. %]
Dif
fere
nti
al
sty
ren
eco
nte
nt
in t
he
po
lym
er
[wt.
%]
100
90
80
70
60
50
40
30
20
10
0
E-SBR
S-SBRin Hexane
Styrene/ButadieneStyrene/Butadiene--CopolymerisationCopolymerisation
Rando-
mizers
(Styrene = M1; Butadiene = M2) Cyclohexane; 25/75 Styrene/Butadiene
Source: H. L. Hsieh, R. P. Quirk, Anionic Polymerization, Principles and Practical Applications, Marcel Dekker, Inc.
Y. Melenevskaya, V. Zgonnik, V. Denisov, E. Dolinskaya, K. Kalnish; Polym. Sci. (USSR), 21, 2215 (1979)
T r1 r2
[°C]
Benzene 25 0,04 10,8
Cyclohexane 25 0,04 15,5
Hexane 25 0,03 12,5
THF 25 4,0 0,3
Diethylether 25 0,4 1,7
Triethylamine 25 0,5 3,5
Anisol 25 0,3 3,4
Diphenylether 25 0,1 2,8
THF -78 11,0 0,04
THF 0 5,3 0,2
THF 25 4,0 0,30
10
20
30
40
50
60
70
0 20 40 60 80 100
Monomer Conversion [%]
To
tal
Sty
ren
e C
on
ten
t o
f P
oly
me
r
[wt.
%]
n-Butyl-Lithium
t-BuOK/n-Buli: 0,067/1
t-BuOK/n-Buli: 0,38/1
Impact of Impact of RandomizersRandomizers on on thethe CopolymerizationCopolymerizationBehaviourBehaviour of of StyreneStyrene and and ButadieneButadiene
Sty
ren
eC
on
ten
t[w
t. %
]
0 10 20 30 40 50 60
Vinyl [%]
- 70°C
+10°C
- 60°C - 50°C
+ 0°C
- 10°C
- 20°C
- 30°C
- 40°C
TgTg of Sof S--SBR: SBR: TheThe Impact of Impact of StyreneStyrene and Vinyl and Vinyl ContentContent
40
30
20
10
0
In In thethe variationvariation of of thethe microstructuremicrostructure ((vinylvinyl--contentcontent) ) thethe SS--SBR SBR technology has a technology has a greatergreater versatilityversatility thanthan thethe EE--SBRSBR--technology.technology.
So
luti
on
tec
hn
olo
gy
wit
ho
ut
ran
do
miz
ers
Solution technology with
randomizers
Sta
nd
ard
Em
uls
ion
Tec
hn
olo
gy
Source: H. Mouri, J. E. Hall, (Firestone) 146th ACS meetin in Pittsburgh, PA., USA
Impact of Impact of TgTg on on ImportantImportant Tyre Tyre TreadTread PropertiesProperties
S-SBR (25% Styrene, 55% Vinyl)
Emulsion BR
high cis Nd-BRLi-BR
S-SBR (18% Styrene, 10% Vinyl)
E-SBR (15% Styrene)
E-SBR 1500 (23.5% Styrene)
E-SBR 1516 (40% Styrene)S-SBR (34% Styrene, 32% Vinyl)
-20
-60
-40
-80
-100
Increase of Heat Build Up and Wet Skid Resistance
Decrease of Rolling Resistanceand Abrasion
Tg
Tg
[[ °°C
]C
]
In order to In order to complycomply withwith manymany conflictingconflicting tyretyre treadtread propertiesproperties thethepreparationpreparation of rubber of rubber blendsblends isis essential in rubber technology. An essential in rubber technology. An alternative to alternative to macroscopicmacroscopic blendingblending wouldwould bebe microscopicmicroscopic blendingblending
as as withwith integral rubber.integral rubber.
Source: K. H. Nordsiek, K. M. Kiepert, Kautschuk Gummi Kunststoffe 38 (1985), p. 178-185
tan
δLi- NR SBR SBRBR 1500 1700
-100 -80 -60 -40 -20 0 20 40 60 80 100
Temperature [°C]
10-1
10-2
10-3
1
Integral-rubber
Integral Rubber is a multi block copolymer the building blocks of
which have well defined Tgs
TheThe „„Integral RubberIntegral Rubber““ ConceptConcept
Integral-Rubber 2 based on butadiene, styrene and isoprene(batch process with sequential monomer- and modifier addition)
Integral-Rubber 1 based on butadiene, styrene and isoprene(full batch process without the sequential addition of either monomer or modifier)
RoutesRoutes forfor thethe PreparationPreparation of Integral Rubbersof Integral Rubbers
Segment: Medium-cis BR Vinyl-BR S-SBR 3,4-IR
Tg [°C] -90°C -50°C -20°C ~ 0°C
Segment: Vinyl-BR S-SBR 3,4-IR
Tg [°C] -90°C -20°C ~ 0°C
butadiene randomizer styrene isoprene
Performance Performance ComparisonComparison of Standard Sof Standard S--SBR SBR withwithEE--SBR in a SBR in a CarbonCarbon Black CompoundBlack Compound
ProcessabilityBlack incorporation timeTackGreen Strength
Vulcanizationt10
t90
t90 - t10
Mechanical PropertiesModuliTensile StrengthTear resistanceAbrasion resistanceHeat build upRolling resistanceWet grip
Price
E-SBR
+++
+-0
++++--++*
S-SBR
---
-++
----+++-
* fully depreciated plants
In a In a carboncarbon blackblack loadedloaded compound compound therethere isis no real no real advantageadvantage forfor SS--SBR.SBR.
ThereforeTherefore therethere was no major breakwas no major break--throughthrough forfor SS--SBR SBR untiluntil thethe greengreen tyretyretechnology technology emergedemerged..
Green Tyre TechnologyGreen Tyre Technology
Si OH
Si OH
SEt-O SiEt-O
Et-OCH
2
CH2
CH2
S
SSCH
2
CH2
CH2
SiEt-OEt-OEt-O
SiO2
0
50
100
150
Rolling Resistance
AbrasionResistance
Carbon black
loaded tread
Green tyre
WetSkid
Performance of the green tyre Additional costs for the green tyre
Patents:DE 2447614; Degussa, Prior.: 05.10.1974; Erf.: K. Burmester, S. Wolf, E. Klötzer, F. ThurnUS 4,709,065; Shin-Etsu; Prior.: 20.09.1985; Erf.: H. Yoshioka et al.EP 299074; Bridgestone; Prior.: 03.10.1987; Erf.: T. Hamada et al. DE 3813678; Bridgestone; Prior.: 23.04.1987; Erf.: M. Takeshita et al. EP 501 227; Michelin, Prior.: 25. 02. 1991; Erf.: R. RaulineEP 447066; Bridgestone; Prior.: 27.02.1991; Erf.: T. Hamada
RußCompound
E-SBR--
Ruß--
++++
SilicaCompound
L-SBRNRBR
SilikaSi 69DPG
----
Rubber
FillerSilaneAdditive
Raw MaterialsMixing Costs
RecentRecent DevelopmentsDevelopments in Sin S--SBR Technology SBR Technology TowardsTowards ImprovingImproving Tyre PerformanceTyre Performance
FunctionalisationFunctionalisation of Sof S--SBRSBR
• Partial or total substitution of activator
• Improvement of silica dispersion
• Iprovement of silica reinforcement
• Reduction of hysteresis loss
• Improvement of wet skid
• Reduction of abrasion loss
Li+
CRn
R C80n
N
R1 R2
CH2
Si OROR
OR
R1C 91
R2
NCH
2
Si
OR
OR
OR
Li+
+
FunctionalizationFunctionalization of of LivingLiving Chain EndsChain Ends
EP 1113024 A1; Prior.: 02.12.1999, Bridgestone, Inv.: K. Morita, H. Kondo "Polymer process for making the polymer and rubber composition using the polymer“
Li+
CH2
Rn
Li+
O
Cln
Cl
O
n
Rn
Rn
Cl
+2
- 2
FunctionalizationFunctionalization withwith Polyether SegmentsPolyether Segments
DE 10057508; Bayer AG, Prior.: 21.11.2000; Erf.: T. Scholl, W. Obrecht, Braubach, E. Giebeler, Grün, A. Müller, M. Graf„Polyether/Diolefin-Kautschuke enthaltende Kautschukmischung“
CH2
C
CH
CH2
N
CH3
CH3
CH2
Incorporation of Incorporation of AminoisopreneAminoisoprene
EP 01165641; Bayer AG, Prior.: 03.02.1999; Erf.: T. Scholl, W. Obrecht, R. Stadler,
R. Morschhäuser, G. Mannebach "Kautschukmischungen basierend auf Aminoisopren"
Dimethyl-Aminoisoprene• is incorporated initially at the chain end• it acts as a randomizer during the whole course of the polymerization• the aminoisoprene containing rubber exhibits increased interaction with silica
Li+
CH2
Rn
Si
O
Si
ORn
Si
O
CH3
CH3
CH3CH
3 CH3
CH3
O
SiO
Si
OSi
CH3
CH3
CH3
CH3
CH3
CH3
Li+
+
D3
FunctionalizationFunctionalization of of thethe LivingLiving Chain End Chain End withwith a a PolysiloxanePolysiloxane Building BlockBuilding Block
Source: EP 0778 311; Michelin, Prior.: 07.11.1995; Erf.: J.-L. Cabioch „Composition de caoutchoucà base de silice et de polymère diénique fonctionnalisé ayant une fonction silanol terminale“
ModificationModification of Sof S--SBR SBR withwith HydroxylHydroxyl--MoietiesMoieties
S
HX
X SH
X: - OH (US 6252008)X: - COOH (US 6365668)
Sources:
US 6252008; Bayer AG; Prior.: 18.07.1998; Inv.: T. Scholl, U. Eisele, J. Trimbach, S. Kelbch
WO 02/31028 A1; Bayer AG; Prior.: 10. 10. 2000; Inv.: Th. Scholl, J. Trimbach, W. Nentwig, R. Engehausen
US 6365668; Bayer AG; Prior.: 16.11.1998; Inv.: Th. Scholl, J. Trimbach
4.3. 4.3. ChemistryChemistry and and ProductionProduction Technology of HighTechnology of High--ciscis--1,4 BR 1,4 BR withwith an an EmphasisEmphasis on Ndon Nd--BRBR
• Technically Relevant Catalyst Systems for the Production of High cis-1,4 BR– Influence of Halides on 1,4-cis Content
– Role of Halides and Electron Donors on Microstructure
– Trans-1,4 BR: Dependence of Melting Temperature on 1,4-cis-Content
– Reaction Scheme of Butadiene Insertion
• Mechanism of Nd-Catalyzed Butadiene Polymerization– Activity of Rare Earth Naphthenates (Cocatalyst: RnAlCl3-n)
– Influence of Solvents
– Influence of Molar Neodymium/Chloride-Ratio on 1,4-cis Content
– Reaction Scheme of Butadiene Polymerization by Nd-Catalysis
– Mechanism of Nd-Catalyzed Butadiene Polymerization
• Technical Options for the Control of Molar Mass in Nd-BR-Production
BR Catalyst System cis-1,4
Content
Li-BR nBu-Li 36 - 38
Co-BR Co(II)Octanoate / DEAC / H20 97
Ni-BR Ni(II)Naphthenate /Bu2O.HF/TIBA 97
Ti-BR TiJ3(OEt) / TiCl4 / TEA 93
Nd-BR Nd(III)Versatate / DIBAH / EASC 98
TechnicallyTechnically Relevant Relevant CatalystCatalyst Systems Systems forfor thetheProductionProduction of High of High ciscis--BRBR
Abbreviations:
nBu-Li n-Butyl-LithiumDEAC Diethyl Aluminum ChlorideTIBA Triisobutyl AluminumTEA Triethyl AluminumDIBAH Diisobutyl Aluminum ChlorideEASC Ethylaluminum Sesquichloride
Molar
Ratios
1 / 7 0-80 / 20-30
1 / 100 / 40
1 / 0,7 / 5
1 / 10-15 / 3
InfluenceInfluence of of HalidesHalides on 1,4on 1,4--ciscis--ContentContent
Ti Co Ni NdF 35 93 98 95,7
Cl 75 98 85 96,2
Br 87 91 80 96,8
J 93 50 10 96,7
Metal Component of
Catalyst SystemHalide
Source: Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian; J. Pol. Sci., Chem. Ed. 18 (1980) 3345-3357
92
93
94
95
96
97
98
0 1 2 3 4
Molar Cl/Nd - Ratio
cis
-1,4
-Co
nte
nt
[%]
Sources:•Lars Friebe: Diploma Thesis TU Munich 2000 •L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
trans -1,4-BR
cis -1,4-BR
trans -1,4-BR
cis -1,4-BR
trans -1,4-BR
cis -1,4-BRNd(CH2Ph)Cl2 + TIBA
Nd(CH2Ph)3 + TIBA
Nd(COOR)3 + DIBAC
Nd(COOR)3 + TIBA
trans -1,4-BR
cis -1,4-BR
Nd(COOR)3 + Mg (Allyl)2
Nd(COOR)3 + Mg (Allyl)2 + R-Cl
Nd(OR)3 + TIBANd(OR)3 + DIBAC
Source:
Shiro Kobayashi; Transition in
Precision Polymerization (1997)
Part 1. H. Watanabe, T. Masuda,
Diene Polymerization, pages 55-66
RoleRole of of HalidesHalides and and ElectronElectron DonorsDonors on on MicrostructureMicrostructure
For the achievement of high 1,4-cis contents the
presence of a halidesource is essential
s - 1,2 - BR
cis - 1,4-BRCo(Oct)2 + AlR2Cl + H2O
Co(Oct)2 + AlR2Cl + H2O + PPh3
Co(Oct)2 + AlR3 + CS2 s - 1,2 - BR
Ni(Oct)2 + BF3 - OEt2 + AlR3 + PPh3
Ni(Oct)2 + BF3 - OEt2 + AlR3 cis - 1,4 - BR
trans - 1,4 - BR
The coordination of electrondonors to vacant catalyst
sites results in a significantreduction of 1,4-cis contents.
As a consequence, syndiotacticBR or trans-1,4 BR are
obtained.
Tm
[°C
]
1,4 - trans-content [Mol %]
- 40
+ 0
40
80
120
160
80 90 1007060
Trans 1,4Trans 1,4--BR: BR: DependenceDependence of Melting of Melting TemperatureTemperatureon 1,4on 1,4--trans trans ContentContent
Data from:
US 5134199 Enoxy Chem Ltd.
GB 2161169 (Asahi)
US 4931376 (Asahi)
US 5596053 (Bridgestone/Firestone)*
*US 5596053 (Bridgestone/Firestone) Prior. 31. 05. 1995; Erf.: J. W. Kang; J. T. Poulton
"High Trans-1,4-BR and Catalyst and Process for Preparing Crystalline High Trans-1,4-BR“
US-A-5089574 (trans-1,4-BR-Herstellung/Goodyear)
EP-A-1092565 Prior.: 11.10.99 D. J. Zanzig, P. H. Sandstrom, J. J. Verthe, E. J. Blok, G. M. Holtzapple
„Tire with silica-reinforced tread comprised of trans-1,4-BR, solution-SBR, polyisoprene and defined amount
of carbon black and amorphous silica“
Goodyear
Source: Porri, Giarrusso, J. Polymer Science, Vol. 4, 93
M
C8
M
C15
M
C22
C29
M
C36
M
C43
`
C54
C60
MBd
Bd
MBd M
Bd
Allyl-Komplex
ReactionReaction SchemeScheme of of ButadieneButadiene InsertionInsertion
For the achievement of high 1,4-cis contents, a vacant coordination siteon the transition metal is a prerequisite. To this site butadiene has to becoordinated in a cisoid mode.
The formation of trans-1,4-BR is thermodynamically favourablewhereas the formation of 1,4-cis-BR ist kinetically controlled.
Source:
Zhinquan Shen, Jun Ouyang, Fasong Wang, Zehnya Hu, Fusheng Yu, Baogong Qian
J. Pol. Sci., Chem. Ed. 18 (1980)3345-3357
La
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
Lu
0
10
20
30
40
50
60
70
80
90
100U
ms
atz
[%
]
Activity of Rare Earth Napthenates (Cocatalyst: RnAlCl3-n)
MechanismMechanism of of NeodymiumNeodymium CatalyzedCatalyzed ButadieneButadienePolymerizationPolymerization
Only rare earth metals in the oxydation state
+III show polymerization activity
Al-alkyls reduce Pm, Sm and Eu salts to the
oxydation stage +II
MechanismMechanism of of NeodymiumNeodymium CatalyzedCatalyzed ButadieneButadienePolymerizationPolymerization: : InfluenceInfluence of of SolventsSolvents
Source: F. Cabassi,G. Ricci, L. Porri; Transition Metal Catal. Polym. (Proc. Int. Symp. 1988, 2nd vol. 655-670)
„Neodymium Catalysts For 1,3-Diene Polymerization. Some Observations On their Activity And Steoreospecificity“
Contrary to other Ziegler–Catalysts,
aromatic solvents have a negative im-
pact on Nd-based catalyst systems
MechanismMechanism of of NeodymiumNeodymium CatalyzedCatalyzed ButadieneButadienePolymerizationPolymerization
AlHO
O R1
R2
R3
Nd
3
Al
ClEt
Et
NdV DIBAH EASC
1 10 - 15 3
Cl
Al
Cl
Et
Literature:
1) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner; Adv. Polym. Sci. (2006) 204, 1-154 (Review); http://dx.doi.org/10.1007/12_094
Neodymium-Based Ziegler/Natta Catalysts and their Application in Diene Polymerization2) Friebe, Lars; Mueller, Julia; Nuyken, Oskar; Obrecht, Werner; Journal of Macromolecular Science, Part A: Pure and Applied Chemistry (2006), 43(6), 841-854.
Comparison of the solvents n-hexane, tert-butyl benzene and toluene in the polymerization of 1,3-butadiene with the Ziegler catalyst system
neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride.
3) Friebe, Lars; Mueller, Julia M.; Nuyken, Oskar; Obrecht, Werner. Pure and Applied Chemistry (2006), 43(1), 11-22.
Molar mass control by diethyl zinc in the polymerization of butadiene initiated by the ternary catalyst system
neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride. Journal of Macromolecular Science, Part A:
4) Friebe, Lars; Nuyken, Oskar; Obrecht, Werner. Macromolecular Science, Part A: Pure and Applied Chemistry (2005), A42(7), 839-851.
A Comparison of Neodymium Versatate, Neodymium Neopentanolate and Neodymium Bis(2-ethylhexyl)phosphate
in Ternary Ziegler Type Catalyst Systems With Regard to their Impact on the Polymerization of 1,3-Butadiene.
5) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) (2004), 45(1), 758-759.
Novel investigations and applications for neodymium based catalysts.
6) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States, March 28-April 1, 2004 (2004)
Novel investigations and applications for neodymium based catalysts.
7) Friebe, Lars; Windisch, Heike; Nuyken, Oskar; Obrecht, Werner. Journal of Macromolecular Science, Pure and Applied Chemistry (2004), A41(3), 245-256.
Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component.
8) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Materials and Engineering (2003), 288(6), 484-494.
In situ preparation of a compatibilized poly(cis-1,4-butadiene)/poly(e -caprolactone) blend.
9) Friebe, Lars; Nuyken, Oskar; Windisch, Heike; Obrecht, Werner. Macromolecular Chemistry and Physics (2002), 203(8), 1055-1064.
Polymerization of 1,3-butadiene initiated by neodymium versatate/diisobutylaluminum hydride/ethylaluminum sesquichloride: kinetics and conclusions about the reaction mechanism.
ReactionReaction SchemeScheme of of ButadieneButadiene PolymerizationPolymerizationbyby NdNd--CatalysisCatalysis
AlH Al O Al
AlH Al
O Al
O
AlO
H Al AlORCH2 (R-CH2-O)2 Nd - H + (R-CH2-O)3 Nd +
CH2
CH3
CH3
CH2
C
CH3
CH3
H (R-CH2-O)2 Nd (R-CH2-O)2 Nd - H +
H Al R-CH2-O AlH
Nd (O-CH2- R )3 + + (R-CH2-O)2 Nd
Nd ( OOC - R )3 + 6 Nd (O-CH2- R )3 + 3
1) Formation of Nd-Alcoholate by the Reduction od Nd-Versatate
2) Formation of a Nd-Hydrodo Compound (Precursor of Active Nd-Species)
Nd ( OOC - R )3 + 3 Nd (O-CHR- R )3 + 1
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
ReactionReaction SchemeScheme of of ButadieneButadiene PolymerizationPolymerizationbyby NdNd--CatalysisCatalysis
CH3
CH3
CH3
AlR 3 (R-CH2 - O)2 Nd(R-CH2 - O)2 Nd - H +
3) Hydride transfer and Formation of a Nd-Allyl Compound
4) Halogenation of the Nd-Allyl Compound
(R-CH2 - O)2 Nd Al2Et3Cl3 Cl2 Nd
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
ReactionReaction SchemeScheme of of ButadieneButadiene PolymerizationPolymerizationbyby NdNd--CatalysisCatalysis
R
Cl
Cl
AlR3
R
Cl
Cl
AlR3
AlR3
R
Cl
ClAlR3
AlR3
Cl
ClAlR3
AlR3
R
Cl
ClAlR3
AlR3R
R
Cl
ClAlR3
AlR3
Nd NdNd+
-
Nd+
-
Nd+
-
Nd+
-
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
5) Formation of polymerization active Nd species (cationic Nd allyl complex)and first butadiene insertion
ReactionReaction SchemeScheme of of ButadieneButadiene PolymerizationPolymerizationbyby NdNd--CatalysisCatalysis
6) Control of Molar Mass by Al-Alkyls and by Al-Hydrido Compounds
Source: L. Friebe, O. Nuyken, H. Windisch, W. Obrecht, Journal of Macromol. Sci.
Active “living“ inactive “dormant“polymer chain polymer chain(attached to Nd) (attached to Al)
R
AlH H AlR
R
Al AlR
NdL
L+ Nd
L
L+
NdL
L+ Nd L
L+
MechanismMechanism of of NdNd--CatalyzedCatalyzed ButadieneButadiene PolymerizationPolymerization
0 50 100 150 200 250
Mon
om
er C
on
ver
sion
[%] 100
80
60
40
20
0
time [min]
0 50 100 150 200 250 300
Time [min]
0
-1
-2
-3
-4
-5
ln(1
-x)
Conversion/time-plots Plot for 1st order monomer consumption
ExperimentalConditions:
Addition Sequence:
1. Hexane
2. Butadiene
3. DIBAH
4. Neodymversatate
5. EASC
Polymerization temperature: 60°C
Solvent n-Hexane
Butadiene 1,85 mol/l
NdV 0,20 mmol/l
EASC 0,13 mmol/l (nCl/nNd = 2/1)
DIBAH2,0; 4,0; 6,0; 10,0 mmol/l
nDIBAH/nNd = 10, 20, 30, 50
Sources: Lars Friebe: Diplomarbeit and der TU München, Dezember 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
nDIBAH/nNd = 10nDIBAH/nNd = 20nDIBAH/nNd = 30nDIBAH/nNd = 50
nDIBAH/nNd = 10nDIBAH/nNd = 20nDIBAH/nNd = 30nDIBAH/nNd = 50
MechanismMechanism of of NdNd--CatalyzedCatalyzed ButadieneButadiene PolymerizationPolymerization
e lu t io n t im e / m in
3 0 3 5 4 0 4 5 5 0 5 5 6 0 6 5
dif
feren
ce
of
refr
acti
on
in
dex
6 6 .4
c o n v e r s io n / %
5 5 .1
5 0 .0
4 3 .5
3 5 .6
3 0 .7
2 2 .7
1 2 .2
4 .8
8 2 .5
7 .8
Elution time[min]
30 35 40 45 50 55 60 65
Dif
fere
nce
in R
efra
ctiv
eIn
dic
esDependence of Molar MassDistribution on Monomer
Conversion
Dependence of PDI (Mw/Mn) on Monomer Conversion
Source: L. Friebe: Diploma Thesis at TU Munich, December 2.000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht;Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
4,0
3,5
3,0
2,5
2,0
1,5
1,00 10 20 30 40 50 60 70 80 90 100
Monomer Conversion [%]
Mw/M
n
nDIBAH/nNd = 10nDIBAH/nNd = 20nDIBAH/nNd = 30nDIBAH/nNd = 50
MechanismMechanism of of NdNd--CatalyzedCatalyzed ButadieneButadiene PolymerizationPolymerization
0 10 20 30 40 50 60 70 80 90 100
Mn
[g . m
ol-1
]
Monomer Conversion [%]
2,5*105
2,0*105
1,5*105
1,0*105
0,5*105
0
Form
al
Nu
mb
erof
Poly
mer
Ch
ain
s fo
rmed
per
Nd
-Ato
m
nDIBAH/nNd = 4,4
0 10 20 30 40 50
nDIBAH/nNd
16
14
12
10
8
6
4
2
0
Dependence of Mn on Monomer Conversion
Molar Mass Controlwith Al-Component
Source:L. Friebe: Diploma Thesis at TU Munich, December 2000 L. Friebe, O. Nuyken, H. Windisch, W. Obrecht; Macromol. Chem. Phys. 8 , 203 (2002) 1055-1064
nDIBAH/nNd = 10nDIBAH/nNd = 20nDIBAH/nNd = 30nDIBAH/nNd = 50
nDIBAH/nNd = 10nDIBAH/nNd = 20nDIBAH/nNd = 30nDIBAH/nNd = 50
TechnicalTechnical OptionsOptions forfor thethe ControlControl of Molar of Molar MassMass in in NdNd--BR BR ProductionProduction
Influence of Butadiene/Nd-ratioD. J. Wilson, Polymer 1993, 34,16, 3504-3508
0
100
200
300
400
500
600
700
800
900
0 0,05 0,1 0,15 0,2 0,25 0,3
Nd (mmol/100 wt.-parts of butadiene]
Mo
lar
Ma
ss
(M
v)
[kg
/mo
l]Influence of Polymerization Temperature
G. Sylvester, B. Stollfuss ACS, Rubber Div. Dallas 1988 „Synthesis of
cis-1,4-Polybutadienes by rare earth catalysts“
0
500
1000
1500
2000
2500
0 10 20 30 40 50 60 70 80 90
Polymerization Temperature [°C]
Mo
lar
Mass (
Mv)
[kg
/mo
l]
Influence of Monomer ConversionM. Bruzzone ACS Symposium Series No. 3 (1982)
33-55
0
10
20
30
40
50
60
0 20 40 60 80 100
Monomer Conversion [%]
ML
1+
4 (
10
0°C
)
Contrary to Catalysts based on Co,
Ni and Ti, for Nd-based catalysts
there is no agents for the control of
molar mass available.
Therefore in Nd-BR technology
molar mass has to be controlled by:• Nd/Al-ratio
• Monomer/Nd-ratio
• Monomer Conversion
• Polymerization temperature
ComparisonComparison of Technologies of Technologies forfor thethe ProductionProduction of of High cisHigh cis--1,41,4--BRBR
Butadiene Vinylcyclohexene (VCH)
* Formation of VCH by Diels-Alder-Reaction
BenzeneBenzeneBenzene
100-200200-25050-10010-50Residual transition metalContent [ppm]
lowvery highhighhighFormation of VCH
nonenoneyesyesMolar mass regulator
18-22%11-12%15-16%14-22%Max. solids concentation
fullyadiabatic
Partiallyadiabatic
Partiallyadiabatic
Partially adiabatic/isothermal
process
Very lowlowhighhighGel formation
< 100%< 95%< 85%55-80 %Monomer conversion
100-120 min120 min120 min150 minResidence time
N-HexaneCylcohexane
TolueneHexaneToluene
TolueneAliphates
Solvents
NdTiNiCo
Advantage
4.4. 4.4. Ethene/PropeneEthene/Propene--CoCo-- and and TerpolymersTerpolymers (EPM/EPDM)(EPM/EPDM)
• Overview– EPM and EPDM, Termonomers, Market, Range of Grades and
Property Profiles
• EPDM-Production– Chemistry of Polymerization , Producers, Capacities, Brand
Names and Production Technologies
• Production Technologies (Flow Charts)– Solution Process
– High Temperature Solution Process
– Gase Phase Process
– Comparison of Manufacturing Technologies
• Metallocenes– Ovewrview on Metallocene Patents
– Metallocene Activation
– Comparison of Catalyst Costs
Ethene/PropeneEthene/Propene--CoCo-- und und TerpolymersTerpolymers(EPM/EPDM)(EPM/EPDM)
Method of Vulcanization
Peroxides
SulfurPeroxides
Phenol resinsetc.
EPM
EPDM
EPM (15%)
Ethene/Propene-Copolymers
Major areas of application:• Oil additives• Impact modification of thermoplastic
polymers (PP)
EPDM (85%)Ethene/Propene/Diene-Terpolymers(30% of grades are oil extended)
Major areas of application:• Technical rubber goods• Cables and wires• TPEs
EPDMEPDM--TermonomersTermonomers
5-Ethyliden-2-norbornene
(ENB)
1,4-Hexadiene
(HD)
Dicyclopentadiene
(DCPD)
Relative polymerization rates of termonomer double bonds
in Vanadium catalysedpolymerizations
~ 40 : 1
~ 15 : 1
~ 5 : 1
Criteria for the selection of the termonomer:
• Large reactivity difference of double bonds during polymerization
• Low impact on the reduction of the polymerization rate
• Low impact on the reduction of the molar mass during polymerization
• Sufficiently long scorch time and high crosslinking efficiency during vulcanization
• Low termonomer costs
time [min]
20
30
40
50
70
0
60
To
rqu
e[N
m]
0 1,0 2,0 3,0 4,0 5,0 6,0
10
Impact of Impact of thethe TermonomerTermonomer on on thethe CuringCuringCharacteristicsCharacteristics
ENB DCPD HD
ENB
DCPD
1,4-HD
Advantages:– good price/performance-ratio– high maximum service temperature– good low temperature performance– broad spectrum of grades (oil extended grades etc.) – ability for vulcanization with sulfur, peroxides and others– high loadability with extender oils and fillers (reduction of compound price)– good mechanical properties of vulcanizates– good weathering and ozone resistance (outdoor applications) – good electrical insulation (low salt content)– Low density
Disadvantages:– low resistance to oil and chemicals– fair ability to covulcanization– low resistance to fungi and bacteria
Property Profile of EPM/EPDM Property Profile of EPM/EPDM basedbasedVulcanizatesVulcanizates
41%16%
15%9%13%
6%
Automotive
Thermoplast Modification
Building
Technikcal Rubber Goods
Electro/Electronics
Oil Additives
Main Main ApplicationApplication AreasAreas of EPM/EPDMof EPM/EPDM
0
100
200
300
400
500
600
700
1986
1987
1988
1989
1990
1991
1992
1993
1994
1995
40
45
50
55A
uto
moti
ve
Pro
du
ctio
n/
Mio
.
Automotive production (world)
EPDM Consumption (world)
Market: 1,050 Mio t (2004)
Growth rate: 3,5 %/a
Source: European Chemical News 10, März 2005, 13
EP
DM
-Con
sum
pti
on
/ k
t
Range of Range of EP(D)MEP(D)M--GradesGrades
0, 25, 30, 50, 100[phr]Oil Content:
16 - 20 20 - 60 60 - 90[MU]Mooney Viscosity:
[ML 1+4 (125°C)]
0 1,7 - 3 4 - 7 8 - 12[wt.%]ENB-Content:
50 - 75[wt.%]Ethene Content
-65
-62,5
-60
-57,5
-55
-52,5
-50
-47,5
-45
40 45 50 55 60 65 70
Ethene content [wt.%]
Tg
[°C
]
DependenceDependence of of TgTg on on thethe EtheneEthene-- and and thethe ENBENB--ContentContent((VV--catalysedcatalysed commercialcommercial productsproducts))
Tg(EPDM) = Tg(EPM) + 1,2°C/wt.% ENB
EPDM/2% ENBEPDM/1% ENBEPM /0% ENB
Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001
0
5
10
15
20
25
30
46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64
Ethene content [wt.%]
En
tha
lpy
of
fusi
on
[J
/g]
35-39°C
40-44°C
45-49°C
50-54°C
55-59°C
60-64°C
65-70°C
DependenceDependence of of thethe CristallinityCristallinity on on thethe EtheneEthene ContentContent and and on on thethe PolymerizationPolymerization TemperatureTemperature of of VV--CatalysedCatalysed EPMEPM
Source: M. Hoch, M. Arndt-Rosenau, Bayer-Report ARO 1, HCM 40 of 16.02.2001
Chemical and Chemical and ProcessProcess AspectsAspects in in EPM/EPDMEPM/EPDM--ManufacturingManufacturing TechnologiesTechnologies
Chemical Aspects
free radicalPolymerization
Ziegler/Natta-Polymerization
anionionicPolymerization
cationicPolymerization
Polyaddition und Polycondensation
Polymer-modification
Process Features
Emulsion Solution Dispersion Bulk Gas-Phase
E-SBR, CR, NBR, E-BR, ACM,FKM, EVM
EVM EVM AEM, EVM, (ENM)
(G-BR)
(G-EPM/EPDM)
BR
EPM/EPDM
BR, L-SBR. IR
CIIR, BIIR, CM, CSM, H-NBR, FZ
ECO, CO
AU, EU
IIR
EU
CM, CSM, (H-NBR)
Q
Q
AU, Q
EPM/EPDM
Process Solution Slurry High temperature Gas phase
solution (Dow) (UCC)
Solvent: Hexane Propene/ethene Hydrocarbon mix. -
Catalyst System Ziegler/Natta CGC/Borane Ziegler/Natta
Catalysts: VOCl3, VCl4, V(acac)3,VO(OR)3, TiCl4 CGC-Catalyst V(acac)3
Cocatalysats: EASC, DEAC Borane (MMAO) Al-Alkyl
Reactivators: PDCAE, TCAE, BPCC - CHCl3Modifier: H2, ZnEt2, (NH3) - H2
Short stos: Stearic acid, water, antioxidants ?
Antioxidans: sterically hindered phenols, phosphites ?
Stripping aids: water soluble polymers etc. - -
Oil: mineral oil fraction with high b. p. - -
Features of Features of thethe EPDMEPDM--ManufacturingManufacturingTechnologiesTechnologies
O
O C2H5
Cl
Cl
C4H
9O
OCl
Cl
Cl ClCl
C2H
5OCl9
O
Cl
Cl
Reactivators: PDCAE BPCC TCAE
Source: R. T. Sylvest, J. A. Riedel, J. R. Pillow; GAK 6/1997 (50) 478-483
+V VOCl3
+IV VCl4
+III VX3 + R2 AlX {R2VX} {R2V+
} + R2AlX2
-
+II VX2 + R3 Al [R2V] [RVX]
R2AlX R3Al
SpeculationSpeculation on on thethe ActiveActive SpeciesSpecies in in thetheVanadiumVanadium--CatalysedCatalysed EPDMEPDM--PolymerizationPolymerization
Source: K.J. Cann, J.W. Nicoletti, X. Bai, F.D. Hussein, K.H. Lee, D.P. Zilker, Presentation at FLEXPO `97
{homogeneously soluble species} [heterogeneous species]
Ak
tivato
r
heatheat
EPDMEPDMProducers, Capacities (Producers, Capacities (ktkt) and Brand Names) and Brand Names
Baton Rouge, Louisiana 180
Notre Dame de Gravenchon 85
Geleen, Niederlande 135 Keltan
Triunfo, Brasilien 35 Nitriflex EP
Plaquemine, Louisiana 100 Nordel-IP
Seadrift, Texas 90 Elastoflo (UCC)
Marl, Deutschland 60 Buna EP G
Orange, Texas 55 Buna EP T
Lion Copolymer Geismar, Louisiana 91 Royalene / Trilene
Polimeri Ferrara, Italien 85 Dutral
Mitsui Chiba, Japan 60 Mitsui EPT
JSR Kashima, Japan 25
Yokkaichi, Japan 45
Sumitomo Chiba, Japan 40 Esprene
Kumho Yeochon, Südkorea 40 KEP
Petro China Jilin, China 30
Nizhnekamsk Nizhnekamsk, Russland 30
Herdillia Maharashtra, Indien 10
total capacity 1076
Vistalon
JSR EP
Exxon
DSM
DPDE
Lanxess
Source: European Chemical News 10, März 2005, 13
Water
Modifier
Reactivator
EASC
VOCl3 /VCl 4 3 / 1
PH-
Control
EPDMEPDM--SolutionSolution--ProcessProcess withwith FullyFully FloodedFlooded ReactorReactor
destillation
Packaging
Externalcooling
loop
baling
Waste water
Steam
Strippingaid
Antioxydant
oil
Stripper
Polymerizationreactor
dewteringscrewg
Expeller
drier
Settler
Azeotropicdestillation
Water containingazeotrope
drier
Condenser
Condenser
Hexane
Flash drum
Propene
drier
destillationEthene
Hexane VNB/ENB
drierDrier
ENB
Boiling point: 146°C
Max. exposure limit/MAK: 1 ppm
Smell limit: 3-5 ppm
Steam
Settler
Precoller-32/-35°C
Waste air
Waste water
Waste water
Process FeaturesPropene precooling: -32°C/-35°C
Temperature: 20-65°C
Pressure: 5-10 bar
Residence time: 6-15 Min.
Soldis conc.: 3 -7 Gew.%
H2 O: < 3 ppm
DowDow‘‘s s HighHigh--TemperatureTemperature Solution Solution ProcessProcess((SourceSource: Dow: Dow--Patents, Patents, PublicationsPublications etc.)etc.)
"Insite-Kat." packaging
Antioxidant(AO)
Flash-drum
Polymerizationreactor
Purification
Condenser
Temperature: 40 - 80 °C Ta: 80°C (>130°C)Pressure: 9-15 barResidence time: < 20 Min.
Evaporator
High boiling
residue
(ENB, AO, etc.)
Destillation
Ta
Scavenger
Solvent and
monomer
Ethene Propene ENB MMAO Borane
Plant location: Plaquemine/Lousiana
baler
Purification Purification
Evaporator
Ageingdrum
In the Dow-HT-Process low
amounts of CGC- catalyst
are required. The catalyst
is not washed out and no
steam stripping is applied
(„leave-in-catalyst“)
Metal Metal ContentContent of Commercial EPDMof Commercial EPDM
Source: J. G. Pillow (Dow) „Ethylene Elastomers made using Constrained Geometry Catalyst Technology“
Kautschuk Gummi Kunststoffe 51, 12/98, 855-859
Cl
R
A
R
R
ZrAlkylation
Zr +
ClZr
Activation by MAO (molar excess of MAO: 10.000 - 10.000 fold)
Activation by Borane/Borates: (with molar B/Zr-ratios)
Activation of Metallocenes
584,19,464440631,94,8EPDM#6
184,14,61609,62,8<15,1EPDM #5
82,85,7646,72,0<12,4EPDM #4
48,81,81,7314,3<11,9EPDM #3
22,31,81,7314,3<18,0EPDM # 2
8,0<1<11,71,31,0<1Dow-CGC
SumNaCaAlFeTiVProduct
CrystallinityCrystallinity of of MetalloceneMetallocene--BasedBased EPDMEPDM
0
5
10
15
20
25
30
40 42 44 46 48 50 52 54 56 58 60 62
Ethene Content [wt.%]
En
thalp
y o
f fu
sio
n [
J/g
]
N
Me2Si
Ti
X
X
CMe3
DOW-Insite-Cat.
ZrCl2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
CH2
EBTHI-Cat.
V-Catalysis
0
10
20
30
40
50
60
70
80
90
100
0 3 5 7 78,
58,
5
10,0
0
12 18 2132
,5 35
37,5
0
37,5
47,5
Enthalpy of Fusion [J/g]
Lo
w-T
em
pera
ture
-Co
mp
ressio
n-S
et
[%]
EPDM/V-Cat.
EPDM/CGC (Dow)
Impact of Impact of CristallinityCristallinity on on LowLow--TemperatureTemperatureCompressionCompression Set of Set of EPDMEPDM--BasedBased VulcanizatesVulcanizates
N
Me2Si
Ti
X
X
CMe3
DOW-Insite-Cat.
UCCUCC‘‘s s EPDMEPDM--GasGas--PhasePhase--ProcessProcess ((nownow Dow)Dow)
Purification
Purification
Product
Compressor
Baling of
Product etc.
Cooler
Temperature: < 90 °C (40°C-60°C)
Pressure: 9-15 bar
Residence time: 0,5 - 1 h
ENB
Boiling point: 146°C
Maximum exposure level: 1 ppm
Smell limit 3-5 ppm
Filter
Monomer degassing
unit
Source: „Carbide starts up Seadrift plant with new technology“ European Chemical News, 1-8 February 1999 ($
12m charge for replacing the purge unit)
Plant location: Seadrift/Texas
Desactivation
ENB
Fluidizing Aid
Suported Catalyst
Ethene
Propene
Modifier
Purification
Purification
Patents:EP 1099715
EP 1099473
EP 1086995
EP 1083192
US 6180738
WO 0000333
WO 9965953
Flow-Chart:US 4994534
ComparisonComparison of of EPM/EPDMEPM/EPDM--ManufacturingManufacturingTechnologiesTechnologies
Process Solution Slurry HT-Solution Gas-PhaseV-Catalysis V-Catalysis CGC/Dow V-Catalysis
Process Economy 4 5 7 10
EPM 10 10 10 10
EPDM 10 10 10 0
Low Mooney 10 8 10 0
High Mooney 5 10 3 10
Oil Extended Grades 7 10 3 0
Process Flexibility 42 48 36 20
Overall Process
Performance 46 53 43 30
• The well established vanadium based solution and slurry processes
are inferior in investment and operation costs, but provide a higher
flexibility.
• The HT-solution and the gas-phase technology are low cost-
technologies, which are superior in the production of specific grades
• The well established vanadium based solution and slurry processes
are inferior in investment and operation costs, but provide a higher
flexibility.
• The HT-solution and the gas-phase technology are low cost-
technologies, which are superior in the production of specific grades
Ranking: 1-10; 1= modest; 10=excellent
MetalloceneMetallocene--PatentsPatents 19801980--2000 (2000 (OctOct. 2000). 2000)
0
50
100
150
200
250
Nu
mb
er
of
Pa
ten
ts (
US
) +
Pa
t. -
Ap
pl.
Exx
on
Hoec
hst
Dow
BA
SF
Phi
llip
sTa
rgor
Mits
ui P
etro
lS
hell
UC
CM
ont
ell
Mits
ui C
hem
.Id
emitsu
DS
M BP
Bore
alis
Fin
a
EN
IM
obil
Du P
ont
Cib
a G
eigy
Alb
emar
leN
r. 2
2 B
ayer
2.923 2.923 DocumentsDocumentsUSUS--Patents and EPPatents and EP-- and WOand WO--Patent Patent ApplicationsApplications
WPIDS-Recherche Dr. Karjetta vom 29. 09. 2000
Cl
R
A
R
Cl
R
R
Zr
Alkylation
(BuLi, AlR3 or MAO)
Zr+
ClZr Zr
Alkylation
(BuLi, AlR3 or MAO)
ActivationActivation of of MetallocenesMetallocenes
Activation by MAO Activation by borates and boranes
CH2
CH2
R
CH2
CH2
R
CH2
CH2
R
CH2
CH2
R
Zr+ Zr
+
Zr+
Zr+
CosseeCossee--MechanismMechanism of of MetalloceneMetallocene CatalysedCatalysedOlefinOlefin Insertion Insertion
HDPE, i-PPHDPE, s-PP, COCHDPE, LLDPE, i-PP, EP(D)MHDPE, LLDPE, a-PP
MAO-ActivationBorate-Activation
MAO-Activation*
MAO-Activation
EP 69951(09.07.1981)
Hoechst (Kaminsky)
EP 4858821(12.11.1990)
Hoechst(Spaleck)
EP 351392(15.07.1988)
Fina(Ewen, Razavi)
EP 468537(30.01.1987)
Exxon(Turner)
EP 129368(06.06.1983)
Exxon(Ewen)
EP 35242(29.12.1980)
BASF(Kaminsky)
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts1.1. Bis 1.1. Bis CyclopentadienesCyclopentadienes
ZrX
X
B ZrX
X
B = Bridge
Me2C
ZrCl2
ZrCl2
Me2Si
* H. C. Welborn, Jr.; J. A. Ewen US 5324800 (Exxon) Prior.: 30.08.1991 „MAO-Activation of Bridged Metallocenes“
HDPE, LLDPE,PP, EPM, EPDM
HDPE, LLDPE, PP,
EPM, EPDM, COC
PE, PPHDPE, PPPolyolefins
MAO-/Borate-Activation
MAO-/Borate-Activation
WO 97/2351(22.12.1995)Hoechst AG(Herberich)
US 5539124(19.12.1994)Lyondell
WO 98/50392(08.05.1997)Nova Chemicals(Spence)
WO 98/01455(05.07.1996)Bayer AG(Ostoja-Starzewski)
WO 96/34021(25.04.1995)Lyondell
US 5554775(17.01.1995)Lyondell
EP 638593(02.08.1993)Shell
ZrX
X
E
E
E = N, P
NBR
R´
ZrX
XB
N
R´
R
ZrX
X
BY
BY
PMe
2Si
Me
MeMe
Ph ZrCl2
B
Cl
Cl
ZrCl
Cl
P
SiMe3
Ph
Ph
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts1.2. 1.2. IsoelectronicIsoelectronic BicyclopentadienylBicyclopentadienyl SystemsSystems
HDPELLDPEEPM
POHDPELLDPEEP(D)MES
S-PS
MAO_/Borate-Activation
Borate-ActivationMAO-/Borate-Activation
MAO-Activation
EP 420436(13.09.1989)Exxon
US 5206197Dow(04.03.1991)
WO 96/13529DSM(Lovocat)
US 5132380(12.09.1991)Dow
EP 416 815(31.08.1998)Dow
EP 210615(29.07.1985)Idemitsu Kosan
Ti
X
XRxE
E= N, O
N
Me2Si
Ti(IV)
X
X
CMe3
NR2
Ti
X
XIII
Ti
OMeMeO
MeO
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts2. 1. 2. 1. MonoMono--CyclopentadienylCyclopentadienyl SystemsSystems
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts2.2. Mono 2.2. Mono CyclopentadienylCyclopentadienyl SystemsSystems
PE, LLDPEEP(D)MEP(D)M
MMAO-ActivationMMAO-ActivationMMAO-Activation
US 6063879
(29.10.1997)
Nova
WO 2008/095687
DSM
WO 2005/005496
DSM
TiCH3
CH3N
P
t-But-Bu
t-Bu
FF
F
F F
TiCH3
CH3N
CN
N
Ti
X
O
N
P
HDPE, PPPolyolefins,
Polyacetylens
PolyacetylensPolyolefinsAlternating
Olefin/CO-Copolymers
(„Carilon“)
EP 571945
(29.05.1992)
Sumitomo
US 5637660
(17. 04. 1995)
Lyondell
EP 606125
(08.01.1993)
Shell
JP 5230133
(19.02.1992)
Mitsui Toatsu
WO 92/12162
(27.12.1990)
Exxon
EP 121965
(05.04.1983)
Shell
P
Pd
P
ArAr
X
X´
ArAr
N
Ti
N
Ar
X
X
Ar
S
O
Ti
O
X
X
t-Bu
t-Bu
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts3.1. Post 3.1. Post MetallocenesMetallocenes
N
OZr
N
O
X
X
N
M
N
X
X´R
R
R
R
R´
R´
M = Ni, Pd
Key Patents in Key Patents in MetalloceneMetallocene-- und und SingleSingle--SiteSite--CatalystsCatalysts
3.2. Post 3.2. Post MetallocenesMetallocenes
N
N
N FeCl
Cl
OO
TiN N
Cl Cl
EPM, EPDMHDPE, EPMHDPE(PP)HDPE, (PP)polar/unpolar
Copolymers, LDPE
EP 1881014
(10.05.2006)
Mitsui
EP 0874005
(24.01.1998)
Mitsui
BPDuPont
(Brookhart)
WO 96/23010
(24. 01. 1996)
DuPont
(Brookhart)
Features of Features of thethe ActivationActivation byby MAOMAO
(CH3)2 Al - [O - Al - CH3]n- O - Al(CH3)2
(CH3) Al - [O - Al - CH3]n- O - Al(CH3)
O
n : 6 - 20
MW : 2.000-2.500
Chemical Structure of Methylalumoxane (MAO):
Features of the activation by MAO:• The details on the mechanism of the activation by MAO are not known
• A 1.000-10.000 fold molar excess of MAO is needed in solution polymerizations
• A 50-100 fold molar excess is needed for supported catalysts (gas phase)
• MAO is capable of alkylating metallocenedichlorides
• MAO is able to abstract chlorides from metallocenemono- or dichlorides
• MAO is an efficient scavenger for impurities
(Polymerizations performed in the presence of MAO are very robust towards impurities)
N
H
PhMe
Me
PhPh
Ph
B
F
FF
F
F
FF
F
FF
F
FF
F F
B
F
F
F
F
F 4
_
B
F
F
F
F
F 4
_
+
+
ActivationActivation of of MetallocenesMetallocenes byby BoranesBoranes and Boratesand Borates
R
R
R
Zr +
Zr
- R-
• For the Activation of metallocenes molar quantities of borane/borates arerequired
• Polymerizations activated by boranes/borates are very susceptible to impurities
Borane
Anilinium Borate
Triphenylcarbenium
Borate
Abstraction of Alkyl-Anions by Borane and Borates
ActivationActivation of of MetallocenesMetallocenes
Zr +
R
Zr
R
R
- R-
N
H
PhMe
Me
A
PhPh
Ph
NPh
MeMe
PhPh
Ph
R
B
B
R
A
-A
-
A-+
+
F5F5
F5
- RH+ R
F5F5
F5
-+ R
-
-
M. Bochmann
(1990)T. J. Marks (1991;JACS 113, 3623)
M. D. Rausch,
J. C. W. Chien (1991)
R. F. Jordan (1986)
Ag BPh4
+
Ag+1/2 R2 + BPh4
-
CH3CN
+ R-
+ R -
-
FF
FFF
B
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
-
A : - EP 468 537 (Exxon) Priorität: 1987
EP 561 479 (Exxon) Priorität: 1987
Nicht oder schwach koordinierende Anionen
"NCA"oder "WCA"
(insbesondere: Tetrakis(Pentafluorophenylborat)
EP 468 537 (Exxon) Priorität: 1987
EP 561 479 (Exxon) Priorität: 1987
Nicht oder schwach koordinierende Anionen
"NCA"oder "WCA"
(insbesondere: Tetrakis(Pentafluorophenylborat)
Turner
1987
Turner
1987
US 5599761 (Exxon) Priorität: 04.02.1987
Erfinder: H. W. Turner
„Ionic Metallocene Catalyst Compositions“
US 5599761 (Exxon) Priorität: 04.02.1987
Erfinder: H. W. Turner
„Ionic Metallocene Catalyst Compositions“
Activation of Cp2ZrCl2 by MAO (BASF/Kaminsky) EP 35242; Prior. 29.12.80
Activation of metallocenesby borates (Exxon/Turner)
Activation of metallocenes by Alkyl/R<C6- Al-Oxanen (Exxon)
Activierung of Cp2ZrRCl by MAO (Hoechst/Kaminsky) EP 69951; Prior.: 09.07.81
Year of Priority
1980
1985
1990
1995
Activation of metalloenes by Al- Alkyls R >C8 - Al-Oxanes (Montell)
Key Patents Key Patents forfor thethe ActivationActivation of of MetallocenesMetallocenes
Activation by boranes (Fina/Ewen) EP 427 697; Prior.: 10. 10. 1989
Activation of CGCby MAO (Dow/Stevens) EP 416815; Prior.: 31.08.89
Activation by borates (Dow/Stevens) EP 418044; Prior.: 14.09.89 [Cp1MXn]+ [BR4]-
CGC/Diene-activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
EP 468 537; Prior.: 30.01.87 [Cp2MX]+ [BR4]EP 561 479; Prior. 30. 01. 1987US 559 976; Prior. 04. 02. 1987 Ionic metallocene catalyst comosition
CGC-Activation by boranes (Dow/Stevens) EP 705 269; Prior.: 24. 06. 1993
WO 01/08691 (Bayer AG)
Prior.: 18.08.2000
Inv.: Becke, Kahlert,
Denninger, Windisch, Obrecht
WO 01/10124 (Bayer AG)
Prior.: 11.09.2000
Inv.: Becke, Denninger,
Kahlert, Obrecht, Schmid,
Windisch,
EP 1066296 (Bayer AG)
Prior.: 24.03.1998
Inv.: Becke, Denninger,
Mager, Windisch
EP 111927 (Bayer AG)
Prior.: 23.06.1999
Inv.: Becke, Mager, Zahalka
Non Non CoordinatingCoordinating AnionsAnions
EP 468537 (Exxon)
Prior.: 30.01.1987
Inv.: Turner, Hlatky
EP 561479 (Exxon)
Prior.: 30.01.1987
Inv.: Turner, Hlatky
FF
FFF
B
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
F
FF
F
FF
F
F
F
FF
F
F
FF
F
FF
F
F
F
F
F
F
F
F
F
F
F
B
F F
FF
FF
F
F
F
FB
F
FF
FF
F
F
F
F
F
Si
B
FF
F
F
FF
F
F
F
F
F
F
F
F
F
B
F
F
F
F
FF
F F
F
F
F
F
F
F
FF
F
F
F
F
--
-
4 -
ComparisonComparison of of CatalystCatalyst CostsCosts
• MAO-activation of metallocenes is not economical in a solution process
• Borate-activation results in catalyst costs which are comparable with
Vanadium-systems
• For an improvement in overall-economy metallocene-technology has to be
combined with process improvements
• Increased catalyst costs might be compensated by the improved property
profile of new products
• MAO-activation of metallocenes is not economical in a solution process
• Borate-activation results in catalyst costs which are comparable with
Vanadium-systems
• For an improvement in overall-economy metallocene-technology has to be
combined with process improvements
• Increased catalyst costs might be compensated by the improved property
profile of new products
Example Catalyst Cocat. Reactivator Total Cat-Costs
[EUR/100 kg] [EUR/100 kg] [EUR/100 kg] [EUR/100 kg]
Plant 1 VOCl3 EASC DCPEE
[EUR/kg] 0,50 3,75 2,00 6,25
Plant 2 V(acac)3 DEAC TEA
[EUR/kg] 1,25 1,30 0,65 3,20
Exxon- Pat. Et(Ind)2ZrCl2 MAO -
[EUR/kg] 13,00 151,00 - 164,00
Exxon- Pat. Et(Ind)2ZrMe2 Borate -
[EUR/100 kg] 2,25 3,45 - 5,70
4.5. Butyl4.5. Butyl-- and Halobutyl Rubber and Halobutyl Rubber
Contents
• Overview– Products, Property Profiles and Areas of Application
– Market, Market Shares, Producers and Range of Grades
• Polymerization Mechanism and Production Technologies– Standard-Butyl Rubber (IIR)
– Halo Butyl Rubber (XIIR)
• Vulcanization and Vulcanizate Properties
Abbreviations:Butyl Rubber: IIR
Bromo Butyl Rubber: BIIR
Chloro Butyl Rubber: CIIR
Brominated Isobutene Paramethylstyrene Rubber: BIMS
IIR-Terpolymer (mainly with Divinyl benzene): XLIIR
ButylButyl-- and Halo Butyl Rubber and Halo Butyl Rubber
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
X
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH3
CH2
CH2
n
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
CH CH2
CH CH2
n
CH2Br CH
3
C
CH3
CH3
X = Cl: Chloro Butyl Rubber (CIIR)
X = Br: Bromo Butyl Rubber (BIIR)
Butyl Rubber (IIR)
Brominated Isobutene-co-p-Methylstyrene Rubber (BIMS)
Isobutene-Terpolymers
Basic Features:
Isoprene content: 0,5 - 2,5 Mol%
Incorporation of Isoprene: random 1,4-trans
Tg: ca. -72°C
Mw/Mn: 3 - 5
C45
CH3
CH3
CH226
C27
CH28
CH3
29CH
2
30
CH223
CH235 CH
221
C15
CH316
CH3
39
C19
CH3
20
CH338
123°
Standard Angle: 109,5°
ButylButyl-- and Halo Butyl Rubber (X)IIR: Property Profile and and Halo Butyl Rubber (X)IIR: Property Profile and AreasAreas of of ApplicationApplication
Property ProfilePositive:• Low gas permeability• high resistance to heat and vapour• high resistance to chemicals• good insulation properties• good covulcanization (XIIR))• product purity
(grades without antioxydants)
Negative:low elasticity /highly damping
Areas of Applications:• XIIR based Innerliners (passenger tyres)• IIR b ased tubes (truck tyres)• bladders (IIR)• ABC-protection clothes• Cable and wiring• Pharmaceutical stoppers• Adhesives and sealants• absorbers for noise and fenders• chewing gum
86%
5% 4% 3% 1%1%
Tyres Pharmaceutical
Others AdhesivesChewing gum Automotive
Source:CHEManager 20/2006, Seite 8 (GIT Verlag Darmstadt)
Butyl and Halobutyl Rubber (X)IIR: GradesButyl and Halobutyl Rubber (X)IIR: Grades
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
X
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH3
CH2
CH2
n
C
CH3
CH3
Halo Butyl Rubber (XIIR) X = Cl: Chloro Butyl Rubber (CIIR) X = Br: Bromo Butyl Rubber (BIIR)
Butyl Rubber (IIR)
X2 (Cl2 / Br2)
Advantages of XIIR over IIR:• Higher speed of vulcanization
•Improved covulcanization without deterioration of basic IIR properties
-75 -50 -25 0 25 50 75 100
Temperature [°C]
20
40
0
60
Reb
ou
nd
Ela
sti
cit
y[%
]
80
IIR
EPDM
NBR
SBR
NR
1,4-cis BR
CharacteristicCharacteristic Features of IIR Features of IIR basedbased VulcanizatesVulcanizates
0,1
1
10
100
0,0029 0,00295 0,003 0,00305 0,0031
1/T x 10exp4
Lu
ftd
urc
hlä
ss
igk
eit
(Q x
10
ex
p8
)
Temperature [°C]
70 60 50
1,4-cis-BR
NREPDM
SBRNBR/28 ACN
NBR/33 ACNNBR/38 ACNIIR
Source: Butyl And Halobutyl Compounding Guide For Non-Tyre Applications, 12/92 Bayer AG -KA 34 166)
Rebound (50 phr SRF, without plasticizer)
Air permeability of vulcanized rubbers(50 phr SRF, without plasticizers)
(X)IIR: Market, Market (X)IIR: Market, Market DevelopmentDevelopment, , ProducersProducersand and ProductionProduction CapacitiesCapacities
0
100
200
300
400
500
600
700
1979
1982
1985
1988
1991
1994
1997
2000
Co
nsu
mp
tio
n [
kt]
IIR
XIIR
Sum
Market Growth (Basis: 2.000):IIR: - 2,3 %/ p.a. XIIR: + 2,3 % p.a. Sum: + 1,2 % p.a.
Main Areas of Application:(90%: Tyres and Tyre Production)•XIIR: Inner liners•IIR: Truck tyre tubes•IIR: heating bladders
Pricing (1996):•IIR: ca. 1,80 €/kg•XIIR: ca. 2 €/kg•BIMS: ca. 3,5 €/kg
1.041
80
45
50
180
252
414
Total
[kt]
Total Capacity
XXJapan Butyl Co.
(X)XSinopec
XTogliatti
XXNizhnekamsk
XXLanxess
XXExxon
Halo-
butyl
ButylCompany
Production capacities (2008)
Range of Commercial IIR and XIIR GradesRange of Commercial IIR and XIIR Grades
Range of Standard Butyl Grades
0
10
20
30
40
50
60
70
80
90
100
0 2 4 6 8 10
Content of double bonds [Mol%]
Mo
on
ey V
isco
sity
ML
(1
+8
) 1
25
°C
Range of XIIR Grades
0
10
20
30
40
50
60
70
80
90
100
0 2 4 6 8 10
Halogen Content [Mol%]
Mo
on
ey V
isco
sity
ML
(1
+8
) 1
25
°C
Chlo
rbuty
l
Bro
mbu
tyl
H2O „slop isoprene“ H2O
Isobutene- Isoprenedrying unit
NH3- Ethene-Heat exchangers
compressor dryer compressor
AlCl3-
solution
drum
Reactor Steam- Flash- Stripping-unit unit
CH3Cl
“catalyst cocatalyst
drum“
Storage tank for
„mixed feed“
Storage
units for
IIR-slurry
in water
Cond
enser
IIR: IIR: FlowFlow Chart of Chart of SlurrySlurry PolymerizationPolymerization(Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
Al2O3
Features of IIR Features of IIR ProductionProduction TechnologyTechnology
Ethylene(liquid)
Ethylene(gas)
mixed feed catalyst
Inlet and Drainfor light
hydrocarbonwash
catalystSources:Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993US 2,356,128; US 2,491,752; US 2,491,710; US3,968,076; US 4,474,924; US 4,068,051; US 5,532,312
Process: Slurry polymerization
Catalyst: AlCl3
Cocatalysts: HCl (Exxon)
H2O (Lanxess)
Diluents: CH3Cl (Exxon and Lanxess)
„mixed feed“(GUS)
Make-up of AlCl3-solution 30 - 45 °C
Polymerization temperature: -90 °C bis - 100 °C
Residence time 0,5 - 1 h
Conversion of monomers:
Isobutene 75 - 95 %
Isoprene 45 - 85 %
Concentration of IIR-Slurry 25 - 35 wt.%
Reactor output: 2 - 4 t/h*Reactor
Operation time of reactors: 18 - 60 h
Additives:
Antiagglomerants: (Stearic acid/Zn-stearate)
0,4 - 1,0 wt.%
Antioxydants: 0,02-0,15 wt.%
-discolouring: alkylated Phenylene Diamines
-None discolouring: phenolic AO
(+ alk. Phenyl phsophites)
-chewing gum: without AO
IIR: IIR: ReactionReaction SchemeScheme of of CationicCationic PolymerizationPolymerization
CH3
C
CH3
CH2
CH3
C+
CH3
CH3H
+ AlCl4
AlCl4
H+ AlCl
4AlCl3 + HCl
AlCl3 + H
2O H
+AlCl
3OH
CH3
C+
CH3
CH3
AlCl4
CH3
C
CH3
CH2
CH3
C+
CH3
CH2H
n
AlCl4
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH3
C+
CH3
CH2H
n
AlCl4
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH3
C
CH3
CHH
n
CH3
C+
CH3
CH3
AlCl4
CH3
C
CH3
CH2
CH3
C+
CH3
CH2H
n
AlCl4
CH3
C
CH3
CH2
CH3
C
CH3
CH2H
n
Cl AlCl3
-
-
-
-
-
+
Initiation of Polymerization:
- +
-
Formation of Cation:
+
+
Chain Propagation (Growth) Reaction:
- +
Transfer Reaction:
n
+ -
+
Termination Reaction:
+
IIR: IIR: LivingLiving CationicCationic PolymerizationPolymerization
CH3
C
CH3
CH2
CH3
C+
CH3
CH2
R
R+ MXR - Cl + MX
CH3
C
CH3
CH2
CH3
C+
CH3
CH2R
n
CH
3
C
CH3
CH2
-
R+
CH3
C+
CH3
CH2
R
CH3
C
CH3
CH2
CH3
C+
CH3
CH2R
n
CH3
C
CH3
CH2
CH3
C
CH3
CH2R
n
Cl + MX
MX-
MX-
MX-
MX-
Initiation:
+
Generation of Carbo Cation:
+
+
Reversible Termination:
n
Propagation:
n+1n
n+1
n+1 n+1
n+1n
ClCl
Cl
Cl
Cl
BCl3 and TiCl
4
MXn (Metal halides) and R-Cl used for the preparation
of Isobutylene based blockcopolymers:
InfluenceInfluence of of PolymerizationPolymerization TemperatureTemperature on Molar on Molar MassMass((PolyisobutylenePolyisobutylene / / withoutwithout IsopreneIsoprene))
Mn
[g/m
ol]
1/T *103 [K-1]
3,5 4,0 4,5 5,0 5,5 6,0 6,5 7,0
107
106
105
104
13 -25 -50 -75 -90 -106 -120 -143
γ-Strahlung
BF3/H2O
EtAlCl2/H2O
AlCl3/H2O
Molar Masses:
γ-Strahlung > EtAlCl2 > BF3 > AlCl3
Source: J. Kennedy, P. D. Trivedi, Adv. Pol. Sci. (1978) 28, 113-151
X-IIR-
Slurry
in water
Antiagglo- steam Caustic
merants soda
Storage tank Halogenation reactor Neutralization reactor
Addition of AO
water
Br2 bzw. Cl2
IIR-solution
in hexane
Hexane
XIIR: XIIR: FlowFlow Chart of Chart of IIRIIR--HalogenationHalogenation
Source: Kirk-Othmer Encyclopedia of Chemical Technology, Fourth Edition, Volume 8, 1993)
XIIR: XIIR: MechanismMechanism of of IIRIIR--HalogenationHalogenation
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH3
CH2
CH2
n
C
CH3
CH3X
X
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH3
CH2
CH2
n
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C C
CH3
CH2
CH2
n
C
CH3
CH3
H
X2
X
X
+
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C C
CH3
CH2
CH2
n
C
CH3
CH3
HX
X
+
- HX
- HX
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
C
CH3
CH3
X
Reaction Conditions:
Solvent: Hexane
IIR-solids 20 - 25 wt.%:
Ratio of Halogen/Isoprene: 1:1 Mol/Mol
Reaction temperature : 40 – 60 °C
Residence time: l h
Stripping-Vapour : 2 - 2 kg/ kg XIIR
Antioxydants / stabilizers: Ca-Stearate,
Epoxydized Soy
bean oil (ESB)
Source:Kirk-Othmer Encyclopedia of Chemical Technology,
Fourth Edition, Volume 8, 1993
Patents:
US 2631984; US 3099644; US 4288575; US 4554326;
US 4632963; US 4681921; US 4650831; US 4384072;
US 4513116; US 5681901
CrosslinkingCrosslinking EfficienciesEfficiencies in in VulcanizationVulcanization bybyPeroxidesPeroxides ((DicumylDicumyl PeroxidePeroxide))
1) Dissertation Th. Früh, TU Hannover 1995
X-linking
efficiency
~ 100 1)
12,5
10,5
1,5
0,4 - 0,7
1,0
1,0
0,5
<<1
1,0
<<1
Type of Rubber Theoretical Cross-
linking efficiencies
M - Rubbers 1
R - Rubbers > 1
Degradating polymers < 1
NumberNumber of of crosslinkscrosslinksXX--linkinglinking efficiencyefficiency ==
PeroxidePeroxide FunctionsFunctions
Rubbber
Vi-BR
(98% Vinyl)
SBR
cis 1,4-BR
EPDM
EPM
NBR
IR
CR
IIR
PE
PP
O O O
O C
C
C
C
2
2 +
(R*)
+ 2 R-H
100 -
- 100
50 50
- 20
130 80
10 -
1 1
- 1,5
- 1,5
6 -
1 -
PropertiesProperties of of SulfurSulfur-- and and PeroxidePeroxide CuredCured IIR and XLIIRIIR and XLIIR
IIR
IIR -Terpolymer*
N 762
Hard Clay
Polarite 102R/EEC Int
Pb3O4
Stearic acid
Bis(t-butylperoxy-isopropyl)benzene
Trimethylolpropanetrimethacrylate
Dibenzoyl chinone dioxime
Dibenzo thiazyldisulfide
Polysar Butyl 402
Polysar Butyl XL 10000
Carbon black
Silicate
Silanised calcinated Clay
-
-
Perkadox 14-40 B/Akzo
Sartomer 350/Sartomer
Actor DQ/Kawaguchi
Vulkacit DM / Lanxess
Source: C. A. Moakes, Bayer „Polynotes“ No B11 „An Improved Seal for Chemical CondensersBased on Polysar Butyl Terpolymer“
* IIR-Terpolymer mit Divinylbenzol (XLIIR)
Butyl Rubber Grade
Compound Properties
Compound Mooney (ML 1+4/100°C)
Mooney-Scorch (125°C) [min.]
Vulkanizate Properties (160°C/12 min.)
Shore A Härte (23°C)
S100 [MPa]
Elongationat break [%]
Tensile Strength [MPa]
Compression Set (70h/105°C [%])
Hot air ageing (100°C/96h)
Shore A Härte (23°C)
S100 [MPa]
Elongation at break [%]
Tensile Strength [MPa]
Electrolyte permeability (g*mm/day*m2)
Ethylenglycol
g-Butyrolactone
Dimethyl formamide
IIR
105
4,0
81
6,0
155
6,8
75
83
7,8
110
8,0
0,38
1,0
7,8
XLIIR
98
6,2
76
6,5
105
7,5
15
78
-
95
8,2
0,21
0,8
1,8
PropertiesProperties of of SulfurSulfur-- and and PeroxidePeroxide CuredCured IIR and XLIIR IIR and XLIIR
VulcanizationVulcanization of BIIR of BIIR byby PeroxidesPeroxides
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
X
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
C
CH3
CH3X
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
C
CH3
CH3
+ DCP
- 2 X*
VulcanizationVulcanization of BIIR of BIIR byby ZnO/NNZnO/NN‘‘--mm--PhenylenePhenylene
BismaleicBismaleic ImideImide
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH2
CH2
n
X
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH CH2
n
C
CH3
CH3
+ ZnO- ZnOHX
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH CH2
n
C
CH3
CH3
CH3
C
CH3
CH2
CH3
C
CH3
CH2
CH2
C CH
CH2
CH CH2
n
C
CH3
CH3
NC
C
N
C
C
O
O
O
O
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92
J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
IIR (Lanxess Butyl 301) [phr]
XIIR (Bromo butyl
Carbon black (N 330) [phr]
Carbon black (N 774) [phr]
Zinc oxide [phr]
Lead Oxide (Pb3O4) [phr]
Stearic Acid [phr]
Sulfur [phr]
MBT [phr]
Benzochinondioxim [phr]
PF-Resin (Amberol) [phr]
CR (Baypren 110) [phr]
Dicumyl peroxide [phr]
Zinc oxide [phr]
Dicumyl peroxide [phr]
BMI (HVA 2) [phr]
temperature [°C]
time [min]
100
-
50
-
5
-
1,0
1,25
1,5
-
-
-
-
-
-
-
160
25
100
-
50
-
5
6
1,0
-
-
-
10
5
-
-
-
-
190
30
100
-
50
-
5
10
1,0
-
-
6
-
-
-
-
-
-
150
12
-
100
-
50
-
-
1,0
-
-
-
-
-
1,5
-
-
-
180
15
-
100
-
50
5
-
1,0
-
-
-
-
-
-
5
-
-
180
3
-
100
-
50
5
-
1,0
-
-
-
-
-
-
1,5
0,5
180
4
-
100
-
50
5
-
1,0
-
-
-
-
-
-
-
1,5
180
20
IIR and XIIR: IIR and XIIR: MethodsMethods of of VulcanizationVulcanization and and VulcanizateVulcanizate PropertiesProperties
IIR und XIIR: IIR und XIIR: MethodsMethods of of VulcanizationVulcanizationand and VulcanizateVulcanizate PropertiesProperties
IIR [phr]
XIIR [phr]
Carb. black (N 330) [phr]
Carb. black (N 774) [phr]
Vulcanization
Compound Properties
ML 1+4 (100°C) [MU]
MS5 (125°C) [min]
MS5 (135°C) [min]
Physical Properties
Shore A Hardnes
M100 [MPa]
M300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
CS (70h/150°C) [%]
100
-
50
-
S/MBT
91
17
-
66
2,5
16,6
530
68
100
-
50
-
Resin
82
>30
-
64
1,9
15,8
590
12
100
-
50
-
Chinon
94
7
-
64
2,1
12,8
400
68
-
100
-
50
ZnO
83
-
16
48
0,9
5,2
12,4
580
58
-
100
-
50
DCP
88
-
12
40
0,5
1,8
8,9
680
53
-
100
-
50
DCP/BMI
88
-
14
54
0,12
9,5
10,5
325
28
-
100
-
50
ZnO/BMI
89
-
16
58
0,19
10,2
13,6
360
13
Source: Butyl and Halobutyl Compounding Guide for Non-Tyre Applications, Bayer AG, Rubber Business Group KA 34166, ed. 12/92
J. Rogers, W. H. Waddell (Exxon) „Isobutylenkautschuke im Kraftfahrzeug: Eine Literaturübersicht, GAK 9/1999-Jahrgang 52, 670-682
100 100
60 60
- 7
4 4
1 1
1,3 1,3
3 3
0,5 0,5
BIIR
Carbon black
Paraffin Oil
Resin
Stearic Acid
MBTS
Zinc oxide
Sulfur
Polysar Brombutyl 2030
N 660
Sunpar/Sunoco Inc.
Pentalyn A / Hercules
Vulkacit DM / Lanxess
InfluenceInfluence of Oil of Oil LoadingLoading on on PropertiesProperties of of BIIRBIIR--VulcanizatesVulcanizates
Butylkautschuk-Typ
Paraffinöl
Mischungseigenschaften
Compound-Mooney (ML 1+4/100°C)
Mooney-Relaxation (MR30) [%]
Monsanto-Tack [N]
Vulkanisateigenschaften (160°C/12 min.)
Zugfestigkeit [MPa]
Bruchdehnung [%]
S 50 [MPa]
S 100 [MPa]
S 300 [MPa]
Shore A Härte/23°C
Shore A Härte/70°C
Rückprallelastizität/23°C [%]
Rückprallelastizität/70°C [%]
Luftdurchlässigkeit/70°C (DIN 53536) [m2/s*Pa])
BIIR
7
62
5,5
2,2
8,9
670
0,8
1,1
4,0
58
40
9
29
3,0
BIIR
-
72
5,1
2,3
10,5
650
0,9
1,7
5,4
60
47
9
30
2,3
InfluenceInfluence of Oil of Oil LoadingLoading on on PropertiesProperties of of BIIRBIIR--VulcanizatesVulcanizates
BIIR
Carbon Black
Paraffin Oil
Resin
Stearic Acid
MBTS
Zinc Oxide
Sulfur
Polysar Brombutyl 2030
N 660
Sunpar/Sunoco Inc.
Pentalyn A / Hercules
Vulkacit DM / Lanxess
InfluenceInfluence of of CarbonCarbon Black Black LoadingLoading on BIIR on BIIR VulcanizatesVulcanizates
100 100 100 100 100
60 40 30 20 0
- - - - -
4 4 4 4 4
1 1 1 1 1
1,3 1,3 1,3 1,3 1,3
3 3 3 3 3
0,5 0,5 0,5 0,5 0,5
100
60
72
5,1
2,3
2,9
6,2
7,9
11,8
730
0,9
1,3
5,4
55
43
10
32
2,14
0,647
0,251
BIIR (Butyl rubber 2030)
Carbon black (N 660)
Compound Properties
Compound-Mooney (ML 1+4/100°C)
Mooney-Relaxation (MR30) [%]
Monsanto Rheometer MDR 165°C
minimal torque [Nm]
t50 [min]
t90 [min]
Maximal torque [Nm]
Vulcanizate properties (160°C/12 min.)
Tensile Strength [MPa]
Elongation at break [%]
M50 [MPa]
M100 [MPa]
M300 [MPa]
Shore A Hardness/23°C
Shore A Hardness/70°C
Rebound at 23°C [%]
Rebound at 70°C [%]
Air permeation at 70°C/E+17 [m2/s*Pa])
tan δδδδ / 0°C (Roelig-test)
tan δδδδ /70°C (Roelig-test)
InfluenceInfluence of of CarbonCarbon Black Black LoadingLoading on BIIR on BIIR VulcanizatesVulcanizates
100
40
62
7,4
1,7
3,3
6,8
5,5
13,1
865
0,7
0,9
2,4
46
33
10,7
39
2,27
0,809
0,215
100
30
56
7,6
1,4
1,3
7,1
4,3
13,7
975
0,7
0,8
1,8
39
27
11,9
42
2,39
0,863
0,190
100
20
51
7,8
1,2
3,3
7,8
3,4
13,5
1055
0,6
0,7
1,2
33
23
12,2
44
2,58
0,900
0,178
100
0
40
7,2
0,8
3,3
6,8
2,2
7,3
1100
0,4
0,5
0,6
22
17
13,8
49
2,78
0,945
0,151
InfluenceInfluence of (of (X)IIR/NRX)IIR/NR--BlendBlend Ratio on Ratio on VulcanizateVulcanizatePropertiesProperties
BIIR
CIIR
NR
Carbon black (N 660)
Paraffin oil
Pentalyn A*
Stearic acid
Zinc oxide
MBTS
Sulfur
100 -
0 100
0 0
60 60
7 7
4 4
1 1
3 3
1,0 1,0
0,5 0,5
60 -
0 60
40 40
60 60
7 7
4 4
1 1
3 3
1,0 1,0
0,5 0,5
40 -
0 40
60 60
60 60
7 7
4 4
1 1
3 3
1,0 1,0
0,5 0,5
80 -
0 80
20 20
60 60
7 7
4 4
1 1
3 3
1,0 1,0
0,5 0,5
Source: W. Hopkins, R. H. Jones, J. Walter “Bromobutyl and Chlorobutyl. A Comparison of Their Chemistry,
Properties and Uses“ paper 16A10 presented at IRC ‘85 Kyoto; International Rubber Conference
80
-
20
5,7
10,0
620
7,6
9,8
420
5,4
14,7
10,0
23,6
-
80
20
5,1
10,7
620
7,9
11,0
465
5,7
4,7
1,6
3,9
60
-
40
7,1
12,8
560
8,4
9,3
320
9,2
15,2
14,7
0,3
100
-
-
4,2
9,3
740
6,8
10,0
550
2,9
16,8
7,5
61,8
-
60
40
5,7
10,3
560
7,7
9,2
365
7,5
9,1
1,9
0,1
-
40
60
4,3
9,7
580
3,6
5,8
475
13,2
5,2
2,9
0,0
InfluenceInfluence of (of (X)IIR/NRX)IIR/NR--BlendBlend Ratio on Ratio on VulcanizateVulcanizatePropertiesProperties
BIIR [phr]
CIIR [phr]
NR [phr]
Unaged:
M300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
Aged (168h/100°C)
M300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
Air permeation at
50psi/65°C (Q x 10-8]
Adhesion at 100°C
Self adhesion / tack [kN/m]
Adhesion to NR [kN/m]
Fatigue to failure after
ageing at 168h/120°C [kcycles]
40
-
60
8,9
14,7
490
6,7
8,8
370
13,8
15,4
20,8
0,0
-
100
-
3,7
9,9
770
5,5
10,9
640
2,9
4,4
1,3
72,7
5. Rubber 5. Rubber SpecialitiesSpecialities::Performance Performance ProfilesProfiles of of VulcanizatesVulcanizates
0
20
40
60
80
100Maximal Service Temperature
Low Temperature Performance
Ozone Resistance
Oil Swelling
Mechanical Properties
Processability
Silicon RubberHydrogenated Nitrile Rubber Fluoro RubberEthylene-Vinylacetate-Copolymers
5.1. 5.1. FluoroFluoro Rubber (FKM / FPM)Rubber (FKM / FPM)
Bond Bond Radiusenergy of atoms[J/mol] [A]
C-H 413 0,37
C-F 485 0,72
Areas of Application:60 % Automotive (75% in Europe)
10 % Aviation and Aerospace
10 % Chemical planty s (Fume treatment
of incineration and power plants)
20 % rest
Rubber goods:30-40 % O-Rings and seals
30-40 % crank shaft seals
10-15 % hoses and profiles
~ 5 % Modification of polyolefins
4.5 % pipes and tubings
10 % rest
Sources: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & SonsA. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)
Maximum Service Temperature:
3.000 h 232°C1.000 h 260°C
240 h 288°C48 h 316°C
Properties of FKM-Vulcanizates:Positive:•Excellent resistance to ozone, UV- and weather
•High service temperature
•Low oil swell
•High resistance to chemicals and acids
•High flame resistancy
Negative:•High price
•Poor low temperature flexibility (except Kalrez)
•Poor resistance to amines and bases
•Poor compounding
•Necessity to oven ageing after vulcanization
FluoroFluoro Rubber: Market, Rubber: Market, ProducersProducers and and CapacitiesCapacities
Market: 2002: ca. 15.000 t
Prices: 20 - 50 EUR/kg (correlated with F-content)
Top price: ~ 500 €/kg (Kalrez)
Growth: 8 - 10% p. a.
Return on Sales: 20 - 25%
Estimated total capacity: 20 kt; capacity utilization: 80-100%
Asia
22%W-
Europe
33%
USA
45%World Market
Source: Kunststof En Rubber; 11 November 2003
1,0Chiba, Jp5AflasAsahi Glass
1,0Jp5NoxtiteUnimatec
2,0Chiba, JpAsahimont
1,0Osaka, Jp10DaielDaikin Kogyo
2,0Spinetta, I15TecnoflonSolvay(Ausimont)
2,02,1
Decatur, ALZwijndrecht, BE
Gendorf, DE
22FluorelDyneon
3,01,01,0
Deepwater, NJDordrecht, NLUtsonomiya, JpKawasaki, Jp
43Viton/KalrezDu Pont
DuPont-Showa
Capacity* [kt]
SiteMarket Share [%]
Tradenames
Producer
FKM: FKM: CompositionComposition of Standard Gradesof Standard Grades
Soures: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & SonsA. L. Logothetis „Chemistry of Fluorocarbon Elastomers“ Prog. Polym. Sci., Vol. 14, 251-296 (1989)
80 60 40 20TFE [wt.%]
HFP
[w
.t%
]
20
4
0
60
80
20
40
60 80
TFE VDF
HFP
VD
F [w
t.%]Am
orphou
s
Polym
ers
(rubbers)
VDF TFE HFP
[%] [%] [%]
X 33 33 33
Y 55 23 22
Z 22 12 65
X
Y
Z
Copolymers fluorine cont.
[wt.%]
TFE/P 54
VDF/HFP 65
VDF/HFP/TFE 67
VDF/HFP/TFE/CSM* 69
TFE/PMVE/CSM* 71
*Cure Site Monomer
C C
F
F
H
H
C C
F
F
F
F
C C
CF3
F
F
F
Fluorine containing monomers
VDF
TFE
HFP
FKM: Performance of Standard GradesFKM: Performance of Standard Grades
Copolymers Fluorine Cont. Volume swell Tg [°C]
[wt.%] benzene gear oil
21°C 121°C
VDF/HFP 65 20 171 -18
VDF/HFP/TFE 67 15 127 -8
VDF/HFP/TFE/CSM* 69 7 45 -5
TFE/PMVE/CSM* 71 3 10 -19
TFE/P 54 - - -2 (0)
0
20
40
60
80
100
120
140
160
180
60 65 70 75
Fluorine Content [wt.%]
Vo
lum
e S
we
ll [
%]
Benzene/21°C
Gear Oil/121°C
d
-80
-70
-60
-50
-40
-30
-20
-10
0
10
0 200 400 600 800 1000
time [h]
red
ucti
on
of
elo
ng
ati
on
at
bre
ak [
%]
HNBR
FKM (68% F)
Storage in motor oil which contains amines (163°C)
FKM: Glass FKM: Glass TransitionTransition TemperaturesTemperatures
Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
-35
-30
-25
-20
-15
-10
-5
0
0 0,5 1 1,5 2
Hydrogen content [wt.%]
Gla
ss
tra
ns
itio
n t
em
pe
ratu
re [
°C]
TFE/VDF/PMVE
TFE/VDF/HFP
F
F
H
H
F
F
F
F
CF3
F
F
F
O
F
F
F
CF3
CH3
H
H
H
VDF Vinylidene fluoride(59% fluorine)
HFP Hexafluoropropene(76% fluorine)
TFE Tetrafluoroethylene(76% fluorine)
PMVE Perfluoromethyl-vinyl ether(69% fluorine)
P Propen
PVDF
Range of FKMRange of FKM--Grades and Grades and VulcanizationVulcanization
55 65 75
Fluorine Content [wt. %]
Ag
ein
gR
esis
tan
ce
in M
ed
ia w
ith
Basic
Ad
dit
ive
s
PTFEAflas Viton A Viton B, GF Viton GLT
Kalrez
peroxi-
disch
Vulcanization with
Peroxides
Vulcanization with
Bisphenols
Vulcanization
with Diamines
FKM: FKM: VulcanizationVulcanization withwith DiaminesDiamines
CF2
CF3
CH2CF
2CH
2
F
CF2
CF2
CF3
CH CF2 CH
2CF
2 CF2
CF3
CH CF CH CF2
CF2
CF3
CH CF CH CF2
CFCF2
CH
CF3
CH CF2
CFCF2
CH
CF3
CH2CF
2
NH
R
NH
CF2
CF3
CH CF CH2 CF
2
CF2 CH
CF3
CH2CF
2
N
R
N
CF2
CF3
CH CH2 CF
2
CF2
CH
CF3
CH2CF
2
N
R
N
CF2
CF3
CH CH2CF
2
CF2
CH
CF3
CH2CF
2
O
CF2
CF3
CH CH2 CF
2
ONH
2
R
NH2
RNH2
NH2
1. Elimination of HF by MgO, CaO und PbO.
- HF - HF
2. Crosslinking by Diamines, which are used in "capped form" (such as carbamates) inorder to increase scorch resistance
- 2HF
Diamine cure yields crosslinks which are liable to hydrolysis (not steam resistant)
H2O
Sources: W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978)W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)
FKM: FKM: VulcanizationVulcanization withwith BisphenolsBisphenols
CF2
CF3
CH2
CF2
CH2
F
CF2
CF2
CF3
CH CF2
CH2
CF2 CF
2
CF3
CH CF CH CF2
CF2
CF3
CH CF CH CF2
CFCF2
CH
CF3
CH CF2
CFCF2
CH
CF3
CH2
CF2
O
CF3
CF3
O
CF2
CF3
CH CF CH2 CF
2CF3
CF3
OH O
CF3
CF3
OH OH P+
CH2
n
Cl
CF3
CF3
OH O P+
CH2
n
- HCl
1. Elimination of HF by MgO, CaO and PbO
- HF - HF
2. Crosslinking with Bisphenols ( such as Bisphenol AF) in the presence of BTPPC (Benzyltriphenyl phosphonium chloride) BTPPC acts as phase transfer catalyst and is often referred to as "accelerator"
+
+
Sources: T. L. Smith, W. H. Chu, J. Polym. Sci A-2, 10, 133 (1972)
A. W. Fogiel, J. Polym. Sci., Symp., 53, 333 (1975)
W. W. Schmiegel, Kaut. Gummi Kunst., 31, 137 (1978)W. W. Schmiegel, Angew. Macromol. Chem., 76/77, 39 (1979)A. Neppel, M. v. Kuzenko, J. Guttenberger, Rubber Chem. Technol., 56, 866 (1983)D. J. Plazek, I. C. Choy, F. N. Kelley, ‚E. von Meerwall, L.-J. Su, Rubber Chem. Technol., 56, 866 (1983)A. N. Theodore, M. Zinbo, R. O. Carter, III, J. Appl. Polym. Sci., 61, 2065 (1996)
FKM: FKM: VulcanizationVulcanization withwith PeroxidesPeroxides
• C-F bonds have a high bond energy. As a consequence, F-radicals cannot be abstracted by peroxides and FKM with high fluorine contents (> 70 wt.%) cannot be vulcanized by the use of peroxides.
•For the vulcanization of FKM with F-contents > 70 wt% special cure sites are required. For this purposebromine and iodine are incorporated into FKM. C-Br and C-I bonds have a lower bond energy thqn C-F bonds. Therefore Br- and I-radicals can be abstracted by the use of peroxides.
• Br- and I- based cure sites are incorporated by chain modifiers and by special comonomers whichcontain Br- and/or iodine.
In the presence of Br- and I- containing compounds (modifiers and monomers) the polymerizationproceeds as a „living radical polymerization“ (this probably was the first example of a living radicalpolymerization). During the course of the polymerization Br- and I are incorporated as end groups.
During peroxide cure of Br- and I- containing FKM and during subsequent annealing toxic compoundsare released which contain bromine and iodine.
CF2
CFBr
CF2
CHBr
CFCF2
O CF2
CF2 Br
Br CF2
CF2 Br
C H2J
2
C F2J
2
J-(C F2) - J4 -6
CFCF2CF
CF3
CF2
CF2
CF2
CF2
CF2
CF2
CF2
CF2
CF2
CF3
Br
Jn
Br/J-Content:
0,5-1 wt.%
Source: D. F. Lyons GAK 3/2005, Jahrgang 58 „ Einfluss der Molmasse auf die Eigenschaften von Bisphenol-AF-vernetzten Fluorkautschuken“
Bond energy
[kJ/mol]
480
405
270
200
Type of
bond
C-F
C-H
C-Br
C-J
FKM: FKM: VulcanizationVulcanization•The method of FKM-cure depends on the fluorine content.
•Copolymers based on vinylidene fluoride and propene (Aflas) are crosslinked by
the use of peroxides.
•Fluoro rubbers with a fluorine content<70 wt.% (such as copolymers based on
VDF and HFP) are liable to HF-elimination which is a prerequisite for the
vulcanization with diamines and bisphenols. MgO and Ca(OH)2 are added to the
rubber compound in order to react with HF which is eliminated during
vulcanization.
•FKM vulcanizates which are cured by diamines and bisphenols contain double
bonds. As a result, their resistance to heat and ageing is inferior to FKM without
double bonds. Also, diamine cured FKM is liable to hydrolysis.
•Fluor rubbers with a fluorine content > 70 wt. % (FKM which contains no or only
a small amount of VDF) cannot elimiminate HF. Therefore vulcanization cannot
be achieved by diamines or bisphenols. FKM with F-contents > 70 wt.% requires
special cure site monomers which enable peroxide cure.
Source: J. Scheirs „Modern Fluoropolymers“ High Performance Polymers for Diverse Applications John Wiley & Sons
5.2. Silicon Rubber (Q)5.2. Silicon Rubber (Q)
Grade Tg [°C] Tm [°C]MQ - 120 - 45
VMQ - 120 - 45
PVMQ - 120 - 70
FMQ - 69
Bond energies [kJ / mol]Si-O 444
C-O 339
C-C 348
C - S 272
S - S 266
Si O Si O
CH3
CH3
CH3
CH3
Si O Si O
CH3
CH3
CH3
CH
CH2
Si O Si O
CH3
CH3
CH
CH2
Si O Si O
CH3
CH3
CH2
CH2
CF3
CH3
)(n
)(
n
)(n
)(n
MQ
VMQ
PVMQ
FMQ
Vulcanizate Properties:
Positive:� Low temperature performance� High temperature resistance� Low dependence of properties on temperature
changes� Ozone-, UV- and Weather resistance� Hydrophopic character� Physiological inertness
Negative:� Low reistance against acids, bases, vapour and
hydrocarbons (significant improvement withFMVQ)
� Mechanical propertiesRTV: poor HTV: better / DVR !
� High gas permeability
Silicon Rubber: Silicon Rubber: PropertiesProperties and and ApplicationApplication AreasAreas
Application Areas:
� Pharmaceutical- and medical rubber
goods
� Rubber goods with food contact
� Cable insulation
� Adhesives
� Moulded articles
� Hoses, sealants (Automotive, Machine
building and E&E)
Temperature [°C]90
121
150
200
250
315
duration40 years
10-20 years
5-10 years
2-5 years
3 months
2 months
Sources:•K. Polmanteer, Rubber Chemistry Technology, Vol 61: 471-502“Silicon Rubber, its Development and Technological Progress“
•T. Maxson GAK 12/1995, Jahrgang 48, 873-884 „Fluor-Silikonkautschuk“
•D. Klages, U. Raupbach, GAK 4/1995, Jahrgang 48, 49-51 „Fluorsilicon-Kautschuk: Ein sehr moderner Werkstoff“
•E. L. Warrick, O. R. Pierce, K. E. Polmanteer, J. C. Saam, Rubber Chemistry Technology, Vol 52: 437-526 „Silicone Elastomer Developments 1967-1977“
•Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
Automotive
industry
40%
Machine building
15%
Medical
Applications
25%
Haushalt
20%
Year 1995 2005
Consumption /t: ~ 110.000 ~ 200.000
ProducersProducers CapacitiesCapacities and Silicon Rubber Marketand Silicon Rubber Market
Growth rate 2005: ca. 3,5 % / a; LSR ca. 10 % / a
Nord-
amerika
44%
Japan
25%
Europe
31%Source:
Winnacker/Küchler Chemische Technik, Prozesse und Produkte. Bd. 5 Organische Zwischenverbindungen, Polymere. Wiley-VCH, 2005
850.000S Western World (2000)
Rhodorsil®60.000Rousillon, FRRhodia
30.000Nünchritz, DE
Elastosil®90.000Burghausen, DE
Wacker
KE, Sylon®95.000Isobe, JapanShin-Etsu
Silopren®65.000Leverkusen, DE
40.000Ohta, Japan
110.000Waterford, USAMomentive
(formerly: GE + Bayer)
110.000Barry, GB
Silastic®260.000Carollton, USADow Corning
Silicone Rubber-
Brand Name
Siloxane-Capacity
[kt]
SiteManufacturer*
*Evonik and Crompton are active in this market without proprietary siloxane production
Silicon Rubber: Silicon Rubber: ProductionProduction
Cl Si
CH3
CH3
Cl
SiO2 + C Si + 2 CO
2 CH3-Cl + Si
Synthesis of Silicium:
Rochow-Process:
Cl Si
CH3
CH3
Cl
OSi
O
SiO
Si
O
Si
CH3
CH3CH
3
CH3
CH3
CH3
CH3
CH3
O
SiO
Si
OSi
CH3
CH3
CH3
CH3
CH3
CH3
Si
CH3
CH3
O n
n + 4 H2O- HCl
D3
D4
Dn
Silicon Rubber: Silicon Rubber: ProductionProduction
OSi
O
SiO
Si
O
Si
CH2
CH3CH
3
CH2
CH3
CH2
CH3
CH
2
CF3
CF3
CF3CF
3
OSi
O
SiO
Si
O
Si
CHCH
3CH3
CH
CH3
CH
CH3
CH
CH2
CH2
CH2CH
2
OSi
O
SiO
Si
O
Si
CH3CH
3
CH3
CH3
After short-stopping of the „polymerization“ residual monomers are removed under vacuum.For standard grades residual monomer contents are specified < 1 wt.% (for specialities: <0,5 wt.%)
O Si
CH3
CH3
O Si OH
CH3
CH3
n
OSi
O
SiO
Si
O
Si
CH3
CH3CH
3
CH3
CH3
CH3
CH3
CH3
Übliche Temperaturen:KOH 140°C NaOH 170°C
85 %
15 %
Katalysatoren:Säuren, Lewis Säuren, Saure Silikate,Basen
Modified silicon rubbers are obtained by the copolymerization with the respective cyclic monomers. As a consequence multibloc copolymers are obtained initially. At extended reaction times randomization occurs.
Silicon Rubber: Silicon Rubber: VulcanizationVulcanization
Chain length [nSi]Viscosityprocessing
Crosslinking methodPeroxidesAddition
Cure temperature
HTV-Kautschuk10.000
Greasy/Highly viscousTransfer moulding
ExtrusionTransfer Moulding
predominantly1C- und 2C-systems
110 -300 °C
Liquid Rubber1.000
Highly viscousTransfer moulding
predominantly2C-Systeme
110 - 200 °C
RTV-Rubber200
liquid / pourable
RTV-1: CondensationRTV-2: Addition
25 - 150 °C
Vulcanization Method Products
Condensation at room temperature Silanol containing(RTV) Silicon rubbers
Platinum catalyzed hydrosilylation Silicon rubbers withat low or elevated temperature silanol and vinyl(RT to 80°C, LSR: 110-200°C) groups
High temperature-Vulcanization MQ, PVMQ, MVQ, with peroxides (HTV: 120-180°C) FVMQ
RTRT--VulcanizationVulcanization of Silicon Rubber (2Kof Silicon Rubber (2K--System)System)
1a) Condensation of polysiloxanes which contain silanol groups by multifunctionalalkoxysilanes
Si OH
R
R
SiOH
R
R
Si OH
R
R
SiOH
R
R
Si OR
OR
OR
RO
S i
R
R
O
S i
R
R O
S i
O
S i
R
R
O
S i
R
R
- 4 ROH
Typical mulftifunctional alkoxysilanes are:
Si OR
OR
OR
RO Si OR
R
OR
RO Si
OR
OR
RO O Si
OR
OR
O( )n
R = Me, Et
Metal carboxylates are often used for catalysis :
Metals: Pb, Zn, Zr, Sb, Fe Sn Ba, Ca
Carboxylates: Naphthenate, Octoate, Hexoate, Laurate, Acetate
Typical examples are:
Tin-(II)-octoate und Dibutyl tin dilaurate in the presence of chloroacetic acid
RTRT--VulcanizationVulcanization of Silicon Rubber of Silicon Rubber
(1K(1K-- und 2Kund 2K--Systems) Systems)
1b) Condensation of polysiloxanes which contain capped silanol groups bymultifunctional alkoxysilanes
SiO
R
R
CCH3
O
SiO
R
R
CCH3
O
Si O
R
R
C CH3
O
Si O
R
R
C CH3
O
Si
OR
OR
RO
RO
Si
R
R
O
Si
R
R O
Si
O
Si
R
R
O
Si
R
R
+ H2O
- CH3COOH
For the condensation reaction the catalysts quoted under 1a) are being used.
RTVRTV--VulcanizationVulcanization of Silicon Rubber of Silicon Rubber (2K(2K--System)System)
1c) Condensation of polysiloxanes with silanol groups by means of multifunctionalsilanes (with evolution of hydrogen)
Si OH
R
R
SiOH
R
R
Si H
O
R
Si R
O
O
H
Si
O
R
Si R
O
O
Si O
R
R
SiO
R
R
- H2
For the condensation reaction the catalysts quoted under 1a) are being used.
Application for Bladder coatings
LTLT--VulcanizationVulcanization of Silicon Rubberof Silicon Rubber(1K und 2K(1K und 2K--Systems) Systems)
Si O Si O
CH3
CH3
CH3
CH2
CH2
Si O Si O
CH3
CH3
CH3
Si O Si O
CH3
CH3
CH3
CHCH
2
O Si O
CH3
CH3
H
CH3
Si
Pt-Compounds as H2PtCl6 (ca. 10 ppm)
)(n
)(n
)(n
)(n
2) Platinum catalyzed hydrosylization (50-150°C)
Inhibitors:
HTHT--VulcanizationVulcanization of Silicon Rubber of Silicon Rubber
3) Peroxide Cure (120-180°C)
Si O
R
Si O
R
R R
Si
R
R
Si O
R
Si O
R
R R
Si
R
R
Si O
R
Si O
R
R R
Si
R
R
Si O
R
Si O
R
R R
Si
R
R
Si O
R
Si O
R
R R*
Si
R
R
Si O
R*
Si O
R
R R
Si
R
R
Peroxide
- 2 H*
Typical Peroxides
Bis(2,4-dichlorobenzoyl)Peroxide
Di-Benzoylperoxide
Di-Cumylperoxide
2,5-Dimethyl-2,5-bis(t-butyl peroxy) hexane
Di-t-Butylperoxide
Temperature °F(t1/2) = 1 min.)
234
271
340
354
379
Impact of Impact of VulcanizationVulcanization MethodMethod on on CostCost of of ArticlesArticlesComparisonComparison of of PeroxidePeroxide-- (HTV) and (HTV) and platinumplatinum catalysedcatalysed LTVLTV--CureCure
HTV3,50
120
60,00
12,00
10
8
3
59,5
7200
885
3.097,31
8.857,31
1,23
0
44.286,55
0
LTV5,00
60
60,00
12,00
10
8
3
59,5
14.400
1.770
8.849,45
14.609,45
1,01
21,25
230.563,76
420,62
Cost FactorRaw materials [$/pound]
Vulcanization time [sec]
Overhead-Costs [$/h]
salaries [$/h]
Hours per shift
Shifts per week
Number of nests per mould
Weight per article + 10% loss
Number of articles per week
Material consumption per week
Raw material costs per week [$]
Total cost per week [$]
Cost per article [$]
Savings per article [%]
Financial result per year [$]
Increase of financial result [%]
Source: Rubber World, 12/1994, S. 20-24
5.3. 5.3. HydrogenatedHydrogenated NitrileNitrile Rubber (HNBR)Rubber (HNBR)
Overview:• Microstructure, Property Profile and Appliecation Areas
• Catalytic Hydrogenation of NBR
• Sequence of Process Steps in NBR- and HNBR-Production
• Producers and Production Capacities
• Chemical and Physical Properties
• Comparison of NBR- and HNBR Properties
»Speed of Ageing
»Tg
»Crystallization
»Stress/strain-Performance
• Vulcanizate Properties of Sulfur- und Peroxide crosslinked Vulcanizates
• Performance of HNBR in Power Transmission Belts
Range of Products: HNBR (partially and fully hydrogenated grades)XHNBRLow-Tg-HNBRLow-Mooney-HNBR
HNBR: HNBR: MicrostructureMicrostructure
CH2
C H
CH2
CH3
CHCH
2
CH
CH
2
HH
Butylidene-Moiety Ethylidene-Moiety Nitrilo-Ehylidene-Moiety
CN
CH2CH
21
δ +δ +δ +δ +
δ δ δ δ −−−−
C
N
CN
HNBR: Property Profile and HNBR: Property Profile and ApplicationApplication AreasAreasPositive:• Broad range of grades (Mooney, degree of hydrogenation, acrylonitile content)• excellent mechanical properties of vulcanizates (high TS, high abrasion resistance and high dynamic resistance)
• high oil resistance (depending on acrylonitrile content)• good adhesion to fibres and cords (Covulcanization)• Low temperature flexibility• High filler loadability of compounds
Negativ:• Max. service temperature < 155°C• High Tg >-30°C• Bad incorporation of softeners• High price (~ € 20/kg)
Ship Couplings
Roll Covers
Blow Out PreventerExpansion Joints
HNBR: HNBR: ApplicationApplication AreasAreas and and ArticlesArticles
15%
25%
4%4%7%
45%
Riemen Schläuche Dichtungen
Kabel Ölförderung Sonstige
Oil well Packers
Rotor/Stator- Pumps
CatalyticCatalytic HydrogenationHydrogenation of NBRof NBR
Homogenous Catalyst Systems:(PPh3)3 RhI Cl and (PPh3)4RhI H (US 3700637, DE 2539132, EP 134023, DE 3541689, DE 3540918, EP 298386, DE 3529252, DE 3433 392, US 4,464,515, US 4,503,196, DE 3921264, US 6084033)
Heterogenous(Supported) Catalyst Systems:Pd/SiO2; Pd/C; Pd/CaCO3; Pd/BaSO4(DE 3229871, US 4337329, US 4384081, US 4510293, DE 3227650, DE 3046008, EP 0298386)
Relative prices of noble metals [€/g]:Rh (150) > Ru (75) > Pd (12,50)
C
N
CN
C
N
CN
H2/Catalyst
Selective Hydrogenation of C=C bonds
C NH2
NH
H
N
H
C- NH3
+
Unselective Hydrogenation of Nitrile-Groups Results in Gel Formation
Requirements for Hydrogention Catalyst:• Selective and quantitative hydrogenation
of C=C- double bonds in the presence of nitrile groups without gel formation
• Low catalyst loadings and/or catalystrecovery
HNBR Grades HNBR Grades withwith Low Low MooneyMooney ViscositiesViscosities
C
N
CNR
C
N
CH2
CN
CH
R
Catalyst
During hydrogenation the Mooney viscosity
increases by a factor 2. Due to high stickiness
the production of NBR-grades with a Mooney
viscosity > 30 MU is not possible. Therefore
the range of standard HNBR viscosities was
limited to >60 MU until recently.
Cross-metathesis of NBR with olefins allows
for the production of NBR with Mooney
viscosities < 30 MU. In-situ hydrogenation of
theseNBR-feedstocks yields HNBR-grades
with Mooney viscosities < 60 MU.
As a consequnece of low TONs, large
amounts of catalysts are required for the
cross-metathesis of NBR.
Metathesis catalysts which are robust
towards nitrile groups are protected by
patents. Their use implies the payment of
licence fees.
CatalystsCatalysts withoutwithout ActivityActivity in in NBRNBR--MetathesisMetathesis **
Ru
PPh3
Cl
PPh3
Cl
Grubbs-I-Catalyst
Cl
PCy3
Ru
SPCy3
Cl
Ciba-Catalyst
R2
Ru
P+
PCy3
Cl
R1
R3
Cl
BF4
Piers-Catalyst
-
Ru
SnCl3
Cl
SnCl3
Cl
P
N
P
Ph
PhPh
Ph
Ph
Ph
Ru
SnCl3
Cl
SnCl3
Cl
N
2-
2
+ 2-
2
+
Catalyst from Prof. Berke' s group (University of Zurich) Catalyst from Prof. Berke' s group (University of Zurich)
Ru
P
Cl
P
Cl
BH3 Ph
BH3
PhPh
Ph
K+
Catalyst from Prof. Berke' sgroup (University of Zurich)
2-
2
Ru
PCy3
Cl
PCy3
Cl
Ph
Fürstner-(I)-Nolan-Catalyst (Umicore)
*Source: Julia-Maria Müller, Dissertation TU München
CatalystsCatalysts whichwhich areare ActiveActive in in NBRNBR--MetathesisMetathesis* * ((„„NumberNumber of of CatalyticCatalytic StepsSteps (TON)(TON)““))
CF3COO
RuCF
3COO
O
N N MesMes
R2
Ru
P+
Cl
R1
R3
Cl
N N MesMes
Ru
PCy3
Cl
Cl
N N MesMes
Buchmeiser-Nuyken-Catalyst Piers-II-Catalyst Grubbs-II-Catalyst
TON = 8 / 23°C TON=12 / 55°C TON=40 / 23°C
Cl
RuCl
O
NO2
N N MesMes
Cl
RuCl
O
N N MesMes
N
N
Ru
Cl
N N MesMes
Cl
Br
Br
Grubbs-Hoveyda-Catalst Grela-Catalyst Grubbs-III-Catalyst
TON=53 / 23°C TON=78 / 23°C TON=120 / 23°C
*Sources: Julia-Maria Müller, Dissertation TU München; M. Schneider, Dissertation TU München,M. Kellner, MSc-Thesis TU München; K. Langfeld, MSc-Thesis TU München; C. Gantner, MSc-Thesis TU München
SequenceSequence of of ProcessProcess StepsSteps in NBR and in NBR and HNBRHNBR--ProductionProduction
Emulsions-
polymerization
Removal of
residual
monomers
Latex-
coagulation
+ crumb wash
Mechanical
dewatering
Thermal
dryingBale
pressing
Bale wrapping
Packaging
and storage
Bale cuttingCemement
preparation-
Removal of
oxygen and
hydrogenation
dilution Catalyst recoverySolvent removal
by evaporation
Bale wrappingPackaging
and storage
Mechanical
dewatering
of crumbs
Thermal
crumb-
drying
Bale
pressing
NBR-Production: Sequence of Process Steps:
HNBR-Production: Sequence of Process Steps
Catalyst recovery
Make-up of
Hydrogenation
catalyst solution
Wet
solvent
stripping
HNBRHNBR--ProducersProducers and and CapacitiesCapacities
Company Site Capacity [t]
Takaoka Japan 2.800
Houston USA 2.000
Leverkusen Germany 3.000
Orange USA 3.600
Total 11.400
Lanxess
Zeon
Producers and Capacities
0
2000
4000
6000
8000
10000
12000
14000
1992 1994 1996 1998 2000 2002 2004
Vo
lum
e [
t]
Consumption
capacity
Markt- und Marktentwicklung
AgeingAgeing of of UnvulcanizedUnvulcanized NBR and HNBRNBR and HNBR((IncreaseIncrease of of MooneyMooney ViscosityViscosity ML 1+4/100ML 1+4/100°°C))C))
lnV
br
1/T *103 [K-1]2,0 2,4 2,6 2,8 3,0 3,2
180 160 140 120 100 80 60 40
T [°C]
+1
+0
- 1
- 2
- 3
- 4
- 5
- 6
- 7
- 8
NBR Hydriergrad: 0 %HNBR Hydriergrad: 96 %HNBR Hydriergrad: 99,5 %
Source: W. Obrecht, H. Buding, U. Eisele, Z. Szentivani, J. Thörmer, Angew. Makromol Chem. 145/146 (1986) 161-179 (2373)„Hydrierter Nitrilkautschuk: Ein Werkstoff mit neuen Eigenschaften“
TgTg of HNBR and NBRof HNBR and NBR
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Acrylonitrile Cont. [wt.%]
Tg
[°C
]
E/ACN-Copolymers
HNBR (fully hydrogenated)
-100
-80
-60
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Acrylonitrile Cont. [wt.%]
Data for Ethene/Acrylonitrile-Copolymers from: R. E. Uschold, I. B. Finlay, Appl. Polym. Symp. 25 (1974) 205
NBR
TgTg of of Ethene/VinylacetateEthene/Vinylacetate-- und und Ethene/VinylchlorideEthene/Vinylchloride--CopolymersCopolymers
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Vinylacetate Cont. [wt.%]
Tg
[°C
]
Levapren
Nielsen et al.*
Source: Ethene/Vinylacete Copolymers: L. E. Nielsen, J. Pol. Sci. 42 (1960) 357-366Ethene/Vinylchloride Copolymers: F. P. Reding, J. A. Faucher, R. D. Whitman, J. Pol. Sci. 57 (1962) 483-498
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Vinylchloride Cont. [wt.%]
Ethene/Vinylacetate-Copolymers Ethene/Vinylchloride-Copolymers
0
2
4
6
8
10
12
14
16
0 10 20 30 40 50 60
Acrylonitrile Content [wt. %]
Cry
sta
llin
ity [
%]
1. DSC-Aufheizung
2. DSC-Aufheizung
InfluenceInfluence of of ACNACN--ContentContent on on CrystallinityCrystallinity of HNBR (DSC)of HNBR (DSC)
TgsTgs of of EthyleneEthylene--CopolymersCopolymers
-200
-150
-100
-50
0
50
100
0 10 20 30 40 50 60 70 80 90 100
Comonomer Content [wt.%]
Tg
[°C
]
EPM
HNBR
EVC
EVM
InfluenceInfluence of of NitrileNitrile ContentContent on on TgTg of HNBRof HNBR
-150
-100
-50
0
50
100
0 10 20 30 40 50 60 70 80 90 100
Acrylonitrile Content [wt. %]
Tg
[°C
]
HNBR (fully hydrogenated)
NBR
?
DependenceDependence of of TgTg on on DegreeDegree of of NBRNBR--HydrogenationHydrogenation ((ACNACN--ContCont.: 34 wt. %).: 34 wt. %)
-34
-32
-30
-28
-26
-24
-22
-20
0 20 40 60 80 100
Degree of Hydrogenation [%]
Tg
[°C
]dyn. mech. (11 Hz)
DSC
Source: U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation BetweenNetwork Structure and Properties of Sulfur- and Peroxide-Cured HNBR Vulcanizates“
0
2
4
6
8
10
12
0 100 200 300 400 500 600 700
strain [%]
str
ess [
MP
a] 11,0%
7,9%
4,0%
1,9%
0,5%
InfluenceInfluence of Residual Double Bond of Residual Double Bond ContentContent on on Stress/StrainStress/Strain--PropertiesProperties of of HNBRHNBR--basedbased VulcanizatesVulcanizates
(34 wt.% ACN; (34 wt.% ACN; unfilledunfilled; ; sulfursulfur vulcanizedvulcanized))
100 phr HNBR0,07 phr Schwefel2,63 phr TMTD2,07 phr DTDC** Dithiodicaprolactam
Source: U. Eisele. Z. Szentivanyi, W. Obrecht J. Appl. Pol. Sci.: Appl. Polym. Symp. 50, 185-197 (1992) „Correlation BetweenNetwork Structure and Properties of Sulfur- and Peroxide-Crosslinked HNBR Vulcanizates“
0,1
1
10
100
1000
10000
-200 -150 -100 -50 0 50 100
Temperature [°C]
E' a
nd
ta
n δδ δδ
[M
Pa
] E'
E''
DependenceDependence of Eof E‘‘ and Eand E‘‘‘‘ on on TemperatureTemperature (HNBR (HNBR withwith38,5 38,5 wtwt .% ACN).% ACN)
NBR and HNBR: Impact of NBR and HNBR: Impact of ACNACN--ContentContent on on Stress/StrainStress/Strain--PropertiesProperties of of UnvulcanizedUnvulcanized RawRaw RubbersRubbers
0
0,1
0,2
0,3
0,4
0,5
0,6
0,7
0,8
0 1000 2000 3000 4000
elongation [%]
Str
es
s [
MP
a]
19,2 wt.%
28 wt.%
34,2 wt.%
39,1 wt.%
49 wt.%
NBR
0
5
10
15
20
25
30
35
40
45
50
0 500 1000 1500
elongation [%]
str
es
s [
MP
a]
18,9 wt.%
28 wt.%
33,9 wt.%
38,5 wt.%
48,3 wt.%
HNBR
Influence of ACNInfluence of ACN--Content of Content of UnvulcanizedUnvulcanized NBR and HNBR on NBR and HNBR on Maximum Stress (YieldMaximum Stress (Yield--Stress) on Stress) on ““TrueTrue““ Tensile StrengthTensile Strength
0
50
100
150
200
250
300
"Tru
e"
Tensile S
trength
[M
Pa]
0
0,2
0,4
0,6
0,8
1
0 10 20 30 40 50
Acrylonitrile Content [wt.%]
Yie
ld-S
tre
ng
th
[MP
a]
InfluenceInfluence of of ExtentionExtention on Permanent on Permanent ElongationElongation of of FullyFullyHydrogeantedHydrogeanted, , UnvulcanizedUnvulcanized HNBR (Variation of HNBR (Variation of ACNACN--ContentContent))
0
20
40
60
80
100
120
140
160
0 100 200 300 400
elongation [%]
perm
an
en
t elo
ng
ati
on
[%
] ε =ε bleibend
ASTM D 1566 - 98Kautschukdefinition
48,3 %
18,8 %
34,9 %
28,2 %
39,0 %
0
20
40
60
80
100
120
0 20 40 60
ACN-content [wt.%]
perm
an
en
t elo
ng
ati
on
[%
]
extension
280%
200%
120%
80%
HNBR-Grade (Therban)ACN-content [wt.%]RDB-content [Mol.%]ML 1+4(100°C) [MU]Compound PropertiesCompound Mooney/ ML 1+4(100°C)Mooney-Scorch (120°C) [min.]Fmax [N]Vulcanizate-PropertiesShore A Hardness(23°C)Shore A Hardness (70°C)M 100 [MPa]M 200 [MPa]M 300 [MPa]TS [MPa]elongation [%]Rebound [%]Compression Set70h/-10°C [%]70h/23°C [%]70h/100°C [%]70h/150°C [%]Hot air ageingD/D0 (150°C/ 5 d) [%]D/D0 (150°C/24 d) [%]Degree fo vol. swelling in fuel100*(V/ V0-1) (48h/50°C) [%]
1706 S33,74,360
6412,556,4
72693,48,8
14,72751038
73-
73-
55-
75
1706 S33,74,360
6614
51,2
72705,6
17,8-
2629536
6810-
27
-54
65
H-NBR 100,0 phrSulfur 0,5 phrStearic acid 1,0 phrZnO 2,0 phrMgO 2,0 phrOCD 1,0 phrZMB-2 0,4 phrN 550 45,0 phrTMTD 2,0 phrCBS 0,5 phr
Vulcanization time: 20 mintemperature: 160°C
H-NBR 100,0 phrZnO 2,0 phrMgO 2,0 phrDDA 1,0 phrZMB-2 0,4 phrN 550 45,0 phrTAIC 1,5 phrPerkadox 1440* 7,0 phr
Vulcanization time: 15 minTemperature: 180°CAnnealing: 6h/150°C
Perkadox 1440Bis(t-butylperoxyisopropylbenzol 40%ig
InfluenceInfluence ofof SulfurSulfur-- and and PeroxidePeroxide VulcanizationVulcanizationon on PropertiesProperties of of PartiallyPartially HydrogenatedHydrogenated HNBRHNBR
VulcanizateVulcanizate PropertiesProperties ofof SulfurSulfur-- and and PeroxidePeroxideCuredCured HNBR (HNBR (PartiallyPartially and and FullyFully HydrogenatedHydrogenated))
HNBR-Grade (Therban)ACN-content [wt.%]Residual double bond cont. [Mol.%]ML 1+4(100°C) [ME]Compound PropertiesCompound Mooney [ML 1+4(100°C)]Mooney-Scorch (120°C) [min.]Fmax [N]Vulcanizate PropertiesSulfur Core (Press 160°C/20`)Peroxide Cure (Press 180°C/15`)Shore A Härte (23°C)Shore A Härte (70°C)M 100 [MPa]M 200 [MPa]M 300 [MPa]Tensile Strength [MPa]Elongation [%]Rebound [%]Compression Set70h/-10°C [%]70h/23°C [%]70h/100°C [%]70h/150°C [%]Hot Air AgeingD/D0 (150°C/ 5 d) [%]D/D0 (150°C/24 d) [%]Degree of Vol. Swelling in Fuel100*(V/V0 -1) (48h/50°C) [%]
1706 S33,74,360
6412,556,4
72693,48,814,72751038
73-
73-
55-
75
1706 S33,74,360
6614
51,2
72705,617,8
-2629536
6810-
27
-54
65
1706 34,50,463
741652
73716,917,7
-2428034
-12-
28
-59
70
Performance of HNBR in Power Transmission BeltsPerformance of HNBR in Power Transmission Belts
Source:M. Mezger; D. Achten “Therban: The high performance elastomer in power transmission systems”9. Tagung “Zahnriemengetriebe” am Institut für Feinwerktechnik und Elektronik-Design der TU Dresden
log
t/h
fo
rε
ε
ε
ε b
= 5
0%
2,1 2,2 2,3 2,4 2,5 2,6
[°C]
HNBR / peroxide cured
HNBR / sulfur cured
10
100
1.000
10.000200 180 160 140 120 100
CR
10 ( K )-3 -11
T
0 20 40 60 80 100-20
Temperature [°C]
0,1
1
10
100
1000-1
CR HNBR
rate
of
cra
ck
gro
wth
Tear-Analyzer-Test / Exp. ConditionsFrequency: 4 Hz Strain Ampli tude: 20%Attenuation mode: sinuoidalRate of crack growth: 1/co (dc/dn)
Materials used forpower transmission
belts
Leather
SBR
CR
HNBR(Sulfur cured)
HNBR(Peroxide cured)
5.4. EVM: Profile of 5.4. EVM: Profile of PropertiesProperties and and ApplicationsApplications
Positive:� Ozone-, UV-, and weather resistance
� Maximum service temperature 175°C
� High filler loadability
� FRNC-applicability
(Flame resistant non corrosive)
� Resistance to water/glycole
� Braod range of grades
� No necessity for post cure in oven
Negative:� fair mechanical properties
� Low temperature flexibility (depending on VAc-
content)
� Fair oil resistance
� Range of products limited to ML 1+4 = 20 - 35
� Vulcanization only peroxides
O O O
CO
CH3
CO
CH3
C
CH3
O
� VAc-content: 40-90 wt.% � radical polymerization in solution� Random monomer incorporation� Low molar masses� Significant degree of short chain branches
Application Araeas:� Automotive- and engineering: seals and
membrandes
� Hoses in high temperature environment
� FRNC-products: cables and floorings
� Sound protection
� FRNC Conveyor belts
� Hot Melt and pressure sensitive adhesives
� Protecting foils
� Blending component for HNBR, EPDM, CM, NBR)
� Rubber modification of thermoplasts (PVC, TPU, SAN, PC etc.)
� Oil additive
� Shoe soles
Source: H. Bartl, J. Peter, Über Äthylen/Vinylacetat-Copolymerisate und ihre Vernetzung; Kautschuk und Gummi, Jahrgang 14, 2 (1961) WT 23-32
1
10
100
1000
10000
0 20 40 60 80 100
Vinylacetate content [wt.%]
pre
ss
ure
[b
ar]
ProductionProduction RoutesRoutes TowardsTowards EVM and EVAEVM and EVA
Emulsion process10-100 bar
30-70°C
Solution process100-500 bar
50-120°C
Producer Process Products
Exxon, BP, High pressure EscoreneMitsui ctc.
Du Pont High pressure ElvaxUSI High pressure Vynathene
Lanxess Solution LevaprenMitsui Solution
High pressure process:• Preferred mprocess for EVA
(thermoplastic polymers with
VAc-content <40 wt.%)
• Monomer conversion: < 20%
• Molar mases decrease with
increasing VAc-content
Solution process:• Preferred process for EVM-r
rubbers (VAc-cont. 40-90%)
• Monomer conversion: 60- 70%
• Solvents: t-Butanol; Methanol
Emulsion Process:• Preferred process for latices with
high gel content (paints)
• Monomer conversion: ~ 100%
EVM-Rubbers
High pressure bulk process750-3000 bar
120-300°C
High Pressure Bulk Process:
US 5089579 (Bayer AG), Prio.: 11. 12.1989; Erf.: H. Sutter, A. Kolwert, W. Obrecht
Solution Process:
US 4937303 (Bayer AG), Prio.: 01.05.1989; Erf.: B. A. Wolf, B. Will, W. Obrecht, R. Casper, W. Baaade, G. Sylvester, K-P. Meurer, H. Zimmermann
EP 0632067 (Bayer AG), Prio.: 30.06.1993; Erf.: R. Steiger, E. Asch, W. Baade, W. Obrecht
EVM: EVM: PhysicalPhysical PropertiesProperties
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Vinyl acetate content [wt.%.]
Gla
ss
Tra
ns
itio
n
Te
mp
era
ture
(T
g)
[°C
]
En
thalp
yo
f fu
sio
n(D
H)[
J/g
]
-40
-20
0
20
40
60
80
100
0 20 40 60 80 100
Vinyl acetate content [wt.%]
Tem
pera
ture
of
Fu
sio
n
(Fp
)[°C
]
Thermoplast Rubber
OCN N C106
N NCO
n
Elastostab H 02
n = ca. 4Stabaxol P 200
n = ca. 4
OCH3 n
N N C
135N N
n
O
O
HH
O
O
O CH3n
EVM: Maximum Service EVM: Maximum Service TempeatureTempeature
The addition of acid scavengers
such as carbodiimides and
isocyanates does not improve hot
air performance
- HAc
O
O
CH3
O
O
CH3
O
O
CH3
-100
-90
-80
-70
-60
-50
-40
-30
-20
-10
0
200 300 400 500 600
Temperature [°C]
weig
ht
loss [
wt.
%]
350 °C
tim
e till
elo
ngation b
ecom
es <
50 %
in h
temperature in °C
200 190 180 170 160 150 140 130 120 110
137°C
20000 h
100
1000
10000
100000
> 170°C
1000 h
EVM: EVM: DependenceDependence of Oil of Oil SwellSwell and LOI (and LOI (LimitingLimitingOxygenOxygen Index) on Vinyl Acetate Index) on Vinyl Acetate ContentContent
LOI according to ASTM-D 2863
0
10
20
30
40
50
60
0 20 40 60 80 100
Vinyl acetetate content [wt.%]
Lim
itin
g O
xy
ge
n I
nd
ex
(L
OI)
[%
]
Al2O3: 190 phr
Al2O3: 0 phr
Source: E. Rohde; DKG-Bezirksgruppentagung; NRW in Bad Honnef; 07.-08. Mai 1992
Storage time in SAE-oil SAE 90 (3 d/125°C)
-40
-20
0
20
40
60
80
0 20 40 60 80 100
Vinyl acetate content [wt.%]
Ch
an
ge
of
Pro
pe
rtie
s [
%]
Delta F/F0 x 100 [%]
Delta D/D0 x 100 [%]
Delta V/ V0 x 100 [%]
Vinyl acetate content [wt.%]
Compound propertiesMooney ML 1+4(100°C)t10/180°C [min]t90/180°C [min]FH-FL/180°C [N]
Vulcanised properties(ISO-Stab Nr. 2, 2mm)Shore A Härte (23°C)S 100 MPa]Elongation at break [%]Tenjsile Strength [MPa]
Compression Set70h/100°C [%]70h/125°C [%]70h/150°C [%]
Hot air ageing (14d/150°C)∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆H/H0 x100 [%]
Storage in SAE Oil90 (3d/150°C)∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆V/V0 x100 [%]
50
231,26,619
684,428512,6
202541
-10211
-8-431
60
251,26,221
715,428012,8
222640
-11-212
8213
40
201,27,217
755,029511,7
232541
-3-210
-26-1969
45
241,26,620
745,727513,6
202338
-12-29
-12-447
70
201,36,919
684,230011,5
212446
10-715
683
80
201,36,117
724,730010,5
273151
-8-1514
10-12-4
EVM 100,0 phr
MgO 2,0 phr
Stearic acid 1,0 phr
Carbon black/N 550 65,0 phr
Vulkanox DDA 1) 1,0 phr
Plasticizer DOS 2) 7,5 phr
Plasticizer ODTM 7,5 phr
PE-Wax 2,0 phr
Aktiplast PP 2,0 phr
TAIC 1,5 phr
Peroxide (40%ig) 3) 6,0 phr
Vulkanization time: 10 min
Temperature: 180°C
no post vulcanization storagein hot air
EVM: EVM: DependenceDependence PropertiesProperties on Vinyl Acetat on Vinyl Acetat ContentContent
1) Styrenated Diphenyl amine (SDPA)2) Dioctylsebacate (DOS)3) 1,3-Bis(tert.-butylperoxyisopropyl)-
benzene (Perkadox 14/40)
Source:
E. Rohde
DKG-Bezirksgruppentagung
NRW in Bad Honnef
07.-08. Mai 1992
Therban 1707Levapren 500Rhenogran P 50
Compounc propertiesRelative compound priceML 1+4(100°C) [ME]t2/177°C [min]t90/177°C [min]
Vulcanized propertiesShore A Härte (23°C)S 100 [MPa]Elongation at break [%]Tensile Strength [MPa]
Compression Set70h/23°C [%]70h/150°C [%]70h/175°C [%]
Hot air ageing(14d/150°C)F/F0 x100 [%]D/D0 x100 [%]H/H0 x100 [%]
Storage in ASTM oil Nr. 3(7d/150°C)
∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆V/V0 x100 [%]
50503
60581,5
10,2
8012,617022,5
1217
25,5
-10-29+4
-36-29+49
25754,5
40401,6
10,2
8112,014518,8
141420
-7,5-21+3
-50-34+67
100--
1001231,511,7
7810,724026
122027
-2,3-37+6
-10-4
+24
75251,5
80991,611,0
8013,119024
121727
-3,8-26+5
-17-11+34
-1006
20321,69,5
778,316518,5
149
15
-1,6-12+2
-56-45+83
EVM/HNBREVM/HNBR--BlendsBlends
Source:
Test Report WR 26/83
(Mobay, Chem. Corp.)
EVM/HNBR 100,0 phr
Rhenogran P 50 1) var.
Carbon black/N 550 50,0 phr
Carnuba Wax 2,0 phr
MgO 10,0 phr
ZnO 2,0 phr
TAIC 1,75 phr
Peroxide (40%ig) 2) 7,0 phr
Vulcanization time: 15 min
Temperature: 177°C
Anealing: 16 h
1) Carbodiimide
2 Vulcup 40 KE
EVM: EVM: InfluenceInfluence of Post of Post CureCure on on PhysicalsPhysicals
0
5
10
15
0 50 100 150 200 250 300
with
post c
ure
without p
ost cure
strain [%]
Str
ess [M
Pa]
0
1
2
3
4
5
6
7
8
9
10
0 20 40 60 80 100 120 140 160 180 200 220 240
time [sec ]
torq
ue
[d
Nm
]
cycle timefor IM
= 75 % of = 75 % of
total total curecure
without post
cure
with post
cure
Tensile Strength [MPa] 10,4 11,8
εεεεb [%] 285 230
M100 [MPa] 1,8 3,1
CS 72 h / 150°C [%] 63 31
CS 168 h / 150°C [%] 71 50
O-Ring: Mechanical properties
Sources:
H. Meisenheimer, Kautschuk Gummi Kunststoffe, 52 (1999) 724
P. J- Pazur, L. Ferrari, H. Meisenheimer, ACS Rubber Div. 165th Spring Meeting, Grand Rapids, Michigan
H. Magg, A. Welle, Nordic Rubber Conf. 2005, Köge, Denmark
Levapren gradeLevaprenTMQN 762ZnOZMB-2Ficon 153 1)
Saret SR 633 2)
Vul-CUP 40 KE
Compound propertiesMooney ML 1+4(100°C) [MU]
Vulcanized properties(ISO-Stab Nr. 2, 2mm)Shore A Härte (23°C)Shore A Härte (150°C)Tensile strength [MPa]Elongation at break [%]M 50 [MPa]M100 [MPa]Rebound/23°C [%]Rebound/100°C [%]
Hot air ageing (14d/150°C)F/F0 x100 [%]D/D0 x100 [%]H/H0 x100 [%]
Storage in SAE-oil 90 (3d/150°C)∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆V/V0 x100 [%]
500100
3)
23
68-
12,6285
-4,4--
-102
11
-8-431
EVM: EVM: „„AcrylateAcrylate ReinforcingReinforcing TechnologyTechnology““ (ART)(ART)
1) 1,2-BR (liequid rubber)2) Zn diacrylate 3)
For further ompound ingredients see
„Stuey on variation of vinyl acetate
content“
Source:
T. A. Brown, Polysar Rubber Corporation,
Technical Report TR 552.92,17 vom
22.05.92
500HV1001,035101,020-
6,5
9,9
7772
13,5806,6-
4362
1-86
-13-6
13,7
500HV1001,035101,0-
206,5
26,8
7773
20,81754,210,54661
-5-298
-22-2912,1
CH2
CH C
O
O2
Zn2+
Z inc diacrylate Saret 633 Sartom er 705
„Acrylate-Reinforcing“ is used for
golf ball cores based on high
ART based “Golf-Ball-Core“-PatentsEP 0496947, Prior.: 29.01.1991 (Bridgestone)
US 6426387, Prior.: 04.08.2000 (Taylor Made Golf
Co.
EP 1227121, Prior.: 24.01.2001 (JSR)
US 6525141, Prior.: 02.04.2001 (Bridgestone)
US 6270428, Prior.: 07.08.2001
US 6517451, Prior.: 11.02.2003 (Titleist)
6. 6. ThermoplasticThermoplastic ElastomersElastomers (TPE)(TPE)
• Principle of Physical Crosslinking, Phase Morphology and Property Profile
• Nomenclature and Range of Available Grades
• Selection of Commercially Available TPEs, Producers and Brand Names
• Market, Areas of Applications and Prices
• Phase Morphology of Rubber Modified Thermoplastics and Thermoset Resins
• Comparison of Technological Properties of Different Classes of Engineering Polymers
– Dependence of Shear Modulus on Temperature
– Dependence of Residual Elongation on Original Elongation
– Comparison of Technological Properties of Chemically and PhysicallyCrosslinked Rubbers (Data from Product Data Sheets)
• TPE-O and TPE-V
– PP-Performance and Price of EPDM/PP-Blends
– Mechanical Properties
• Advanced technologies for the production of PP-based TPEs
• TPEs from the viewpoint of a producer of technical rubbber goods
Positve:• Good vulcanizate properties at low / moderate temperatures• No compounding and vulcanization know-how necessary• Short cycle times no time consuming vulcanization• Recycling of waste (due to thermo labile/reversible crosslinks)
Negative:• High permanent set after (tension set, compression set)• Poor mechanical properties at elevated temperatures (tensile strength, compression set) • Deterioratioon of mechanical properties in appropriate solvents• High heat-build-up in dynamic applications• Limited range of grades (particularly no soft grades available) • Anisotropic properties of injection moulded articles (particularly for TPEs with uncrosslinked rubber phase)
TPE: Phase TPE: Phase MorphologyMorphology and Property Profileand Property Profile
Soft SegmentHard Segment
A coherent soft or rubber phase (coherent matrix) isrepresentative for most TPEs
The hard phase which contains the physical cross-linksis dispersed within the soft phase. The hard phase isonly physically and never chemically crosslinked
The soft phase can either be uncrosslinked orcrosslinked
Examples for physical crosslinks• Hydrogen bonds /Crystallization• Dipol/Dipol - Interaction• Glassy Hardening (vitrification)• Ionomers
Scheme of the Phase Morphologyof A-B-A, (A-B)n and (A-B)x-
Multiblock Copolymers
Type of Bond energy
bond [kJ / Mol]
covalent 260 - 350physical 10 - 20
Nomenclature and Range of Available Nomenclature and Range of Available TPEsTPEs
1 Consists of an elastomer finely dispersed in a thermoplastic matrix 2 Rubber and thermoplastic segments are chemically bonded by block- or graft copolymerization
Sources: SRI Elastomers Overview 2008; Stratley Consultants
Thermoplastic Elastomers
TPE-O mechanical and reactor-blends (unvulcanized)
TPE-SStyrenic Block-Copolymers
Polyblends1
Multi-Block-Copolymers2
Thermoplastic
Polyolefins
TPE-UPolyurethane Block Copolymers
TPE-ECopolyester Block Copolymers
TPE-A Polyamide Block Copolymers
Olefin TPE-V (dynamically vulcanized)
High Performance TPE-V
(without polyolefines(dynamically vulcanized)
PVC based blends(without dynamic vulcanization)
Examples
EPM / PPEPDM / PP
EPDM / PPNBR/ PP
NBR / PVCEVM / PVCACM / PVC
HNBR / PA HNBR / PBTNBR / PA EVM / PAEVM / PBT
SBC (SBS, SIS, SEBS, SIBS)
Polyester-Urethanes, Polyether-Urethanes
COPE based on aromatic Polyesters (Terephthalates) PBT´/ PTHF; PET / PTHF
PEBA based on PA 6 and PA 12
SelectionSelection of of CommerciallyCommercially AvailableAvailable TPEsTPEs, , ProducersProducersand Brand and Brand NamesNames
Kraton®Styrolux®
ShellBASFFirestone, PolimeriDow
Glassy hardening(vitrification)
TPE-S SBS, SIS, SEBS
Surlyne®
Pebax®Estamid®
Hytrel®Pelprene®
Desmopan/Texin®Elastollan®Estane®
Sibstar®Taxus®SIBS®
?
Denka LS®
Santoprene®Geolast®
Flexomer®Spherilene®Exxtral®
Brand Name
AES (Advanced Elastomer Systems)AES (Advanced Elastomer Systems)
CrystallizationTPE-V
UCCBassellExxon
CrystallizationTPE-O (reactor blends)
Du PontIonomer
AtochemDow
Hydrogen bonds /Crystallization
TPE-A
DuPontToyobo
CrystallizationTPE-E
BayerBASFGoodrich
Hydrogen bonds /Crystallization
TPE-U
KanekaBoston ScientificInnovia
SIBS
ZeonHigh performance TPE-V
Denki KKDipol/DipolPVC-based blends
ProducerCrosslinking
Principle
Type of TPE
TPE: Market, TPE: Market, ApplicationApplication AreasAreas and Range of Pricesand Range of Prices
IRP
18%Hoses
5%
Cables
3%
Medical
Appl.
3%Asphalt
Mod.
12%
Ad-
hesives
12%
Auto-
motive
32%
Shoe
15%TPO-V SBC
TPO-
Blends
COPE
TPU
PEBA
Rest
WO-TPE-Market: 1,5 Mio t
W.-Europe:: 576a t (2001)
Type 2.000 2.005 Growth
[%]
SBC's 195 226 3
TPO's 135 172 5
TPV's 36 59 10,5
TPU's 62 79 5
COPE's 20 30 8
COPA's 7,5 10 5
Sonstige
Sum 455,5 576 4,5
PP/EPM-Reactor Blends 0,90-1,20
PP/EPM-TPE-V 2,00-2,50
SBC 1,00-3,30
SBS 1,30-1,50
SIS 1,50-1,70
SEBS 2,60-3,30
TPE-U (TPU) 3,00-4,00
TPE-E (COPE) 3,50-4,40
TPE-A (PEBA) 3,60-7,00
TPE Price [€/kg]
Areas of Application
Source:European Rubber Journal 184,no.1 (January 2002)
SofteningTemperature of
Thermoplast Phase
SchematicSchematic PresentationPresentation of of thethe DependenceDependence of of thetheShearShear ModulusModulus on on TemperatureTemperature
Sh
ear
Mo
du
lus
[MP
a]
10-1
100
101
102
103
104
TemperatureTg of Rubber Phase
Tempeatureof Use
Temperature of Processability
DependenceDependence of of ModulusModulus on on TemperatureTemperature: Target and : Target and RealityReality
Sh
ear
Mo
du
lus
[MP
a]
10-1
100
101
102
103
104
-100 - 50 0 50 100 150
Temperature [°C]200
Target
Reality
SchematicSchematic PresentationPresentation of of thethe DependenceDependence of of thethe ShearShearModulusModulus on on TemperatureTemperature forfor Different Engineering PolymersDifferent Engineering Polymers
Sh
ea
rM
od
ulu
s[M
Pa
]
10-1
100
101
102
103
104
Temperature
0 50 100 150 200- 50- 100
4 3 2 15
6
7
8
1. Thermoplastic Polymer(Polycarbonate, PP.PA)
2. Thermoplastic(Polystyrene, PMMA)
3. Rubber ModifiedThermoplastic
4. Elastomer (crosslinked)
5. TPE
6. TPE
7. Elastomer (crosslinked)
8. Unvulcanized Rubber
Sh
ea
rM
od
ulu
s[M
Pa
]
10-1
100
101
102
103
104
Temperature
0 50 100 150 200- 50- 100
4 3 2 15
6
7
8
DependenceDependence of of ShearShear ModulusModulus on on TemperatureTemperature forfor Different Different Engineering PolymersEngineering Polymers
SchematicSchematic PresentationPresentation of of Stress/StrainStress/Strain Diagrams Diagrams of Block of Block CopoymersCopoymers
str
es
s [
MP
a]
strain [%]
A-B-A, (A-B)n und (A-B)x-Block Copoymers
A-B Block Copolymers
Residual elongation
elongation
original elongation ( ) [%]
300
resid
ual
elo
ng
ati
on
(
)
[%
]
vulcanized gum stock (unfilled NR)
TPE-O (EPDM / PP: 60/40)
0 100 2000
100
200
300 εoriginalεresidual =
DependenceDependence of Residual of Residual ElongationElongation on Original on Original ElongationElongation forfor Different Engineering PolymersDifferent Engineering Polymers
ASTM D 1566 - 98„Definition of Rubber“ TPE-V (EPDM / PP: 78/22)
SBS with 27 wt.% styrene
NR/BR-tyre tread (with filler)
εoriginal
εR
es
idu
al
CompressionCompression -- SetSet
ho h2h1
hoh2
h1
ho- h1
ho- h2
CS = x 100 [%]ho- h2
ho- h1
In compression set (CS) measurements ho , h1, compression, exposition time, and exposition temperature are well defined(DIN, ASTM). Most commonly, thedeformation is 25%. In order to achieve thesame deformation „ho-h1“ the pressure has to be adjusted to the degree of x-linking
ComparisonComparison of of TechnologicalTechnological PropertiesProperties of of ChemicallyChemically and and PhysicallyPhysically CrosslinkedCrosslinked Rubbers Rubbers
(Data (Data fromfrom ProductProduct Data Data SheetsSheets))
SBC T PE-U T PO
mech. T PV T PV
EPDM/PP EPDM/PP EPDM/PP
blend (pa rtia lly (highly
x-linked) x-linked)
Shore A 10 to 80 71 52 75 92 93 78 72 75
Shore D - 44 42 25 40 63 32 54
T ensile Stre ngth [MPa ] 10 to 35 32 20 34 45 40 79 36 51 15,4 47 12 5,5 8,5
Elongation a t brea k [%] 300 to 800 880 1200 500 450 380 715 485 380 880 660 650 350 490
CS (22h/70°C) 5 to 30 75 60 38
CS (24h/70°C) 5 to 40 60 60 62 21 5 90 53
CS (22h/100°C) 5 to 40 88 44
CS (70h/150°C) 30 (HNBR, FKM)
T PE-ESEBS Este r Ether
T PE-APropertiesClassica l
Elastome rs SBS SIS
Technologische Eigenschaften von Technologische Eigenschaften von TPEsTPEsund von und von HauptvalenzelastomerenHauptvalenzelastomeren
-100
0
100
200
0 50 80
Geb
rau
ch
ste
mp
era
tur
[°C
]
Shore D Härte
Shore A Härte30 50 7040 60 80
100
SBC
TPO
PEBA
TPU
COPE
klassische Elastomere
PPPP--Performance and Price of Performance and Price of EPDM/PPEPDM/PP--BlendsBlends
Source: Robert Eller Associates, Inc. 1996
0
1
2
3
4
5
6
7
0 0,5 1 1,5 2
Price [$/kg]
Perf
orm
an
ce [
arb
itra
ry u
nit
s]
TPE-O (Reactor-Blends)
TPE-O (mechanical
blends)
TPE-V (EPDM/PP partially
cross-linked)
TPE/SEBS-Blends
TPE-V (EPDM / PP-blend, highly crosslinked)
0
20
40
60
80
100
120
140
160
180
20 40 60 80 100
Isotacticity [%]
Me
ltin
g t
em
pe
ratu
re [
°C]
Source: T. Sasaki, T. Ebara, H. Johoji; Polymers for AdvancedTechnologies 4, pp. 406-414 „New Polymers from New Catalysts“
PP-Properties:• Low Price• High Softening Temperaure• Good Ageing Resistance(Residual Catalyst Content)
PP-Properties:• Low Price• High Softening Temperaure• Good Ageing Resistance(Residual Catalyst Content)
TPETPE--O and TPEO and TPE--V: Basic V: Basic PropertiesProperties
PropertiesTPE-O
(Mechanical PP/EPDM Blend)
TPE-V (PP/EPDM-Blend withpartially crosslinked
EPDM-phase)
TPE-V(PP/EPDM-Blend with
highly crosslinkedEPDM-Phase)
Shore A-Hardness
Tensile Strength [MPa]
Elongation at break [%]
Compression Set
(22 h /70°C) [%]
Volume Swell in ASTM-
Oil Nr. 3 [Vol%]
78
12
650
75
soluble
72
5,5
350
60
90
75
20
490
38
50
Direction
of Flow Direction
of Flow
Uncrosslinked rubber phase Crosslinked rubber phase
TPETPE--O and TPEO and TPE--V: V: MechanicalMechanical PropertiesProperties
Str
es
s [
MP
a]
Elongation [%]
0
5
10
15
20
100 200 300 400 5000
10
15
20
25
35
0
30
600
Elongation at break [%]
400
5
Te
ns
ile
Str
en
gth
[MP
a]
0 200
1,0-1,5
5,4
17
39 72
µm]Particle diameter [
535505500495Elongation at break [%]
1590150015201530Tensile Strength [psi]
600620630650M100 [psi]
5321
no. of recyclesProperties
Shore D Hardness: 50
Shore A Hardness: 87
Shore A Hardness: 64
TPETPE--O: O: PP/EPMPP/EPM--ReactorReactor--BlendsBlends
Propylene
Ethylene
Supported
catalyst
ventilator
packaging
Cooler
Temperature: < 90 °C (40°C-60°C)
Pressure: 9-15 bar
Residence time per reactor: 0,5 - 1 h
Filter
Removal of
residual monomer
Filter ventilator
Cooler
Gas Phase Technology
PE* PP**UCC Montell
BASF Fina
BP Phillips
Hoechst Solvay
Exxon UCC
Amoco BASF
Montell Amoco/Chisso
Sumitomo
Source: T. W. Klimek (Quantum Chemical Corp.) ANTEC `91, 1382-1384
purification
purification
Product
outlet
Sources:* Ind Eng. Res. 33 (1994) 449-479 ** Chem. Systems (April 1992)
"Polypropylene"
Rubber Content [wt.%]
6040 503020
300
700
600
500
400
800
900
1000
E-M
od
ulu
s[M
Pa
]
Catalyst Fragmentationduring Polymerization
PropertiesProperties of PP/EPMof PP/EPM-- ReactorReactor--BlendsBlends
Catalyst System A
Catalyst System B
Source: H. Schwager (BASF); Kunststoffe 82, 499 (1992)T. Sasaki, T. Ebara, H. Johoji; Polymers for Advanced Technologies 4, pp. 406-414 „New Polymers from New Catalysts“
PreparationPreparation of of TPETPE--VsVs byby ReactiveReactive ProcessingProcessingBlendingBlending
Definitions:
1) “Reactive Processing” stands for a chemical reaction in the course of which
polymers are modified without the use of solvents.
2) “Dynamic Blending” stands for the solvent free blending process during which
a chemical reaction occurs.
3) “Dynamic Vulcanization” is used for vulcanization reactions (without solvent)
with simultaneous shearing.
4) Every vulcanization method can be performed dynamically
5) Resin cure was the first vulcanization method applied for the production of
EPDM/PP based TPE-V
1. Preparation of a PP/EPDM-Block Copolymer in order to partially compatibilizePP and EPDM
1a) Reaction of PP with Dimethylol Phenol Resin in order to “activate” PP
PreparationPreparation of a TPEof a TPE--V V byby thethe DynamicDynamic VulcaniztionVulcaniztionof a EPDM/PP blend of a EPDM/PP blend withwith Phenol Phenol ResinResin
PP
1) Melting PP at 185°- 190°C2) Addition of dimethylol resin at 185°-190°C (5 Min.)3) Addition of the catatalyst SnCl2 x 2H20 (2 Min.)
OH
CH2 OHHOCH
2
PP
+
OH
CH2 OHCH
2
1b) Preparation of block copolymer by the reaction of “activated PP” with EPDM
PreparationPreparation of a TPEof a TPE--V V byby thethe DynamicDynamic VulcaniztionVulcaniztion of a of a EPDM/PP blend EPDM/PP blend withwith Phenol Phenol ResinResin
1) Addition of EPDM and additional Phenol Resin at 185°- 190°C (5 Min.)2) Addition of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)
PP
OH
CH2 OHCH
2 + EPDM
PP
OH
CH2
CH2 EPDM
EPDM-
Phase
2) Addition of PP und EPDM with subsequent vulcanization of the EPDM-Phase
PreparationPreparation of a TPEof a TPE--V V byby thethe DynamicDynamic VulcaniztionVulcaniztion of a of a
EPDM/PP blend EPDM/PP blend withwith Phenol Phenol ResinResin
1) Addition of EPDM and PP at 185°- 190°C (5 Min.)2) Addition of of more SnCl2 x 2H20 at 185°- 190°C (5 Min.)
PP
OH
CH2
CH2 EPDM
PP -
Phase
OH
CH2
CH2 EPDMPP
In reality, the series of reactions from 1a), 1b) to 2) do not occur in a sequenceof reactions, which are well separated but rather in a concurrent fashion
CompatibilisingCompatibilising EffectEffect of of DimethylolphenolDimethylolphenol ResinsResins in in DynamicDynamic VulcanizationVulcanization of of PP/NBRPP/NBR--BlendsBlends
Polypropylene
Dimethylolphenol resin
SnCl2 . 2 H2O
Polypropylene
NBR +
Aminino terminated NBR
Dimethylolphenol resin +
SnCl2 . 2 H2O
Tensile Strength [MPa]
M100 [MPa]
E-Modulus [MPa]
Elongation at break [%]
Permanent elongation [%]
0
0
0
50
50
0
0
0
7,2
0
149
36
0
185-190°C
5 min.
2 min.
185-190°C
5 min.
5 min.
50
2
0,4
0
50
0
0
0
10,1
0
170
66
50
2
0,4
0
50
0
1,67
0
10,1
0
157
170
50
2
0,4
0
45
5
5
0,5
15,3
10,2
107
390
54
CompatibilisingCompatibilising EffectEffect of of DimethylolphenolDimethylolphenol ResinsResins in in DynamicDynamic VulcanizationVulcanization of of PP/NBRPP/NBR--BlendsBlends
25
1
0,2
67,5
7,5
9,38
1,13
1,13
17,0
15,8
33
330
20
185-190°C
5 min
2 min
5 min 5 min
37,5
1,5
0,3
56,25
6,25
7,81
0,78
0,94
19,6
15,7
92
400
33
50
2
0,4
45
5
6,25
0,5
0,75
23,0
15,2
221
500
50
62,5
2,5
0,5
33,75
3,75
4,69
0,28
0,56
22,7
16,2
320
490
63
75
3
0,6
22,5
2,5
3,13
0,13
0,38
21,5
17,1
456
480
70
Polypropylene
Dimethylolphenol resin
SnCl2 . 2 H2O
Polypropylene
NBR +
Aminino terminated NBR
Dimethylolphenol resin +
SnCl2 . 2 H2O 5 min
Tensile Strength [MPa]
M100 [MPa]
E-Modulus [MPa]
Elongation at break [%]
Permanent elongation [%]
ReactiveReactive BlendingBlending von EPDM/SAN: von EPDM/SAN: ResultsResults
1
10
100
1000
elo
ng
ati
on
at
bre
ak
[%]
0 10 20 30 40 50 60 70 80 90 100
EPDM-content [wt.%]
Reactive Processing2 wt.% PF-Harz/0,2 wt.% Catalyst/130°C
(without fillers/without oils)EPDM-grade: EP T 2370 (Lanxess)
Sources:• M. Vierle: MSc Thesis TU Munic December 2001• DE 10127402, Bayer AG, Prior.: 06.06.2001, Inv.: M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht• M. Vierle, N. Steinhauser, O. Nuyken, W. Obrecht, Macromol. Mater. Eng. 2003, 288, 209-218„Blend Preparation by Reactive Processing
SAN EPDM
0
10
20
30
40
Te
ns
ile
Str
en
gth
[M
Pa
]
AdvancedAdvanced technologiestechnologies forfor thethe productionproduction of of PPPP--basedbased TPEsTPEs
R
R595
Zr
R2
R1
R608
Zr
R2
R1
R622
ataktisches Polymer
IsotaktischesPolymer
BP/Amoco BP/Amoco startedstarted to to manufacturemanufacture PPPP--basedbased multimulti--blockblock copolymerscopolymers in in thethe pilotpilot--plantplant scalescale in in CaliforniaCalifornia ((MenloMenlo Park)Park)Baxter Healthcare Corp., Round Lake, IL Baxter Healthcare Corp., Round Lake, IL cooperatescooperates in in thethe performanceperformance of of teststests towardstowards thethereplacementreplacement of soft PVC in of soft PVC in medicalmedical devicesdevicesA. A. KhareKhare; S. Y. Ding; M. T. K. Ling; L. Wood; Modern ; S. Y. Ding; M. T. K. Ling; L. Wood; Modern PlasticsPlastics, September 1999; 94, September 1999; 94--99 99 „„HeatHeat--resistantresistant, flexible , flexible olefinsolefins meetmeet toughtough medicalmedical demandsdemands““--SingleSingle--SiteSite metallocenemetallocene catalystscatalystsyieldyield autoclavableautoclavable, , highhigh--clarityclarity elastomerselastomers withwith cost/performancecost/performance benefitsbenefits of flexible PVC.of flexible PVC.
Preparation of PP-Blockcopolymers by the
use of the „Waymouth-Catalyst“
The length of building blocks is determined
by the ratio of propagation rates versus
Rotation rate
Source:R. Waymouth, J. Coates, A-L. Mogstad, K. Stein, D. Fischer,
S. Borkowsky
Stepol `94; Milano June 6-10, 1994 "Stereospecific
Polymerization and Copolymerization of Functionalized Olefins"
AdvancedAdvanced technologiestechnologies forfor thethe productionproduction of of PPPP--basedbased TPEsTPEs
ZrCl
Cl
P
EtEt
B
ClCl
PEt
Et
ZrCl
Cl
B
ClCl
Polymers with high tacticity atactic polymers
PP-based multi-block copolymer
Temperature
PreparationPreparation of of PPPP--basedbased multiblockmultiblock copolymerscopolymers byby thetheuseuse of of Donor/AcceptorDonor/Acceptor MetallocenesMetallocenes ((OstojaOstoja StarzewskiStarzewski))
100
101
102
103
104
Elastomeric PP
Schubm
odul (M
Pa)
G''
G'
-160 -120 -80 -40 0 4010
-2
10-1
100
-120 -80 -40 0 40
Temperatur (°C)
tan δ
PPPP--BasedBased TPETPE
Sample Sample fromfrom Prof. Prof. AladyshevAladyshev
Temperature [°C]
Ko
mp
lex m
od
ulu
s(G
*) [
MP
a]
PPPP--BasedBased TPETPE
0 200 400 600 800
0
2
4
6
Elast.PP
Spannung σ
[N
/m
m 2
]
Abb.
Probenform: S1-Stab
Anlieferzustand: Platte
Meßdatum: 05.06.02
Dateiname: S14308sd (Graph 1)
Dehnung ε [%]
Sample Sample fromfrom Prof. Prof. AladyshevAladyshev
strain (εεεε) [%]
str
ess σσ σσ
[N/m
m2]
10-1
100
101
102
103
104
G' G" HAIFA 1
G' G" HAIFA 2
kom
ple
xer
Sch
ub
mod
ul
[MP
a]
-160 -120 -80 -40 0 40 80 12010
-3
10-2
10-1
100
-120 -80 -40 0 40 80
tan
( δδ δδ)
Temperatur [°C]
PPPP--BasedBased TPETPE
Sample Sample fromfrom Prof. Eisen/HaifaProf. Eisen/HaifaTemperature [°C]
Ko
mp
lex m
od
ulu
s(G
*) [
MP
a]
PPPP--BasedBased TPETPE
0 100 200 300 400 500 600 700 800 900
0
2
4
6
HAIFA-1
HAIFA-2
Spannung σ
[N
/m
m2
]
Dehnung ε [%]
Sample Sample fromfrom Prof. Eisen/HaifaProf. Eisen/Haifastrain εεεε [%]
str
ess σσ σσ
[N/m
m2]
• Reduction of Manufacturing Costs– Reduction in number of raw materials and associated costs for logistics (ordering,
transportation and storage,)
– Reduction/elimination of compounding costs including energy savings
– Significant reduction of cycle time and increase of output (seconds instead of minutes)
– Cost reduction by recycling of waste (no costs for incineration and land fill)
• New Technology for Rubber Processors– Installation of equipment for the processing of thermoplastic materials
– Know-how in thermoplastics and their processing not available
– Know-how for the compounding and processing of rubbers becomes abundant
• TPE- Range of Products and Proeprties– Limited availability of soft grades with Shore A Hardness < 50
– Open questions on the production of composites
– High hysteresis which results in p high permanent set (after elongation and compression)
– Losses on dynamic stress bei dynamischer Beanspruchung
– Irreversible damage of articles if service temperature is increased above thresholdtemperature
TPEsTPEs fromfrom thethe ViewpointViewpoint of a of a ProducerProducer of of TechnicalTechnicalRubber Rubber GoodsGoods
1
7. Test 7. Test QuestionsQuestions
Given Name
Family Name
PleasePlease do do notnot forgetforget to to writewrite youryour namename
on on eacheach pagepage of of thethe questionnairequestionnaire
2
WhichWhich AbbreviationsAbbreviations Are Are UsedUsed forfor thethe FollowingFollowingRubbers?Rubbers?
AbbreviationRubberNr.
Smoked Sheets based on NR
Standardized NR from Vietnam
Polyphosphazene modified with perfluorinated alcohols
Vinylmethylsilicon Rubber, which also contains fluorine
Brominated Isobuylen/Isoprene-Copolymers
Butadiene/Acrylonitrile-Copolymers
Silicon Rubber with Viny Groups
Natural Rubber
Styrene/Butadiene-Copolymers
Isobutene/Isoprene-Copolymers
Synthetic Polyisoprene
Acrylic Rubber
Fluororubber
Epoxydized Natural rubber
Ethene/Propene-Copolymers
Ethene/Propene/Diene-Terpolymers
Chlorosulfonated Polyethylene
Chlorinated Polyethylene
Polychloroprene
Polybutadiene
19
20
17
18
16
15
14
13
12
11
10
9
8
7
6
5
4
3
2
1
Given Name
Family Name
3
PleasePlease AssignAssign thethe followingfollowing Rubbers to Rubbers to thetheCorrectCorrect Position in Position in thethe Matrix:Matrix:
Chemical Features
RadicalPolymerization
Ziegler/Natta-Polymerization
anionicPolymerization
CationicPolymerization
Polyaddition und Polycondensation
Polymer-modification
Process Features
Emulsion Solution Dispersion Mass or Gas-(slurry) Bulk Phase
ACM, BIIR, BR, CM, CSM, EVM, FKM, HNBR, IIR, SBR
Given Name
Family Name
4
WhichWhich of of thethe CurvesCurves Matches Matches thethe Performance of Performance of thetheMaterials Materials MentionedMentioned BelowBelow ? ?
Nr.: Questions Answers1 Thermoplastic Polymer ?
2 Unvulcanized HNBR at 20°C ?
3 Unvulcanized HNBR at 120°C?
4 Unvulcanized BR with Mn = 10 kg/mol at 50°C ?
5 Unvulcanized BR with Mn = 500 kg/mol at 20°C?
6 SBS at 20°C?
7 SBS at 120°C
8 TPU at 20°C
9 NR (unfilled and vulcanized) at 60°C
10 NR (filled and vulcanized) at 60°C
elongation [%]
Resid
ual
Elo
ng
ati
on
[%] 1
2
3
456
300
200
100
00 100 200 300
Given Name
Family Name
5
Nr.: Frage Right Wrong1 Unvulcanized NR does not crystallize
2 Today, Malaysia is NR-Producer No. 1
3 For NR plantations China is ideal.
4 For NR plantations Brasil is ideal.
5 A smallholder earns ~ 10000 €/a
6 SMR 20 is a NR-grade with high purity
7 SMR CV vulcanizes faster than SMR 10
8 NR has to be masticated before use
9 IR has to be masticated before use
10 For the mastication of NR, mastication aids have to be used
Given Name
Family Name
NaturalNatural RubberRubber
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
6
Nr.: Frage Right Wrong1 A tyre tread based on NR performs well on a wet road
2 A tyre tread based on NR exhibts a low rolling resistance
3 The vulcanizateion of NR with peroxides yields good dynamic properties
4 NR has a lower Tg than ENR
5 NR can be vulcanized with multifunctional isocyantes
6 CV grades can be vulcanized with diisocyantes
7 NR can be vulcanized with phenol/formaldehyde resins
8 NR based compounds have a higher tack than SBR-based compounds
9 NR crystallizes at 35°C
10 NR crystallizes faster at -50°C than at -20°C
Given Name
Family Name
NaturalNatural RubberRubber
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
7
SyntheticSynthetic PolyisoprenePolyisoprene
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Nr.: Question RIGHT WRONG1 The mechanical properties of IR do depend on the 1,4-cis-content
2 Li-based catalysts produce IR with a high 1,4-cis-content
3 Nd-based catalysts produce BR with a high 1,4-cis-content
4 Ti-based catalysts produce IR with the highest 1,4-cis-content
5 Tg of IR does not depend on 1,4-cis content
6 IR has to me masticated before use
7 IR can be crosslinked with diisocyantes
8 IR with a high 3,4-content is good for tyres with a high wt grip
9 IR with a high cis-1,4-content provides tyres with good wet grip
10 Poly-1,4-trans-Isoprene has a lower Tg than Poly-1,4-cis-Isoprene
Given Name
Family Name
8
Emulsion RubbersEmulsion Rubbers
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Nr.: Question Right Wrong
1 The term "emulsion" is used for a dispersion of polymer particles in water
2 The term "latex" is used for a dispersion of rubber particles in water
3 Polymer dispersions are obtained by slurry (precipitation) polymerization
4 Latices are obtained by emulsion poymerization
5 Latices with a solids content > 50 wt. % can not be made
6 The addition of emulsifier increases the stability of latices
7 The addition of emulsifier increases the stability of emulsions
8 At freezing temperatures latex stability is higher than at 23°C
9 At elevated temperatures (>100°C) latex stability is higher than at 23°C
10 The addition of electrolytes increases latex stability
Given Name
Family Name
9
Rubber recovery from a solution by steam stripping causes waste water9
Emulsion rubbers cause air pollution10
There are no biodegradable emulsifiers6
Emulsion rubbers yield considerable amounts of water water7
Dry finishing of solution rubbers does not cause water pollution8
Wrong
BOD < COD5
COD < BOD4
BOD = COD3
BOD = 02
COD = 01
RightQuestionNr.
Given Name
Family Name
Pollution of Water and Air:Pollution of Water and Air:
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
10
Nr.: Frage Right Wrong
1 Additives can increas the rate of crystallization
2 Additives can reduce the rate of crystallization
3 SBR is a crystallizing rubber
4 NBR is a crystallizing rubber
5 NR is a crystallizing rubber
6 Rubber compounds crystallize slower than raw rubbers
7 Vulcanizate crystallize faster then the respective rubber compounds
8 Strain induced crystallization is a wanted property
9 Low temperature performance of vulcanizates is improved by spontaneous
crystallization
10 The compression set performance of vulcanizates at low temperatures is
is improved by spontaneous crystallization
CrystallizationCrystallization of Rubbersof Rubbers
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
11
Nr.: Question Right Wrong1 SBR exhibits spontaneous crystallization
2 NBR is a crystallizing rubber
3 CR is a crystallizing rubber
The rate of CR crystallization depends on polymerization temperature
4 NR is a crystallizing rubber
5 Spontaneous crystallization is a wanted property
6 Strain induced crystallization provides high abrasion resistance
7 The rcrystallization rate of CR depends on temperature
The crystallization rate of rubbers shows a temperature maximum
8 The crystallization rate of rubbers shows a temperature minimum
The rate of crystallite nucleation increases with increasing temperature
9 The rate of crstallite growth decreases with increasing temperature
10 The rate of crystallization of vulcanizates can be monitored
by Shore A measurements
CrystallizationCrystallization of Rubbersof Rubbers
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
12
Nr.: Frage Right Wrong1 NBR which is polymerized under azeotropic conditions has 2 Tgs
2 NBR which is polymerized under azeotropic conditions has 1 Tg
3 A batch polymerization with incremental monomer addition can result in 2 Tgs
4 Low monomer conversions result in NBR with chemical heterogenity
5 High amounts of emulsifier improve chemical homogenity
6 High amounts of modifier improve chemical homogenity
7 Rebound of NBR increases with the content of acrylonitrile
8 The degree of oil swelling increases with acrylonitrile content
9 Shore A hardness of NBR vulcanizates dempend on acrylonitrile content
10 The compression set of NBR vulcaniaztes depend on acrylonitrile content
NBRNBR
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
13
Nr.: Frage Right Wrong1 The properties of NBR depend on the emulsifier used for polymerization
2 The properties of NBR depend on the electrolytes used for latex coagulation
3 The tendency to gelling increases with increasing polymerization temperature
4 The tendency to gelling decreases with increasing polymerization temperature
5 Molar masses increase with increasing monomer conversion
6 Molar masses do not depend on monomer conversion
7 Molar masses do not depend on modifier level
8 Molar masses decrease with increasing amounts of modifier
9 Molar masses increase with increasing amounts of modifier
10 The properties of NBR depend on the modifier used
NBRNBR
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
14
In In thethe literatureliterature youyou find find thethe followingfollowing TgsTgs forfor polybutadienepolybutadiene (BR) and (BR) and
polyacrylonitrilepolyacrylonitrile (PAN:(PAN:
PleasePlease selectselect thethe relevant relevant TgsTgs and and calculatecalculate thethe TgTg of an NBR grade of an NBR grade
whichwhich containscontains 50 wt.% 50 wt.% acrylonitrileacrylonitrile. .
TheThe calculatedcalculated TgTg isis: : ………………....°°CC
NBRNBR
+100°CPAN
-80°CBR (emulsion polymerization)
-110°CBR (Nd-catalysis)
-100°CBR (Ti-catalysis)
-90°CBR (Li-catalysis)
Given Name
Family Name
15
Nr.: Frage Right Wrong1 The compatability of NBR and PVC depends on acrylonitrile content
2 Vulcanizates based on NBR perform well in ozone containing air
3 Vulcanizates based on CR perform well in ozone containing air
4 NBR/BIIR-Blends are useful for innerliners
5 Blends based on NBR and EPDM are compatible
6 Sulfur cure of NBR/HNBR-Blends result in high temperature resistance
7 Precrosslinked NBR yields compounds with low die swell
8 NBR can be vulcanized with phenol/formaldehyde resins
9 The swelling of NBR vulcanizates in oil increases with acrylonitrile content
10 The swelling of NBR vulcanizates in oil decreases with acrylonitrile content
NBR:NBR:
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
16
Nr. Question Right Wrong1 The properties of CR do not depend on the temperature of polymerization
2 Vulcanization with ETU* results in crosslinks which contain 1 sulfur atom
3 CR-based adhesive grades contain 2-3-Dichlorobutadiene-1,3
4 CR rubber grades are polymerized at a lower temperatures than
CR adhesive grades
5 CR-latices can not be coagulated with electrolytes
6 CR crystallinity is disturbed by copolymerized sulfur
7 Mercaptane modification results in higher tensile strength of vulcanized CR
than the modification with xanthogendisulfides
8 The ageing resistance of vulcanized CR sulfur grades is higher than those of
mercaptane modified CR grades
9 CR-sulfur grades have to be masticated prior to use
10 Precrosslinked CR grades are used for vulcanizates with good dynamic
performance
CRCR
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
Given Name
Family Name
17
Nr.: Question Right Wrong1 Tg of HNBR does depend on the degree of hydrogenation
2 The rebound of HNBR vulcanizates depends on ACN content
3 HNBR and EVM are fully compatible at all copolymer compositions
4 The compatibility of PVC and HNBR depends on the acrylonitrile content of HNBR
5 Compatibility of HNBR and EVM depends on the vinyl acetate content of EVM
6 The crystallinity of HNBR depends on acrylonitrile content
7 Ethene sequences are prone to crystallization
8 Tg of amorphous PE is at -200°C
9 Tg of amorphous PE ist at + 0°C
10 Unvulcanized HNBR with a low acrylonitrile content performs like a TPE
HNBR:HNBR:
PleasePlease Mark Mark „„RIGHTRIGHT““ oror „„WRONGWRONG““
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18
Nr.: Question Right Wrong1 Pd-Catalysats can be used for the selective hydrognation of C=C bonds in NBR
2 Raney-Nickel can be used for the selective hydrogenation of C=C bonds in NBR
3 Li[AlH4] can be used for the selctive hydrogenation of C=C bonds in NBR
4 NN=NH can be used for the selective hydrogenation of C=C bonds in NBR
5 Supported catalaysts can be recovered by centrifugation
6 Supported catalaysts are not quantitatively recovered after hydrogenation
7 Homogeneous catalysts can be recovered by filtration
8 Ethene and acrylonitrile can be radically copolymerized
9 Metallocenene-based catalysts readily copolymerize ethene and propene
10 In the hydrogenation on NBR, gel formation is a major problem
HNBR:HNBR:
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19
Nr.: Question Right Wrong1 At a polymerization temperature of -100°C molar masses of IIR are too high
2 At a polymerization temperature of 23°C °C molar masses of IIR are too low
3 IIR is a feedstock for the preparation of BIIR
4 NR/BIIR-Blends are used for the production of innerliners
5 IIR has a good performancde in the covulcanization of layers
6 BIIR has a good performancde in the covulcanization of layers
7 IIR can be vulcanized by the use of peroxides
8 BIIR can be vulcanized by the use of peroxides
9 Bladders which are used for the vulcanization of tyres are based on
resin cured IIR
10 Bromination of IIR is performed in CH3Cl
IIR, CIIR and BIIR:IIR, CIIR and BIIR:
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20
Nr. Question Right Wrong
1 The hard phase is not crosslinked
2 The hard phase is crosslinked
3 The soft phase can be polar
4 The soft phase can be crsslinked
5 Tg of soft phase > Tg of hard phase
6 Tg of soft phase < Tg of hard phase
7 Hard- and soft phase have to be mechanically coupled
8 Hard- and soft phase have to be compatible
9 Dynamic vulcanization can be performed in a twin
screw extruder
10 Dynamic vulcanization can be performed on a mixing mill
ThermoplasticThermoplastic ElastomersElastomers::
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21
PleasePlease assignassign thethe CurvesCurves
Sch
ub
mod
ul
[MP
a]
Temperatur
-100 -50 0 50 100 150 200
104
103
102
101
100
10-1
Nr.: Frage Number of curve(s)1 Which curve(s) matches the performance of unvulcanized NR ?
2 Which curve(s) matches the performance of unvulcanized SBR ?
3 Which curve(s) matches the performance of vulcanized SBR ?
4 Which curve(s) matches the performance of unvulcanized NBR ?
5 Which curve(s) matches the performance of vulcanized NBR ?
6 Which curve(s) matches the performance of isotactic Polypropylene?
7 Which curve(s) matches the performance of Polycarbonate?
8 Which curve(s) matches the performance of atactic Polytyrene?
9 Which curve(s) matches the performance of ABS with 30 wt.% BR ?
10 Which of the curve(s) matches the performance of SBS ?
1
234
5
6
7
8
9
22
Rubber A [phrRubber B [phr]Rubber C [phr]
Carbon black (N 220) [phr]
Shore A Hardness/23°C Modulus300 [MPa]Tensile Strength [MPa]Elongation at break [%]Rebound/23°C [%]Goodrich HBU [°C]CS (24h/70°C) [%]
Volume swell (70h/70°C)ASTM-oil Nr. 1 [%]ASTM-oil Nr. 2 [%]ASTM oil Nr. 3 [%]
Air permeation/23°C [1018 x m4/s.N]
WhichWhich seriesseries of of modifiedmodified rubbersrubbers and and whichwhich modificationmodificationresultsresults in in thethe followingfollowing propertiesproperties
100--
30
597,827,1550784417
66114191
27,0
-100
-
30
566,9
25,9590256046
7328
108
8,0
--
100
30
598,8
27,8560155217
-5621
1,98
Given Name
Family Name
Rubber B
Rubber A
Rubber C
modification
23
Metal
Microstructure [%]
1,4-cis 36-38 97 97 93 98 12,9
1,4-trans 52 1 2 3 1 68,3
Vinyl 10-11 2 1 3-4 <1 18,8
Vinyl/1H-NMR*** 10,4 1,9 4,0 <1 18,1
Vinyl/FT-IR*** 11,4 1,0 5,4 0,6 17,7
Vinyl/Metathese*** 10,7 1,7 4,6 0,7 17,8
Tg -93 -106 -107 -103 -109 -80
WhichWhich Metal Metal isis usedused forfor thethe productionproduction of BR in order to of BR in order to obtainobtain thethe PropertiesProperties belowbelow ??
CH2
1
CH2
CH3
CH2
4
CH2
1
CH2
CH3
CH24
CH21
CH2
CH3
CH24
24
Rubber ARubber B
Compound PropertiesML 1+4(100°C) [MU]t2/177°C [min]t90/177°C [min]
Vulcanizate PropertiesShore A Härte (23°C)Modulus 100 [MPa]Elongation at break [%]Tensile Strength [MPa]
Compression Set70h/23°C [%]70h/150°C [%]70h/175°C [%]
Heat ageing (14d/150°C)F/F0 x100 [%]D/D0 x100 [%]H/H0 x100 [%]
Oil swelling (7d/150°C)ASTM-Öl Nr. 3∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆V/V0 x100 [%]
5050
581,5
10,2
8012,617022,5
1217
25,5
-10-29+4
-36-29+49
2575
401,6
10,2
8112,014518,8
141420
-7,5-21+3
-50-34+67
100-
1231,511,7
7810,724026
122027
-2,3-37+6
-10-4
+24
7525
991,611,0
8013,119024
121727
-3,8-26+5
-17-11+34
-100
321,69,5
778,316518,5
149
15
-1,6-12+2
-56-45+83
PleasePlease AssignAssign Rubber A and Rubber BRubber A and Rubber B
Given Name
Family Name
Rubber B
Rubber A
25
Rubber A
Rubber B
Fmin. [Nm]
Fmax.
ts [min]
t90 [min]
t95 [min]
Shore A
Modulus100 [MPa]
Modulus200 [MPa]
Modulu300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
Abrasion Index
Ageing at 70h/121°C
∆ Dehnung [%]
CS (70 h/121°C) [%]
100,0
0
9,0
86,3
3,0
10,0
21,5
83
5,2
11,0
18,6
25,5
430
493
- 42
34,1
50,0
50,0
10,2
78,7
2,7
7,0
11,0
80
4,5
10,0
15,5
21,0
415
159
- 35
27,1
0
100,0
8,0
60,0
2,8
6,8
8,3
67
1,7
4,8
11,0
18,2
500
73
- 30
14,7
PleasePlease AssignAssign Rubber A and Rubber BRubber A and Rubber B
Given Name
Family Name
Rubber B
Rubber A
26
Hard phase(coherent phase or matrix)
Soft phase(dispersed phase)
PleasePlease assignassign 5 polymer 5 polymer blendsblends forfor whichwhich thetheschemescheme belowbelow appliesapplies
Nr.: Hard phase Soft phase
1
2
3
4
5
Given Name
Family Name
Rubber
Compound propertiesMooney ML 1+4(100°C)t10/180°C [min]t90/180°C [min]FH-FL/180°C [N]
Vulcanised properties(ISO-Stab Nr. 2, 2mm)Shore A Härte (23°C)S 100 MPa]Elongation at break [%]Tenjsile Strength [MPa]
Compression Set70h/100°C [%]70h/125°C [%]70h/150°C [%]
Hot air ageing (14d/150°C)∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆H/H0 x100 [%]
Storage in SAE Oil90 (3d/150°C)∆∆∆∆F/F0 x100 [%]∆∆∆∆D/D0 x100 [%]∆∆∆∆V/V0 x100 [%]
C
231,26,619
684,428512,6
202541
-10211
-8-431
D
251,26,221
715,428012,8
222640
-11-212
8213
A
201,27,217
755,029511,7
232541
-3-210
-26-1969
B
241,26,620
745,727513,6
202338
-12-29
-12-447
E
201,36,919
684,230011,5
212446
10-715
683
F
201,36,117
724,730010,5
273151
-8-1514
10-12-4
WhichWhich SeriesSeries of Rubbers of Rubbers YieldsYields thethe PropertiesProperties GivenGiven in in thethe Table Table BelowBelow??
Given Name
Family Name
Variation
Rubber
28
PleasePlease AssignAssign Rubber A and Rubber BRubber A and Rubber B
80
20
5,7
10,0
620
7,6
9,8
420
5,4
14,7
10,0
23,6
60
40
7,1
12,8
560
8,4
9,3
320
9,2
15,2
14,7
0,3
100
-
4,2
9,3
740
6,8
10,0
550
2,9
16,8
7,5
61,8
Rubber A [phr]
Rubber B [phr]
Unaged:
M300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
Aged (168h/100°C)
M300 [MPa]
Tensile Strength [MPa]
Elongation at break [%]
Air permeation at
50psi/65°C (Q x 10-8]
Adhesion at 100°C
Self adhesion / tack [kN/m]
Adhesion to NR [kN/m]
Fatigue to failure after
ageing at 168h/120°C [kcycles]
40
60
8,9
14,7
490
6,7
8,8
370
13,8
15,4
20,8
0,0
Given Name
Family Name
Rubber B
Rubber A
29
Rubber A [phr]Carb. black (N 774) [phr]
VulcanizationCompound PropertiesML 1+4 (100°C) [MU]MS5 (125°C) [min]
MS5 (135°C) [min]
Physical PropertiesShore A HardnesM100 [MPa]M300 [MPa]Tensile Strength [MPa]Elongation at break [%]CS (70h/150°C) [%]
10050
ZnO
83-
16
480,95,2
12,458058
10050
DCP
88-
12
400,51,88,968053
10050
DCP/BMI
88-
14
540,129,5
10,532528
10050
ZnO/BMI
89-
16
580,1910,213,636013
PleasePlease AssignAssign Rubber A Rubber A
Given Name
Family NameRubber A
