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2553
2553
SYNTHESIS AND MECHANICAL PROPERTIES OF A THERMO - REVERSIBLE
THERMOPLASTIC ELASTOMER
By
Pensri Anurak
A Thesis Submitted in Partial Fulfillment of the Requirements for the Degree
MASTER OF ENGINEERING
Department of Materials Science and Engineering
Graduate School
SILPAKORN UNIVERSITY
2010
“
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2. .
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( . ) ( . )
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51402227 :
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:
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. 129
(soft segment) p-toluenesulfonyl isocyanate (PTSI)
(hard segment) (ENR)
3 20, 34, 45 mol%
ENR
latex NH4OH silica gel (70-230 mesh)
2 (diamine)
PTSI
FT-IR, 1H-NMR, TGA, DSC, SEM, DMA FT-IR 1H-NMR FT-IR
S=O hard segment
TGA 2
240-320 C 350-500 C
TPEs SEM
hard segment DSC
DMA TPEs Tg hard segment
(-NH-CO-NH-SO2-) (G'
tan ) TPEs thermo-sensitive
2553
........................................
1. ....................................... 2. .......................................
51402227 : MAJOR : POLYMER SCIENCE AND ENGINEERING KEY WORDS : NATURAL RUBBER/ EPOXIDIZED NATURAL RUBBER/THERMOPLASTIC ELASTOMER/ THERMO-REVERSIBLE
PENSRI ANURAK : SYNTHESIS AND MECHANICAL PROPERTIES OF A THERMO-REVERSIBLE THERMOPLASTIC ELASTOMER. THESIS ADVISORS : ASST. PROF. WANCHAI LERDWIJITJARUD, Ph.D., AND AMNARD SITTATTRAKUL, Ph.D. 129 pp.
The aim of this research is to study the synthesis of a thermo-reversible thermoplastic elastomer based on natural rubber. In this study, a novel thermoplastic elastomer (TPE) was prepared by using natural rubber (NR) as soft segment and p-toluenesulfonyl isocyanate (PTSI) as hard segment. In the first step, the epoxidized natural rubber (ENR) was prepared from the reaction of NR latex with formic acid and hydrogen peroxide. The epoxidation level was varied at approximately 20, 34, and 45 mole% and the degree of modification is quantitatively controlled by epoxidation reaction. The ENR latex was further reacted with NH4OH by using silica gel (70-230 mesh) as a catalyst for the opening of epoxide rings to yield diamino compounds. The final step, the product obtained after ring opening reaction was reacted with PTSI (hard segment) for synthesis of TPEs. The natural rubber, ENRs, the product obtained after ring opening reaction, and TPEs were characterized by using FT-IR, 1H-NMR, TGA, DSC, SEM, and dynamic mechanical analyses. It was found that the completion of each modification step was confirmed by FT-IR and 1H-NMR spectra. FTIR spectra also showed a shift of S=O stretching to lower frequency with increasing hard segment content as a result of the formation of hydrogen bonds between sulfonylurea hard segments. TGA analysis showed that a two-step decomposition around 240-320 C and 350-500 C which referred to the decomposition of sulfonylurea hard segment and natural rubber soft segment, respectively. The SEM analysis showed that the phase-separated morphology in TPEs. The micrographs show a randomly dispersion of hard domains in a continuous rubber matrix. The glass transition (Tg) of TPEs was elevated to higher temperatures with increasing hard segment content. Because of the introduction of sulfonylurea groups (-NH-CO-NH-SO2-) which are prone to hydrogen-bonding networks. The DMA results indicate that the dynamic mechanical properties (G and tan ) of TPEs were changed with temperature which might be ascribed to the thermo-sensitive characteristic of hydrogen-bonds.
Department of Materials Science and Engineering Graduate School, Silpakorn University Academic Year 2010
Student's signature...................................................
Thesis Advisors' signature 1. …………………………… 2. .........................................
.
.
- ( )
Dynamic mechanical analysis (DMA)
....................................................................................................................
...............................................................................................................
.....................................................................................................................
............................................................................................................................
...............................................................................................................................
1 ............................................................................................................................. 1
................................................................ 1
...................................................................................... 2
....................................................................... 2
......................................................................... 3
.................................................................................... 3
............................................................................................... 4
2 ...................................................................................... 5
(natural rubber) ............................................................................... 5
................................................................ 5
............................................................ 8
.................................................. 9
......................................................................... 10
................................... 12
............................................ 12
.................... 13
......... 14
(HTNR) ...... 22
(CTNR) ...... 22
..... 24
(Thermoplastic Elastomer; TPE) ........................ 24
.............. 25
.......................................... 28
(block copolymer) ............... 28
..................... 30
.................................................. 30
.................... 32
.............................................................................................. 34
.................... 36
................................. 38
................................................................... 39
............................................................................ 40
........ 41
3 ........................................................................................................... 43
.................................................................................... 43
.................................................................................... 43
................................................................................ 44
............................................................................................ 45
(ENR) ........................................... 47
ENR ........................................................ 47
1,2-amino alcohol ................................................................ 47
1,2-diamine .......................................................................... 48
(hard segment) ....... 49
............................................................ 50
(Thermal properties) ................................ 51
(Dynamic mechanical testing) .................... 52
...................................................................... 52
Dynamic mechanical analyzing ........................................ 53
.............................................. 53
4 ....................................................................... 55
FT-IR
1H-NMR ................................................................................................ 55
(ENR) ........................................... 55
ENR ........................................................ 59
1,2-amino alcohol .......................................................... 59
1,2-diamine .................................................................... 62
hard segment ......................... 64
........................................................................... 67
TGA ............................... 67
DSC ......................... 71
.................................................................. 72
Dynamic mechanical analysis (DMA) ....... 75
5 .............................................................................. 83
................................................................................................ 83
.......................................................................................................... 84
............................................................................................................................. 86
.................................................................................................................................. 91
FT-IR spectra .................................................................. 92
1H-NMR spectrum ......... 100
TGA DTG thermogram .......................................... 108
DSC thermogram ............................................................ 116
DMA thermogram ......................................................... 124
.............................................................................................................................. 129
1 ENR............................................ 21
2 ..... 42
3 ............................ 49
4 ENR 3
1H-NMR spectra 2.7 ppm 5.1 ppm .......................... 57
5 1,2-amino alcohol 1,2-diamine
absorbance FT-IR spectra .. 64
6 hard segment
1H-NMR TGA............................................... 67
7 thermal decomposition ................... 70
8 (dynamic property) ............. 82
1 (Hevea Brasiliensis) .................................................... 6
2 (cis-1,4-polyisoprene) ...................... 7
3 cyclized NR .................................................................................... 9
4 depolymerization NR ultraviolet nitrobenzene .... 10
5 LNR phenylhydrazine/oxygen ................................... 11
6 hydrogenation .............................................................. 12
7 epoxidation peracid ....................................... 15
8 (side reaction) epoxidation NR 17
9 ................................. 18
10 glass transition temperature (Tg)
................................................................... 19
11 (calibration curve) (mole %)
IR ............................................................ 20
12 flexural modulus
thermoplastic elastomer .................................................................................. 26
13 SBS PS physical crosslink ( )
PB rubbery phase ( ) .................................................................... 28
14 block copolymer ................................................................. 28
15 S-B-S block copolymer ................................... 29
16 ....... 39
17 ................ 46
18 Fourier Transform Infrared Spectrophotometer (Bruker Vertex70) ............ 50
19 Nuclear Magnetic Resonance Spectrometer (Bruker 300 Ultrasheild) ........ 50
20 (a) Thermogravimetric Analyzer (TGA/DSC1, Mettler Toledo, Switzerland),
(b) Differential Scanning Calorimeter (DSC1, Mettler Toledo,
Switzerland) ......................................................................................... 51
21 compression molding ............................. 52
22 ..................................................... 52
23 Dynamic Mechanical analyzer (SDTA861e, Mettler Toledo) ................... 53
24 Scanning Electron Microscope (MX-2000, CamScan) .............................. 54
25 FT-IR spectrum (NR) ENR 3 ........................ 56
26 1H-NMR spectrum (a) NR, (b) low-ENR, (c) med-ENR,
(d) high-ENR................................................................................................ 58
27 FT-IR spectrum 1,2-amino alcohol ENR 3 ............. 59
28 1H-NMR spectrum (a) high-1,2-amino alcohol, (b) med-1,2-amino alcohol,
(c) low-1,2-amino alcohol .................................................................... 61
29 FT-IR spectrum 1,2-diamine ENR 3 ....................... 62
30 1H-NMR spectrum (a) low-NR-NH2, (b) med-NR-NH2,
(c) high-NR-NH2 .......................................................................................... 63
31 FT-IR spectrum TPE ENR 3 ................................... 65
32 1H-NMR spectrum (a) low-NR-PTSI, (b) med-NR-PTSI,
(c) high-NR-PTSI .......................................................................................... 66
33 TGA thermogram (NR) ENR 3 .................... 68
34 TGA thermogram TPE 3 ............................................................ 69
35 TGA thermogram TPE 3 ............................................................ 70
36 DSC thermogram (NR), ENR, TPE ......... 71
37 SEM micrographs a) natural rubber, b) low-ENR, c) med-ENR,
d) high-ENR 500 ............................................................. 73
38 SEM micrographs a) low-NR-PTSI, b) med-NR-PTSI, c) high-NR-PTSI
500 .................................................................................. 74
39 SEM micrographs a) low-NR-PTSI, b) med-NR-PTSI, c) high-NR-PTSI
1,000 ............................................................................... 75
40 storage modulus (G ) ...... 77
41 storage modulus (G ) ENRs ..................................... 78
42 storage modulus (G ) TPEs ...................................... 80
43 tan ................................................................................ 82
44 FT-IR spectrum (NR) ............................................................... 93
45 FT-IR spectrum ENR low-ENR ...................................................... 93
46 FT-IR spectrum ENR med-ENR ...................................................... 94
47 FT-IR spectrum ENR high-ENR ..................................................... 94
48 FT-IR spectrum low-1,2-amino alcohol .................................................. 95
49 FT-IR spectrum med-1,2-amino alcohol .................................................. 95
50 FT-IR spectrum high-1,2-amino alcohol ................................................. 96
51 FT-IR spectrum low-1,2-diamine ............................................................ 96
52 FT-IR spectrum med-1,2-diamine ........................................................... 97
53 FT-IR spectrum high-1,2-diamine ........................................................... 97
54 FT-IR spectrum low-NR-PTSI ................................................................ 98
55 FT-IR spectrum med-NR-PTSI ................................................................ 98
56 FT-IR spectrum high-NR-PTSI ............................................................... 99
57 1H-NMR spectrum (NR) .......................................................... 101
58 1H-NMR spectrum low-ENR ......................................................................... 101
59 1H-NMR spectrum med-ENR ........................................................................ 102
60 1H-NMR spectrum high-ENR ....................................................................... 102
61 1H-NMR spectrum low-1,2-amino alcohol .................................................... 103
62 1H-NMR spectrum med-1,2-amino alcohol ................................................... 103
63 1H-NMR spectrum high-1,2-amino alcohol .................................................. 104
64 1H-NMR spectrum low-1,2-diamine .............................................................. 104
65 1H-NMR spectrum med-1,2-diamine ............................................................. 105
66 1H-NMR spectrum high-1,2-diamine ............................................................ 105
67 1H-NMR spectrum low-NR-PTSI .................................................................. 106
68 1H-NMR spectrum med-NR-PTSI ................................................................. 106
69 1H-NMR spectrum high-NR-PTSI ................................................................ 107
70 TGA thermogram ..................................................................... 109
71 TGA thermogram low-ENR .......................................................................... 109
72 TGA thermogram med-ENR ......................................................................... 110
73 TGA thermogram high-ENR ......................................................................... 110
74 TGA thermogram low-1,2-amino alcohol ..................................................... 111
75 TGA thermogram med-1,2-amino alcohol .................................................... 111
76 TGA thermogram high-1,2-amino alcohol .................................................... 112
77 TGA thermogram low-1,2-diamine ............................................................... 112
78 TGA thermogram med-1,2-diamine .............................................................. 113
79 TGA thermogram high-1,2-diamine .............................................................. 113
80 TGA thermogram low-NR-PTSI ................................................................... 114
81 TGA thermogram med-NR-PTSI .................................................................. 114
82 TGA thermogram high-NR-PTSI .................................................................. 115
83 DSC thermogram (NR) ............................................................ 117
84 DSC thermogram low-ENR ........................................................................... 117
85 DSC thermogram med-ENR .......................................................................... 118
86 DSC thermogram high-ENR ......................................................................... 118
87 DSC thermogram low-1,2-amino alcohol ...................................................... 119
88 DSC thermogram med-1,2-amino alcohol ..................................................... 119
89 DSC thermogram high-1,2-amino alcohol .................................................... 120
90 DSC thermogram low-1,2-diamine ................................................................ 120
91 DSC thermogram med-1,2-diamine ............................................................... 121
92 DSC thermogram high-1,2-diamine ............................................................... 121
93 DSC thermogram low-NR-PTSI .................................................................... 122
94 DSC thermogram med-NR-PTSI ................................................................... 122
95 DSC thermogram high-NR-PTSI .................................................................... 123
96 DMA thermogram (NR) ............................................................ 125
97 DMA thermogram low-ENR ........................................................................... 125
98 DMA thermogram med-ENR .......................................................................... 126
99 DMA thermogram high-ENR .......................................................................... 126
100 DMA thermogram low-NR-PTSI .................................................................... 127
101 DMA thermogram low-NR-PTSI .................................................................... 127
102 DMA thermogram low-NR-PTSI .................................................................... 128
1
1
1.1
(natural rubber; NR) (elastomer)
[1-3]
(vulcanization)
vulcanized rubber
(thermoset)
(degradation)
“ ” (thermoplastic elastomer; TPE)
[2, 4]
(crosslink) TPE (phase
separation) (crystallization) (ionic interactions)
2
(hydrogen bonding)
thermo-reversible crosslink crosslink
crosslink
(recycle)
TPE
TPE
TPE
1.2
1.2.1
(thermo-reversible)
1.2.2 (soft segment)
(hard segment)
1.3
(TPE)
(soft segment)
(hard segment) phase-separated
Tg
Tg
(physical crosslink)
(soft segment) TPE
3
(hard segment)
TPE
grafted
copolymer
TPE
TPE
TPE
1.4
TPE
p-toluenesulphonyl isocyanate (PTSI)
latex form
non-aqueous phase
TPE
1.5
1.5.1
1.5.2
1.5.3
1.5.4
1.5.4.1 (epoxidized natural rubber,
ENR) ENR 3
4
ENR FTIR 1H-NMR
1.5.4.2
2 (1,2-diamine)
FTIR 1H-NMR
1.5.4.3 hard segment
(TPE) p-toluenesulfonyl
isocyanate (PTSI) hard segment TPE
FTIR 1H-NMR
1.5.4.4 TPE
morphology
1.5.5
1.5.6
1.5.7
1.6
1.6.1
(thermo-reversible)
1.6.2 soft segment hard segment
5
2
2.1 (natural rubber)
2.1.1
(natural rubber; NR)
Hevea Brasiliensis (hevea)
Perthenium Argentatum (guayule) [5]
(latex) (dry rubber) 30%
(centrifuge)
60% (concentrated latex)
95 (
) cis-1,4-polyisoprene (C 5 H 8 ) n
50,000-3,000,000 60
1,300,000 [6] 2
(benzene), (hexane), (toluene)
(amorphous)
(crystalline)
(low temperature crystallization)
6
(strain-induced crystallization)
(tensile strength)
(tear resistance) (abrasion resistance)
(elasticity)
( )
(tack) (assemble)
[7]
1 (Hevea Brasiliensis) [8]
(NR)
( heat build up
)
(renewable material) [7,1]
(vulcanization)
7
(elastomer) [9]
C=CCH2
H
CH2
CH3n
~~
2 (cis-1,4-polyisoprene) [10]
[5]
- (tensile
strength)
- (tear resistance)
- (dynamic mechanical properties)
(elasticity) (heat build-up)
(tack)
(double bond)
( antidegradant)
[5]
8
(thermosetting polymer)
(degradation)
100% 2-3%
stress macromolecules
(crosslink)
glass crystalline domain
creep [9]
2.1.2
(chemical modification)
(physical modification)
[11]
(NR)
ageing
[12]
(chemical modification) (C=C)
latex (dry phase)
chlorinated rubber, hydrochlorinated rubber, cyclized
rubber, oxidized rubber
9
(cross-linking) (epoxidation)
(maleinisation) (grafting) (depolymerisation)
( )
( )
( )
( ) (
) [11]
3
[13]
2.1.2.1 (bond rearrangement)
carbon-carbon cross-
linking, cyclisation, cis, trans-isomerisation, depolymerisation cyclized
NR treat (proton donor) sulphuric
acid, sulphonic acid, stannic chloride
(cyclisation)
(NR latex)
70 C -100 C cyclized NR
40-50% 3 cyclized NR
blend
modulus, hardness specific gravity CH3H2
C
CH2
CH3
3 cyclized NR [12]
10
(liquid natural rubber; LNR)
(LNR) depolymerize
crosslink (Mw) 105 LNR
depolymerization
peptization (thermal) (mechanical) (photolysis)
(redox) LNR mechanochemical peptization
thermal depolymerization LNR
depolymerize, recombine, (crosslink)
LNR
mastication
photolysis solar radiation, ultraviolet light, visible light
nitrobenzene, hydrogen peroxide,
photosensitiser 4 depolymerization
ultraviolet nitrobenzene
4 depolymerization NR ultraviolet nitrobenzene [12]
11
reducing agent p-methyl-benzene
sulfinic acid, phenylhydrazine, sodium chlorite, sodium nitrite, sodium hypochlorite
oxidizing agent hydrogen peroxide
depolymerization phenylhydrazine/oxygen 5 LNR
(viscosity modifier) sealing agent
compatibilizer polyolefin blend blend
polypropylene/natural rubber (PP/NR) LNR compatibilizer
PP NR polyisoprene
blend HDPE/NR LNR plasticizer blend
40/60 LNR tensile strength elongation at break
5 LNR phenylhydrazine/oxygen [12]
12
(hydrogenated NR)
Hydrogenated NR
(degradation) hydrogenated NR
hydrogenated NR alternated copolymer ethylene propylene
6 hydrogenated NR 3
homogeneous heterogeneous hydrogenation
homogeneous catalyst organotransition metal cobalt (Co)
nickel (Ni) reducing agent R3Al n-BuLi
6 hydrogenation [13]
palladium calcium
carbonate heterogeneous hydrogenation homogeneous
hydrogenation chain scission
homogeneous hydrogenation
hydrogenation diimide
p-toluenesulfonyl hydrazine (TSH) Hydrogenated NR Tg
NR hydrogenated NR
2.1.2.2
(addition reaction) (substitution reaction) (olefinic double
bond)
chlorinated NR, hydrochlorinated NR, epoxidized NR (ENR)
chlorination hydrochlorination
13
latex chlorinated NR (CNR)
ageing
chlorination
(latex) chlorinated
NR NR chlorination
(chlorinated
natural rubber; CNR)
Zhong [13] CNR
NR latex stabilize
(1% potassium persulfate)
CNR
toluene hypochloric acid hypochorite
chlorination chlorination
pH 1 45
chlorination 60% chlorination
30%
chlorination
CNR
30% carbonide 360 C-700 C
CNR
100% 560 C Zhong
CNR 2
dehydrochlorination
14
(epoxy group)
(Epoxidized natural rubber; ENR)
(ENR)
[14-16] epoxidation
. . 1992 ENR
. . 1980 epoxidation
latex [12] ENR
cis-1,4-polyisoprene
(NR)
(epoxidation)
10-50 strength ENR
25 50 mole %
strain crystallization Tg
solubility parameter ENR
[17]
epoxidation
NR latex epoxidation NR latex
in situ epoxidation performic acid
formic acid hydrogen peroxide ENR
latex 20%
epoxidation NR
60%
peracid epoxidation
latex
epoxidation 7 in situ epoxidation
formic acid (HCOOH) hydrogen peroxide (H2O2)
rate-determining step performic acid (HCOOOH) (1)
15
( 7) isoprene unit NR
ENR 50 C
10-12 ENR
50 mole % H2O2 isoprene unit
epoxidation ENR performic acid
(HCOOOH) (2) NR
peracid (HCOOOH) in situ epoxidation
HCOOOH peracid
(1)
(2)
7 epoxidation peracid [12]
16
7
epxidation ENR 2 ENR25%
ENR50% ENR ENR
HCOOH H2O2 (ring-opening)
( 8) ENR
50 mole % ENR
elastic
gel ENR ( epoxidation
)
peel strength NR EPDM
Tg ENR
(mole %) 1 mole %
Tg 0.93 C [18] 10
Tg
ENR-25 Tg
-47 C ENR-50 Tg -22 C Tg
Tg
ENR damping
ENR ENR
ENR neutralize sodium
carbonate, magnesium oxide, calcium oxide calcium stearate ENR
semi-efficient vulcanisation (semi-EV)
efficient vulcanisation (EV) ENR 2
ageing ENR
ENR crosslink
aminosilane curing crosslink
cross-linking site carbon black ENR50
cure p-phenylenediamine (p-PDA) bisphenol-A ( )
17
cure cure
Tg Tg
crosslink bisphenol A
ENR 1
8 (side reaction) epoxidation NR [19]
epoxidation
-
ENR (HBr)
(a) Ring-opening reaction
(b) Cross-link of ENR
18
HBr
9 [20]
HBr
ENR 15
15 mole %
- DSC
DSC Tg (onset)
Tg ENR
1/Tg (onset) 10 Tg 0.85 K
1 mole % 3 0.2 K
DSC 0.25 mole %
Tg 10 C
Tg
19
10 glass transition temperature (Tg)
[18]
-
15 mole %
- IR spectroscopy :
870 cm-1 1,240 cm-1
(olefinic band) 830 cm-1
(calibration internal
standard) 11
870 cm-1 1,375 cm-1 C-H
[21]
100%870830
870
AAAepoxide
A870 A830 870 cm-1 830 cm-1
20
11 (calibration curve) (mole %)
IR [22]
-1H-NMR spectroscopy:
ENR CDCl3
epoxidation olefin proton 5.14 ppm
methine resonance 2.70 ppm
olefinic
epoxy methine proton epoxidation
Mole percent of epoxide = 10014.570.2
70.2 xAA
A
A2.70 A5.14
C=C isoprene unit [23]
Absorbance ratio=DCBA
BA/log/log
/log
21
20-75 mole %
1.5 mole %
- 13C-NMR spectroscopy:
chemical shift olefinic resonance
125 ppm oxirane carbon 64.5 ppm [24]
1H-NMR
64.5 ppm 125 ppm
Mole percent of epoxide = 1007.125,125,4.1245.64
5.64 xAAA
A124.4, A125 A125.7
A64.5
1 ENR [12]
ENR
Oil resistance, high strength ENR25, ENR50
Low gas permeability ENR25
Wet grip, low rolling
resistance
ENR25, ENR50
Damping
ENR25, ENR50
Adhesion
PVC ENR25, ENR50
22
(hydroxyl-
terminated liquid natural rubber; HTNR)
Ravindran [24] HTNR
depolymerization hydroxylation UV (photochemical)
UV HTNR
HTNR 2
(depolymerization) UV
(hydroxylation)
masticate 40 C
30 masticate toluene ( 10% w/v)
photochemical reactor
5% toluene stir
THF ( 25% toluene) methyl alcohol (
15% toluene) homogenizer
UV UV
UV 2
depolymerization hydroxylation
HTNR reagent
UV
HTNR
(carboxyl-
terminated liquid natural rubber; CTNR)
Dileep Avirah [25] CTNR
photochemical maleic anhydride (NR) masticate
CTNR
CTNR 2
(depolymerization) UV (photochemical)
maleic anhydride
(mastication) 50 C 30
23
toluene ( 10% w/v) UV UV
photochemical reactor depolymerization
50 maleic anhydride ( 20%
) methanol stir
UV (1-15 )
methanol
toluene/methanol (1:1 v/v) maleic
anhydride
CTNR
UV 10
FT-IR 1H-NMR depolymerization
maleic anhydride CTNR
.
[26]
(LENR)
(ENR) (H5IO6)
30 C 24
70 C (H2O2)
24
(CLNR) FT-IR 1H-NMR
(CLNR)
(TMAH)
24
2.1.2.3 (grafting)
vinyl monomer methyl
methacrylate (MMA) styrene graft
PMMA emulsion polymerization MMA hydroperoxide
NR latex stir tetraethylenepentamine
60-80% PMMA
hardness, modulus, abrasion, electrical
resistance impact PS
blend
latex (adhesive)
PVC [12]
2.2 (Thermoplastic elastomer; TPE)
(degradation)
“ Thermoplastic Elastomers; (TPEs) ”
physical crosslink
thermo-reversible crosslink
[27]
[1]
TPEs
glassy crystalline domains
crosslink
(large deformation)
25
stress
chemical crosslink
glassy crystalline domains
[2]
TPEs
( ) TPEs
TPEs
(blow molding machine)
(injection molding machine) (extruder) TPEs
TPEs
[7]
2.2.1
physical crosslink thermo-reversible network
TPEs (phase-separated)
hard segment
block graft polymerization [27]
- (hard, crystalline segment) TPEs
physical crosslink
glass transition temperature (Tg)
- (soft, elastic segment)
glass transition temperature (Tg)
Tg Tm
26
12
flexural modulus 3
(1) Tg
(stiff) (brittle)
(2) Tg
(3) modulus ( rubbery
plateau) vicous
fluid
12 flexural modulus
thermoplastic elastomer [27]
(hard phase)
hard phase
27
[27] hard segment
soft segment ( physical crosslink)
soft segment
soft segment hard segment TPEs
soft segment hard segment
TPEs
morphology [28]
TPEs hard segment crosslink
( )
hard segment physical crosslink TPEs hard
segment chemical crosslink
hard segment
[29]
- (ionic interaction)
- (hydrogen bond)
-
- hard segment
soft segment hard segment
- crosslink (covalent bond)
TPEs block copolymers
hard soft blocks polystyrene-polybutadiene-polystyrene triblock
copolymers (SBS) 13 Tg polystyrene
blocks rigid domains soft polybutadiene matrix cross-links
rubbery TPEs [1]
28
13 SBS PS physical crosslink ( ) PB
rubbery phase ( ) [30]
2.2.2
2.2.2.1 (block copolymer)
TPEs
block copolymer
linear block copolymer
star block copolymer linear
block (branch point)
polymerization block
copolymer 14
14 block copolymer [27]
29
- Anionic polymerization
block copolymer
block copolymer
TPEs SBS
- Cationic polymerization ( carbocationic
polymerization) polymerize anionic
polymerization styrenic TPEs isobutylene monomer
(S-B-S) 15
15 S-B-S block copolymer [31]
- Contrlled/living radical polymerization (CLRP)
TPEs CLRP
dynamic equilibrium free radical
free radical propagate terminate free
radical polymerization
- Polymerization with Ziegler-Nata catalyst
TPEs block polyolefin
thermoplastic elastomer olefins (TPOs) ethylene-propylene copolymer, ethylene-
higher -olefin copolymer
30
- Polyaddition multiblock
thermoplastic polyurethane diisocyanate, long-chain diol, chain extender
2.2.2.2
- Dynamic vulcanization thermoplastic
vulcanizates (TPVs)
- Esterification and polycondensation
polyamide elastomers
- Transesterification copolyester elastomers
(COPEs)
- Catalytic copolymerization of olefins reactor
thermoplastic polyolefins (RTPOs)
- Direct copolymerization copolymerization
ethylene methacrylic acid ionomeric TPEs
2.2.3
TPEs 5
1. Thermoplastic polyurethanes (TPUs)
2. Styrenic block copolymers (SBS)
3. Elastomeric alloy
4. Copolyester (COPs)
5. Polymer blends (1) Rubber-Polyolefin blends (TPOs)
(2) Thermoplastic Vulcanisates (TPVs)
TPEs 4 block copolymer
TPEs 4
31
TPEs
polyurethane
TPUs
compression set
diisocyanate polyether, polyester,
caprolactone glycol
styrene copolymer
TPEs block copolymer hard polystyrene segment
soft segment matrix polybutadiene, polyisoprene, ethylene-propylene,
ethylene-butylene tensile strength elongation SBR
styrene-
butadiene block copolymer
elastomeric alloys
elastomeric alloys
2 melt processible rubber (MPRs) thermoplastic vulcanizates (TPVs)
MPRs TPVs
copolyester
injection
molding, extrusion, rotational molding, flow molding, thermoforming, melt casting
dynamic properties modulus,
elongation, tear strength
32
[32]
2.2.3.1
(thermoplastic elastomer blends)
TPE
(immiscible)
TPE
morphology ( )
( ) (continuous phase)
[33]
[34]
(chemical cross-linking)
chain polymerization
PE, PP, PS, PET [35]
crosslink
33
rubbery polymer
stress
crosslink crosslink
crosslink Tg
[33]
crosslink
elastified thermoplastic impact-modified thermoplastic
NR/PP, NR/HDPE, NR/LLDPE, EPDM/PP polyolefin
TPE “ thermoplastic elastomer
olefins; (TPOs) ”
2
1. compatibilizer
compatibilizer block graft copolymer
compatibilizer (interfacial tension)
2. (crosslink)
dynamic vulcanization
vulcanizing agent
(curative) vulcanization
vulcanization crosslink
crosslink
34
dynamic vulcanization TPE
TPE
“thermoplastic vulcanisated; (TPVs)” TPVs TPE
crosslink TPVs
crosslink
compression set
TPVs TPEs TPUs TPEs
[36] TPVs dynamic vulcanization
rubbery polymer thermoplastic rubbery
polymer TPE
thermoplastic rubbery polymer
thermoplastic
3 [27]
2.2.3.2
(Block or segmented copolymers)
TPE
(hard segment)
(soft segment) segmented copolymer
block, graft, star-shaped copolymer
soft segment hard segment hard segment
(
) hard segment crosslink
( )
(
)
35
hard segment
crosslink
hard segment physical crosslink
hard segment
soft segment (network)
hard segment
crosslink
block copolymer
(triblock multiblock copolymer)
hard-soft-hard graft star-shaped
copolymer hard segment
TPE triblock copolymer
TPE styrene-butadiene-styrene (SBS) triblock copolymer
polystyrene (rigid) Tg hard segment
polybutadiene (flexible)
Tg soft segment hard segment
styrene block copolymer, thermoplastic
polyurethane (TPU), poly (ether ester) block copolymer (COPE), poly (ether amide) block
copolymer (COPA)
hard segment TPE
. . 2005 Peng Abetz [37]
polybutadiene 3
polybutadiene ( epoxidation)
( ring-opening) sulfonyl isocyanate
( sulfonyl isocyanate addition)
sulfonyl isocyanate hard segment
36
graft copolymer
polybutadiene sulfonyl urethane
1H-NMR, FTIR, DSC, DMA sulfonyl urethane
polybutadiene
polybutadiene thermo-reversible
crosslinking rubber TPE
polybutadiene
2.2.4
TPE
TPO TPV ( EA)
thermoplastic polyurethane (TPU), styrenic block copolymer, poly (ether ester) block
copolymer, poly (ether amide) block copolymer
TPE styrenic block
copolymer polystyrene (PS) hard segment soft segment
polybutadiene, poly (ethylene-propylene),
poly (ethylene-butylene), hydrogenated polyisoprene TPE
soft segment TPE
TPE
TPE
Thermoplastic polyurethane (TPU) TPE
TPE TPU
polyurethane (PU) hard segment polyester polyether
soft segment TPU
37
(TPU polyester) (TPU
polyether) TPU
thermoplastic copolyester
(COPE) thermoplastic copolyamide (COPA) hard segment
polyester polyamide TPE polyether soft
segment COPE
(creep) (fatigue)
COPE TPE COPA
(dynamic properties)
COPA TPE
TPE
TPE TPO TPV
(
polyolefin PP, PE) ( NR, EPDM)
TPO crosslink TPV crosslink
TPE
(grip),
(knob), (gasket)
38
2.3 (Thermoplastic Elastomer with
Natural Rubber; TPNR)
TPE
(compound)
TPE (reactive blending)
(twin-screw extrusion)
(internal mixer) TPE (phase)
TPE
TPE
TPE
TPE
TPE
39
[38]
16 [38]
2.3.1
TPE
NR/PP [39], NR/HDPE [40], NR/LLDPE [41]
(immisible blend)
compatibilizer
block
graft copolymer compatibilizer
Oommen Thomas [42] TPE
NR/ PMMA
natural rubber-g-poly (methyl methacrylate) (NR-g-PMMA) 10%
tensile strength 150% melt blending
230% solution blending tear strength Izod impact strength
40
graft copolymer
graft copolymer 10% compatibilizer
TPE
interphase
compatibilizer (phase
modification) TPE
Ibrahim [40, 41] liquid natural rubber (LNR)
compatibilizer NR/PP, NR/HDPE, NR/LLDPE
(LNR
LNR ) LNR ( –OH )
interaction
epoxidized natural rubber (ENR)
NR/PE
ENR maleic anhydride-graft-polyethylene (MA-g-PE) ( maleic modified PE)
tensile strength compatibilizer
NR/PP
ENR maleic modified PP tensile strength
NR/PP PP [39]
2.3.2
TPE segmented
copolymer
soft segment
hard
segement Ravindran [43]
(hydroxyl-terminated liquid natural rubber; HTNR)
hydrogen peroxide photochemical
depolymerization hydroxylation TPE
block copolymer Ravindran [44] block
41
copolymer HTNR poly (ethylene oxide) (PEO) toluene2,4-diisocyanate (TDI)
coupling agent HTNR
PEO
PEO TPE
(rubber-toughened plastic)
morphology
soft segment hard segment
Paul Nair TPE HTNR
polyurethane (PU) hard segment propylene
glycol-toluene diisocyanate (TDI) oligomer [45], 1,3-butanediol-TDI oligomer [46],
bisphenol A-TDI oligomer [47] PU hard segment
rigid
morphology Tg
DSC DMA hard segment
Ravindran hard
segment TPE
morphology
2.4
TPE TPE
TPE
( , shaping, vulcanization,
(scrap) ) TPE
TPE TPE
TPE
42
TPE
soft hard segment
TPE
TPE TPE
TPE TPE
(Tm)
crosslink
(Td)
TPE TPE TPE
( )
TPE
TPE
2
1. 1.
2. 2.
3.
3.
4.
4.
compression set (
)
5.
5.
6.
TPEs
6.
43
3
3.1
1. High ammonia natural rubber latex (60% DRC)
2. Polyoxyethylene (40) nonylphenyl ether [Igepal CO-890: Sigma-Aldrich, U.S.A.]
3. 98% Formic acid [UNIVAR: Merck, Germany]
4. 30% Hydrogen peroxide (UNILAB: Ajax Fine Finechem)
5. 99.5% Methanol (commercial grade: Union Intraco Co., Ltd.)
6. 98% Sulfuric acid (analytical reagent grade: Labscan Asia Co., Ltd.)
7. Sodium hydroxide [reagent grade: Ajax Fine Finechem]
8. Ammonium hydroxide [reagent grade: Mallinckrodt Baker, Inc.]
9. para-Toluenesulfonyl isocyanate (technical, 96% (HPLC): Sigma-Aldrich, U.S.A)
10. Silica gel [70-230 mesh ASTM: Merck, Germany]
11. Chloroform [analytical reagent grade]
12. Deuterated chloroform [Wilmad Labglass]
13. Distillate water
3.2
1. 3-Necked round bottom flask
2. Conical flask
3. Beaker
4. Pressure equalizing dropping funnel
5. Buckner funnel
6. Condenser
7. Conical flask with joint
8. Clamp/Clamp holder
44
9. Suction flask
10. Pipette
11. Burette
12. Hot plate with stirrer
13. Magnetic bar
14. 14. Mechanical stirrer
15. Stopper
16. Stirring rod
17. Thermometer
18. Vacuum oven with pump
19. Dropper
20. Water bath with temperature controller
21. pH indicator paper
22. Filter paper
23. Vial tube
24. Spatula
3.3
1. Differential scanning calorimeter (Mettler Toledo: DSC1, Switzerland)
2. Fourier transform infrared spectrometer (Bruker Optik GmbH: Vertex70, Germany)
3. Nuclear magnetic resonance spectrometer (Bruker: 300 Ultrasheild, Germany)
4. Thermogravimetric analyzer (Mettler Toledo: TGA/DSC1, Switzerland)
5. Dynamic mechanical analyzer (Mettler Toledo: SDTA861e, Switzerland)
6. Scanning electron Microscope (CamScan: MX-2000, England)
45
3.4
3 (1)
(ENR) (2) ENR
(-NH2) 2 (diamino compond) ENR latex
NH4OH, H2SO4, NaOH, NH4OH (3) p-toluenesulfonyl isocyanate
(PTSI) hard segment –NH2
3 17
hard segment
epoxidation ENR
epoxidation reagent (formic acid hydrogen
peroxide) ENR
reagent (HCOOH H2O2) epoxidation
epoxidation 8 epoxidation
reagent ( ) ENR
“NR” “low-ENR”, “med-ENR”, “high-ENR” ENR
(45% reagent), (75% reagent), (90% reagent)
“low-NR-NH2”, “med-NR-NH2”, “high-NR-NH2” ENR
2
“low-NR-PTSU”, “med-NR-PTSU”, “high-NR-PTSU”
ENR
PTSI
46
C CH
CH2 H2C *
H3C
*n
HCOOH+H2O
2
8 hr, 60 C
C CH
CH2 H2C CH2
H3C
*
O
C CH
CH2 *
H3C
n-xNR ENR
x
NH4OH (T
room; 10 days)
C CH
CH2 H2C CH2
H3C
*
C CH
H2C
H3C
x-yy
NH2 NH2 NH2NH2
CH2
C CH
H2C *
H3C
n-x
1.2x S NCOO
OH3C 24 hr, T
room
C CH
CH2 H2C CH2
H3C
*
C CH
H2C
H3C
x-yy
NH
CH2
C CH
H2C *
H3C
n-xNHNH
HN
SNHO
OCH3C
O
SNHO
OCH3C
O
SHN
O
OH3C C
SHN
O
OH3C
O
C
O
NR-PTSI
silica gel (70-230 mesh)
C CH
CH2 H2C CH2
H3C
*
C CH
H2C
H3C
x-yy
OH NH2 NH2OH
CH2
C CH
H2C *
H3C
n-x
1,2-amino alcohol
1,2-diamine
1. H2SO
4(60 C, 2 days)
2. NaOH (60 C, 3 days)
3. NH4OH (60 C, 5 days)
4. silica gel (70-230 mesh)
17
47
3.4.1 (Epoxidized natural rubber; ENR)
ENR (NR latex)
60% (dry rubber content; DRC) 84 conical flask
250 ml 30% (DRC)
non-ionic surfactant (Igepal CO-890) 2.5000 (5 phr)
84 ml stir 24
3
500 ml 98% HCOOH ( 3)
pressure equalizing dropping funnel stir
60 C reflux
condenser 3
30% H2O2 ( 3) pressure equalizing dropping funnel
( 20-30 / ) stir
8 sampling ENR latex
methanol
surfactant
ENR FT-IR 1H-NMR
3.4.2 ENR
3.4.2.1 1,2-amino alcohol
ENR ENR
latex 3 2000 ml
silica gel (70-230 mesh)
5.0000 (10% ) stir
30 (NH4OH)
700 ml (15 moles/isoprene unit) (10-15 C) pressure equalizing
dropping funnel stir mechanical stirrer
reflux 3 condenser 10
sampling 1,2-amino alcohol
48
60 C 1
methanol
FT-IR 1H-NMR
3.4.2.2 1,2-diamine
ENR
(-NH2) 2 1,2-amino alcohol latex
(centrifuge) (silica gel)
stir
1000 ml 1
( pH 10 8) 3
2000 ml (98% H2SO4) 5 M
pH 4
60 C reflux condenser
stir mechanical stirrer 2
NaOH pH 10 stir
mechanical stirrer 3 silica gel
(70-230 mesh) 5.0000 (10%wt) stir 30
NH4OH 700 ml (15 moles/isoprene unit)
pressure equalizing dropping funnel stir 60 C
mechanical stirrer reflux 5
centrifuge (silica gel)
stir 1
60 C 2
methanol
methanol
49
FT-IR 1H-NMR
3
reagent ENR NH4OH
/1 isoprene
unit H2O2/ 1
isoprene unit
HCOOH/
1 isoprene unit
low-ENR
(ENR-45%)
1.35
(3.82 ml)
0.135
(94.00 ml)
15
(700 ml)
med-ENR
(ENR-75%)
1.50
(4.25 ml)
0.150
(104.50 ml)
15
(700 ml)
high-ENR
(ENR-90%)
2.25
(6.40 ml)
0.225
(156.70 ml)
15
(700 ml)
3.4.3 (hard segment)
p-toluene sulfonyl isocyanate (PTSI)
hard segment amine group
(-NH2) ENR 1,2-diamine
( ) stir conical flask 500 ml
PTSI 1.2 moles/isoprene unit
stir PTSI
flask 24
methanol methanol
PTSI
FT-IR 1H-NMR
50
3.4.4
FT-IR 1H-NMR FT-IR
Fourier Transform Infrared Spectrophotometer Bruker Vertex70 ( 18)
TR 4000-600 cm-1
(resolution) 1 cm-1 1H-NMR Nuclear
Magnetic Resonance Spectrometer Bruker 300 Ultrasheild ( 19)
deuterated chloroform (CDCl3) tetramethylsilane (TMS)
18 Fourier Transform Infrared Spectrophotometer (Bruker Vertex70)
19 Nuclear Magnetic Resonance Spectrometer (Bruker 300 Ultrasheild)
51
3.4.5 (Thermal properties)
TGA DSC
Thermogravimetric analyzer TGA/DSC1 ( 20 a)
35 C 700 C
10 C/min (thermal transition)
Differential scanning calorimeter DSC1 ( 20 b) -85 C
100 C 10 C/min
2 (heat-cool-heat) thermal history
-85 C
100 C -85 C 100 C
20 (a) Thermogravimetric Analyzer (TGA/DSC1, Mettler Toledo, Switzerland),
(b) Differential Scanning Calorimeter (DSC1, Mettler Toledo, Switzerland)
(a) (b)
52
3.4.6 (Dynamic mechanical testing)
3.4.6.1
DMA
NR, ENR TPE
compression molding
5-7 mm 1-1.5 mm
3 stage hold 100 C 5,000 10
15,000 5 20,000
5
21 compression molding
22
53
3.4.6.2 Dynamic Mechanical Analyzing
-
5-7 1-1.5
- shear mode 5 Hz force
amplitude 5 N displacement amplitude 10 um -100 C
100 C 10 C/min
23 Dynamic Mechanical analyzer (SDTA861e, Mettler Toledo)
3.4.7
NR, ENR
TPE SEM
slit
SEM
30 100,
500, 1,000 15 kV
54
24 Scanning Electron Microscope (MX-2000, CamScan)
55
4
4.1 FT-IR 1H-NMR
4.1.1 (epoxidized natural rubber, ENR)
(ENR)
(HCOOH) (H2O2)
epoxidation 8 epoxidation
reagent ( ) ENR
25 FT-IR spectra (NR) ENR
FT-IR TR 3285, 2962, 2856,
1663, 1535, 1447, 1372 830 cm-1 stretching O-H N-H
( amide ), C-H stretching (-CH3), C-H
stretching (-CH2), C=C stretching, N-H (2 vibration), C-H bending (-CH2), C-H bending (-CH3),
C=C bending in-situ
epoxidation formic acid hydrogen peroxide
1,250 cm-1 870 cm-1
(symmetric stretching) (asymmetric stretching)
ENR 870 cm-1
830 cm-1 reagent
ENR
reagent isoprene unit
4
56
25 FT-IR spectrum (NR) ENR 3
epoxidation 17
H2O2 cure H2O2
oxidizing agent formic acid
ENR ENR 3
ENR cure H2O2
57
1H-NMR ( 26)
ENR
1H-NMR spectrum ENR 5.1 2.7 ppm
(vinylic proton) ENR
(oxirane proton) 1H-NMR spectrum NR
5.1 ppm 2.7 ppm
1.30, 1.58, 1.70, 2.05, 2.17 ppm methyl proton, methylene
proton ENR methyl proton, methylene proton
( ) ENR
1H-NMR spectra 2.7 5.1 ppm
(mole %) = 1001.57.2
7.2
III
7.2I 1.5I 1H-NMR spectra ENR 2.7 5.1 ppm
ENR reagent
3 high-ENR, med-ENR, low-ENR 45.36,
33.77, 20.00 mol%
4 NR ENR 3
1H-NMR spectra 2.7 ppm 5.1 ppm
1H-NMR spectrum
(mole %) I5.1 I2.7
NR 0 n/a 0
low-ENR 1.00 0.25 20.00
med-ENR 1.00 0.51 33.77
high-ENR 1.00 0.83 45.36
58
FT-IR
1H-NMR
(ENR)
26 1H-NMR spectrum (a) NR, (b) low-ENR, (c) med-ENR, (d) high-ENR
(d)
(c)
(b)
(a)
c
ba
c g
a
b e f
d
59
4.1.2 ENR
4.1.2.1 1,2-amino alcohol
1,2-amino alcohol
(NH4OH) nucleophilic reagent
silica gel 70-230 mesh
FT-IR 1H-NMR 27 FT-IR spectra
ENR ENR
1,2-amino alcohol 3,485-3,270 cm-1, 1,600-1,585
cm-1, 1,100 cm-1 stretching O-H N-H
(primary amines) bending N-H stretching
C-N
27 FT-IR spectrum 1,2-amino alcohol ENR 3
60
1H-NMR ( 28)
1H-NMR spectrum 1,2-amino alcohol
ENR 1.30, 1.50-1.60, 2.0, 2.7, 3.6-3.8 ppm
methyl proton [-CCH3-(OH)-CH(NH2)-], methylene proton [-CH2-CCH3(OH)-
CH(NH2)-CH2-] , amine proton (-NH2), methine proton
[-C-CH (NH2)], alcohol proton [-OH]
ENR (-OH) (-NH2)
-C-C-
silica gel (70-230 mesh)
2 (H+) silica gel Lewis acid
protonate (O) ( )
NH4OH
2 NH3 NH4OH attack
(-C-CH3) (-CH)
NH3 attack
–OH attack
NH3 methine
proton 2.7 ppm NH3
attack
61
28 1H-NMR spectrum (a) high-1,2-amino alcohol, (b) medium-1,2-amino alcohol,
(c) low-1,2-amino alcohol
(a)
(b)
(c)
c ng, m d
a, i
bf
e, h, j
62
4.1.2.2 1,2-diamine
diamine
1,2-amino alcohol
silica gel 29
FT-IR spectra diamine ENR
1,100 cm-1 stretching C-N 2
1,2-amino alcohol 1,250 cm-1
(symmetric stretching)
C-N C-N 2
( 5) imine diamine (-NH2)
1 2
ENR 1,2-amino alcohol diamine
FT-IR spectrum
870 cm-1
(asymmetric stretching)
29 FT-IR spectrum 1,2-diamine ENR 3
63
30 1H-NMR spectrum (a) low-NR-NH2, (b) med-NR-NH2, (c) high-NR-NH2
(c)
(b)
(a)
c g, m
a, i
d
b f
e, h, j
64
5 1,2-amino alcohol 1,2-diamine
ENR absorbance FT-IR spectra
A1100 (C-N stretch) /A1450 (CH3 bend) mole %
1,2-amino alcohol 1,2-diamine
high-ENR 37.98 62.36
med-ENR 33.86 57.28
low-ENR 29.56 54.31
1H-NMR ( 30)
1H-NMR spectrum 1,2-diamine
ENR 1.30, 1.50-1.60, 2.0, 2.7 ppm
methyl proton [-CCH3-(NH2)-CH(NH2)-], methylene proton [-CH2-CCH3(NH2)-CH(NH2)-CH2-]
, amine proton (-NH2), methine proton [-C-CH (NH2)]
2.0 2.7 ppm 1,2-diamine 1,2-amino alcohol
3.7 ppm
4.1.2 hard segment
diamine
solf segment para-toluenesulfonyl isocyanate (PTSI) hard
segment thermoplastic elastomer (TPE) PTSI
–NH2 2 ENR
(-NH-CO-NH-SO2-)
FT-IR 1H-NMR
FT-IR TPE 31
3,250 cm-1 ( ) stretching N-H
1,750 cm-1, 1,350 cm-1 1,160 cm-1
stretching C=O isocyanate (O=C=N)
(-NH2) urea-linkage S=O PTSI
65
S=O
hard segment (
) 1,356 (low-NR-PTSI), 1,349 (med-NR-PTSI),
1,349 cm-1
S=O H-N Peng Abetz [37]
C=O C=O H-N
C=O
1,750 (low-NR-PTSI),
1,747 (med-NR-PTSI), 1,744 (high-NR-PTSI)
1,640-1,600 cm-1 stretching C=C ( NR ),
C=C ( aromatic) N-H bending
860-580 cm-1 C=C
aromatic
31 FT-IR spectrum TPE ENR 3
66
32 1H-NMR spectrum (a) low-NR-PTSI, (b) med-NR-PTSI, (c) high-NR-PTSI
(a)
(b)
(c)
c qp
v
a
e
b, d
fs t
67
1H-NMR
32 1H-NMR spectra TPE p-toluenesulfohyl
isocyanate (PTSI) hard segment
1,2-diamino compound
(methyl proton) (2.45 ppm)
urea-linkage (methine proton) isocyanate
(4.17 ppm), (4.76 ppm)
(7.33 7.91 ppm) FT-IR 1H-NMR
isocyanate hard segment
1,2-diamino compound
[-NH-CO-NH-SO2-]
6 hard segment 1H-NMR TGA
Epoxide content
(mole %)
1H-NMR
I7.90ppm/I2.04ppm
(moel %)
I7.33 ppm /I2.04 ppm
(mole %)
I2.45ppm/I2.04ppm
(mole %)
low-ENR 20.00 23.90 20.41 20.32
med-ENR 33.77 40.98 33.33 46.30
high-ENR 45.36 49.40 40.23 53.76
4.2
4.2.1 TGA
TGA
33 (NR) ENR
(one-step decomposition) 384 C
ENR 3
387°C, 392°C, 394°C low-ENR
68
med-ENR high-ENR
10 C ENR
ENR
TPE
34 TGA themogram TPEs 3
2 (two-step decomposition) ( )
(-NH-CO-NH-SO2-) hard segment
240-320 C
hard segment (PTSI)
( 7)
[-NH-CO-NH-]
33 TGA thermogram (NR) ENR 3
69
34 TGA thermogram TPEs 3
TPEs
3 hard segment (PTSI)
1H-NMR
hard segment
soft segment
( )
soft segment
350-500 C [48]
TPE soft segment
p-toluenesulfonyl isocyanate (PTSI) hard segment
( )
( )
TPEs
ENRs ( 35)
hard segment
hard segment
70
(physical crosslink)
high-NR-PTSI
35 TGA thermogram NR, ENRs, TPEs
7 thermal decomposition
( C)
Weight loss (%) Onset Inflection point End set
NR 286.7 384.3 493.6 100.00
low-ENR 338.8 387.4 474.2 98.87
med-ENR 349.1 393.6 483.0 100.00
high-ENR 358.0 393.0 478.4 99.02
low-NR-PTSI 246.4
(1st)
341.7
(2nd)
291.4
(1st)
425.0
(2nd)
321.3
(1st)
473.3
(2nd)
34.84
(1st)
65.16
(2nd)
med-NR-PTSI 249.7
(1st)
355.9
(2nd)
297.0
(1st)
423.0
(2nd)
320.8
(1st)
462.3
(2nd)
62.20
(1st)
37.80
(2nd)
high-NR-PTSI 244.0
(1st)
360.7
(2nd)
294.4
(1st)
418.5
(2nd)
325.80
(1st)
457.0
(2nd)
65.16
(1st)
34.84
(2nd)
: (% weight loss) residue
71
4.2.2 DSC
36 DSC thermogram
(NR) glass transition temperature (Tg)
-64.8 C epoxidation ENR 3
Tg Tg low-ENR,
med-ENR, high-ENR -52.2, -36.3, -28.4 C
ENR 3
PTSI low-NR-PTSI, med-NR-PTSI, high-NR-PTSI
Tg -6.2, 12.0, 23.6 C
36 DSC thermogram (NR), ENR, TPE
72
DSC
ENR 3
PTSI hard segment Tg
hard segment
[-NH-CO-NH-SO2-]
(stiff)
Tg hard segment
DSC
hard segment TPE block
copolymer hard segment Tm
hard segment PTSI
4.3
(morphology)
(fracture surface) SEM 37 SEM
micrograph ENR 500
ENR
(continuous phase) (homogeneous)
73
37 SEM micrographs a) natural rubber, b) low-ENR, c) med-ENR, d) high-ENR
500
TPE
ENR 500 38 SEM
micrographs TPE
2 (soft segment)
hard domains
hard segment (agglomerate)
1,000 ( 39)
hard segment
hard segment ( )
( )
a b
c d
74
(two phase separation)
2 (two-stage decomposition) TGA
38 SEM micrographs a) low-NR-PTSI, b) med-NR-PTSI, c) high-NR-PTSI
500
SEM
hard segment
phase-separated
TGA TPE
2 (two-stage decomposition)
a b
c
75
39 SEM micrographs a) low-NR-PTSI, b) med-NR-PTSI, c) high-NR-PTSI
1000
4.4 Dynamic mechanical analysis (DMA)
DMA
5 Hz -100°C 100°C 40-43
40 storage modulus (G ) G
(
) stiffness
(-90 C -70 C) G (NR)
(ENR) (TPE) G
a b
c
76
2
( Tg)
free volume
ENRs TPEs
G ENRs
NR
free volume NR
G TPEs G TPE
(free volume )
G
( ) G TPEs ENRs
G G NR ENRs
1 MPa (rubber state)
( ) free volume NR ENRs
side
chain main chain [49] NR
G (
Tg) ENRs G NR
dipole-
dipole interaction free volume ENRs
NR
( glassy state ENRs NR) TPEs
stiffness NR ENRs TPEs
77
hard domains
physical crosslink soft segment (rubber phase)
soft segment
free volume TPEs
G TPEs NR ENRs
40 storage modulus (G )
G ENRs 41
8 ( -80 C) high-ENR G
low-ENR G high-ERN med-ENR G
high-ENR
dipole-dipole interaction
free volume
G low-ENR
78
(free volume
)
G high-ENR
med-ENR G
high-ENR
high-ENR
low-ENR G
G
ENR G
G
41 Storage modulus (G ) ENRs
79
G TPEs 42 8
( -80 C -20 C) low-NR-PTSI G
med-NR-PTSI high-NR-PTSI G
(free volume )
hard segment
hard segment
low-NR-PTSI hard segment
stiffness
G
high-NR-PTSI hard segment
(free volume )
G
( 25 C) med-NR-PTSI G high-NR-PTSI
low-NR-PTSI G med high-NR-PTSI hard
segment
( physical crosslink ) hard segment
crosslink
hard domains stiffness TPE G
[50] med-NR-PTSI G high-NR-PTSI
high-NR-PTSI
2
G low-NR-PTSI hard
segment
(physical crosslink )
G TPEs
G
low-NR-PTSI hard segment G
physical crosslink hard domains
80
high-NR-PTSI G
med-NR-PTSI crosslink
G
( 50 C) 8 G
TPEs high-NR-PTSI G
med-NR-PTSI low-NR-PTSI G
(physical crosslink) hard segment
soft segment
hard segment G
high-NR-PTSI low-NR-PTSI
hard segment G
42 Storage modulus (G ) NR TPEs
81
43 tan
DSC tan DMA Tg
G
(structural material)
glass transition
tan
Tg
-52.00°C ENR tan
Tg -43.20, -28.83,
-19.37°C TPEs tan
ENR 7.57, 54.16,
52.17°C
hard segment
hard domains
soft segment Tg TPEs
[50] hard segment high-NR-PTSI
transition 2 tan 2
transition relax ( )
transition (hard segment)
relax
82
43 tan
8 (dynamic mechanical properties)
Samples Tg (oC) G at -80°C
(MPa)
G at Tg
(MPa)
G at 25°C
(MPa)
G at 50°C
(MPa)
NR -52.0 1129 179 0.8 0.7
low-ENR -43.2 791 230 1.0 0.9
med-ENR -28.8 543 209 0.9 0.8
high-ENR -19.9 901 214 1.1 0.9
low-NR-PTSI 7.6 436 16 12.1 1.2
med-NR-PTSI 54.2 75 12 47.1 1.4
high-NR-PTSI 52.2 22 10 13.5 2.3
83
5
5.1
(thermo-reversible)
3
2
diamino compound hard segment
para-toluenesulfonyl isocyanate (PTSI)
hard segment 3 (mol%)
ENR 3 low-ENR (20.00 mol%), med-ENR (33.77 mol%),
high-ENR (45.36 mol%) hard segment
ENR
FT-IR 1H-NMR
FT-IR
S=O hard segment
hard segment 1H-NMR isocyanate
(-NH-CO-NH-SO2-)
DSC
Tg ENR
Tg hard segment -6.2, 12.0, 23.6 C
TGA
84
2
240-320°C
hard segment
350-500 C soft segment
two-step decomposition
2 (phase
separated) SEM
2
hard domain (continuous
phase) storage modulus (G ) tan
hard
segment thermo-reversible
5.2
ENR
hard segment
ENR
hard segment
H2SO4
(% yield)
hard segment
ENR
10-30 mol%
hard segment
compression molding
85
2
hard segment
physical crosslink
thermo-reversible
hard segment
hard segment
hard segment
86
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92
FT-IR spectra
93
44 FT-IR spectrum (NR)
45 FT-IR spectrum ENR low-ENR
94
46 FT-IR spectrum ENR med-ENR
47 FT-IR spectrum ENR high-ENR
95
48 FT-IR spectrum low-1,2-amino alcohol
49 FT-IR spectrum med-1,2-amino alcohol
96
50 FT-IR spectrum high-1,2-amino alcohol
51 FT-IR spectrum low-1,2-diamine
97
52 FT-IR spectrum med-1,2-diamine
53 FT-IR spectrum high-1,2-diamine
98
54 FT-IR spectrum low-NR-PTSI
55 FT-IR spectrum med-NR-PTSI
99
56 FT-IR spectrum high-NR-PTSI
1H-NMR spectrum
101
57 1H-NMR spectrum (NR)
58 1H-NMR spectrum low-ENR
102
59 1H-NMR spectrum med-ENR
60 1H-NMR spectrum high-ENR
103
61 1H-NMR spectrum low-1,2-amino alcohol
62 1H-NMR spectrum med-1,2-amino alcohol
104
63 1H-NMR spectrum high-1,2-amino alcohol
64 1H-NMR spectrum low-1,2-diamine
105
65 1H-NMR spectrum med-1,2-diamine
66 1H-NMR spectrum high-1,2-diamine
106
67 1H-NMR spectrum low-NR-PTSI
68 1H-NMR spectrum med-NR-PTSI
107
69 1H-NMR spectrum high-NR-PTSI
TGA DTG thermogram
109
70 TGA thermogram
71 TGA thermogram low-ENR
110
72 TGA thermogram med-ENR
73 TGA thermogram high-ENR
111
74 TGA thermogram low-1,2-amino alcohol
75 TGA thermogram med-1,2-amino alcohol
112
76 TGA thermogram high-1,2-amino alcohol
77 TGA thermogram low-1,2-diamine
113
78 TGA thermogram med-1,2-diamine
79 TGA thermogram high-1,2-diamine
114
80 TGA thermogram low-NR-PTSI
81 TGA thermogram med-NR-PTSI
115
82 TGA thermogram high-NR-PTSI
DSC thermogram
117
83 DSC thermogram (NR)
84 DSC thermogram low-ENR
118
85 DSC thermogram med-ENR
86 DSC thermogram high-ENR
119
87 DSC thermogram low-1,2-amino alcohol
88 DSC thermogram med-1,2-amino alcohol
120
89 DSC thermogram high-1,2-amino alcohol
90 DSC thermogram low-1,2-diamine
121
91 DSC thermogram med-1,2-diamine
92 DSC thermogram high-1,2-diamine
122
93 DSC thermogram low-NR-PTSI
94 DSC thermogram med-NR-PTSI
123
95 DSC thermogram high-NR-PTSI
DMA thermogram
125
96 DMA thermogram (NR)
97 DMA thermogram low-ENR
G
G
Tan
G
G
Tan
126
98 DMA thermogram med-ENR
99 DMA thermogram high-ENR
G
G
G
Tan
Tan
G
127
100 DMA thermogram low-NR-PTSI
101 DMA thermogram med-NR-PTSI
G
G
Tan
G
G
Tan
128
102 DMA thermogram high-NR-PTSI
G
G
Tan
129
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59/1 6
80130
(089) 173-0784
E-mail address [email protected]
. . 2547 -
. . 2551
. . 2551
. . 2551-2553
1. Pensri Anurak, Wanchai Lerdwijitjarud, and Amnard Sittattrakul, “Effect of Catalyst
Types on The Ring-Opening Reaction of Epoxidized Natural Rubber in Latex Form”,
The 1st National Research Symposium on Petroleum, Petrochemicals, and Advanced Materials
and The 16th PPC Symposium on Petroleum, Petrochemicals, and Polymer, April 22, 2010,
Bangkok, Thailand.