Upload
dinhbao
View
266
Download
11
Embed Size (px)
Citation preview
Nanostrength® :
- Copolymères acryliques nanostructurés
- Technologie et applications
LIEU Innov’days / DijonNOM DE L’INTERVENANT Jean- Marc BOUTILLIERDATE 22 Novembre 2012
Plan de la présentation :
Nanostrength dans Arkema
Présentation des Nanostrength
Technologie utilisée pour Nanostrength
Exemples d’applications
Plan de la présentation :
����Nanostrength dans Arkema
Présentation des Nanostrength
Technologie utilisée pour Nanostrength
Exemples d’applications
Arkema Introduction : Three business segments
4
Global and integrated industrial niches
Solutions for decorative paints, industrial coatings and high-growth acrylic applications
World of high value and innovative solutions
Downstream
● Thiochemicals
● Fluorogases● Altuglas International
● Hydrogen peroxide
● Acrylic monomers
● Coating resins● Sartomer
● Coatex
● Specialty polyamides
● Fluoropolymers● CECA
● Functional additives
Industrial Specialties Coating Solutions High Performance Materials
Innovation is the heart of Arkema’s strategy
5
10 research centers
€150 m allocated to R&D
1,200 researchers
Coating Solutions
Carling
Coating Solutions
Verneuil
Coating Solutions
Genay (Coatex)
Pierre-Bénite Changshu (end 2012)
Industrial Specialties
Lacq
Coating Solutions
Cary
Industrial Specialties
High Performance Materials
Industrial Specialties
King of Prussia
High Performance Materials
Industrial Specialties
Serquigny
High Performance Materials
Kyoto
High Performance Materials
ARKEMA Incubator platform : A new Business Unit launched in 2008 dedicated to New products
4 departments :
�Carbon Nanotubes� Graphistrength ®
10 nm
�Nanostructured polymers and initiators�Nanostrength ®, BlocBuilder ®, Flexibloc ®
�customised polymers
•Technical Polymer : • Kepstan ®
• Grafted copolymer : • Apolhya ®
Plan de la présentation :
Nanostrength dans Arkema
����Présentation des Nanostrength
Technologie utilisée pour Nanostrength
Exemples d’applications
8
Nanostrength : What is it ? Why Nanostructured ?
Nanostrength = Acrylic block copolymers
8
Incompatibility between blocks � organization at the nanometer scale
Diblockcopolymer
ABA triblockcopolymer
ABC triblockcopolymer
Block copolymers
9
Nanostrength : Why acrylic ?
Very broad range of monomers :
9
O
OH
AA
O
OH
MAA
O
OO
PEGMA
n
O
OOH
HEMA
Main Skeleton :Alkyl Acrylate:
R= n or t-Bu, Et, Me,Lauryl, Methoxyethyl…
Ex : Polybutylacrylate
O
OR
O
OR
Alkyl Methacrylate:R= Bu, Et, Me, …
Ex : PMMA
Specialty/Functional Monomers :
O
NR2
R = Alkyl(DMA, ...)
O
OO
GMA
O OO
MAHMAH
O
ONH
TBAEMA
Nanostrength : Acrylic Block Copolymers
PMMA -b- poly(Butyl Acrylate) -b- PMMA
Triblock with Functional groups (amide, acid,
OH…) in the hard blocks and/or in the soft block
M A MM A MM A MM A MM A MHard Soft Hard
• Nanostrength “MAM” :
• Nanostrength “MAM” Functionalized :
Functionalization � to increase special properties� to improve the compatibility with some polymers� to introduce a reactive site
Structure / Properties relationship of Nanostrength
FunctionalizationComposition control
Property compromise• Impact / Transparency• Impact / Thermal properties• Impact / Rigidity• Adhesion / Viscosity• …
Additional Functionalities• Miscibility• Reactivity• Hydrophilicity• Hydrophobicity• …
Nanostructuration of Nanostrength
PMMA and PBA are not compatible : phase separation
● PMMA domains = physical “cross links” � hard phase, cohesion
● PBA domains = soft domains � soft phase, impact
● Thermoplastic behaviour
AFM structure of a PMMA rich M-A-M block
copolymer
AFM structure of a PBa rich M-A-M block copolymer
NANOSTRENGTH : structure – properties relationships
PMMA PBA PMMA
HIGH PMMA CONTENT
PBA / PMMA ratioIn Nanostrength
HIGH PBA CONTENT
Scratch resistanceThermal resistanceRigidityTransparency
ImpactElongation
Flexibility ESCR
Tackiness
low
high
low
high
Nanostrength Product Range
Nanostrength Type
Grade% soft block
Mw Soft block
Functionality
M22 40 low NoRigid M51 50 low NoMAM M52 50 medium No
M53 50 medium NoM55 55 high No
Soft M65 65 high NoMAM M75 70 high No
M85 85 high NoS55M 55 high No
SAS S55M 55 high Acid
M22N 40 medium acrylamid
Functionalized M52N 50 medium acrylamidMAM M75M 70 high Acid
M85M 85 high acid
Diblock MA D51N 50 low acrylamidM1H 85 high PEGMA
M55HM 55 high OH
Development MS53M series 50 low noMS35M series 35 low noMS20M series 20 low no
Plan de la présentation :
Nanostrength dans Arkema
Présentation des Nanostrength
���� Technologie utilisée pour fabriquer les Nanostrength
Exemples d’applications
Nanostrength : based on Blocbuilder technology
PO
O
O
N O
OOH
Controlled Radical Polymerization initiator
Block Copolymers PBAPMMA PMMA
Double Innovation :
● Functionalizable Acrylic block copolymers
● Controlled Radical Polymerisation (CRP)
– Controls nature and length of blocks– Addition of functional co-monomers in hard and/or
soft blocks possible – Bulk, solvent, suspension, emulsion polymerisation
processes are possible
Arkema patented technology
Neat, Blended or dissolved
Nanostructuration
Living PBA
Difunctional acrylateMonomer 1
Monomer 2
SG1
SG1 SG1
Product offer based on BlocBuilder technology
Arkema propose different products based on the Blocbuilder technology :
BlocBuilder : CRP initiator ���� make your copolymers by yourself !
Flexibloc : living polymer ���� Customize your copolymers by yourself !
Nanostrength : copolymer ���� just use it !
Plan de la présentation :
Nanostrength dans Arkema
Présentation des Nanostrength
Technologie utilisée pour Nanostrength
����Exemples d’applications
Examples of applications
Nanostructured PMMA● Very high impact resistance without transparency loss at
high temperature● Very high chemical resistance● Flexible PMMA
Thermoset resins toughening● High impact resistance while keeping Tg and modulus
Structural Adhesives● High performance structural adhesives
Pressure Sensitive Adhesives● New balances of properties for PSA
Nanostrength / Applications
- The French company AEC Polymers has developed an i nnovative range of methacrylic structural adhesives ( SAF® [Strengths Are Flex] ) based on Nanostrength
- Nanostrength leads to high elasticity and superior strength
- Key Properties of SAF adhesives :
- Primer free ; no preparation of the surface to bond ; substrates versatility- High mechanical performance : Strength, elasticity � absorb thermal
expansion and vibration. - Large open time (from 2 min to 2h) followed by a rapid and tunable curing time
For more info: [email protected]
21
Nanostrength for Structural Adhesives : example of AEC P olymers
Traditional Adhesives vs. SAFTraditional Adhesives vs. SAFTraditional Adhesives vs. SAFTraditional Adhesives vs. SAF®®®®
22
2-c PU Epoxy SAF®
primerless adhesion on a wide variety of substrates
Requires surface pretreatment
Requires surface pretreatment
No sandblasting and primer is
needed
modulus <10 N/mm2 >10 N/mm2 2-15 N/mm2
elongation < 150 % < 5% 30 – 400%
bond strength (LSS) 5 – 15 N/mm2 15 – 30 N/mm2 5 – 25 N/mm2
peel strength High Low High
vibration absorption Excellent Poor Excellent
temperature resistance -40oC – 80oC -40oC – 120oC -40oC – 150oC
weather resistance and general durabiliy
Poor Excellent Excellent
shrinkage after cured <1% <1% <1%
density g/cm3 1.2 – 1.4 1.3 – 1.5 0.98 - 1.0
open time Up to 200 mins. Up to 90 mins. 5 – 120 mins.
curing speed Slow in curing, needs 48 hrs for
full cure
Slow in curing, needs 48 hrs for
full cure
Can acheive 80% of full cure within
2 hrs
AEC Polymers SAF structural adhesives based on Nanostre ngth
AEC Polymers SAF structural adhesives based on Nanostrength
Nanostrength for Epoxy Toughening
Affinity between epoxy monomer and PMMA block
Repulsion between epoxy monomer and central block
� Nanoscale dispersion of MAM in the epoxy resin
Hardener
T°°°°C
100%
soluble
DGEBA
MAM
1. Dissolution 2. Process/formulation 3. Curing
PMMA PBA PMMA
• During the curing of the epoxy systems, the soft phase (PABu) phase separates
• The Nanostrength is dispersed at the nanometric scale thanks to the PMMA miscible block until the end of the reaction
• The miscibility of the PMMA block depends on the epoxy-hardener system. A range of Nanostrength with functionalized PMMA blocks (N grades) has been developed in order to keep miscibility in different systems
Nanostrength for Epoxy TougheningNanostrength allows to increase mechanical performance without impairing thermal resistance
Morphology drives the end properties : impact, transparency
Morphology is driven by the nature of blocks
Functionalization of Nanostrength allows to keep transparency of epoxy
Applications : aeronautics, sports, wind energy, …
M22N (functional) gives a miscellar type
morphology for medium impact and
transparency
10% M53 10% M22N
979792Tg (°°°°C)
8803437183GIC (J.m²)
1.542.780,76KIC
(MPa.m0.5)
Pure
Resin
Resin/Hardener system: DGEBA-Jeffamine
M53 (non functional) gives a “spider
web” morphology for very high impact
Nanostrength for Pressure Sensitive Adhesives
Nanostrength for PSA : Adhesive properties
Adhesive properties of Nanostrength in formulation
Substrate: PET film 50 µm
Basic material: stainless steel
DIDA: Di Iso Decyl Adipate
0,2 pIrganox 1010
10 pDIDA
90 – X pKE311 (Arakawa)
X pM85 (85%)
Hot Melt Formulation40
% B
CP
4
50%
BC
P4
The low viscosity of M85 (MFI = 300 @ 190°°°°C/2.16kg) allows the use of high loading in the Hot Melt formulation
MeasurementFINAT test
methodX = 40 X = 50
Weight (g/m²) FTM 12 24.3 25.7
180° Peel (20mn), N/25 mm 25.8 (0.9) 18 (0.2)
Type of failure cohesive Clean plate
180° Peel (24h), N/25 mm 26.3 (0.7) 17.5 (0.8)
Type of failure cohesive Clean plate
Loop Tack (N) FTM 9 23.3 (1.2) 14.4 (1.7)Lap shear, 25x25 mm, 1 Kg
(mn)FTM 8 3870 1980
SAFT 25x25 mm, 1Kg (°C) ASTM 4498 52.2 56.6
Brookfield viscosity (mPa.s) 170°C 1315 2600
Brookfield viscosity (mPa.s) 190°C 700 1300
FTM 1
FTM 1
Values of Nanostrength For PSA
Transparent
UV resistant (acrylic nature)
Fully thermoplastic
Intrinsically tacky
Soft (Tg mid block around –50°°°°C)
Functionalizable
Suitable to Solvent and Hot melt systems
No need to formulate or easy to formulate
Removable without residues
Can be coloured for innovative designs
Good adhesion on polar substrates
Nanostrength For Nanostructured PMMA applications
Controlled Radical Polymerization initiator
Block Copolymers PBAPMMA PMMA
Living PBA
MMAResins for injection molding
and extrusion
Altuglas® Shieldup
Cast sheet for thermoforming
MMA
sheet and resins offer :
Additional values of Nanostrength Vs Classical impact PMMA
+ frosted+ matt+ flame retardant
Flexibility
Fluidity
Low T Process
ability
Aesthetics :
Clarity
Light Transmission
Color depth
Chemical
Resistance
Scratch
Resistance
Very High
Impact
NanostrengthWeathering
Impact
PMMA
No Haze
with T
Nanostrength For Nanostructured PMMA applications
Medium
impact
Soft touch, anti-slip
Altuglas ShieldUp cast sheet : a technical breakthrough
PMMA basic values
ShieldUp PMMA additional values
PMMA
AESTHETICS :•Transparency•Optical distorsion•Color depth
SCRATCH RESISTANCE
WEATHER RESISTANCE
HIGH IMPACT RESISTANCE•Even at low T•Large Impact&
modulus range
NO HAZE WITH
TEMPERATURE
CHEMICAL RESISTANCE
Altuglas ShieldUp : the first impact acrylic which does not become hazy when temperature increases
Typical value: ShieldUp PolycarbonateHaze 0.5% 3%Light transmission 92% 88%
No fracture
Fracture
Fracture
No fracture
ALTUGLAS® SHIELDUP sheet : very high impact resistance
Ball drop test performed under the same conditions
Altuglas ShieldUP : an unmet Chemical Resistance
SCRATCH AND ABRASION RESISTANCE
ClipShield_Master_3.mp4
20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500 3000 3500
Stiffness (Flexural Modulus MPa)
Impa
ct s
tren
gth
U-C
harp
y(k
J/m
²)
Usual range highimpact castsheets
• Cast sheets with unmet impact properties can be made in a large range of modulus• while keeping optical properties and T resistance
Achievablerange withFlexiblocTechnology
A large range of Modulus / Impact balance achievable
ShieldUp
Properties summary of Altuglas ShieldUp
ALTUGLAS® SHIELDUP : typical applications
Thanks to its new balance of properties, Altuglas ShieldUp sheet becomes a new candidate of choice in applications like :
Transport Glazing : Electrical car, licence free car, caravan, motorhome, motorbike windscreen, concept car, boats, aeronautics
Safety Glazing : bulletproof, anti-noise wall, industrial sheet, …
New energies : PV, …
Any application requiring very high chemical resistance
Illustration of industrial applications of Altuglas ® ShieldUp
Peugeot Onyx Concept Car
Peugeot Onyx Concept Car
Peugeot Onyx Concept Car at “Mondial de l’Automobile”
• Key properties of Nanostrength grades for injection moulding and extrusion :
very high impact , flexibility, easy processing, transparency not sensitive to temperature, blendability with PMMA, Soft touch, anti-slip (frosted or matt versions)
• Nanostrength grades under development
2 � 1200.8 - 3MFI ( 230 C/3.8 kg ; g/10’) ISO 1133
88- 9290Light Transmittance (%) ASTM D-1003
2 � 102Haze (%) ASTM D-1003
100 � 25001 700Module (MPa) ISO 178
75 � 105108Vicat 10N (°C) ISO 306A50
20 � 9040Elongation at break (%) ISO 527-2
4 �257Notched Charpy (kJ/m2) ISO 179-1
35 � no break60Un-notched Charpy (kJ/m2) ISO 179-1
Nanostrengthrange
High impact PMMA
(typical values)
Nanostrength For Nanostructured PMMA applications
NoyesHaze with temperature
Conclusions
Arkema has developed a full range of Nanostructured acrylic block copolymers called Nanostrength based on the proprietary Blocbuilder Technology.
Nanostrength materials offer a very wide and tunable balance of properties, leading to performance increase and/or savings.
Nanostrength are used in a large range of applications :
● Structural adhesives ���� Aeronautic, automotive, boats, building, …
● Pressure sensitive adhesives ���� tapes, labels, high performance adhesives, …
● Thermoset thoughening ���� aeronautic, wind energy, sport, composite
● Nanostructured PMMA :
- Sheet : auto glazing, motorbike windscreen, safety glazing, high chemical resistant glazing…
- Resins : auto glazing, auto lighting, lighting, cosmetic, medical, new energies, coextruded sheet…