Les Polymères Nanostructurés d’Arkema
Colloque NanomatériauxOrganisé par le groupe Nano-mines
Paris, 22 septembre 2009
Jean-Pierre DISSON, Responsable Développements EuropeDaniel LEBOUVIER, chef du département Nanopolymères
[email protected], [email protected]
The world is our inspiration
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Lay out of the presentation
Introduction : Arkema investment into Nanotechnologies Access to acrylic polymers having controlled architecture
through living polymerisation Two examples of application
Transparent high impact PMMA sheets Adhesives and thermoplastic elastomers with water abosrption
ability Conclusions
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ARKEMA : innovation through Nanostructured materials
On september 1st 2008, a new Business Unit « New products incubator » has been launched. 3 departments
Nanopolymers and initiatorsNanostrength®, BlocBuilder®, Flexibloc®
customised polymers
Carbon NanotubesGraphistrength®
Supramolecular chemistry
Reverlink®
Driving forces towards Acrylic Block Copolymers
The robustness of Nitroxide Mediated Controlled Radical Polymerisation
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Motivation for acrylic block copolymers
Acrylic polymers known as Exceptionally transparent UV resistant Chemically resistant Easily printable, paintable Taylorable to design adhesives, materials, coatings, additives, etc… Compatible with many polymers
Acrylic monomers offer a large range of functionalised groups
ARKEMA target :Design New Acrylic copolymers of controlled architecture,
using efficient and versatile processes
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Strength of ARKEMA Controlled Radical Polymerisation technology
Based on living polymerisation controlled through a commercial proprietary Nitroxide, BlocBuilder
Applicable to various processes : solvent, mass, emulsion Almost all kind of functionalised acrylic monomers can be
introduced : a great opening to creativitiy
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Achievable structures
PMMA -b- poly(Butyl Acrylate) -b- PMMA
PS -b- poly(Butyl Acrylate) -b- PS
Triblock with Functional groups (amine, alcohol, epoxy, amide, acid, alkoxy, long alkyl…)
Diblock (based on PMMA, PS, functional groups)
Random copolymers with narrow polydispersityAnd controlled chain to chain composition
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From Nanostructuration to « more in one » propertiesCombining in one Polymer monomers with antagonistic properties to
achieve enhanced performances through controlled architecture
MMA/BA, Acid modified MMA/BA,…
adhesives/SoftHard
EADMA/AA/EADMAStress responsive polymers, encapsulation, controlled release
Acid sensitive
Base sensitive
Acid sensitive
Surfactants, Dispersants
Reactive hot melt, polymer compatibiliser, thermosets
Adhesives for humid systems, controlled release
Thermoplastic elastomersAdhesives
Thermoplastic & thermoset toughenersCompatibiliser
Application
St/AA/Hydrophobic
Hydrophilic
ReactiveSoftReactive
PMMA/(BA-AA)/PMMAHydrophobic
Hydrophilic
Hydrophobic
PMMA/BA/PMMAHardSoft (high level)
Hard
PMMA/BA/PMMAHardSoft (low level)
Hard
Typical structureBlock CBlock BBlock A
Two examples of application
PMMA sheets with enhanced optical and mechanical propertiesAdhesives and elastomers with water absorption capability
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1) New types of clear, high impact acrylic materials
200 nm
crazing cavitationClassical high impact PMMA modified with core shell particles
High impact PMMA modified with Acrylic block copolymers : Nanostructure
Consequences of the Nanostructuration ?
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1) New types of clear, high impact acrylic materials
20
30
40
50
60
70
80
90
0 500 1000 1500 2000 2500 3000 3500Flexural Modulus (MPa)
Impa
ct s
tren
gth
U-C
harp
y (k
J/m
²)
Usual range high impact cast sheets
Usual range high impact extruded sheets
Achievable range with Block Copolymers
Increase BAcontent
Cast sheets with unmet impact properties can be madeOptical and chemical properties of cast sheets are keptNo haze versus T°, Vicat 105-110°C even at low modulus
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1) New types of clear, high impact acrylic materials
Main advantage versus classical core-shell high impact PMMA: Excellent optical stability (no haze versus temperature)Excellent solvent resistance (> standard cast sheets)
0
5
10
15
20
25
10 20 30 40 50 60 70 80 90 100 110Temperature (°C)
Haz
e %
Particles technology
Block copolymer technologyCI30
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1) New types of clear, high impact acrylic materials
Two PMMA cast sheets heated at 60°C and positionned over a picture.•Standard “High impact” cast sheet on the left•Nanostructured cat sheet on the right
Example of application : Lightweight sunroof for automobileExcellent transparencyExcellent UV stabilityWeight saving versus glassHigh impactLarge dimensions achievable
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2) Adhesives and elastomers with water absorption capability
Acrylic block copolymers with high amount of soft phase Elastomeric behaviour Adhesive properties (inherent tack) : hot melt Combined with usual benefits of acrylics : UV resistance,
transparency, oil resistance,… Hydrophilic monomers can be introduced in either mid or end
blocks to provide water absorption properties Opportunities :
“Hot melt elastomeric adhesives” : would provide the polarity and water absorption not offered today by SIS resin
New thermoplastic elastomers with water absorption properties
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2) Adhesives and elastomers with water absorption capability
Principle of action : hydrophobic blocks maintain structuration while hydrophilic ones provide water absorption
Illustration in the case of hydrophilic monomer added to the soft mid block :
Soft & Hydrophilic Segment
Hard & HydrophobicSegments
nanostructuration
Swell w/ water
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2) Adhesives and elastomers with water absorption capability
Fields of application under investigation : adhesives in contact to skin, cosmetics, HMPSA, Thermoplastic elastomers
4 mm Tape of soft functional acrylic block copolymer
Initial
1 h in water : 23% weight gain
Elastomeric behaviour
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Conclusion : A unique technology and multiple breakthroughs in applications A new polymerisation technology now gives
access to Acrylic copolymers having controlled architecture
Based on Arkema proprietary nitroxide, BolcBuilder
Very versatile process These block copolymers are under development
in numerous areas : Polymer modification, paints, dispersion,
epoxies, oil rheology modifiers, adhesives,… Semi industrial production assets are available ARKEMA ambition : become the first supplier
worldwide of acrylic block copolymers
The world is our inspiration
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Merci pour votre attention