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

Jean-pierre.disson@arkema.com, daniel.lebouvier@arkema.com

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