présentation Nanostrength Innov'days Nov2012 · Specialty polyamides

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: christian.bret@aecpolymers.com

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Nanostrength for Structural Adhesives : example of AEC P olymers

Traditional Adhesives vs. SAFTraditional Adhesives vs. SAFTraditional Adhesives vs. SAFTraditional Adhesives vs. SAF®®®®

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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…