Polymersand

Polymer Additivesof

Tomorrow

Chris RogerDirector, Corporate & External Research and

Thiochemicals R&D

Arkema Inc.

Tulane Engineering Forum – April 3, 2009

� Sales: € 5.7 B ($ 7.7 B)

� Employees: ~ 14,700 (worldwide)

� 78 Industrial sites

� R&D: 3% of sales, 6 research centers

Arkema – Facts and Figures - 2008

Performance Products

Vinyl Products

Industrial Chemicals

24 %

36 %

40 %

Sales per business segment

Europe

54% of sales

50 plants

4 R&D centers

76 % of personnel

Asia

17% of sales

10 plants

1 R&D center

8 % of personnel

North America

25 % of sales

18 Plants

1 R&D center 16 % of personnel

Main countries (aggregate sales = 80 % of total)

Other significant countries

Sport & leisure

Vinyl compounds,

PMMA,

Technical Polymers

PaperChlorochemicals,

Hydrogen Peroxide,

Acrylics

Packaging

PVC,

Technical Polymers,

Additives,

Organic Peroxides

Water treatment

Chlorochemicals,

Acrylics,

Hydrogen Peroxide,

Specialty Chemicals

Hygiene & beauty

Chlorochemicals, Acrylics,

PMMA, Thiochemicals,

Hydrogen Peroxide,

Technical Polymers

ConstructionVinyl Products, Acrylics,

Fluorochemicals,

Technical Polymers,

Specialty Chemicals,

Additives, Urea resins,

Organic Peroxides

Chemical industry

Chlorochemicals,

Acrylics, Thiochemicals,

Technical Polymers,

Specialty Chemicals,

Organic Peroxides

Electronics

Vinyl Compounds,

Thiochemicals,

Technical Polymers,

Specialty Chemicals

Agrochemicals

Thiochemicals,

Specialty Chemicals,

Agrochemicals

AutomotiveVinyl Compounds,

PMMA, Fluorochemicals,

Technical Polymers,

Additives,

Organic Peroxides

Wide range of end-markets

Bio-resourced Polymers

Economical

Rising costs of finite resources

Increased disposal costs

Polluter pays carbon credits

Increased competition

Technical

Technological developments in molecular science, genetic engineering, fermentation and plant breeding

Filler incorporation and compounding advances

Economies of scale

Design oriented for recycling

Social

Acceptance of bioplastic

Greening of consumers

Political

Legislative instruments

Governments incentives

Polylactic acid (PLA)

Lactic Acid

FermentationCH3-CH(OH)CO2H

Condensation

- 2 H2O

Lactide

PLA

� Produced by:� NatureWorks (USA)� Toyota (Japan)� PURAC Biomaterials (The Netherlands)� Hycail (The Netherlands)� Galactic (Belgium)� Several Chinese producers� Others…

First created by Dupont (1932) and process developed in 1954

Polyhydroxyalkanoates - PHAs

Switchgrass

Bacterial

Fermentation

H

O

O

OH

R

n

R = CH3 – Polyhydroxybutyrate

R = CH2CH3 - Polyhydroxyvalerate

First discovered in 1925 – Process developed in 1980s by ICI

� Produced by:� Metabolix (USA)

Polyamide 11 – PA 11

CastorPlants

CastorSeeds

CastorOil

FeedstockIndia, China, Brazil

FoodCosmetics

PharmaceuticalsC3

Jet lub, Fridge lub

Butter tracerFragrance, Flavors

C7

CosmeticsPerfumesPharmaceuticals

C11

Concrete demolderMetal working

LubricantsRoad buildingEsters

Amino11

Polyamide 11100% biobased

Co-Polyamide100 % biobased

PEBA elastomer20-95 % biobased

� Produced by:� Arkema (FR, USA)

Developed in 1942 by Arkema

Bio-derived Polyethylene

FermentationCH3CH2OH

DehydrationCH2=CH2

Polymerization

� Should be produced:� Braskem (BR) in 2010� Dow Chemicals (BR) in 2011

although delays have been announced due to

economical situation

Advanced Polymers

�Blends (at the nano-scale)

�Designed by controlled polymerization (living polymerization)

� Anionic� Atom Transfer Radical (ATRP)� Reversible Addition Fragmentation Chain

Transfer (RAFT)� Iodine-Transfer� Nitroxide Mediated (NMP)� Others…

Polymer Blends

�Decouple properties that may not be available in one polymer

�Most polymers are immiscible with one another

� Macro phase separation� Compromise in properties

� Nano-scale phase separation� Best of both polymers

Nano-scale Phase Separation Example

�H2 Fuel Cell Membranes

Ballard Power Systems

Nano-scale Phase Separation Example - 2

�Nafion used as proton-exchange membrane

� Good ionic conductivity� Relatively poor mechanical properties� Expensive ($$$$$)

Developed and commercialized by DuPont in the late 1960s

Nano-scale Phase Separation Example - 3

�Decoupling properties

PVDF

Kynar®

� Acid Resistant� Oxidation Resistant� Electrochemically Stable� Mechanical Strength� High Purity� Relatively low cost ($$)

C C

H F

FH n

PolyelectrolyteEndless Possibilities

� Water Absorption� Proton Conductivity� Relatively low cost ($)

Advanced MaterialsDesigned Polymers

Controlled Polymerization

�Various techniques

� Anionic

� Atom Transfer Radical (ATRP)� Reversible Addition Fragmentation Chain

Transfer (RAFT)� Iodine-Transfer� Nitroxide Mediated (NMP)� Others…

Controlled Radical Polymerization (CRP)

� Classical Radical Polymerization� No control of termination� Wide Polydispersities� Random monomer sequencing

� Controlled Radical Polymerization� Simultaneous initiation� Reduced polydispersity� “Living” chain ends experience

reduced termination� Controlled monomer addition� Block copolymers possible� Gradient copolymers possible

How does CRP work?

� NMP - Stable radicals (nitroxides)

� ATRP - Organometallic complexes

� RAFT - Thio derivatives

Trap:kd, kc: f(Trap/M relation, T)

kt, kp: f(M)

RR

�

+

RR

Propagation & Termination Dormant species

Key Equilibrium: Reversible trap of propagating polymer chains

kp kt kp kt

kc

kdInitiator InitiatorTrap Trap

RR

�

+

RR

Propagation & Termination Dormant species

Key Equilibrium: Reversible trap of propagating polymer chains

kp kt kp kt

kc

kdInitiator InitiatorTrap Trap

Arkema’s Nitroxide Mediated Technology

Initiator (I) Radical Trap (SG-1)

Heat < 80oC O N

PO

OEtEtO

••

BlocBuilder

ON

PO OEt

OEt

HO

O

HO

kd

kcR

R

O

+

OO

O

OBDDA

Di-functional Initiator

OO

S G-1

O

O

S G-1

I

I

Example of what can be made

A B A B A

� A Blocks (hard)

� Main monomer: styrene, methyl methacrylate

� Co-monomer: methacrylic acid, acrylic acid

� B Blocks (soft)

� Main monomer: butyl acrylate, ethyl acrylate

� Co-monomer: acrylic acid, 2-hydroxyethyl acrylate

R = H or Me

N

O

MeMe

DMABA, MA or MMA

O

O

R

O

O

R

LA or LMAStyrene

O

O

OH

R

HEA or HEMA

HO

O

R

AA or MAA

NVP

O

O

O

MEA

O

O

ORn

PEGA

GMAO

O

O

N O

Polymer Design � Structure Control

� Complete control of copolymer & block structures...

...Miscibility, Mechanical, Gloss, Tack, etc.

AB diblock ABA triblock ABC triblockLow PDI Gradient AB diblock ABA triblock ABC triblockLow PDI Gradient AB diblock ABA triblock ABC triblockAB diblock ABA triblock ABC triblockLow PDILow PDI GradientGradient

�...Nanostructuration � due to block incompatibility...

�...Properties inherent to each block maintained! – no property trade off!

Synthetic Flexibility →→→→ tailoring of polymer end-use properties!

Example - Tailored Mechanical Properties

PBAPMMA PMMA

PBA content ����

Tough Thermoplastics Thermoplastic Elastomers

Domains = 20 -70nmDomains = 20 -70nm

Example – Tailored Hydrogel Properties

Hard Thermo-

Plastic (eg, MMA)

High Tg

Low Tg

Adhesive

Elastomer

� In addition to absorption - solubility, adhesion etc…

Potential Applications of Hydrogels

� Hydrocolloids/ Wound Dressings / Adhesives

� Utilize processability benefit: extrusion, film, fibers,

etc…

� Personal Care / Cosmetics / Health Care

� Creams, patches, controlled delivery, etc…

� Hydrophilic Coatings / Additives

� Lubricious coatings (catheter), medical devices, etc…

� Membranes/Filters

� Batteries, water filtration membranes, etc.

But…

high-performance applications

durable goods

disposable goods

DURABILIT

Y

HDPEPPPS

ABS PMMA PET

PA6/66 PBT

PC

PC/ABS

TPUCOPE

PA12

PEBA

LCPHTPA

PVDF

LDPE

…

PLA

PA11

PA11 + ABS, PLA, etc.

High performances

Engineering

Commodity

PVC

POM

PUR

Epoxy

PPE

PPS

PI

PTFE

PHAs

PEKK

� AB diblock copolymers (surfactant-like polymers)

� Dispersants for paints, agrochemicals, paper coatings

� Compatibilizers

� Aids for emulsion polymerization

� Surface modification - improved paintability, adhesion, etc.

� ABA triblock copolymers

� Tougheners with nanostructuration for styrenics, unsaturated polyester resins, acrylic resins, epoxies, etc.

� Improved impact properties while retaining transparency

� Controlled phase separation - electronics, adhesives, etc.

� Thickeners for a variety of applications

� Unique aesthetic properties for personal care

Used as Polymer Additives

Adhesive Additives S-BA-S vs. SBS (Kraton)

� Much higher adhesion for S-BuA-S formulation to polar and non-polar surfaces

180°Peel Test (N/mm)

S-BA-S SBS

SUBSTRATE

PET 0.34 0.17PC 0.17 0.06PMMA 0.34 0.12PE 0.31 0.10

� Formulation: 30% Polymer/56% Resin/14% Oil

Surface Modification/Compatibilizers

Block copolymers – efficient use of surface active segment

� Surface active incompatible block:� repellent & resistant coatings, paints, films, etc.

� Compatible block:� segment adhesion, solubility, compatibility, permanence, etc…

� Same concept can be applied to Compatibilizers

matrix compatiblesurface active

(or ‘B’ compatible)

matrix

Polymer A

Polymer Bmatrix compatiblesurface active

(or ‘B’ compatible)

matrix compatiblesurface active

(or ‘B’ compatible)

matrixmatrix

Polymer A

Polymer B

Polymer A

Polymer B

Rheology Modifiers

Unique rheology through nano-structuration: VI Improvers, Thickeners

Reduced Viscosity vs Concentration

0

10

20

30

40

50

0 0.05 0.1 0.15 0.2

Conc. (g/mL)

Re

du

ce

d V

isc

os

ity

Blue = Block

Orange = Homopolymer

Polymer in Oil Solution

• Micelle interaction leads

to divergent behavior

vs.

Blue segment insoluble

Impact Modifiers

Core-Shell Block Copolymers

0.1 ~ 0.8 µm 10-50 nm 100 nm

100 nm

Arkema Capabilities

Composites

�Thermoplastics or Thermosets� Strength and toughness� More and more towards metal replacement

� Lighter weight, stronger parts

� Automotive, wind turbine blades, etc.

�Traditional� Fiber reinforcement (glass, carbon)

� Strengthen but does not toughen

� Need for stronger materials

Carbon Nanotubes (Multi-walled)

�Strengthening

0.60.00816Wood

1.250.0053.5Epoxy

7.80.4208Steel

2.01501200MWCNT

Density(g/cm3)

Breakingstress (GPa)

Young’s modulus(GPa)

Material

Carbon Nanotubes Applications

ThermoplasticsThermoplastics

Materials

ElastomersElastomersThermosetsThermosets

Sporting goodsSporting goodsAdhesives and Adhesives and

coatingscoatingsAutomotiveAutomotive

Markets

� Bio-resourced polymers will continue to grow� Need for additives for performance improvements

� Nano-structuration leads to tailored properties� CRP is a versatile tool

� Other additives are needed for additional property improvements

� More developments (Organic Photovoltaics, etc.)

� Recycle

Conclusions