Nanostrength Block Copolymers for Epoxy …

1 Nanostrength Block Copolymers for Epoxy Toughening100 nmPABuPMMAPMMA / EpoxyNanostrength for Epoxy toughening Arkema Overview Nanotechnology Platform at Arkema Nanostrength Nanostrength Block Copolymers for Epoxy Value Drivers Epoxy toughening with Nanostrength Range of properties achievable using Nanostrength How it works Application Specific Properties- Composites and Adhesives2 Arkema 2007 overviewSales by regionEurope (excl. France)39%Sales: bn ($ )Capital employed: 31bn39%France18%North America25%Sales per yearCapital employed: bnCapex: 4%of sales18%Row5%Asia13%2007R&D.

2 3% of sales15 200employeesIn ,200employees3200520062007R&D accelerates product innovationOverview (2007)3% of sales 1 350 researchersR&D by segment12%Vi lBreakthrough1,350 researchersNear 100 joint projects with universities6 R&D centersPortfolio around 5,700 patents12%12%51%25%Vinyl ProductsPerformanceProductsIndustrial Chemicals2005 Chemicals Recent breakthroughsRecent breakthroughs4 Nanotechnology Platform at ArkemaOur customers :Compounds, Thermosets, Pigments, Engineering resins,Paints, Coatings,Adh iAdhesives.

3 Functionalized Specialty Block CRP* initiator&FlexiBloc CopolymersFlexiBloc CRP* &Reactive Block CopolymerBlock Copolymersmacroinitiator5pyNanotechnolog y Platform at ArkemaBlock Copolymers for Epoxy toughening6 Classical vs. Controlled Free Radical Classical Radical Polymerization Controlled Radical Polymerization No control of termination Living chain ends experience reduced Wide polydispersities Random sequencing fitexperience reduced termination Reduced of monomer unitspolydispersities Block Copolymers possiblepossible7 Complete Control of Block Structure Block copolymersClassicalBlock copolymersClassicalBlock Copolymers Incompatibility between blocks organization at the nanometer scaleRandomcopolymerDiblockcopolymerABA

4 TriblockcopolymerABC triblockcopolymerscale8 Nanostrength Triblock Polymers Controlled Radical Polymerization (CRP) ABA, ABPl[(Mthl) thlt]bl(BtlA lt)bl[(M th l)thl t ] Functional comonomers can be added (AA, MAA, PEGMA, HEMA,..)Poly[(Methyl)methacrylate] -b-poly(Butyl Acrylate)-b-poly[(Methyl)methacrylate]Po ly[(Styrene] -b- poly(Butyl Acrylate)-b- poly[(Styrene] Anionic polymerization SBM Outstanding control of molecular weight, molecular weight polyStyrene -b- polyButadiene-b- poly[(Methyl)methacrylate]9gggdistributi on, composition, chain architecture, functionalizationBlock Copolymers for Epoxy toughening Structural Adhesives(Automotive, Industrial, Assembly, Wind Energy, Electronics.)))

5 Coating(Solvent, Powder,..) Composites(Aerospace, Sports and Leisure,..)p(p,p,) Epoxy compoundsNanostrength is suited for every application that needs an increase in resistance to crack propagationwhile maintaining Tgand Modulus of the to the unique nanostructuration achievable with Nanostrength , it is possible to achieve identical toughnessto competiti e modifiers (CTBN) b tsing red ced loading10to competitive modifiers (CTBN) but using reduced loading Copolymers for Epoxy TougheningAdvantages of Nanostrength .

6 toughening with little loss of Tg or Modulus Outstanding toughening at lower loading due to unique modifier morphologies Ease of Processing-additive dissolves in Epoxy resinEase of Processingadditive dissolves in Epoxy resin Nanoscale self-assembled particles allow for toughening adhesive bond coatings3. Composites with small inter-fiber spacingCore-ShellCTBN / ~ m1 ~ 5 m10 ~ 100 nmBlock Copolymers for Epoxy TougheningLow Tg systems: DGEBA + JeffamineTMT403 Low Tg systems: DGEBA + JeffamineTMT403 Loading LevelK1CG1 CTgK1CG1 CTgM53 CTBN0% Superior toughening at equivalent loadings Equivalent toughening at lower loadings12 Block Copolymers for Epoxy TougheningIntermediate Tg systems: DGEBA + DICYI ntermediate Tg systems.

7 DGEBA + DICYL oading LevelK1 CTgK1 CTg0% +- +- +- +- +- +- +- +- (Dicy) is hardener representative of:Adhesives-Adhesives- Sports and Leisure composites-Coatings13-CoatingsA Self-assembling Nanotechnology- Affinity between epoxymonomers and PMMA- Repulsion between epoxymonomers and the middle Block (s) Nanophase separation ofPBuAblocks:DGEBAM-A-M Nanophase separation of PBuAblocks:PABuPMMAPMMA / EPABuPMMA / Epoxy14 PMMAPMMA / EpoxyToughening of Epoxy systems Many mechanisms contribute to Epoxy toughness : Shear yieldingShear yielding Shear yieldingShear yielding Multiple crazing Crack pinning Crack bridgingCrack bridging Crack deflection.

8 Th iithfl ibili tiToughening is more than flexibilization. Flexibilization lowers the modulus of the material to decrease brittleness (CTBN - flexibilizer) by reacting to the backbone of the Epoxy . Nanostrength (and hll) itidlhil t h iPearson (1993)HYd Ki lh A J J M tS i 27 2763 (1992)core shells) maintain modulus while , Y., and Kinloch, , J. Mater. Sci., 27, 2763 (1992). toughening of Epoxy systemsThe most efficient mechanisms to toughen are system & condition dependant: Low Tg systems, high T or low speed testing conditions: Shear yieldingMatrix network has enoughMatrix network has enough mobility to activate plasticity High Tg systemsHigh Tg systems, low T or high speed testing conditions.

9 Multiple crazing Crack bridging CkiiMatrix network too cross-linked to activate plasticity Crack pinning Crack deflectionpyR A Pearson"An overview of organic toughening agents for Epoxy resins"ERFDS pring 2000 Pearson, An overview of organic toughening agents for Epoxy resins, ERFD Spring 2000 Conference, April 16-18, 2000, San Antonio, TX toughening of Epoxy systems Existing tougheners have specific toughening mechanisms: Liquid reactive rubbers shear yieldingqyg Thermoplastics crack bridging, pinning & deflection Acrylic Block Copolymers : all mechanisms Shear Yielding (cavitation of the rubber phase) Nanoscale modifiers lead to high density of shear band Acrylic Block Copolymers .

10 All mechanisms Nanoscale modifiers lead to high density of shear band formation Unique morphologies lead to better toughening Crack Bridging Crack Pinning (strong matrix adhesion)17 Crack DeflectionToughening of Epoxy systemsCavitation of nanodomains 18 toughening of Epoxy systemsModifier morphology in cured Epoxy dependent on: Crosslinking/Resin chemistry Block copolymer ChemistryM51, M52, M53: PMMA- Block -PBuA- Block -PMMADGEBA + MDEADEGBA + Jeffamine19 DGEBA + M-DEADEGBA + Jeffamine T403 toughening of Epoxy systemsBlock copolymer Chemistry dictates Modifier Morphology MAM exp15 m DGEBA + DDS5 mRef+10% MAM exp1+10% MAM exp2+10% MAM M22 NMAM exp23 mM22N2 mDevelopment of functionalized grades to further improve nanostructuration with alltypes of Epoxy systems: M22N or M52N:PMMA/DMAblockPBuAblockPMMA/DMA20M22 N or M52N.