SURFACE TREATMENTS TO OPTIMIZEDISPERSION OF HALOGEN FREE FLAME       RETARDANT MINERALS  Intro to Water-based Coatings
Agenda     Motivation     -Hazards     -Regulatory Influence     -Technology Shift     Mineral Dispersion     -Introductio...
Motivation – Hazards & Regulation     Increase in synthetic content in homes produces hotter and     more toxic fires and ...
Motivation – Hazards & Regulation     Restriction of Hazardous Substances Directive (RoHS)     -Adopted in EU 2006, China ...
Technology    Flame retardant plastics have    become more critical than ever    before    $827 million FR market segmente...
Introduction     Surveyed W&C industry to identify outstanding difficulties     transitioning to non-halogenated flame ret...
Introduction to Dispersion                Property                Dispersant            Coupling Agent          Flow (MFI/...
Effective Dispersant Chemistry         Filler Type            Best Dispersant      2nd Best               3rd BestCalcium ...
Alternative Chemistry         Functionality        SMA®   Ricon®   Commercially Available       Maleic anhydride         ...
Maleated Polymers  Material                             Anhydride   Tg  Molecular                           Structure   Cl...
Literature Evidence     Maleated Polybutadiene (MBPD) historically used as mineral     surface treatment     -Calcium carb...
Dispersing ATHExperimental composition:                           Mn       Functionality     Vinyl                        ...
Introduction - Materials       Method 1                 Method 2               Method 3     • PBD dispersed         • ATH ...
Dispersing Large Diameter ATH                                                                                             ...
Alternate Chemistry                              6.5                                                           160        ...
Dispersing Small Diameter ATH                                      13                                                     ...
Filled Summary     Plasticization effect apparent in filled systems     -Unfunctionalized LPBD significantly reduced tensi...
Surface Treatment Method                       600                       500      Elongation (%)                       400...
Improving Dispersion         Base                Mechanical          Starve Coated     Fewer instance of large aggregate i...
Influence on Flammability                      39                      38                      37                      36 ...
Heat & Smoke Generation                                                                                4.5                ...
Summary     Pre-dispersing a functionalized liquid polybutadiene on ATH is     an effective way to promote ductility throu...
Cray Valley HSC     Leading global supplier of hydrocarbon resins, diene-based     resins, and specialty monomers     - Wi...
Cray Valley HSCA Division of Total SA                     Upstream               Downstream                 Chemicals     ...
Cray Valley HSCFocus Markets              • Performance                    • Pressure                     • Printed circui...
Cray Valley    Global Presence                                          vv                                         vvv v  ...
Cray Valley HSC For additional information about Cray Valley, its products     or its work in Hydrocarbon Specialty Chemic...
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Intro to Water-based Coatings

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This presentation by Cray Valley talks about surface treatments for optimizing dispersion of halogen-free, flame retardant minerals. It highlights water-based coatings and the reasons behind investigating fire-resistant plastics. This slideshow reveals Cray Valley's investigation into relevant surface treatments for specific mineral systems, methods to coat filler and elongating dispersion.

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Intro to Water-based Coatings

  1. 1. SURFACE TREATMENTS TO OPTIMIZEDISPERSION OF HALOGEN FREE FLAME RETARDANT MINERALS Intro to Water-based Coatings
  2. 2. Agenda Motivation -Hazards -Regulatory Influence -Technology Shift Mineral Dispersion -Introduction -Relevant Chemistries Technical Results -Functionality Selection -Charging Method -Correlating Ductility with Dispersion Summary & Conclusions2 Cray Valley HSC
  3. 3. Motivation – Hazards & Regulation Increase in synthetic content in homes produces hotter and more toxic fires and has dropped escape time from 17 to 3 minutes (1975) Increasingly stringent fire codes and flammability requirements in Building Materials & Construction (BM&C) products3 Cray Valley HSC
  4. 4. Motivation – Hazards & Regulation Restriction of Hazardous Substances Directive (RoHS) -Adopted in EU 2006, China & South Korea in 2007 -Restricts six hazardous materials in electronic/electrical applications - Lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls, polybrominated diphenyl ether - Skin disorders, nervous and immune system effects, liver, kidney and thyroid malfunctions, and possible carcinogen Waste Electrical and Electronic Equipment Directive (WEEE) -Legislative initiative to solve the problem of toxic e-waste -Targets for collection, recycling and recovery of electrical goods -Responsibility for disposal of e-waste imposed on manufacturer4 Cray Valley HSC
  5. 5. Technology Flame retardant plastics have become more critical than ever before $827 million FR market segmented*: -Halogenated: 36% -Non-halogenated: 64% Plastics industry lagging -Halogenated FR remain dominant Aluminum trihydrate (ATH) projected Brominated Phosphorous Mineral Antimony Other as largest volume flame retardant through 2011 * Freedonia Market Study # FW35019 -Comprising 45% of demand -Growing inline with the market (3%/yr)5 Cray Valley HSC
  6. 6. Introduction Surveyed W&C industry to identify outstanding difficulties transitioning to non-halogenated flame retardants Matching FR performance on halogenated compounds required greater than 60% by weight mineral filler Elevated loadings of additive caused: -Poor ductility -Low tensile strength -Significant change in flow Objectives: -Improve elongation via dispersion -Identify surface treatment options relevant to specific mineral systems -Investigate methods to coat filler6 Cray Valley HSC
  7. 7. Introduction to Dispersion Property Dispersant Coupling Agent Flow (MFI/MFR) ↑↑ ↑↑ or ↓↓ Modulus = = Yield Strength = ↑↑ HDT = ↑↑ Impact resistance ↑ ↓ Elongation to break ↑ ↓↓ *Courtesy of Phantom Plastics Dispersants promote homogeneity and prevent defect sites via agglomeration Coupling agents are bi-functional and effectively immobilize filler and polymer chains through A—B—C structure: -Anchor --- Buffer/Bridge --- Couplant7 Cray Valley HSC
  8. 8. Effective Dispersant Chemistry Filler Type Best Dispersant 2nd Best 3rd BestCalcium carbonate Anhydride Carboxylic acid Primary amineDolomite Sulfonic acid Carboxylic acid AnhydrideMagnesium hydroxide Anhydride Silane Carboxylic acidMica Primary amine Silane Sulfonic acidTalc Silane --- ---Silica Silane Sulfonic acid AnhydrideWollastonite Primary amine Anhydride Carboxylic acidTitanium dioxide Anhydride Carboxylic acid Silane *Courtesy of Phantom Plastics Vast majority of surface treated minerals leverage silane chemistry Cray Valley chemistry can fill the void beyond silane surface chemistry8 Cray Valley HSC
  9. 9. Alternative Chemistry Functionality SMA® Ricon® Commercially Available Maleic anhydride   Carboxylic acid  Epoxy  Imide   Sulfonated  Hydrogenated  Acrylated   Amine   Brominated  Developmental Siloxy  Chemistry and processes are core competencies for Cray Valley; Alternative functionalities are routinely explored9 Cray Valley HSC
  10. 10. Maleated Polymers Material Anhydride Tg Molecular Structure Class Range Range WeightStyreneMaleic 110°C 10.5 to 42%Anhydride to 5k to 24k by weight(SMA®) 155°CCopolymerLiquid -86°CFunctional 3 to 20% to - 5k to 10kPolybutadiene by weight 30°C(Ricon®) 10 Cray Valley HSC
  11. 11. Literature Evidence Maleated Polybutadiene (MBPD) historically used as mineral surface treatment -Calcium carbonate – water soluble variants to ‘pre-treat’ minerals with dispersant -Aluminum trihydrate – formation of carboxylate salt to cover mineral surface by ‘loopy’ adsorption -Clays, talcs, etc… -Rothon, R. Particulate Filled Polymer Composites. 2nd edition, Shrewsbury, UK: Rapra Technology Limited, 2003.11 Cray Valley HSC
  12. 12. Dispersing ATHExperimental composition: Mn Functionality Vinyl Additive (g/mol) (type/%) (%) -60% ATH (1 & 50 m) Ricon® 156 1,400 - 70 -36% EVA (28% vinyl acetate) Ricon® 131 4,500 - 28 -4% Additive Ricon® 156MA17 2,500 Anhydride/ 17% 70 Ricon® 131MA17 5,500 Anhydride/ 17% 28Additives were based on Ricon® 131MA5 4,700 Anhydride/ 5% 28functional liquid PRO-5052 4,500 Epoxy* / 5% 28polybutadienes (LPBD): (developmental) NXT-6715 5,000 Amine** / 5% 28 (developmental) Poly bd® R45 2,700 Hydroxyl*** 20 * Internally epoxidized ** Tertiary amine grafted *** Terminal hydroxyl12 Cray Valley HSC
  13. 13. Introduction - Materials Method 1 Method 2 Method 3 • PBD dispersed • ATH pre-charged • ATH treated with onto porous with PBD H2O based silica • Eliminates ‘extra’ dispersion of • Approximately mineral content PBD 70% PBD • Ease of content introduction Pre-treated ATH tended to aerate less (EH&S) Material process improvements: torque & throughput (Productivity) Reduced dilution of EVA matrix (formulation)13 Cray Valley HSC
  14. 14. Dispersing Large Diameter ATH 100 6.5 90 6 80 Tensile Strength (MPa) 5.5 70 Elongation (%) 60 5 50 4.5 40 4 30 20 3.5 10 3 0 Neat Ricon® Ricon® Ricon® Ricon® Neat Ricon® Ricon® Ricon® Ricon® 156 131 156MA17 131MA17 156 131 156MA17 131MA17 Tensile strength was reduced in filled systems; anhydride functionalized systems to a lesser extent Elongation increased 200 – 350%14 Cray Valley HSC
  15. 15. Alternate Chemistry 6.5 160 140 6 120 Tensile Strength (MPa) 5.5 Elongation (%) 100 5 80 4.5 60 4 40 3.5 20 3 0 Neat Ricon® PRO-5052 NTX-6715 Neat Ricon® PRO-5052 NTX-6715 131MA5 131MA5 Low anhydride, amine or epoxy functionality LPBD increased elongation 500 – 700% Less variation in data with LPBDs over base filled material15 Cray Valley HSC
  16. 16. Dispersing Small Diameter ATH 13 350 12 Tensile Strength @ Break (MPa) 11 300 10 Elongation (%) 9 250 8 7 200 6 5 150 4 3 100 Neat Ricon® 131MA5 Poly bd® R45 Neat Ricon® 131MA5 Poly bd® R45 Ricon® 131MA5 met target for tensile strength and elongation Average elongation for neat material met requirement, but was highly variable16 Cray Valley HSC
  17. 17. Filled Summary Plasticization effect apparent in filled systems -Unfunctionalized LPBD significantly reduced tensile strength -Anhydride functionalized analogues helped disperse the ATH by polar interactions with the EVA and mineral surface Ductility of EVA regained by improved dispersion of ATH -Believed that surface wettout dispersed the ATH and prevented re- agglomeration during molding -Reducing the average particle size of the ATH lessened the likelihood of providing a defect site during void formation while under strain -Owing to the low molecular weight and high functional loading (17%) LBPD-3 likely enveloped the ATH versus17 Cray Valley HSC
  18. 18. Surface Treatment Method 600 500 Elongation (%) 400 300 200 100 0 Base Mechanical Starve Coated Flood Coated Mechanical coating and wet coating were equally viable methods Integration of functional polybutadiene can coincide with mineral surface treatment18 Cray Valley HSC
  19. 19. Improving Dispersion Base Mechanical Starve Coated Fewer instance of large aggregate in coated samples and relative aggregate size reduction Dispersion efficiency of functional LBPD was comparable between mechanical and wet coating methods19 Cray Valley HSC
  20. 20. Influence on Flammability 39 38 37 36 LOI (%) 35 34 33 32 31 30 Base Mechanical Starve Coated UL94 V-2 UL94 V-0 UL94 V-2 Pre-coating ATH with LPBD dispersant not only maintained the flammability performance, but also improved it Dispersing augments the ‘self-extinguishing’ nature of the filled polymer20 Cray Valley HSC
  21. 21. Heat & Smoke Generation 4.5 250 Base Base 4.0 Mechanical Mechanical 200 3.5 Starve Starve RSR [(m2/s)/m2] 3.0 HRR [kW/m2] 150 2.5 2.0 100 1.5 1.0 50 0.5 0 0.0 0 100 200 0 50 100 150 200 Time (s) Time (s) Heat release rate (HRR) improved by introduction of LPBD coating Rate of smoke release (RSR) was lowest in composition prepared using starve coating Method 3 LPBD coatings in general imparted better HRR and RSR to EVA/ATH composite21 Cray Valley HSC
  22. 22. Summary Pre-dispersing a functionalized liquid polybutadiene on ATH is an effective way to promote ductility through dispersion -Mechanical and wet coating methods proved adequate Molecular weight, functionality and functional loading are leading factors when selecting an appropriate dispersant Appropriate functionalities vary by surface chemistry of the mineral -Judicious selection maximizes dispersion potential Flammability performance likely linked to improved dispersion of water containing minerals22 Cray Valley HSC
  23. 23. Cray Valley HSC Leading global supplier of hydrocarbon resins, diene-based resins, and specialty monomers - Wingtack® and Norsolene® (C5 & C9 tackifiers) - Poly bd®, KrasolTM, and Ricon® (low molecular weight liquid polybutadiene resins) - SMA® (styrene-maleic anhydride copolymer resins) - DymalinkTM (metal centered monomers) Annual sales over $350 million and has more than 340 employees worldwide Company’s more than 250 products are manufactured at 9 sites in 4 countries23 Cray Valley HSC
  24. 24. Cray Valley HSCA Division of Total SA Upstream Downstream Chemicals • Oil & gas exploration • Trading & shipping • Base chemicals • Production • Refining & marketing • Industrial & consumer Focus • Gas & power • Commodity & specialty market specialty • Alternative energy fluids chemicals Sales $24.6 $163.4 $23.2 (billion)Employees 17,192 32,631 41,658 Total, a partner in your challenges24 Cray Valley HSC
  25. 25. Cray Valley HSCFocus Markets • Performance • Pressure • Printed circuit Growth Markets additives sensitive boards Adhesives • Tire & hose • Reactive • Electronics Rubber applications adhesives • Thermoplastic • Co-curing • IGS additives agents25 Cray Valley HSC
  26. 26. Cray Valley Global Presence vv vvv v v v v v v vv v v Global HQv Regional HQ vv Sales Officev Researchv Manufacturing Distribution Network 26 Cray Valley HSC
  27. 27. Cray Valley HSC For additional information about Cray Valley, its products or its work in Hydrocarbon Specialty Chemicals, visit www.CVPolymerAdditives.com.

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