Recent developments in flame retardants for sustainable fire safety solutions

Transcription

1 Recent developments in flame retardants for sustainable fire safety solutions Dr. Grace Han 4 th International Conference on Flame Retardants Chinese and International Markets Requirements, Challenges and Innovations May 2013

2 Agenda Great Lakes Solutions Overview Greener Innovation Strategies Emerald Innovation TM 1000 polymeric Flame Retardant Solutions for Antimony Trioxide Reduction Emerald Innovation TM 3000 polymeric Flame Retardant

3 Global specialty chemical company listed on the New York Stock Exchange ( CHMT ) Major markets served are energy & electronics, transportation, and agriculture Committed to global sustainability and engineering chemical solutions that meet our customers evolving needs More than 4,300 employees worldwide Manufactures in 31 countries and sells products in over 100 countries Global headquarters in Philadelphia, Pennsylvania Regional headquarters and shared service centers in Sao Paulo, Brazil; Shanghai, China; Middlebury, Connecticut; and Manchester, United Kingdom

4 KEY GROWTH DRIVERS KEY BUSINESSES Great Lakes Solutions, an Industry Leader INDUSTRIES SERVED Flame Retardants Electrical & Electronics Insulation & Furniture Automotive Brominated Performance Products Mercury control Greener innovation Rapid growth in electronics Fine Chemical/ Pharmaceutical Biocides Energy: Oilfield & Mercury Control Automotive Tires Flame retarded energy efficient thermal insulation Increased global fire safety standards Fine Chem/ Pharma Auto Fumigation Energy Electrical & Electronics Fumigation Biocides Other Insulation & Furniture

5 The Sustainability Challenge for Flame Retardants In today s society, products are expected to be green But, what is green? Ideally, this includes: Total Carbon Footprint Recyclability Green Chemistry & Engineering Principles Chemical Hazard Classification and Risk Assessment 5

6 Factors Affecting Flame Retardant Selection Meet Fire Safety Standard Environment & Human Health Functional Requirements End-of-Life Aspects Economic Feasibility 6

7 Greener Innovation How Do We Move Towards Environmentally Friendly, Sustainable FR Solutions? Chemtura is applying a Greener is Better philosophy...

8 Greener is Better FR Design Strategy Greener Alternatives That Achieve targeted fire safety standards Meet or exceed baseline performance and manufacturability Are cost effective based on total system cost Minimize transition costs Strive for zero environmental release VECAP to prevent release from manufacture to fabrication Durable & recyclable to allow low-risk rework and recycling Structures that are inherently Not migratory Not bioavailable Not toxic

9 Conclusions of USEPA Decabromodiphenyl ether alternatives assessment 2 - Large polymers (greater than 1,000 daltons) had generally low concerns because they cannot be absorbed or easily metabolized. - Large discrete chemicals and large polymers (both halogenated and non-halogenated) had generally low ecotoxicity hazards. The larger chemicals and compounds with high Kow are not expected to be bioavailable in the water column. Most hazard designations based on SAR predicted no effects at saturation. 2. Lavoie, E.. USEPA, Conference Procedings, Fire Retardants in Plastics 2012, June

10 DRAFT Assessments Classical BFRs 10 4/19/2013

11 DRAFT Assessments Polymeric BFRs 11 4/19/2013

12 DRAFT Assessments Phosphorus and Nitrogen FRs 12 4/19/2013

13 Great Lakes Solutions Polymeric and Reactive Flame Retardant Technologies Polymer Technology Products Polyamides Polycarbonate, PBT Polybromostyrene Brominated Oligomer Polybromostyrene Firemaster CP44-HF Firemaster PBS64-HW, PDBS-80 BC-52, BC-58, Firemaster CP44-HF Firemaster PBS64-HW, PDBS-80 Unsaturated Polyesters Reactive Intermediate PHT-4, BA-59P Polyurethane Polyolefins, HDPE, PP Styrenics, PS, HIPS, ABS Epoxy Reactive Intermediate Proprietary Polymeric Reactive Intermediates PHT-4 Diol, PHT-4 Diol LV, Firemaster 520 Emerald Innovation 1000 Emerald innovation 3000 BA-59P Emerald Innovation

14 Introducing Emerald Innovation Our Next Generation of Flame Retardant Products Why Emerald Innovation? Products are innovative, reliable and also minimize the impact on our environment and human health while maintaining superior performance and quality

15 EMERALD INNOVATION 1000 VERSATILE, EFFICIENT, SUSTAINABLE FLAME RETARDANT SOLUTION FOR IGNITION RESISTANT POLYMERS

16 Emerald Innovation 1000 Polymeric structure, not readily bioavailable 1, offers sustainability replacement solutions for decabromodiphenyl oxide (DE-83R ) and decabromodiphenyl ethane (Firemaster 2100R) High bromine content, more efficient than other alternatives to DE-83R and Firemaster 2100R Offers an excellent balance of physical properties, flammability performance and process ability Cost-effectively provides UL-94 V-0 performance in Polyolefin and Styrenic based formulations and other resins 1 49 Federal Register (Nov. 11, 1984), 40 CFR

17 Emerald Innovation 1000 Typical Properties EMERALD INNOVATION 1000 IS A POLYMERIC BROMINATED FLAME RETARDANT DESIGNED FOR USE IN A BROAD SPECTRUM OF APPLICATIONS Appearance Property Emerald Innovation 1000 Off-white powder Bromine, % 78 Average particle size, (µm) 5-6 5% wt loss, 0 C (Thermogravimetric Analysis (@ 10 0 C/min under N 2 ) C High content with excellent thermal stability

18 Emerald Innovation 1000 in HDPE* Property Emerald Innovation 1000 FR-1 FR-2 FR-4 FR-5 FR Load, % ATO % UL-94, at 1.6 mm V-0 V-0 V-0 V-0 V-0 Gardner Multi-Axial Impact, J Elongation at Yield, % Whiteness Index, CIE *LYONDELLBASELL PETROTHENE R (0.8MFI) LABEL DESCRIPTION FR-1 DECABROMODIPHENYL OXIDE (DE-83R ) FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R) FR-4 POLY(PENTABROMOBENZYL) ACRYLATE FR-5 ETHYLENEBIS(TETRABROMOPHTHALIMIDE) Emerald Innovation 1000 offers an excellent balance of efficiency, physical properties and flammability performance in HDPE formulations

19 Viscosity, Pa-sec Comparison of Melt Viscosities Capillary Rheology of HDPE Formulation Containing Emerald Innovation 1000 Emerald Innovation 1000 Emerald Innovation 1000 FR1 FR FR2 FR2 FR4 FR3 FR4 FR Shear Rate, 1/sec Comparable viscosities in HDPE formulations indicate that Emerald Innovation 1000 will process under similar conditions as current flame retardant formulations

20 Gardener Multi-Axial Impact of HDPE* with Emerald Innovation 1000 vs. FR-4 FR-4 Emerald Innovation 1000 Brittle failure and delamination Ductile yield *LYONDELLBASELL PETROTHENE R (0.8MFI) * Tested at room temperature Superior compatibility of Emerald Innovation 1000 with HDPE results in significantly better toughness vs. FR-4 for demanding applications

21 Emerald Innovation 1000 Performance in Talc-Filled PP* Emerald Innovation 1000 FR 1 FR 2 Flame retardant % ATO % Talc % UL-94, 1.6 mm V-0 V-0 V-0 Melt flow index, g/10min 230 o C/2.16kg Notched Izod Impact, J/m Elongation at Yield % *Profax SG702 copolymer16 MFI 30.0% + Profax 6323 homopolymer 12 MFI 21.0% LABEL DESCRIPTION FR-1 DECABROMODIPHENYL OXIDE (DE-83R ) FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R) Emerald Innovation 1000 is an effective replacement for FR 1 or FR 2 for talc-filled PP Excellent performance also demonstrated in PP homopolymer and copolymer

22 Emerald Innovation 1000 Performance in HIPS All formulations contain 4.0% antimony trioxide *afterglow LABEL DESCRIPTION FR-1 DECABROMODIPHENYL OXIDE (DE-83R) FR-2 BIS (PENTABROMOPHENYL) ETHANE (FIREMASTER 2100R) FR-3 2,4,6-TRIS(2,4,6-TRIBROMOPHENOXY)1,3,5 TRIAZINE Excellent impact performance Efficiency at equal or lower load levels Equivalent Vicat softening performance Melt flow similar to DE-83R, superior to Firemaster 2100R

23 SOLUTIONS FOR ANTIMONY TRIOXIDE REDUCTION

24 Why the Need for ATO Alternatives? Antimony trioxide (ATO) is typically used as a synergist with aromatic brominated flame retardants (BFR) in plastics ATO functions via the formation of flame quenching antimony tri-halides through a gas-phase mechanism. It is not absolutely necessary but makes the system more cost effective Alternatives to ATO are sought due to: Cost volatility of antimony metal Higher cost of ATO

25 Cost Volatility of Antimony Metal 18,000 Monthly average LMB price of Sb metal in $/MT 17,000 16,000 15,000 14,000 13,000 12,000 11,000 10,000 9,000 8,000

26 Metal Salts 20% Talc filled Polypropylene* Emerald Innovation 1000, % ATO TMS, % Zn Borate, % Ca/Zn molybdate, % Zn molybdate, % Zn phosphate, % mm V-0 V-0 V-0 V-0 V-0 Avg. Burn Time *Profax 6323 homopolymer 12 MFI Significant reduction in ATO content Potential cost reduction Reduced smoke emissions? Kemgard is marketed by J.M.Huber Inc., ZB 467 = Zn Borate Kemgard 981 = Zn phosphate Kemgard 911A = Ca/Zn molybdate Kemgard 911B = Zn molybdate

27 Modified Clays Unfilled PP Homopolymer* Emerald Innovation 1000, % ATO, % Modified clay* % Avg. Burn time, sec 4.2/ / / /4.2 Total Burn time, sec mm V-0 V-0 V-0 V-0 V-0 *Profax 6323 homopolymer 12 MFI Total FR loading can be reduced ATO loading significantly reduced Reduced smoke emissions possible? *Modified clay: quaternary ammonium and siloxane treated montmorillonite clay. Charex 44PSS Amcol/Nanocor

28 Modified Clays Unfilled PP Copolymer* Emerald Innovation 1000, % ATO, % Modified clay*, % Avg. Burn time, sec 0/ / / /1 2/0.8 2/5.2 Total Burn time, sec mm V-0 V-0 V-0 V-0 V-0 V-0 MFI, g/10min *Profax SG702 copolymer 18MFI *Modified clay: quaternary ammonium and siloxane treated montmorillonite clay. Charex 44PSS Amcol/Nanocor Modified clay effectively replaces up to about 50% ATO Cost saving potential Minimum effect on flow

29 Modulus (MPa) Mechanical Properties of Unfilled PP Copolymer Containing Modified Clay Notched Izod impact (J/m) FR/ATO/Nanoclay FR/ATO Tensile Strength, MPa Break, % Yield, % FR, % ATO, % Modified clay, % 2 Izod Impact, J/m Tensile strength, MPa Strain at yield, % Strain at break,% Modulus, MPa Mechanical properties slightly better

30 Burn time, seconds Burn time, seconds wt % FR Flammability time, seconds PPE/HIPS Blends Antimony Oxide free UL94 Rating 1.6 mm V V V V-0 V-2 V-1 V-0 y = 0.75x x R² = V HIPS 5511, PPO640 PPE/HIPS (1:1) PPE/HIPS (1:3) FR-1, wt % wt % FR-1 V-1 Flammability time, seconds UL94 Rating 1.6mm V V V V-0 V-1 V-0 y = -0.1x x R² = V FR-1, wt %

31 1:1 PPE/HIPS Control FR-1 FR-7 FR Load level, % Notched Izod Impact Strength, 1/8 J/m HDT 1.8 MPa Tensile Strength, MPa Elongation at Yield, % Elongation at Break, % Flexural Strength, MPa Flexural Modulus, MPa Melt flow index, 280 ºC/5kg; g/10mins Mechanical properties for FR-1 are similar to base resin unlike FR-7 FR-7 = bisphenol-a bisdiphenyl phosphate

32 PPE/HIPS Emerald innovation 1000 BAPP Flexural Modulus, Mpa HDT, C MFI g/10min Notched Izod Impact J/m Tensile Strength, Mpa Flexural Strength, Mpa Yield (%) Emerald Innovation 1000 does not detract properties of PPE/HIPS Break (%)

33 ATO Free HIPS based Formulations FR-1 FR-2 FR-3 FR-4 FR, % PPE, % HIPS, % Kraton D1101, % Alkanox 240, % PETS wax, % mm V-0 Fail Fail Fail Average Burn time, secs 2.6 >30 >30 >30 Emerald Innovation 1000 demonstrates unique performance Does not require ATO synergist unlike other BFRs FR-1 = Emerald Innovation 1000 FR-2 = decabromodiphenyl ethane FR-3 = decabromodiphenyl ether FR-4 = 2,4,6-Tris(2,4,6-tribromophenoxy)-1,3,5 triazine

34 FR-1/PPE vs FR-2/ATO Formulation FR-1 FR-2 FR % PPE, % ATO, % HIPS, % Kraton D1101, % mm V-0 V-0 Average Burn time, secs Notched Izod Impact Strength, 3.2 mm J/m Gardner Multi Axial Impact, J HDT, 1.8 MPa Vicat softening temperature, C Tensile Strength, MPa Elongation at Yield, % Elongation at Break, % Flexural Strength, MPa Flexural Modulus, MPa Melt flow index, 200 C/5kg; g/10mins

35 MFI, g/10mins Melt Viscosity as a Function of Temperature FR2/ATO Temperature, C PPO 640 PPO C MFI at 240 C for FR-1/PPE is equivalent to FR/ATO at 200 C

36 PC/ABS* Blends (80/20) % FR-1 Burn Time, seconds UL mm 14 0 V V V V V V-0 FR-1 = Emerald Innovation 1000 PC = Lexan 141 ABS = Hival G

37 ATO Free PC/ABS Blends (80/20) FR-1 FR-5 FR-6 FR-7 FR % UL-94, 1.6 mm V-0 V-2 V-2 V-0 Average Burn time, secs Melt flow index, 260ºC/2.16kg; g/10mins HDT 1.8 MPa Notched Izod Impact, 3.2mm J/m Tensile Strength, MPa Elongation at Yield, % Elongation at Break, % Flexural Strength, MPa Flexural Modulus, MPa FR-1 = Emerald Innovation 1000 PC = Lexan 141 ABS = Hival G All formulations contain 0.1% Ultranox 626 & PETS wax FR-6 formulation contains 0.1% PTFE FR-5 = brominated carbonate oligomer FR-6 = poly(pentabromobenzyl acrylate) FR-7 = bisphenol-a bisdiphenyl phosphate

38 FR-1 vs. FR MFI Flexural Modulus, MPa Izod Impact Strength FR-1 FR-7 Flexural Strength, MPa 20 0 HDT, C Elongation at Break, % Tensile Strength MPa Elongation at Yield, % Emerald Innovation 1000 does not plasticize the resin unlike FR-7 Improved overall HDT, impact and mechanical properties

39 % FR-1 ATO-free PC/ABS Blends (Variable Composition) %PC % FR FR-1 = Emerald Innovation 1000 PC = Lexan 141 ABS = Hival G FR-1 in PC-ABS % PC in PC-ABS

40 Conclusions Performance comparisons for Emerald Innovation 1000 in polyolefins and styrenics demonstrate comparable efficiency at similar load levels over DE-83R and Firemaster 2100R Emerald Innovation 1000 provides higher multi-axial impact strength than other polymeric brominated flame retardants tested Evaluation of metal salts and modified clays show great potential to significantly reduce the use of high cost ATO in polyolefins whilst maintaining flammability performance HIPS formulations containing Emerald Innovation 1000 & PPE exhibits V-0 performance without ATO In PC/ABS blends Emerald Innovation 1000 exhibits V-0 without ATO over a wide range V.2.0

41 Sustainable, Innovative, High Performance Polymeric Flame Retardant for Polystyrene Foams V 2.0

42 V 2.0 The Value of Emerald Innovation 3000 The polymeric structure of Emerald Innovation 3000 renders it not readily bioavailable *, thus addressing the environmental concerns that threaten the sustainability of many current products. Emerald Innovation 3000 is an efficient, sustainable replacement for HBCD requiring minimal modification to current formulations or production processes. Applicable fire safety standards covering polystyrene foam insulation can be achieved with Emerald Innovation Synergists commonly used for EPS and XPS production are compatible with Emerald Innovation Our strategy of greener innovation provides you with proven, sustainable alternatives

43 Emerald Innovation 3000 Appearance Property CAS# Emerald Innovation 3000 white powder Bromine, % 64 Softening point, 0 C 120 5% wt loss, 0 C (Thermogravimetric Analysis (@ 10 0 C/min under N 2 ) C

44 Emerald Innovation 3000 Flammability Performance Compared to HBCD V 2.0 Emerald Innovation 3000 demonstrates comparable thermal stability and fire retardant efficiency versus HBCD at similar bromine levels

45 Flammability Performance V 2.0 Emerald Innovation 3000 demonstrates comparable fire safety performance versus HBCD at similar bromine levels

46 DfE Screen Results for Polymeric FR 1 1.Davis, J.W. et. al., Strategic Approach Towards Developing More Environmentally Sustainable Flame Retardants, 12 th Workshop on Brominated and Other Flame Retardants, vl= very Low L= Low vh= veryhigh NE= no evidence

47 Emerald Innovation 3000: Your Sustainable FR Solution for EPS and XPS V 2.0 The polymeric nature of Emerald Innovation 3000 renders it more sustainable than other flame retardant alternatives. Emerald Innovation 3000 is the best choice when developing a sustainable product portfolio. In EPS and XPS, Emerald Innovation 3000 demonstrates comparable efficiency at similar bromine content to HBCD. Handling and processing of Emerald Innovation 3000 is comparable to HBCD. Unlike HBCD, Emerald Innovation 3000 does not interfere in polystyrene polymerization chemistry, providing improved control of molecular weight during EPS production. The high solubility of Emerald Innovation 3000 in styrene monomer allows for easy introduction into EPS production processes. Emerald Innovation 3000 can be easily incorporated into a masterbatch for use in XPS.

48 Conclusions GREAT LAKES SOLUTIONS IS COMMITTED TO GREENER INNOVATION 4/19/

49 CONCLUSIONS Recent introductions of new polymeric flame retardant platforms demonstrates the feasibility of sustainable flame retardant This approach applies to both halogenated and nonhalogenated flame retardants Versatile, cost-effective approach across most polymer systems Great Lakes Solutions provides Versatile, Sustainable Flame Retardant Solutions for a variety of applications

50 Acknowledgements and Thanks Great Lakes Solutions Applications Research Laboratory Dr. Subra Narayan Harry Hodgen Julie McKeown Ken Bol Applied Market Information Ltd