Recent developments in flame retardants for sustainable fire safety solutions: Emerald Innovation 3000 polymeric flame retardant Presentation to AMI Masterbatch 2013 Patrick Jacobs, Technical Business Service EMEA Great Lakes Solutions, a Chemtura business
Agenda Chemtura / Great Lakes Solutions Overview Greener Innovation Strategies Emerald Innovation TM 3000 Polymeric Flame Retardant Introduction: structure Fire performance vs. HBCD / other aliphatic FRs Thermal stability in MB and at use levels Conclusions 2
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 more than 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
KEY GROWTH DRIVERS KEY BUSINESSES Great Lakes Solutions, an Industry Leader INDUSTRIES SERVED Flame Retardants Electrical & Electronics Insulation & Furniture Automotive Brominated Performance Products Fine Chemical/ Pharmaceutical Biocides Energy: Oilfield & Mercury Control Automotive Tires Fumigation Mercury control Greener innovation Rapid growth in electronics Flame retarded energy efficient thermal insulation Increased global fire safety standards Fine Chem/ Pharma Auto Energy Electrical & Electronics Fumigation Biocides Other Insulation & Furniture 4
Greener Innovation How Do We Move Toward Environmentally Friendly, Sustainable FR Solutions? Great Lakes Solutions is applying a Greener is Better philosophy... 5
Greener 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 persistance Not bioavailable Not toxic 6
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 3000. Synergists commonly used for EPS and XPS production are compatible with Emerald Innovation 3000. * Per criteria described in US Federal Register notice 40 CFR 723 Our strategy of greener innovation provides you with proven, sustainable alternatives 7
Results of Screening Versus Design for The Environment Assessment Framework PolyFR = Emerald Innovation 3000 Source: Davis, J.W. et. al., Strategic Approach Towards Developing More Environmentally Sustainable Flame Retardants, 12th Workshop on Brominated and Other Flame Retardants, 2011 vl= very Low L= Low vh= very High NE= no evidence Persistent by Design, Required for Service Life & Stability Low to Very Low in All Health and Environmental Effects 8
Emerald Innovation 3000 Appearance Property Emerald Innovation 3000 Compacted powder Bromine, % 64 Softening point, 0 C 120 5% wt loss, 0 C (Thermogravimetric Analysis (@ 10 0 C/min under N 2 ) 262 0 C 9
Emerald Innovation 3000 Flammability Performance Compared to HBCD Emerald Innovation 3000 demonstrates comparable fire retardant efficiency versus HBCD at similar bromine levels 10
Comparison to Partially Aliphatic Bromine Source Formulation % Br % Synergist DIN 4102 B2 Swiss Fire Testing (5.1) HBCD 1.60 - Pass Pass Emerald Innovation 3000 1.00 0,2 Pass Pass FR1 1.90 0,25 Fail Fail FR1 2,40 0.30 Fail Fail Data provided by the Dow Chemical Company FR1 = Tetrabromobisphenol A bis (2,3-dibromopropyl ether), a.k.a. PE-68 Synergist = An organic compound having labile C-C linkages capable of generating radicals in the early stages of ignition process which can reduce the molecular weight of the host polymer. Aliphatic C-Br bonds are the key to efficiency in PS foams Only one half of the bromine in FR1 is aliphatic FR1 is not effective at >50% higher load level 11
Thermal Stability Testing Emerald Innovation 3000 is an efficient FR for extruded polystyrene (XPS) but lacks thermal stability, like HBCD, during processing Goal is to determine a suitable stabilization package for processing Emerald Innovation 3000. All formulations were run on a single screw extruder for multi-pass evaluation in Polystyrene Nova PS1600 @ 200 C Pellets from extrusion pass 1, 3 & 5 were set aside for melt flow and color determination on molded plaques 12
Color and MFI Data 24-01 24-02 24-03 24-04 24-05 24-06 24-07 24-08 24-09 24-10 % Emerald Innovation TM 3000-2 2 2 2 2 2 2 2 2 % Epon 164 - - 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 % Anox 20 - - 0.1 0.1 0.15 - - - 0.1 - % Naugard 445 - - - 0.1 0.15-0.1 0.15 - - % TBM6 - - - - - 0.1 0.1 0.15 - - % Ultranox 626 - - - - - - - - 0.1 - % Irganox 565 - - - - - - - - - 0.2 % Nova PS 1600 100 98 97.7 97.6 97.5 97.7 97.6 97.5 97.6 97.6 Color Values YI D1925 1st Pass 2.04 10.12 5.72 3.23 2.50 3.80 4.75 4.53 0.04 4.65 3rd Pass 3.51 22.90 7.62 6.01 5.24 8.60 7.82 8.25 1.11 8.03 5th Pass 3.95 44.27 7.80 9.15 7.37 13.77 12.17 12.67 2.31 11.52 WI CIE 1st Pass 70.52 39.07 50.45 57.16 58.26 56.58 53.69 53.97 66.02 52.39 3rd Pass 64.23-2.55 42.88 47.49 48.8 40.32 43.13 42.18 61.34 40.79 5th Pass 63.06-75.81 41.78 36.8 41.46 24.64 29.92 28.83 56.71 29.42 MFI @ 200C/5kg, g/10min 1st Pass 7.04 7.62 6.09 5.55 5.86 5.86 5.08 6.08 5.39 5.71 3rd Pass 7.85 8.79 6.11 6.23 6.15 6.38 6.53 6.58 5.64 6.16 5th Pass 8.67 9.67 6.64 6.58 6.87 7.04 7.40 7.47 5.69 6.38 13
Yellowness Index 50 45 40 35 1st pass 3rd pass 5th pass 30 25 20 15 10 5 0 0.1% Anox 20/0.1% Ultranox 626/ 0.2% Epon 164 appears to be most effective 14
Processing at Higher Temperature Extruder Temperature Profile, C 200, 230, 260, 260 250, 260, 260, 260 % Emerald Innovation 3000 2 2 % Epon 164 0.4 0.4 % Anox 20 0.1 0.1 % Ultranox 626 0.2 0.2 % Nova PS 1600 97.3 97.3 YI D1925 6.57 18.97 WI CIE 44.12 6.67 MFI @ 200 C / 5kg / g/10min 5.96 6.16 Increasing the Stabilization package and using a gradually increasing temperature profile in extrusion allows for processing at higher temperatures 15
Emerald Innovation 3000 thermal stability testing vs. stabilised HBCD Masterbatch samples 62.5% FR + Epon 164/Anox 20/Ultranox 626 (6.25%/3.125%/3.125%) Extrusion temps: 190, 195, 200, 200 C Masterbatch pellets pressed via compression molding into thin plaques Compression molding carried out at 150 C 16
Emerald Innovation 3000 thermal stability testing vs. HBCD Masterbatch compression molded Emerald Innovation 3000 MB Stabilised HBCD MB 17
Emerald Innovation 3000 thermal stability testing vs. HBCD Masterbatch pellets subject to oven aging at 200 C for 30 min. Let-down in Polystyrene (zinc free) @ 2% FR loading Let-down samples injection molded into 0.8mm plaques and subject to oven aging at 200 C for 30 min. 18
Emerald Innovation 3000 thermal stability testing vs. HBCD Masterbatch pellets subject to oven aging Emerald Innovation 3000 MB Stabilised HBCD MB 19
Emerald Innovation 3000 thermal stability testing vs. HBCD Let-down at 2% and subject to oven aging Emerald Innovation 3000 Stabilised HBCD 20
Summary Emerald Innovation 3000 is a highly efficient fire safety solution for XPS foam insulation. An optimized stabiliser solution (0.1% Anox 20/0.1% Ultranox 626 along with 0.2% Epon 164) has been developed for XPS containing Emerald Innovation 3000. This stabilisation package produced an excellent balance of Yellowness Index, Whiteness Index and MFI of Polystyrene after 5 extrusion passes. Emerald Innovation 3000 stabilised with the optimized package has a better thermal stability compared to stabilised HBCD. 21
Acknowledgements and Thanks Great Lakes Solutions Applications Research Laboratory West Lafayette, Indiana Dr. Subra Narayan Harry Hodgen Julie McKeown Ken Bol For More Information: patrick.jacobs@chemtura.com 22