Sustainable Flame Retardant Developments for the Polyurethane Industry

Transcription

1 Sustainable Flame Retardant Developments for the Polyurethane Industry Greg Symes Global Polyurethane BU Manager Munjal Patel Global Market Support Manager November 11 th 13 th, 2014

2 Outline Brief introduction on ICL(-IP) Flame Retardant (FR) Basics Flame Retardant Trends Status TDCP and TCPP Product Development of sustainable FRs Fyrol HF-10 as TDCP-alternative in automotive foam E06-16 New reactive TCPP-alternative in PIR boardstock Conclusions

3 Mining Chemistry Formulation Israel Chemicals Ltd Leading specialty minerals company fulfilling essential needs in Agriculture, Food and Engineered Materials Turnover US$ 6.3 billion; employees (2013) Unique minerals K Processing expertise ESSENTIAL NEEDS* P Agriculture 55% S Food 8% Br Engineered Materials 29% Mg * Percentages represent share of 2013 sales

4 ICL-Industrial Products ICL-IP is the Industrial Products segment of ICL Leading producer of elemental Bromine Bromine inorganics Bromo-organics Biocides Flame Retardants Phosphorus Leading producer of P-based Flame Retardants Inorganics Magnesia Products Emphasis on innovation & new product development

5 ICL-IP Headquarters Beer Sheva, Israel Production Sites Israel France Germany The Netherlands USA China Sales Offices Europe North America Brazil Japan China Hong Kong Israel R&D/Technical centers Israel: Beer Sheva Haifa USA: Ardsley Germany: Bitterfeld China: Shanghai

6 FR Basics Flame retardants play an important role in public fire safety They have a long history in polyurethane (PU) and polyisocyanurate (PIR) foam applications such as consumer products (furniture & automobile) and thermal insulation in buildings (rigid foam for building envelope) Why/How are they used: FR products are carefully formulated into highly combustible raw materials to minimize their flammability, thereby allowing the safe use of these raw materials in commercial products FR products help prevent fires from starting and/or dramatically slow combustion For economic reasons, FR products are typically used at minimal levels to prevent ignition from the most logical combustion sources (cigarette and open flame) Products with flame retardant additives can still burn. The addition of FR s helps manage the combustible nature of urethanes. New flame retardant products are exhaustively tested and approved for intended uses by regulatory agencies in North America, Europe and Asia

7 Temperature FR Basics Prevent ignition.. primary purpose Resist large fire not usually Start of fire flash over Slow down the spread of fire Time

8 FR Trends - General Public and governmental scrutiny of chemicals has increased over the years; FRs are no exception Growing concerns about chemical exposure and their migration into our environment Currently, most widely used FRs in PU foam are: TDCP Furniture (US) Automotive (EU) TCPP Furniture (EU) Insulation

9 FR Trends Status TDCP EU: Risk approach (Risk = Hazard * Exposure) Labelling since many years, but low exposure R40 = Limited evidence of a carcinogenic effect R51/53 = Toxic to aquatic organisms; may cause long term effect in aq. environment Oct, 2009: German TV (ZDF, Frontal21) measures air quality in car interiors Feb 24 th, 2014: Ban on a.o. TDCP in toys and children s goods US: Hazard approach Oct 12 th, 2011: California Proposition 65 listing => Cal. TB117 dropped Bills passed in states of New York, Maryland and Vermont to ban TDCP in consumer products based on structural similarity to TCEP (EPA DfE) Bills submitted in Illinois, Connecticut, North Carolina, Maine, Massachusetts and Washington. More are expected TDCP is a declarable substance according to GADSL (#128: D/FA) Oct 2014: TDCP included in SIN list ( NGO blacklist )

10 FR Trends Status TCPP Read across and structural similarity TDCP/TCEP US Ubiquitous claim: Found in breast milk, fish, household dust, indoor air and surface water EPA National Toxicology Program Carcinogenicity study Negative assessment in Design for Environment study No bans yet, but Vermont and California are assessing

11 FR Trends Status TCPP EU H302 Harmful if swallowed Banned in toys and toddlers goods (not evidence based; just read-across) Banned in Ecolabels (based on halogen-content) IKEA repeatedly asking for alternatives How will outcomes US affect EU?

12 FR Trends Results Push towards more sustainable reactive, polymeric and/or halogenfree new product offerings with an improved HSE profile and minimal potential for migration out of matrix However, new developments require R&D resources, time and investment ICL announced voluntary phase out of TDCP for furniture applications by Jan 1 st, 2013 and for automotive applications by end of 2015 ICL still believes TCPP to be safe in use and plans to continue producing TCPP until stopped by regulatory action or a move by the value chains to other technologies

13 New Product Development Criteria for Sustainable FRs for PU-foam POLYMERIC REACTIVE CLEAN HSE PROFILE REDUCED LOADING LOW FOAM SCORCH LOW VOC, NON-FUGITIVE GOOD STABILITY NOT PBT (PERSISTENT, BIOACCUMULATIVE, TOXIC) NOT VPVB (VERY PERSISTENT, VERY BIOACCUMULATIVE) NOT CMR (CARCINOGENIC, MUTAGENIC, REPROTOXIC) COST EFFECTIVE (TO PRODUCE AND USE) COMMERCIALLY VIABLE SYNTHETIC ROUTE

14 TDCP-alternative: Fyrol HF-10

15 Automotive PU FRs - History Fyrol A710 (2000) Halogen-free FR for mid-high densities Fyrol PNX (2000) Very efficient FR; scorch potential Fyrol PNX-LE (2004) Reduced volatiles Fyrol HF-5 (2010) All densities; moderate scorch potential Fyrol HF-10 (2014) Low emission product for automotive New development: Reactive FR

16 Fyrol HF-10 Foams with like densities, air flows, and overall foam quality were produced and tested Results compared to known commercial FR s, like TDCP, Fyrol A710 and Fyrol PNX Flammability loading levels (FR efficiency) Fog/VOC Foam physical properties Discoloration

17 Typical Properties Property Fyrol HF-10 Fyrol FR-2 (TDCP) / 300TB Fyrol A710 Fyrol PNX-LE Appearance CTL CTL CTL CTL Color (APHA) < 100 < 100 < 100 < 350 Viscosity 25 C) / P-content (%) 12,7 7,1 / 7,1 8,4 19 Density (kg/m 3 ) / Acid number (mg KOH/g) Water content (wt%) Remark < 1,0 < 0,02 < 0,02 < 2.0 < 0,1 < 0,1 < 0,1 < 0.1 TPP content Only for ether foam

18 Performance in PolyETHER foams

19 PolyETHER formulation Hand-Mix PU Formulations Used for Evaluation (24 & 29 kg/m 3 density) Ingredient Level Level Polyether polyol, Voranol 3136 (Dow) Flame retardant variable variable H 2 O Catalyst, Dabco BLV (Air Products) Silicone surfactant, Niax L-620 (Momentive) Stannous octoate, Dabco T-10 (Air Products) TDI Index Foam Density (pcf / kg/m 3 ) 1.5 / / 29

20 Passing Level (php) PolyETHER foam FMVSS kg/m3 29 kg/m Fyrol PNX Fyrol HF-10 TDCP Fyrol A710

21 Fogging and VOC OEMs require automotive interior parts to have excellent fogging properties, which also applies to the FR products used in the parts Reducing volatiles in car interiors, while at the same time providing flame retardancy to meet the FMVSS-302 flammability standard is of growing importance for automobile manufacturers worldwide There are many different methods for measuring the emission of volatile components from PU foams; test conditions vary widely

22 Deposit (mg) DIN Results PolyETHER Fogging - Gravimetric Method 8,7 9,2 5,6 4,4 1,2 1,7 No FR Foam Fyrol PNX-LE Fyrol HF-10 Fyrol A710 TDCP Fyrol PNX

23 PolyETHER foam VDA 277 Fyrol A300TB (TCDP-based) Fyrol A710 VDA 277 test in µgc/g Specs VW 50 and Audi 20 Components related with FR 3 µgc/g -> 1,3 dichloro-2- propanol 3 µgc/g -> Phenol Fyrol HF-10 4 µgc/g -> Phenol

24 PolyETHER foam Compression Set Compression set test in ether foam at 26 kg/m 3 density 22 hours at 70 C 75% compression Fyrol FR-2 (TDCP) 10 % Fyrol HF % Fyrol PNX-LE 10 %

25 Delta E PolyETHER foam - Scorch 80,00 70,00 Scorch Performance 60,00 50,00 40,00 30,00 20,00 10,00 0,00 50,00 70,00 90,00 110,00 130,00 150,00 Time (min) Fyrol PNX TDCP Fyrol HF-10 Fyrol A710

26 Performance in PolyESTER foams

27 PolyESTER formulation Desmophen 2200B Water Niax C-131NPF 1,1 1,1 1,1 Niax DMP 0,2 0,2 0,2 Niax Silicone L-537XF 1,3 1,3 1,3 Fyrol A300TB 7 Fyrol HF-10 8 Fyrol A Index Tests Air flow [l/min] Density [kg/m 3 ] 32,1 31,7 29,7 Density [pcf] 2 2 1,9 Automotive FMVSS 302 SE NBR SE NBR SE NBR Compression Set (%) 32,6 30,2 26

28 pphp PolyESTER foam FMVSS Polyester foam 30 kg/m FR level for SE/NBR 2 0 Fyrol A710 Fyrol HF-10 Fyrol A300TB Fyrol PNX/LE

29 PolyESTER foam VDA 277 Fyrol A300TB Fyrol A710 VDA 277 test in µgc/g Specs VW 50 and Audi 20 Components related with FR Pass -> 1,3 dichloro-2- propanol Pass -> Phenol Fyrol HF-10 Pass -> Phenol

30 PolyESTER foam Compression Set Compression set test in ester foam at 30 kg/m 3 density 22 hours at 70 C 75% compression Fyrol A300TB 33 % Fyrol A % Fyrol HF %

31 TCPP-alternatives: Fyrol HF-10 (Flexible Foam) & E06-16 Reactive (Rigid Foam)

32 Fyrol HF-10 in BS-5852 Crib Flame Retardant (pphp) Melamine (pphp) Weight Loss (grams) Foam Density = 32 kg/m TCPP Fyrol HF-10 Fyrol PNX TDCP

33 E06-16: Reactive TCPP-alternative for use in rigid foam PIR rigid foams were made using a discontinuous panel manufacturing process Results are compared to industry control (Fyrol PCF) to ensure a reference point is always present Physical Properties Compressive strength, Closed cell content Insulation R-values measured at 10 C Flammability Cone calorimeter and DIN 4102 tests - Predictive small-scale tests ASTM E84 Steiner tunnel test (US building code requirement) and SBI test (European building code requirement) - Large-scale fire tests

34 PIR Boardstock formulation Ingredient Level (PHP) Polyester polyol Flame retardant 15 Surfactant 1-3 Catalyst A Catalyst B 3-5 Catalyst C Water mfc/245fa MDI Index 270 Density (kg/m 3 ) 32

35 Results E06-16 vs TCPP Parameter Fyrol PCF (TCPP) E06-16 (Reactive) Compressive strength (kpa) Closed cell content (%) 97,3 96,1 10 C (m 2.K/W) 1,19 1,24 Cone THR (MJ/m 2 ) 3,3 3,9 Cone TSR (m 2 /m 2 ) Char yield (%) DIN 4102 (cm) 8,7 8,2 ASTM E84 Class I Class I

36 Single Burning Item (SBI) PIR boards with Fyrol PCF and E06-16 were tested in the Single Burning Item (SBI) test, EN PIR board (FR) FIGRA (W/s) THR (MJ) SMOGRA (m 2 /s 2 ) TSP (m 2 ) Fyrol PCF (C) 1238 (s3) 180 (s2) E (C) 1133 (s3) 159 (s2) Fyrol PCF and E06-16 PIR panels achieved a comparable fire performance and E classification for FIGRA and C classification for THR in the SBI test with naked panels

37 Conclusions Growing demand for halogen-free, reactive and/or polymeric FR products for the flexible and rigid PU-foam markets ICL-IP has had a long history in developing new flame retardant products and will continue to develop safe and sustainable products that respond to the challenging needs of the market Fyrol HF-10 is a sustainable, halogen-free TDCP-alternative for automotive flexible foam applications (both in Polyether and Polyester) Fyrol HF-10 is a sustainable, halogen-free TCPP-alternative for furniture flexible foam applications (BS-5852) E06-16 is a sustainable, reactive TCPP-alternative for use in PIR Rigid foam ICL is currently commercializing both Fyrol HF-10 and E06-16 Negative publicity and potential deselection of PU-foam can be avoided by choosing sustainable alternatives now

38 Acknowledgements ICL-IP America Dr. Andrew Piotrowski Manny Pinzoni Munjal Patel Dr. Jeffrey Stowell Greg Symes Kali Suryadevara Barbara Williams ICL-IP Bitterfeld Jens Leopold Dr. Mike Hildebrand Dr. Horst Fedgenhauer Joop Wuestenenk

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