FluoroCouncil and its Activities. July 23, 2013 Place:JCIA Hosted by FluoroCouncil Japan Subgroup Cooperated by JCIA

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1 FluoroCouncil and its Activities July 23, 2013 Place:JCIA Hosted by FluoroCouncil Japan Subgroup Cooperated by JCIA

2 Today s Contents Fluoro-technology: The Chemistry, Its Uses and Its Benefits Fluorotelomer-based Water & Oil Repellents What s happening in PFOA related areas since 2000 FluoroCouncil: An Overview Global Regulatory Update Current FluoroCouncil Activities Alternative C6 Chemistry Toxicology Profile

3 FluoroTechnology: The Chemistry, Its Uses, and Its Benefits 3

4 Fluoro-technology: Fluorinated Polymers and Surfactants - Fluoropolymers - Fluorochemicals Fluorinated Polymers and Surfactants Includes Fluorotelomers & ECF chemistry short fluorine chains some attached to organic polymer backbones [F(CF 2 ) n -] n > 4 surface modification & protection, surfactants, water & oil repellency Fluoropolymers High MW (10 7 ) polymers PTFE & Melt Copolymers fluorinated backbone cookware, CPI linings, aerospace, automotive, apparel, construction, etc. Fluorochemicals small molecules 1-8 carbons refrigerants cleaning solvents blowing agents CFC alternatives (e.g. HFC s) Not in FluoroCouncil scope Fluorotelomers: Asahi Glass, Clariant, Daikin, DuPont and others Fluoropolymers: Arkema, Asahi Glass, Daikin, DuPont, Solvay Specialty Polymers and others 4

5 Fluoro-technology: Products Are Valuable to Society Unique in their physical and chemical properties: thermal stability, chemical resistance Used in applications where their functionality and societal benefits are unique: improved safety through fire-fighting foam applications durability and fuel-efficiency in applications like cars and airplanes, buildings and electronics used to make products with enhanced surface properties such as water, oil and stain resistance Protect people and property and extend the lifetime of consumer goods 5

6 Fluorinated Polymers and Surfactants Applications 6

7 Fluoropolymer Applications Telecomm Wire & Cabling Semiconductor Manufacture High Purity Liquid Handling Low Permeable Automotive Fuel Hose Chemical Processing Valves, Lined Piping, Tanks Aerospace Materials Hydraulic tubing Wire & Cabling Flares Construction Architectural Fabric Non-stick Coatings for Cookware and Small Electrical Appliances 7

8 Fluorotelomer-based Water & Oil Repellents 8

9 General Chemical Structure Of Fluorotelomerbased Water & Oil Repellents k, l, m & n: representing molar ratios of each monomer. They vary according to products. R1 : H or CH3 R 1 C H 2 C C H 2 C C H 2 C C H 2 C C O C O X Y O C H 2 C H 2 R f Water Repellency Oil Repellency Soil Release Rf: C 2 F 5 (C 2 F 4 ) n - n = 2 C6 telomer n = 3 C8 telomer R 1 k l m n O R 2 Film Formation Soft Texture R2 : hydrocarbon alkyl R 1 Durability Hard Texture Adhesiveness with resins R 1 Y : crosslinking functional group

10 How does the polymer structure give water & oil repellency on the surface of a substrate? Fiber Oriented fluoroalkyl chains Thermal Cure Hydrocarbon Polymer Chain -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 -A-(CF 2 -CF 2 ) n -CF 2 -CF 3 A: Spacer Created Fiber

11 How Do Traces Of PFOA Occur In C8 Fluorotelomer-based Water & Oil Repellents? PFOA is not used on the manufacturing process of C8 fluorotelomer-based water & oil repellents but it occurs as unintended byproduct in trace amounts during the process. Telomerization 5F 2 C = CF 2 + IF 5 + 2I 2 5CF 3 CF 2 -I CF 3 CF 2 -I + nc 2 F 4 C 2 F 5 (C 2 F 4 ) n -I (=Rf-I, Telomer) Ethylene Addition Rf-I+ CH 2 = CH 2 Rf CH 2 CH 2 -I Alcoholization RfCH 2 CH 2 -I + H2O RfCH 2 CH 2 OH + HI Esterification RfCH 2 CH 2 OH + CH2=CHCOOH RfCH 2 CH 2 O-CO-CH=CH 2 (Monomer) One of suggested reaction routes to PFOA C 2 F 5 (C 2 F 4 ) 3 -I H2O C 2 F 5 (C 2 F 4 ) 3 -OH C 2 F 5 (C 2 F 4 ) 2CF2-COOH PFOA: C7F15COOH

12 What s happening in PFOA related areas since

13 What s happening in PFOA related areas since M discontinues PFOS/PFOA related businesses 2000 Fluoro Industry forms two industry associations (FMG and TRP) Begins long-term engagement with U.S EPA 2003 U.S.EPA initiates process leading to ECA s for testing on PFOA 2006 U.S.EPA proposes 2010/2015 PFOA Stewardship Program. Eight major fluorochemical companies participate 2009 U.S.EPA announces a Long-Chain PFC Action Plan 2010 Stewardship Program companies achieve at least 95% reduction of PFOA from product releases and product content 2011 FluoroCouncil formed 2012 U.S.EPA announces three relevant SNURs 2013 Europe designates PFOA as an SVHC 2015 (planned) Stewardship Program Participating companies virtually eliminate PFOA and precursors from manufacturing releases and product content 13

14 FluoroCouncil Overview 14

15 About FluoroCouncil The FluoroCouncil represents the world s leading fluoro-technology manufacturers. Our membership includes companies that manufacture: fluoropolymer products fluorotelomer-based products fluoro-surfactants fluoro-surface property modification agents 15

16 FluoroCouncil Membership Arkema France Asahi Glass Co., Ltd. Clariant International, Ltd. Daikin Industries, Ltd. DuPont Company Solvay Specialty Polymers 16

17 Focus of the FluoroCouncil Facilitate the successful global transition from long chain PFCs to alternative chemistries such as C6/short chain fluoroproducts that are generally equally efficacious and have improved environmental and biological profiles Advocating for regulatory action that creates consistent good industry stewardship globally Ensuring the appropriate evaluation of alternatives Supporting the classes of new chemistries with sound science Work toward appropriate regulatory outcomes for historical products based on sound science 17

18 Situation Evolving concern about fluorine-containing materials, including chemicals and polymers Down-the-supply-chain pressure to identify materials in retail products, often activist-driven Tendency of regulators to group all PFCs together for regulatory efficiency, incorrectly assuming that all have similar properties Emerging science with regulatory implications: lowdose, epidemiology, etc. 18

19 Key Areas for FluoroCouncil Engagement Regulatory Agencies (Country level and below, as appropriate) International Treaties and Inter-Governmental Organizations Elected Officials Other Industry Groups Non-Governmental Organizations Academia Public 19

20 Global Regulatory Action Update 20

21 Global Regulatory Action Update C8/Long chain products are under consideration, reevaluation and/or restrictions, or bans in multiple countries and regions including: United States European Union Japan China 21

22 US EPA Regulatory Update /2015 PFOA Stewardship Program (2006) U.S.EPA proposes, and the eight major fluorochemical companies voluntarily participate, in a program where the companies commit to: Reduce environmental releases and content in products of PFOA 95% by 2010 compared to a base year Virtually eliminate environmental releases and content in products of PFOA by Long Chain PFC Action Plan Proposal (2009) U.S. EPA proposes to ban manufacture and import of Long Chain Perfluorinated Chemicals and treated articles from 2016, when the Stewardship Program will end. 22

23 US EPA Regulatory Update SNUR (Significant New Use Rules) (2012) 3 SNURs Enacted regulating C8 Chemistry SNUR for Carpet (Effective ban on C8 products in carpets) SNUR for specific chemicals (Controls on 25 chemicals, including 14 related to C8 chemistry and PFOA) SNUR for specific chemicals(controls on 20 chemicals, including 1 related to C8 chemistry and PFOA) EPA affirms that C6 is not targeted by the LCPFC Action Plan (2013) PFAC chemicals with fewer than eight carbons, such as perfluorohexanoic acid (PFHxA), are not considered long-chain PFAC chemicals. These shorter-chain PFAC chemicals are not part of this action plan because data in non-human primates indicate that they have substantially shorter half-lives in these animals than PFOA and are less toxic than long-chain PFAC chemicals. 23

24 EU Regulatory Update Harmonized Classification and Labeling December 2011, Classification of PFOA/APFO as Carcinogenicity 2, Reproductive Toxicity 1B (Classification, Labeling, and Packaging - CLP Regulation). Expected implementation date is January 1, Substance of Very High Concern June 2013, Europe member states decision to list PFOA/APFO as SVHC Restriction of Marketing and Use Probable Restriction proposal PFOA by year-end

25 Japan Regulatory Update and Situation in China Japan PFOA and PFOS were listed as Type 2 Chemical Monitoring Substance in (Persistent, non-accumulative in humans, concern for long term health effects in humans. In 2007, long chain perfluorinated carboxylic acids (12 to 16 carbons) were listed as Type 1 Chemical Monitoring Substance. (Persistent, accumulative, no ban on production). China In 2008, PFOA listed as a Type 1 Specified Chemical Substance. (Adverse effects on humans and organisms, wide distribution in the environment, potential for exposure). There is no apparent regulatory activity with regard to perfluorinated carboxylic acids, including PFOA. There is currently monitoring taking place with regard to PFOS in rivers and streams. 25

26 Current FluoroCouncil Activities 26

27 Marketplace Initiatives and Actions by FluoroCouncil Zero Discharge of Hazardous Chemicals (ZDHC) Program Comprised of numerous apparel retailers/brands Focused on identifying alternatives to long-chain PFCs Working with U.S.-based Outdoor Industry Association and European Outdoor Group Some brands/retailers have signed commitments to various phase-out schedules for chemicals in these campaigns, including PFCs. FluoroCouncil has engaged the outdoor apparel industry and provided supporting data on alternatives. 27

28 Engagement with Governmental Bodies U.S.EPA HC/EC (Health Canada/Environment Canada) UBA (Germany) METI (Japan) OECD/UNEP Stockholm Convention 28

29 Engagement with Industry Associations SPI(The Society of Plastic Industry) CEFIC/Plastics Europe JCIA (Japan Chemical Industry Association) JFIA (Japan Fluoro-resin Industry Association) China Association of Fluorine and Silicone Industry ZDHC(Zero Discharge of Hazardous Chemicals) OIA (Outdoor Industry Associations) EOG (European Outdoor Group) 29

30 Alternative C6 Chemistry Toxicology Profile and Recent Comment by U.S.EPA Concerning LCPFC Action Plan 30

31 Toxicological Data on C6/short chain products and their raw materials Pharmacokinetics in Monkeys Pharmacokinetics in Rats Mammalian Toxicity Toxicology Profile of C6-fluorotelomer Chemistry 31

32 Pharmacokinetics in Monkeys 32

33 (ng/ml) Pharmacokinetics in Monkeys Serum concentration of PFHxA after single intravenous administration (10mg/kg) 1,000, ,000 10,000 1,000 PFHxA-Male PFHxA-Female (hr)

34 hr Pharmacokinetics in Monkeys Blood Half Life of PFHxA and PFOA after single intravenous administration (10mg/kg) Half life is the time required for the amount of a chemical in the body to decrease to 1/2 its starting level. A shorter half-life means that a substance is more quickly eliminated from the body. 34

35 ng h/ml Pharmacokinetics in Monkeys Area Under the Curve after single intravenous administration of PFHxA and PFOA (10mg/kg) 2,500,000 2,000,000 1,500,000 PFHxA Male PFHxA Female PFOA Male PFOA Female 1,000, ,000 0 Area Under the Curve to Infinity (AUCINF) Shown is a comparative measurement of how long a chemical substance remains in a living organism. 35

36 L/h/kg Pharmacokinetics in Monkeys Apparent Systemic Clearance after single intravenous administration of PFHxA and PFOA (10mg/kg) Apparent Systemic Clearance PFHxA Male PFHxA Female PFOA Male PFOA Female Systemic Clearance is the apparent volume of reference fluid such as blood, cleared of a chemical substance per unit time. 36

37 Pharmacokinetics in Cynomolgus Monkeys The results of pharmacokinetics of PFHxA and PFOA after single intravenous administration (10mg/kg) PFHxA PFOA (1) Male Female Male Female AUC 0- (ng h/ml) 84,002 75,157 1,235,000 2,293,000 Half-life (hr) Cl (L/h/kg) Vd (L/kg) Cl: Apparent systemic clearance Vd: Apparent volume of distribution (1): data from draft risk assessment on PFOA, Jan by US EPA 37

38 Pharmacokinetics in Monkeys Summary PFHxA treatment resulted in significantly lower systemic exposure in monkeys than PFOA (15 30 fold) at equivalent dosages. The half-life of PFHxA in serum is 2 orders of magnitude shorter than that of PFOA. 38

39 Pharmacokinetics in Rats (Toxicokinetics in OECD422 study) 39

40 (ng/ml) Pharmacokinetics in Rats < Dosage level : 300mg/kg/day > Day 0 Day (hr) Male Female Serum concentration of PFHxA on Day 0 and Day 25 in the repeated oral dose study (OECD422) 40

41 Mammalian Toxicity of Perfluorohexanoic Acid (PFHxA) and its Salts 41

42 Mammalian Toxicity of Perfluorinated Acids Acute Oral Toxicity and Genotoxicity Study PFHxNa 1) APFO 2) Acute Oral LD50 Genotoxicity Bacterial Reverse Mutation (Ames) Chromosome Aberration Micronucleus 1,750mg/kg Negative Negative : 680mg/kg : 430mg/kg Negative Positive Negative 1) DuPont 2) EPA Draft Risk Assessment (Jan. 2005) 42

43 Mammalian Toxicity of Perfluorinated Acids 90-day Oral Toxicity Study in Rat PFHxA 1) PFHxNa 2) APFO 3) 10mg/kg( )* 50mg/kg( )* 50mg/kg<: Lower body weight gains, lower Cholesterol and calcium 200mg/kg: Lower globulin 20mg/kg(, )** Target organ: Nose, Liver mg/kg( )** 0.64mg/kg<: Lower body weight gains, Increase of liver weight, Hepatocellular hypertrophy * : NOEL **: NOAEL 1) Asahi 2) DuPont 3) EPA Draft Risk Assessment (Jan. 2005) 43

44 Mammalian Toxicity of Perfluorinated Acids Reproductive / Developmental Toxicity PFHxA 1) PFHxNa 2) PFHxNH 4 3) APFO 4) (OECD422) One-Gen. Repro / Developmental Reproductive / Developmental (OPPTS ) Rat Rat Mouse Rat F0 ( ) : 300/450mg/kg** F1: ( ) 300/450mg/kg** 100mg/kg** F0: 100mg/kg( )* F1: 100mg/kg( )** F1: 3mg/kg( )**, 10mg/kg( )** F2: 30mg/kg( )** F1( ): No reproductive changes NOAEL 100 mg/kg/day; no effects on reproductive parameters F1 ( ): Effects in pups occurred only at doses that also produced maternal toxicity F1( ): Lower post weaning BW F2: No repro changes * : NOEL **: NOAEL 1) Asahi 2) DuPont 3) Daikin 4) EPA Draft Risk Assessment (Jan. 2005) 44

45 Mammalian Toxicity of Perfluorinated Acids 2-Year Chronic and Carcinogenicity Study in Rat PFHxA 1) APFO 2) No carcinogenicity at 100mg/kg( ) 200mg/kg( ) Non-neoplastic 15mg/kg( )* 30mg/kg( )* a) Leydig cell tumor, Mammary tumor at 30 and 300 ppm diet*** b) Leydig cell tumor, Liver adenoma, Pancreatic tumor at 300ppm diet (only male tested) b) Non-neoplastic 1.3mg/kg( ) **** 1.6mg/kg( ) **** : NOEL **: NOAEL ***: Correspond to 1.3 & 14.2mg/kg ( ) and 1.6 & 16.1mg/kg ( ), respectively ****: LOAEL 1) Asahi / Daikin 2) EPA Draft Risk Assessment (Jan. 2005) 45

46 Mammalian Toxicity Summary PFHxA and its salt are much (2-3 order of magnitude) less systemically toxic than PFOA. PFHxA and its salts are not selective reproductive toxic agents. PFHxA is not carcinogenic. APFO is carcinogenic in two rat studies, but the human relevance of these data is equivocal. PFHxA is not mutagenic. PFHxA, in contrast to PFOA, is quickly eliminated from living organisms. 46

47 Elimination Half-life in Plasma There is a big difference between long and short chain. Short chain eliminate rapidly and are significantly less toxic. Short Chain Long Chain Elimination t 1/2 (Days) PFHxA PFOA Rat Monkey 1 21 Human <28* 1,100-1,500 * Nilsson, et al, Biotransformation of fluorotelomer compound to perfluorocarboxylates in humans, Environment International ,

48 Toxicology Profile of C6-Fluorotelomer Chemistry 48

49 Toxicology Profile of C6-fluorotelomer Chemistry Commercial polymer product (example) Raw materials: 6:2 alcohol 6:2 methacrylate Perfluorohexanoate (PFHx) 49

50 Tox profile of a Fluorotelomer based Polymer: C 6 F 13 CH 2 CH 2 -side chains appended to the polymer backbone Aqueous polymer dispersion (DuPont commercial product) Acute Mammalian Oral LD50 (rat): >11,000 mg/kg Eye Irritation (rabbit): mild irritant, reversible within 48 hours Skin Irritation (rabbit): non-irritating Local Lymph Node Assay (LLNA; mouse): negative for skin sensitization Genetic Toxicity Bacterial Reverse Mutation (Ames), Chromosome Aberrations in Mammalian Cells, both negative Neither genotoxic nor mutagenic Repeated-Dose Mammalian (rat) Oral 90-day sub-chronic, One generation reproduction, Development NOAEL 1000 mg/kg/day Limit dose Acute Aquatic Fish: 96Hr LC50 >100 mg/l Daphnia: 48Hr EC mg/l Algae: 72-hour EC50 >100 mg/l Summary Not classified for mammalian toxicity. R51/53 for aquatic toxicity. Not a selective developmental or reproductive toxicant Not damaging to DNA, not genotoxic or mutagenic. Rapid elimination, not bioaccumulative. 50

51 Tox Profile of 6:2 Fluorotelomer Alcohol C 6 F 13 CH 2 CH 2 OH Raw Material 6:2 Fluorotelomer Alcohol * Acute Mammalian Oral LD50 (rat): 1,750 mg/kg Eye Irritation (rabbit): mild irritant, Skin Irritation (rabbit): non-irritating Dermal LD50: 5,000 mg/kg Local Lymph Node Assay (LLNA) (mouse) : negative Inhalation: 4Hr. ALC > 3.6 mg/l vapor Genetic Toxicity Bacterial Reverse Mutation (Ames), Chromosome Aberrations in Mammalian Cells, both negative Repeated-Dose Mammalian (rat) Oral 90-day sub-chronic: NOAEL 5 mg/kg/day Reproduction, One-generation: NOAEL 25 mg/kg/day Development: NOAEL 25 mg/kg/day Inhalation 5 day, 28 day: NOAEL 10ppm Target: Teeth (F - ), blood, liver Pharmacokinetics (rat) Single and repeated dose oral and inhalation. Rapid bioelimination Acute Aquatic Fish: 96Hr LC mg/l Daphnia: 48Hr EC mg/l Algae: 72-hour EC mg/l Summary Not classified for mammalian toxicity. R51/53 for aquatic toxicity. Not damaging to DNA, not genotoxic or mutagenic. Rapid elimination, not bioaccumulative. Repeated-dose toxicology similar to published results for other fluorotelomer alcohols studied. Not expected to be harmful to human health or the environment at environmentally relevant concentrations. DuPont; Presented at 4 th INTERNATIONAL WORKSHOP on Perand Polyfluorinated Alkyl Substances PFAS (Nov. 9, 2012, Idstein, Germany) *Serex et al., Toxicologist, 2009, 108(1): 842. Toxicologist, 2012, 126(1):

52 Tox Profile of 6:2 Fluorotelomer Methacrylate C 6 F 13 CH 2 CH 2 OC(O)C(CH 3 )=CH 2 Raw Material 6:2 Fluorotelomer Methacrylate * Acute Mammalian Oral LD50 rats and mice: > 5,000 mg/kg Eye Irritation: non irritating Skin Irritation: non irritating Acute Dermal LD50: > 5,000 mg/kg Local Lymph Node Assay: not a skin sensitizer Genetic Toxicity In-vitro Bacterial Reverse Mutation Assay Negative Chromosome Aberration Positive (Structural w/o act.) In-vivo Mouse Lymphoma, Micronucleus and Chrom. Ab. : Negative Repeated-dose (rat) 14d Oral repeated-dose NOAEL 1000mg/kg/day 28d Oral repeated-dose NOAEL 5 mg/kg/day (unpublished study) Target: Teeth (F - ), liver wt. Acute Aquatic Fish: 96Hr LC50 > 14.5 mg/l Daphnia: 48Hr EC50 >120 mg/l Algae: 72-hour EC50 > 24.6 mg/l Summary Not classified for mammalian toxicity. R52/53 for aquatic toxicity. Not damaging to DNA, not genotoxic or mutagenic. Metabolized rapidly to 6:2 FTOH Repeat-dose toxicology similar to 6:2 FTOH DuPont; Presented at 4 th INTERNATIONAL WORKSHOP on Perand Polyfluorinated Alkyl Substances PFAS (Nov. 9, 2012, Idstein, Germany) *Anand et al., Toxicology 2012, 292(1):

53 Tox Profile of Perfluorohexanoate C 5 F 11 CO 2 - Degradation product- Perflurohexanoate (PFHx) * Repeated-Dose Mammalian (Oral) 2-year chronic (rat) NOAEL M 15 mg/kg/day; F 30 mg/kg/day Not carcinogenic 90-day sub chronic (rat) NOAEL 20 mg/kg/day Target: nose, liver One-Generation Reproduction (rat) NOAEL 100 mg/kg/day No effects on reproductive parameters Repro/Development (mouse) NOAEL 100 mg/kg/day Development (rat) NOAEL 100 mg/kg/day Pharmacokinetics (rat, mouse, monkey) Single and repeated dose studies completed: rapid elimination M&F all species DuPont; Presented at 4 th INTERNATIONAL WORKSHOP on Perand Polyfluorinated Alkyl Substances PFAS (Nov. 9, 2012, Idstein, Germany) Summary Not damaging to DNA, not genotoxic or mutagenic. Not a selective developmental or reproductive toxicant. Benchmark dose analysis. Rapid bioelimination, not bioaccumulative. Not expected to be harmful to human health or the environment at environmentally relevant concentrations. *Loveless et al., Toxicology 2009, 264(1-2), Chengelis et al., Repro Tox, 2009, 24(3-4), Gannon et al., Toxicology 2011, 283(1): Conder et al., Environ Sci Technol 2008, 42(4):

54 The recent U.S.EPA comments on C6-fluorotelomer chemistry 54

55 Moving from C8 to C6/Short Chain chemistry is the right move US EPA June 2013 PFAC chemicals with fewer than eight carbons, such as perfluorohexanoic acid (PFHxA), are not considered long-chain PFAC chemicals. These shorter-chain PFAC chemicals are not part of this action plan because data in non-human primates indicate that they have substantially shorter half-lives in these animals than PFOA and are less toxic than long-chain PFAC chemicals. plans/pfcs.html 55

56 Summary Durable water and oil repellents are valuable to users, and valuable to the textile industry. The best water and oil repellents in the past have been those based on C8 chemistry. There is regulatory concern about C8 chemistry. The fluorochemical industry has worked with regulators to address the concerns about C8, and as part of that work has developed C6 oil and water repellents which have an improved ecological and biological footprint. It is time for the textile and apparel industry to transition to C6 chemistry. 56