Technologies and Alternatives

Richard HoltBIAC

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Limitations for any Discussion of AlternativesNumerous alternativesTime constraintsCompetitive considerationsAnti-trust considerationsKnowledge base – proprietary uses and formulations

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Primary Current Transition Path Surfactants

From >6-Carbon to 4-Carbon-based sulfonate chemistryFrom >8-Carbon to <6-Carbon Fluorotelomer chemistry From 8- and 9-Carbon Perfluorocarboxylate

Polymerization Aids (PFOA/PFNA) to certain Mono- and Poly-perfluoroethers or other substances

Surface Modification PolymersFrom >6-Carbon to 4-Carbon-based sulfonate chemistryFrom >8-Carbon to <6-Carbon Fluorotelomer chemistry

Requires cooperation from manufacturers in a wide range of downstream industries, from consumer product manufacturers to defense and aerospace industries

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Potential AlternativesIn Kind: Fluorinated

C6: Fluorotelomer-based six fluorinated carbon functionality compounds

C4: Electrochemical fluorination-based four fluorinated carbon functionality compounds - Perfluorobutane sulfonate (PFBS)

Mono- and poly-fluorinated ether functionality compounds (e.g., CF3 or C2F5 fluoroalkyl polyethers)

Fluorinated oxetanesOther fluorinated polymers

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Potential AlternativesNot-in-kind

Hydrocarbons Propylated naphthalenes or biphenyls Fatty alcohol polyglycol ether sulfate Sulfosuccinate Hydrocarbon surfactants Naphthalene derivatives

Siloxanes and silicone polymers

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Do The Alternatives Work?

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The transition from the current highly effective products to suitable alternatives has been accomplished with the following criteria as guidelines:•Efficacy of use be maintained•Reduced biopersistence•Minimization of customer disruption •Value in use be maintained•Critical societal uses are not compromised•Reduction of the environmental footprint

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Non-Fluorinated AlternativesNon-fluorinated alternatives, such as

different hydrocarbon surfactants and silicone products, have been identified… however, in most cases or at least in larger application areas, other fluorinated compounds are used instead…. non-fluorinated alternatives do not work as well, especially in situations, where extreme low surface tension is needed (Danish EPA, 2006). 

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Effectiveness of Newer Alternatives: What are we finding?C-6 and C-4 chemistries adequately meet the criteria for replacement of most current C-8 and higher homologue uses.

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New Chemical Review of Alternatives*US EPA is reviewing substitutes for Long Chain

PFCs as part of its review process for new chemicals under EPA's New Chemical Program

– Ongoing since 2000– Consistent with the approaches to alternatives encouraged under the PFOA Stewardship Program

– Over 100 alternatives of various types have been received and reviewed by EPA

More information at http://epa.gov/oppt/pfoa/pubs/altnewchems.html

* EPA presentation April 19, 2010 (Las Vegas, Nevada USA) and various other industry and trade meetings

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Unique Properties•Lower aqueous surface tension = wetting power

•the power to spread and coat surfaces•Function at very low concentrations

•100 parts per million•Work well in tandem with hydrocarbon and silicone surfactants•Unique function in “dynamic” systems

Synthesis OriginElectrochemical

fluorination (ECF)FluorotelomerFluoro(poly)etherFluorinated

oxetane

Fluorinated Products - Technology

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Electrochemical Fluorination (ECF) Products

F(CF2)nSO2N(R)CH2CH2OH

Perfluoroalkyl sulfonamido ethanol

An Example of New Products based on n=4

Perfluorobutane sulfonyl (PFBS)

Chemistry

C4F9SO2 - R

H(CH2)nSH aliphatic mercaptan

F(CF2)nSO3XF(CF2)nSO2F

PFDS n = 10

PFOS n = 8

PFHxS n = 6

PFBS n = 4

HF, e-

Sulfonyl fluoride

PFBS = C4F9SO3-

Potential degradation product

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Fluorotelomer-based ProductsCF2=CF2 (TFE)

F(CF2)6I

F(CF2)6CH2CH2I

F(CF2)6CH2CH2OH

An Example of New Products based on

n = 6

PhosphateEthoxylate

Betaine

Fluorotelomer Alcohol

Fluorotelomer Iodide

Perfluoroalkyl Iodide

Potential degradation product

PFHxA, perfluorohexanoate: F(CF2)5CO2-

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Serum concentration of PFHxA or PFBS after

single intravenous administration

1

10

100

1,000

10,000

100,000

1,000,000

PFHxA-MalePFHxA-FemalePFBS-MalePFBS-Female

(hr)

(ng/

mL)

PFHxA

PFBS

Pharmacokinetics in Monkey: PFBS and PFHxA

Fluoropolyether (PFPE) SurfactantsPFPE-diol raw material

MW 1500 AMU; Made by photooxidation including tetrafluoroethylene (TFE)

Phosphate ammonium saltCarboxylate ammonium saltEthoxylated diol

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HOCH2-CF2O-(CF2O)m-(CF2CF2O)n-CF2CH2OH

Summary for the AlternativesAlternatives exist for nearly all current usesThere are some uses still for which adequate

replacements have not yet been identifiedAlternatives with a shorter fluorinated alkyl

chain are still environmentally persistent but not bioaccumulative

The C4 sulfonate and the C6 carboxylate have shown different pharmacokinetics (shorter half-life) and lower toxicity than PFOA and PFOS

Non-fluorinated alternatives do not work as well

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Summary for the AlternativesPFOS and PFOA are some of the most

studied chemicals, therefore ...Alternatives will almost always have less

supporting data, however ...Adequate supporting data have been

submitted to obtain regulatory approval, generally subject to requirements to submit additional data to robustly define hazard and exposure profiles.

Good business move for the future! 17