Transcript Technologies and Alternatives Richard Holt BIAC Limitations for any Discussion of Alternatives  Numerous alternatives  Time constraints  Competitive considerations  Anti-trust considerations  Knowledge base –

Technologies and Alternatives
Richard Holt
BIAC
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Limitations for any Discussion of
Alternatives
 Numerous alternatives
 Time constraints
 Competitive considerations
 Anti-trust considerations
 Knowledge base – proprietary uses
and formulations
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Primary Current Transition Path
 Surfactants
 From >6-Carbon to 4-Carbon-based sulfonate chemistry
 From >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 Polymers
 From >6-Carbon to 4-Carbon-based sulfonate chemistry
 From >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 Alternatives
 In 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 oxetanes
 Other fluorinated polymers
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Potential Alternatives
 Not-in-kind
 Hydrocarbons
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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 Alternatives
 Non-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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Fluorinated Products - Technology
Synthesis Origin
 Electrochemical
fluorination (ECF)
 Fluorotelomer
 Fluoro(poly)ether
 Fluorinated oxetane
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
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Electrochemical Fluorination
(ECF) Products
H(CH2)nSH
aliphatic mercaptan
HF, e-
F(CF2)nSO2F
Sulfonyl fluoride
An Example of New Products based on n
F(CF2)nSO3X
PFDS n = 10
PFOS n = 8
PFHxS n = 6
PFBS n = 4
F(CF2)nSO2N(R)CH2CH2OH
Perfluoroalkyl sulfonamido ethanol
Perfluorobutane sulfonyl (PFBS)
Chemistry
C4F9SO2 - R
PFBS = C4F9SO3Potential degradation product
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Fluorotelomer-based Products
CF2=CF2
(TFE)
F(CF2)6I
Perfluoroalkyl Iodide
F(CF2)6CH2CH2I
Fluorotelomer Iodide
F(CF2)6CH2CH2OH
Fluorotelomer Alcohol
An Example of New
Products based on
n=6
Phosphate
Ethoxylate
Betaine
Potential degradation product
PFHxA, perfluorohexanoate: F(CF2)5CO213
Pharmacokinetics in Monkey: PFBS and PFHxA
1,000,000
100,000
PFBS
(ng/mL)
10,000
PFHxA-Male
PFHxA-Female
PFBS-Male
PFBS-Female
1,000
100
PFHxA
10
1
0
4
8 12 16 20 24
48
(hr)
Serum concentration of PFHxA or PFBS after
single intravenous administration
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Fluoropolyether (PFPE) Surfactants
 PFPE-diol raw material
HOCH2-CF2O-(CF2O)m-(CF2CF2O)n-CF2CH2OH
 MW 1500 AMU; Made by photooxidation including
tetrafluoroethylene (TFE)
 Phosphate ammonium salt
 Carboxylate ammonium salt
 Ethoxylated diol
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Summary for the Alternatives
 Alternatives exist for nearly all current uses
 There are some uses still for which adequate
replacements have not yet been identified
 Alternatives 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 halflife) and lower toxicity than PFOA and PFOS
 Non-fluorinated alternatives do not work as well
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Summary for the Alternatives
 PFOS 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!
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