PFOA/PFSA overview and
regulations
Jin Yang
6/17/2011
Outline

History of PFOA/PFSA

EPA regulations

Replacements of PFOA/PFSA

Conclusions
PFOA/PFSA

Chemistry
◦ PFOA
CF3(CF2)nCO2X
n=6
X=-H, NH4, etc.
◦ PFSA
CF3(CF2)nSO2X
n=7
X=F, OH, ONa, phosphate ester etc.
Applications and unique properties

Applications
◦ Surfactants
◦ Emulsifiers in fluoropolymers
(C7F15CO2NH4)
◦ Building block for introducing Rf chain.

Unique properties:
◦ Chemical inert and stable
◦ C8F17 is both hydrophobic and oleophobic.
History of PFOA/PFSA issues

3M announced phase-out of PFSA in May 2000
◦ Blood test results of 3M employees showed high level
of PFSA (ppm level in manufacturing workers, ~3020ppb level in blood bank)
◦ EPA also concerned the PFOA

EPA stepped in and other fluorine chemical
companies were pressed to do the similar thing.

Environment groups and state/local
administration stepped in.
EPA responses and actions

PFOA/PFSA 2010/2015 stewardship program
◦ Voluntary base program
◦ Arkema, Asahi, BASF Corporation (successor to
Ciba), Clariant, Daikin, 3M/Dyneon, DuPont, Solvay
Solexis

Participating companies:
◦ Submitted baseline year 2000 data on emissions and
product content.
◦ Report annual progress toward goals and report
progress in terms of both U.S. and global operations.
◦ Reduce 95% of PFOA/PFSA in 2010.
◦ Totally ban PFOA/PFSA in Dec. 2015.
The power of EPA-TSCA

TSCA (Toxic substances control act)
◦ It was established in 1976
◦ Scope of TSCA:




Manufacture in US (PMN-pre-manufacture notice)
Import
Blend/mixing
Export from US
◦ TSCA not only apply in new chemicals but
also apply in new applications of existing
chemicals.
PMN regulations

Exempts of PMN (pre-manufacture
notice):
◦ R&D only
◦ LV (Low Volume (<25,000lb/year))
◦ Export only

Fluorine-containing compounds are not
entitled to be LV exempt.
Anti-fluorine panic in US
Halogenated compounds (flame-retard
materials) had been strictly regulated by
various environment groups and green
movements such as cable manufactures,
green building movement and furnish
manufactures.
 There is totally ban fluorine compounds
movement in US. Fluorine compounds are
under attacked by different groups.

What we can learn from US

Be pro-active.
◦ Involving the regulations decision in the
beginning.

Be open mind.
◦ Don’t deny and defend some fluorine
compounds are not health.

Be scientific mind.
◦ Using solid scientific data/evidences to
support the decisions. Do not be emotional.
International regulations

Organization for Economic Co-operation
and Development (OECD)
◦ 2000 - OECD developed a Hazard
Assessment of PFOS and Its Salts.
◦ 2006 - OECD released a Survey on the
Production and Use of PFOS, PFOA, PFAS,
PFCA, and related substances.
◦ 2006 - OECD held a workshop on PFCs and
precursors and published a Workshop Report
in 2007.
International regulations

United Nation's Economic Commission for Europe
(ECE)on Long-range Transboundary Air Pollution
(LRTAP)
◦ December 2005 - LRTAP parties agreed to consider PFOS as a
persistent organic pollutant (POPs).
◦ 2006 United Nations ECE published a report on existing
information on PFOSproduction, use, emissions and pathways to
the environment

United Nations Environment Program (UNEP)
◦ February 2009 - UNEP, in cooperation with U.S., hosted an
International Workshop on Managing PFCs and Transitioning to
Safer Alternatives
International regulations

Stockholm Convention on Persistent
Organic Pollutants (POPs)
◦ June 2005 - Sweden proposed the listing of
PFOS and its precursors in Annex A of POPs.
◦ May 2009 - The production and use of PFOS
and its salts, were restricted under Annex B.
Read more information on the chemicals
listed under Annex A and B.
International regulations

May 2009 - UN Strategic Approach to
International Chemicals Management
(SAICM)
◦ Agreed to consider stewardship programs
and regulatory approaches to reduce
emissions and product content of PFAC and
PFAS chemicals and to work toward their
elimination , where feasible
Expanding stewardship program

Reaching out to other countries,
especially to China

Chinese fluorine chemicals companies are
invited to join this stewardship program

Deadline for phase out PFOA/PFSA is
soon (Dec. 2015)
EPA regulations

The point view of EPA (PBT of
PFOA/PFSA)
◦ Persistent
◦ Bio-accumulative
◦ Toxic
◦ In Dec. 2015 phase out of PFOA/PFSA totally.
Regulations changed for F-polymers

Fluoro-polymers are treated as normal
polymers in term of EPA regulation
polymer exempt is gone.

Fluoro-polymer with CF3-CF2- chain
length of 2 or more need file TSCA and
PMN (pre-manufacture notice).

PMN is not only required for manufacture
in US but also for import from oversea.
Long-chain perfluorinated chemicals

Long-chain perfluorinated chemicals (LCPFC) are the
targets by EPA

EPA treats long chain perfluorinated chemicals as
PBT.

In Dec. 2009, EPA published actions plan on LCPFCs.
◦ Given the concerns with LCPFCs, it can reasonably be
anticipated that continued exposure could increase body
burdens to levels that would result in adverse outcomes
◦ TSCA section 6 provides EPA the authority to ban or
restrict the manufacture, processing, and use of these
chemicals
Some exempts for PFOA/PFSA
applications

Since the critical roles of PFOA/PFSA in
some industrials. So some industrials can
continue to use PFOA/PFSA
◦
◦
◦
◦
◦
Imaging/photography
Auto industrial
Aero-space industrial
Military applications
Semi-conductor industrial
Replacements of PFOA/PFSA

Currently EPA are reviewing over 120
chemicals for PFOA/PFSA replacements.

F(CF2)n- type compounds, n>=6 will be
considered PBT like PFOA/PFSA

C4F9- type compounds showed less toxic
and shorter half-life time in environment.
Approaches for PFOA/PFSA
replacement

Short perfluorinated chain:
◦ C4F9 or shorter than C4

Short perfluorinated chain with CH2 as
linkage:
◦ C4F9CH2C4F8CH2◦ -(CF2)n(CH2)m-, n<=3 and m>=1
Conclusion

PFOA/PFSA is Persistent, bio-accumulative
and toxic.

PFOA/PFSA will be totally phase out in Dec.
2015

Long-chain perfluorinated chemicals (n>4)
will be strictly monitored by EPA.

Short-chain perfluorinated chemicals will be
the focus for future development.