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iPont Overview o f
Fluoi
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Parker; _
Operations
P resented to th e State o f O hio E nviroi
February, 20i Columbus, Obi
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Fluoiopo lymers "Super" Polymers
Chemical resistance across brol temperature range
"Slipperiest substance known to m aif Unique properties/High value in use
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Fluoropolynter- 2000 Global Market Demaiwk($Billions)
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Major Indtrstties Served by F lu orop olym ers/elastom ers
Aerospace/Military Automotive/Transportation Chemical/Petrochemical Processing Semiconductor/Electronics Manufacture Telecommunications Power Generation/Pollution Control Consumer Housewares
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Confidential DuPont Business Information
Key requirements: Temperature and chemical resistance; electrical performance; low flammability
M ^orfises:, Wire and cable insulation Fuel and hydraulic hoses
Seals/bushing Space apparel Societal Benefits: Passenger
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Key requirements: Chemical and temperature resistance; electrical performance; lubricity Major uses: Seals,bushings Fuel and brake hoses/tubing Control cables
Underhood wire Societal Benefits: Lower vehicle weight and emissions; reliability
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ASH028139
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C hem icals
Kev requirements: Chemical and applications temperature resistance; non-stick Major uses: *Lined pipes5valves, pumps *Tank and reactor linings * Gaskets, seals *Wire insulation Societal benefits; Worker and public safety; industry
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troch em ieals
Sem icon du cfi
Key requirements: Chemical and temperature resistance; purity; electrical performance
Major uses:
High-purity fluid handling equipment
Silicon wafer carriers
Clean room garments
Societal benefits: Consumer product quality and cost;
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Kev requirements: Chemical and temperature resistance; flexibility Major uses: Acid resistant filter bags Radiation resistant wire insulation
Expansion joints Societal benefits: Fewer emissions to the environment; worker and public safety; process reliability ^
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Key requirements: Electrical performance; fire resistance; optical properties . Major uses:
- LAN Cable
Mainframe wiring
Satellite wiring Fiber optic cladding and cable
Societal benefits: Public safety;
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Key requirements: Non-stick; temperature resistance; easy to clean; hydrophobic
Major uses:
Non-stick cookware and bakeware
Waterproof/breathabie clothing
Appliance wiring
Societal benefits: Enables low-fat cooking; supports healthy lifestyle; consumer convenience
Confidential DuPont Business Information
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Fluoropolymcr Applications
SumiMi _
Fluoropolymers provide uniqu^fld critical performance properties in "systenM itical" applications that protect and benefit1 and the environment.
For virtually all applications, fluoropolymers are the only materials tha1 meet system performance needs.
Application design and best-available
technology based on fluoropolymers.
Confidential DuPont Business Information
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investment based on fluoropolym Not-in-kind technologies for some applications have negative environment impact and/or are cost prohibitive.
Confidential DuPont Business Information
mportance o f C-8 in Fluoropolymer D ispersion
Polymerisation Process
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DISPERSION POLYMERIZATION PROCESS
IN G R E D IE N T S
> M on om er(s) w ith extrem ely h igh p u rity > W a ter (dem ineralized) > In itia to r (an oxidizing agen t w ith high_g > S urfactan t tnoin-telogenic. h igh p u rity) > O ptional other ingredients
EO TJ..I.P..M...E..NT > G en tly stirred heated reactor
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CRITICA L AQUEOUS POLYMERIZATION FACTORS
> Facilitates: > Efficient heat removal
. > Particle architecture and/or size >Molecular weight and its distribution > Comonomer content and its distribution >H igh to extremely high molecular weight
Confidential DuPont Business Information
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30+ Year Effort M illions o f Dollars Invested in Re: More than 40 Compounds Identified Evaluated
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PHASES OF SUKFA< [T EVALUATION
Surfactant
v D esign and synthesis. V Prepare candidates in a quantity large enough for research? V Get. sam ples o f suitable surfactants from non-DuPont soured!
e v a lu a tio n .
Polymerization
A Experim ent w ith variety o f product lines w here the candidate surfac!
m ay be suitable. A Evaluate processing performance in post-reactor steps. A Characterize products and compare the properties and application
perform ance with standard products.
Health and E nvironm ental
>T oxicological/persistence testing at H askell Lab.
Total A ssessm ent
A fter gathering all o f the above, assess i f a large scale test is appropriate. Confidential DuPont Business information
Requirements ForTAC-8 Alternative
> Low Persistence, BioaccumulaSlai and Toxicity
> Allows High-Quality Polymer Manufacturing
> Does Not Affect Performance In U se
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Confidential DuPont Business Information
POTENTIAL FACTANT CANDIDATES EVbUATED
(1971-19
CHF2(CF2)7C 0fN H 4+ (Poly)
CF3(CF2)8C 0 2-NH4+ (Poly)
CF3(CF2)7C 02-NH4+
(T ox)
CF3(CF2)3CH2(CF2)2C 0 2-NH4+ (T ox)
CF3(CF2)3CH2CF2C 0 2-NH4+ (T ox)
CF3(CF2)3CH2CH2CF2C 02-NH4+ (Poly)
CF3(CF2)5(CH2)2CF2C02-NH4+ (T ox)
CF3(CF2)3CH2C tt2CF(CF3)COfNH4+ (Tox)
CF3(CF2)3(CH2)3CF2C 02-K+ (Poly)
C8Fi7C 02 NH4+ (Branched) 3M confidential (Poly)
C9Fi9C 02NH4+ (Branched) 3M confidential (Poly)
CiqF2iC 0 2`NH4+(Branched) 3M confidential (Poly)
F(CF2)n(CH2J ! H j^ I+ (Poly)
M ~ M lN a .L i.N F h (Poly)
F(C F2) 6(CH 2) 2SO:
F(CF2)6(CH2)4S03H C3F7OCF(CF3)CF2OCF(
i3"Na+ (PT) Ph= phenyl
CF3(CF2)7S 0 3-K+ (Poly)
F(CF2)n(CH2)20 S 0 3-M+ (Poly)'
M= Li, NH4
H(CF2) 10CH2OSO3-NH4+ (Poly)
F(CF2)7CH20 S0 3-NH4+ (Poly) N H 402C[CF(CF3)0C F 2]2CF2S 0 2NH2
Tox - Toxicity (acute or sub-acute),
Persistence Poly - Deficiency in polymerization PT - Deficiency in post-treatment
Confidential DuPont Business Information
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POTENTIAL SURFACTANT CANDIDATES EVALUATED (contd.)
(1971-199?
C9F17O PhS03-Na+ Ph= phenyl (PT) C9Fl70P h S 03-NH4+ Ph = phenyl (PT) C6F ,, 0P h S 03-Na+ P h-pheny (PT)
CFJ(CF2)20[CF(CF3)CF20]2CF(CF3)C 02- W (T ox) CF20(C F 20)3C F2C 02-NH4+ (Poly)
CF30(C F 20 )sCF2C 02-1SIH4+ (Tox) CF3CH20C F 2CHFCF2CF(CF3)0C F 2CF2C 02NH4+ (T ox) CF:,C1CFC10CF2CF(CF3)0CF2CF2C 02-NH4+ (Poly) CF3(GF2)5SCH2C 02-NH4+ (Poly) CF3(CF2)5CH2C 02-NH4+ (Poly) CF3(GF2)sCH2C 0 2-K+ (Poly) CF3(CF2)7CH2C 02:NH4+ (Poly)
CF3(CF2)5C;
C 02'NH4+ (Poly)
CF3(CF2)4COOf iy)
CF3(CF2)7S 02-NH4:
CF3(CF2)7S 02-Na+
CF3(CF2)5S 02-NH4+ (P o |
CF3(CF2)3S02-NH4- (Poly}
CF3(CFz)3S 0 2-NH4+ (Poly)
CF3(CF2)6CN4 NH4+ (Poly)
CF3(CF2)5CH2CH2CH2N(CH3)3+
CF3(CF2)6CH20 P 0 3=(NH4+)2 (P o l*
CF3(GF2)nCH2CH20 P 0 3=(NH4+)2(P i
Tox - Toxicity (acute or sub-acute),
persistense Poly - Deficiency in polymerization PT - Deficiency in post-treatment
Confidential DuPont Business Information
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ical Sum m ary
> F lu orop olym ers can b e m ade into u sb f^ p a r ts o n ly w h en th ey h a v e h ig h m olecu lar w eight. For som e app lication s, extrem ely h ig h m o lecu la r w eig h t is critical.
> T h e m ajority o f D uP ont's products are d isp ersio n p o l j ^ j i z e d and
require v ery pure ingredients, in clu d in g th e surfactant,
h ig h
m olecular w eight.
> Im purities containing hydrogen cause a sig n ifica n t red u ction i l m olecu lar w eight.
> A ll o f th e above create a lim it in the ch o ice o f surfactant. C -8 is currently the o n ly suitable surfactant for m o st flu orop olym ers, and is u sed b y D uP ont and other m anufacturers w orld w id e.
> O ver th e last 30 years, D uPont has in vested substantial resou rces to fin d an alternative to C -8 but has b een u n su ccessfu l.
Confidential DuPont Business Information
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Association o f Plastics Manti acturers Europe (APME)
Society o f Plastics Industry Fluoropolymer Manufacturing Group'1 (SPI-FMG)
Confidential DuPont Business Infonnation
Industry Groun Activities
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Global Material Balance Toxicity and Environmental TestidJ Voluntary Commitment to Contain DuPont Technology Sharing
- Capture for Destruction - license free - Capture for Recycle
Alternatives Discussion
Confidential DuPont Business Information
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C-8 History at
1950s: Surfactants used for PTFE^p^lymerization, C-8 selected as surfactant for DuPont PTFfe^roduction.
1970s: C-8 use expanded to co-polymer and fluoroelastomer production. Alternatives first ini
Late 1970s: C-8 persistence first recognized in work* Began programs to reduce worker exposure.
1 9 8 2 : Began R&D to reduce emissions
1989: DuPont installs first C-8-specifc scrubber.
Confidential DuPont Business Information
Elements 199i
educe Releases Reduce Use Recycle
estroy valate Alternatives
>
wardship
ASH028163
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A ll major emission points have device installed.
Efficiency varies from >90% to abou. due to technological difficulties.
Additional programs identified to take to site emissions to <5 tonnes/yr.
Confidential DuPont Business Information
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5-8 Use, Recovery arid Emissions n Washington Works Area
11990 through 2010 :.............
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Summary^fEfforts to Reduce Emissions addExposure
s> DuPont has been working on C-8 emissio] luction for 20+ years.
> More than $15 million invested since 1988; anoi planned by 2003.
illion
i 75% of C-8 recovered or destroyed in 2001; will be n3 90% by 2004. Rest of industry capturing little or none.
i DuPont making recovery/recycle technology available to
competitors.
Working with EPA and other agencies to increase knowled wM5oHM00! C-8.
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LETART LANDFILL
WASHINGTON WORKS FACILITY/ LOCAL LANDFILL
DRY RUN LANDFILL
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tial Sources o f C-8 in Little H o ck in g P u M c Water System s
Groundwater migration from WaMyngton Works,site.
- U pdating groundw ater m odel to in clu d e lr ft^ n a tio n p rovid ed b y
the LH PW S. W ill b e sam pling groundw ater in L H PW S m onitd! discern direction o f source.
m&lls to
Air deposition from plant emissions migrating to
groundwater.
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- A m bient A ir and d eposition m od elin g (E P A m o d els) com plete ^
- W ill com b in e d ep osition w ith m o d elin g o f transport from surfac to groundw ater (u sin g estab lish ed E P A p rotocols fo r crop
protection chem ical studies). - W ill com p are resu lts to m ea su rem en ts to d eterm in e i f d e p o sitio n is
sig n ifica n t contributor.
Confidential DuPont Business Information
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"To determine whether there has been any health or the environment as a result of releasd environment from DuPont operations."
Entered into with WVDEP and WVDHHR Effective Nov 15, 2001
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Consent OrderReguirement #1
A. Establish a Groundwater Investigation S t o i g Team (GIST)
Purpose: Assess presence and extent of C8 groundwater, surface water at and around WW
ing water, fills
WYDEP, WVDHHR, EPA Region HI, DuPont
Funded by DuPont _ Report findings and conclusions regarding groundwate
Report recommendations regarding further work or actio:
Confidential DuPont Business Information
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Key Tasksofthe GIST
Groundwater use and well survey Identify and sample all groundwater wells radius of WW and landfills, with provisions to sampling range based upon results
Assess groundwater and surface water monitoring data develop a groundwater monitoring plan and schedule Determine the extent of any C8 impacted groundwater
Confidential DuPont Business Information
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Requirerant #2
B. NPDES Sampling Monthly sampling for C8 at Landfills and at outfalls 1,2, 3, 5,7, and 105 Sample each surface or alluvial water intake water supplies along Ohio River for 1 mi. upstream mi. downstream if detected, successive expansion of sampling range
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Confidential DuPont Business Information
Establish a "C-8 Assessment of Toxicity Purpose: Assess the toxicity and risk to hum environment associated with exposure to C-8 rele* DuPont activities WVDEP, WVDHHR, EPA Region III, NICS, ATSD Funded by DuPont Report findings and conclusions as to what extent there m of health risk associated with C-8 at the facilities
Confidential DuPont Business Information
Key Tasks ottheiCAT Team
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Hold Public Meeting to introduce the p arfa^ re la te historical C8 levels in LPSD water, relate ensuing a c tiv iM y n d invite participation in sampling and survey efforts (PoM t o /01)
Review available toxicology and epidemiological du
Develop Screening Levels for protecting human heal
Conduct a risk assessment comparing exposures to Scree!
Levels
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Second Public Meeting to present results of GIST and CAT Team efforts, air modeling results, and any further actions
Confidential DuPont Business Infomiation
D. Air Emissions Modeling Assessment * Provide information to WVDEP DAQ to including: building dimensions allowable and actual emission rates
stack parameters
physical property data
ASH028180
particle characterization
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scavenging coefficients
Confidential DuPont Business Information ?
irement #5
E. -8 Reduction Program
1. Limit overall C8 emissions to air to yearS^OO levels
report emissions monthly, transitioning to q ^ g g rly upon issuance of Screening Level
2. Reduce emissions to air and discharges to water col 50% from actual 1999 levels by year-end 2003
3. Operate and maintain filter and carbon bed system w ith 90-95% C8 removal efficiency in major C8-containing wastewater stream
4. Install improved scrubber filter in Fluoropolymer area
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5. Conduct scrubber optimization and recovery improvement program and implement if encouraging
Confidential DuPont Business Information
ent #6
F. In event of demonstration of C8 exposures Screening Levels developed per this Consent On plan for reducing such exposures below the a reasonable time
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Confidential DuPont Business Information
