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manufacture of PTFE via emulsion process without the use of
fluorinated polymerisation aids
Aprili275, 2022
CHEMSERVICE
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Contents
[I LeTs [FooTy]
Background information
NFPA use in emulsion PTFE manufacture
Analytical information Technical performance
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CHEMSERVICE
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CHEMSERVICE WORLDWIDE
Global presence
Chemservice is supporting customers globally, is present with offices in seven countries and has strategic partnerships in another eight countries. Main locations: Germany, Luxembourg, Korea Further locations: Switzerland, Spain, UK, USA Affiliates & strategic partnerships: Belgium, Canada, China, France, India, Japan, Taiwan, Turkey
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CHEMSERVICE 4
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International chemical control legislation
consulting, e.g. REACH, K-REACH
Only Representative & Third Party Representative
REACH-Code-Model
Global chemical inventory listings/notifications
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Biocides & plant protection products compliance
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Our business philosophy?
Dedication to find the best solution to suit your needs!
GHS, CLP & Safety Data Sheets
Risk, hazard & exposure assessments
Regulatory Data Sheets
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EH&S consulting, GLP & GMP consulting
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Authorisation & restriction processes,
socio-economic analysis
Product stewardship & advocacy
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Consortia & Letter of Access management
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Gujarat Fluorochemicals Limited (GFL)
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_
GUJARAT FLUOROCHEMICALS
VALUE THROUGH GREE
E
ST
* GFL is an Indian chemicals company with over 30 years of expertise in fluorine chemistry.
* Headquartered in Noida (India), employing >2000 people globally, the company operates and manages:
-- 3 manufacturing sites in India -- Fluorspar mine in Morocco -- Subsidiaries in USA and Germany -- Warehouses, sales and distribution offices globally -- Research Centre (GFRC) in India, focused on development of sustainable manufacturing technologies
* [SO 9001:2015, ISO 14001:2015, ISO 37001:2016 and ISO 45001:2018 certified organisation.
* Clear focus on high standards for quality, health, environment & safety, and sustainability.
* GFL manufactures fluoropolymers since 2007 and is a major supplier to European Economic Area.
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Key Messages
CHEMSERVICE 6
* GFL manufactures fluoropolymers since 2007 and is a major supplier to European Economic Area. * GFL has developed a manufacturing process that does not use Fluorinated Polymerisation Aids (FPA) / surfactant
for part of its portfolio. * GFL has initiated the commercialization of the new product. * This presents a major milestone, and the company is working towards converting its entire portfolio to processes
that do not use FPAs.
* Next steps are significantly more complicated and need more development and commercialization time. * Fluoropolymers are substantially different from side-chain fluorinated polymers in terms of potential emissions of
low carbon chain PFAS.
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1. Introduction
CHEMSERVICE 7
* Due to their chemical structure, Fluoropolymers (FPs) are considered to fall under the group of PFAS substances, and thus they may be impacted by the upcoming REACH restriction on PFAS.
* The main FPs (> 96%) are considered to meet Polymer of Low Concern (PLC) criteria as per an on-going study.
* FPs are substantially different from side-chain fluorinated polymers.
* Concerns related to FPs have been focused on the use of FPA leading to potential PFAS emissions through the lifecycle, as well as to by-product generation and End of Life (EOL) considerations.
* FPs are used in many high-performance industrial applications (transport, semiconductors, renewable energy, electronics, chemicals, medical devices & pharma) for which they provide a unique combination of valuable properties.
* FPs are typically used under harsh or very demanding conditions where other materials fail to perform. They are high-cost materials used only when no alternative will deliver the combination of desired properties.
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1. Introduction (2)
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* Polytetrafluoroethylene (PTFE) is the most common FP manufactured and used globally. * PTFE may be manufactured via suspension or emulsion manufacturing process, the latter requiring use of FPAs. * PTFE products manufactured via either process will be used for different applications. * GFL has successfully developed the use of a Non-Fluorinated Polymerisation Aid (NFPA) in the manufacture of
PTFE aqueous dispersions. * Relevant patent applications have been filed and obtained by GFL for this development. * GFL is an active member of various industry associations like FPG (PlasticsEurope), PFP (ACC) and FPP4EU (Cefic),
and has actively engaged in technical studies to develop scientific data on FPs for the development of the PFAS restriction proposal.
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CHEMSERVICE 9
1. Introduction (3)
Fluoropolymers
Volume
(tonnes)
% |
% of total Fp volume
% vOlUME that
volume thatdo
Use of
FPA do not require not require use of
use of FPA FPA (future scenario
)
At present, >500% of total global FP production does not require the use of FPAs
PTFE Total
PTFE Suspension PTFE Emulsion
Lana PVDF (H lymerymer +
FEP
Ee
PFA
ETFE
FKM TOTAL
FKM Copolymer FKM Terpolymer[1]
THV
ECTFE (Copolymer + eran
r
PCTFE
Others
TOTAL CONFIDENTIAL
169,759 84,879,5 84,879.5
51.248
32,030
p: y 3,203
3,203 35,000 25,000 10,000
800
2,200
8,600 7,851 320,300
53%
26.5%
N
26.5%
Y
or
10%
Y
or-
y
1%
Y
1%
Y
10.9%
7.8%
N
3.1%
Y/N
0.3%
Y
0.3%
N
2.7%
N
2.5%
26.5% on
7.8% 1.6% 0.3% 2.7% 54.8%
26.5% 26.5%
16%
7.8% 1.6% 0.3% 2.7% 81.3%
* PTFE represents >50% global FP production
* With this development, if adopted globally,
i
>809% of FPs do not require the use of FPAs
.
;
* After full implementation of the development,
~98% of total FPs produced by GFL will not
require the use of FPAs
wor [J ar
gontinues
Bio
'
on
developments for remaining FPs
Siimmiilar
[1] assumed 50% FKM terpolymer does not require FPA Source: IHS Markit report on FPs (2019)
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2. Background information
Dark Waters - use of PFOA as a polymerisation aid for the manufacture of some FPs and resulting emissions
Regrettable substitution - PFOA replaced mainly by
C6 PFAS for the manufacture of some FPs
Desired solution -- use of non-PFAS polymerisation
aids for the manufacture of FPs
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CHEMSERVICE
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2. Background information (2)
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* FPs are different from side-chain fluorinated polymers, although they are usually confused; FPs are not used in fire-fighting foams.
Fluoropolymers
Side-chain fluorinated polymers
Have carbon polymer backbone with the fluorine atoms attached directly to the carbon backbone
Have a hydrocarbon polymer backbone with fluorinated side
chains
Do not lead to the formation of long-chain PFAS or PFCA as a result of degradation
Mostly used in industrial applications
Depending on the side chain, these types of polymers can potentially lead to the formation of PFAS substances as a result of degradation
Mostly used in consumer applications
Have material properties - durability, mechanical strength, inertness, thermal stability, resistance to chemical, biological, and physical degradation
Have surface properties - polymer dispersions in water used as coatings applied to textiles, carpets, non-wovens and paper to provide water, soil, oil and stain resistance
Satisfy OECD's polymers of low concern (PLC) criteria
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Not known
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2. Background information (3)
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* FPs are different from other plastics.
Fluoropolymers
Most Other Plastics
Relatively highly priced: 20 x Polyethylene, 10 x Polyamide for the lowest cost
FP
High performance polymers used only in critical applications where other materials simply cannot perform
Relatively low priced as a result of economies of scale, low raw material prices and less complicated manufacturing processes
Used in commodity applications, in less extreme circumstances
Commercial volume is in thousand of tonnes per year
Commercial volume is in millions of tonnes per year
FP applications have a long service lifespan in measured in decades
Relatively shorter lifespan measured in months (single use food packaging)
Mostly used in industrial applications (>95%) resulting in controlled collection Mostly used in consumer applications (>95%), disposal of which is random and safe disposal
EOL waste is well regulated under ELV, WEEE
Most common current EOL scenario - incineration or landfills, while recovering the matrix (metals)
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EOL fate depends on local regulation Incineration, some re-use
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3. NFPA use in emulsion PTFE manufacture
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* The NFPA used by GFL is an organic compound based on sulfonated hydrocarbon chemistry.
* According to the information available the substance is not considered to be PBT/vPvB nor PMT/vPVM.
The substance is classified under CLP/GHS, C&L would not make the substance candidate for SVHC identification.
* Potential emissions of the NFPA at the GFL sites in India have been assessed and fully controlled by efficient abatement techniques.
-- Air scrubbing systems -- Different absorption materials have been tested -- Activated carbon bed systems coupled to effluent water streams for absorption of organic impurities
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4. Analytical information
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* Several batches of PTFE manufactured with NFPA have been tested, with the aim to confirm that the final product is free of oligomers, unreacted monomers or PFAS by-products.
* Some studies were commissioned to external laboratory -- Intertek; others performed internally by GFL.
* Analytical techniques used:
-- Spectrometry techniques (HS-GC/MS, PTV-GC/MS, TD-GC/MS) -- Thermogravimetric analysis (TGA) -- X-Ray diffraction analysis (XRD) -- Fourier Transform Infrared Spectroscopy (FTIR) -- Differential Scanning Calorimetry (DSC) -- Total Organic Fluorine content (TOF)
* Unintended PFAS-content was determined by means of Liquid Chromatography/Mass Spectrometry (LC-MS/MS) according to US EPA method 537.1.
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4. Analytical information (2)
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* Results from all tests show that neither oligomers nor unreacted monomers were identified.
* 45 different PFAS were analysed for in PTFE batches produced with the NFPA; PFAS concentrations were always
below detection limits*.
* Water samples were analysed for Total Fluorine (TF) and Total Inorganic Fluorine (TIF) content by bomb combustion ion chromatography (CIC) according to ASTM D7359M.
* The Total Organic Fluorine (TOF) content was calculated by subtraction of TIF from TF.
* Insignificant amount of FPA were detected, but this is due to the fact that the batches were produced at the same reactor in
which PTFE with such FPA was manufactured in the past. GFL will continue to monitor concentration of FPA in future batches which
is expected to progressively decrease. Based on the chemistry from the reaction process, the detected FPA is not a substance expected to be formed as a by-product of PTFE polymerisation via emulsion process with the NFPA. Amounts of FPA detected are extremely low to consider that FPA may play a role in the successful polymerisation of PTFE.
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5. Technical performance
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* In order to demonstrate that the physio-chemical properties of PTFE manufactured by emulsion polymerisation process with NFPA meet the required technical specifications, additional studies were run on PTFE batches.
* Some of the critical properties tested were:
-- Melting point -- Critical cracking thickness -- Thermal instability index
* Results were compared with values obtained from PTFE samples manufactured via emulsion process with FPA.
* The results obtained demonstrated that PTFE manufactured with the use of NFPA exhibit equal or even better properties under certain parameters than the original PTFE.
* Higher values of stability and critical cracking thickness had been achieved, which means an improved performance over PTFE manufactured with FPA.
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6. Conclusions
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* GFL has successfully developed the use of an NFPA to manufacture PTFE aqueous dispersions via the emulsion polymerisation process.
* The NFPA is not PBT/vPvB nor PMT/vPvM, hence removing concerns on use of PFAS as FPAs from FP manufacture.
* Oligomers, unreacted raw materials or PFAS by-products are not detected in PTFE manufactured via emulsion polymerisation with the NFPA, according to different analytical results.
* PTFE manufactured via emulsion polymerisation with the NFPA exhibits equivalent technical performance (even improved) compared to batches manufactured with FPA.
* Emissions resulting from the use of NFPA are adequately controlled at manufacturing sites.
* Global implementation of this development could lead to drastic cut on use of FPAs in FP manufacture.
* GFL has filed patent applications which were granted, on the novel use of an organic compound based on sulfonated hydrocarbon chemistry as NFPA in the PTFE emulsion polymerisation process.
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7. Next steps
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* GFL expects to place PTFE aqueous dispersions manufactured without FPAs on the market in the coming months.
* GFL operates several pilot reactors for R&D purposes dedicated to finding alternative NFPAs for the remaining FP products.
* Precaution is still needed as it could occur that for some specific FPs, replacement of FPAs may not be possible in
the short term.
* Effective abatement techniques should reduce emissions to below detectable levels.
* New projects on-going related to:
-- EOL assessment of FPs -- management of waste streams from various industries/major applications -- Analysis of alternatives, including socio-economic impacts of substitution for key applications
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Key Messages
CHEMSERVICE
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* GFL manufactures fluoropolymers since 2007 and is a major supplier to European Economic Area. * GFL has developed a manufacturing process that does not use a Fluorinated Polymerisation Ais (FPA) / surfactant
for part of its portfolio. * GFL has initiated the commercialization of the new product. * This presents a major milestone, and the company is working towards converting its entire portfolio to processes
that do not use FPAs.
* Next steps are significantly more complicated and need more development and commercialization time. * Fluoropolymers are substantially different from side-chain fluorinated polymers in terms of potential emissions of
low carbon chain PFAS.
CONFIDENTIAL
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