Document NE9ZvB6RM5keYKx87DrOjmZjV
PETITIONER SUMMARY DATA SHEET ("P-SDS")
SUBSTANCE : Perfluoro acetic acid, a-substituted with the copolymer of perfluoro-1,2-propylene glycol and perfluoro-1,1-ethylene glycol, terminated with chlorohexafluoropropyloxy groups.
USE OF SUBSTANCE : additive
REF No.: 71943
CAS. N.: 329238-24-6
SOCIETY: SOLVAY SOLEXIS PERSON RESPONSIBLE FOR THE TECHNICAL DOSSIER: ADDRESS OF THE RESPONSIBLE:
PHONE: e-mail:
FAX:
Request for re-evaluation
A technical dossier for Perfluoro acetic acid, a-substituted with the copolymer of perfluoro-1,2propylene glycol and perfluoro-1,1-ethylene glycol, terminated with chlorohexafluoropropyloxy groups has been submitted initially on March 1, 2007, EFSA/AFC/FCM/992.
After evaluation of the data submitted, the Working Group of the Scientific Panel on Food Additives, Flavourings, Processing Aids and Materials in Contact with Food (AFC) of EFSA has classified the substance in the SCF-list 7, because of the lack of data as set out below:
1. Information supporting the statement that the sample tested corresponds to a worst case situation: Can the substance quantitatively evaporate during compression moulding? 2. Clarification on the procedure used for identification and quantification of migrating oligomers. - What in the procedure ensured that there is no loss of the substances to be analyzed during solvent evaporation? - Why was 1H-NMR used, rather than 19F-NMR? 3. The rationale of the procedure to determine the residual concentration of the substance.
- Is methanol a swelling solvent for the polymer? - Why was an extraction solution like that not used for identification and quantification of oligomers? 4. A clear differentiation is needed between intended applications: which ones are for elastomers and which for non-elastomers?
With the present technical dossier, additional information as requested by EFSA is submitted.
Annexes 1-9 are not included in this technical dossier as they were provided already in the initial technical dossier submitted in 2007.
Annex 10-11 contain additional information and are included in the present technical dossier and summarized in this P-SDS.
The additional information has been added to the initial P-SDS dated March 1, 2007 and can be recognized as text on a gray background.
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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REMARKS: CONFIDENTIALITY
Certain sections of this filing contain confidential business information that should not be released to third parties. The information marked "Confidential" should be reviewed only by authorized members of EFSA and the European Commission in connection with its evaluation of the suitability of the petitioned substance for use in food contact materials. More specifically the following information is considered confidential information:
- the proprietary manufacturing process (see 1.3.6); - part of the information related to the substances formed (see 1.3.7); - information on the purification process (see 1.3.8); - information on the by-products formed (see 1.3.9)
Clearly, public disclosure of this information would harm Solvay Solexis' competitive position, as competitors could potentially improve their own process by learning the details of Solvay Solexis' process. The confidential information has been removed from the "non-confidential" version of the filing, provided on CD-ROM.
The information considered to be treated as confidential can be recognized as text on a yellow background.
INFORMATION REQUESTED
INFORMATION PROVIDED
1.
IDENTITY OF SUBSTANCE
1.1
individual substance:
NO
1.2
defined mixture:
NO
1.3
Non-defined mixture:
YES
1.3.1 chemical name:
1-propene,1,1,2,3,3,3,-hexafluoro-, telomers with chlorotrifluoroethene, oxidized, reduced, hydrolyzed
1.3.2 1.3.3
synonym(s): trade name(s):
1.3.4 1.3.5
CAS nr: starting substances:
Chloro-fluoropolyether acid
FLUOROLINK 7800; FLUOROLINK 7850
Both products are covered by the same CASRN: the differences are in Molecular Weight (lower in 7800) and Molecular Weight Distribution (wider in 7850)
329238-24-6
1.3.6 manufacturing details:
THIS INFORMATION IS CONFIDENTIAL
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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1.3.7 substances formed:
1.3.8 purification by: 1.3.9 by-products:
1.3.10
molecular and structural formula:
Ref: Annex 1
Fluorolink 7800 and 7850 are mixtures of perfluoro-acids with the following simplified notation:
species n m Molecular weight
N1 0 0
296,5
N2 1 0
462,5
M3 1 1
578,5
N3 2 0
628,5
M4 2 1
744,5
N4 3 0
794,5
N5 4 0
960,5
Where n and m are the coefficients of the general formula:
C3F6ClO-[CF2-CF(CF3)-O]n-[CF(CF3)-O]m-CF2COOH
where n ranges from 1 to 4 and m from 0 to 2 in the active species.
The repeating unit -O-[CF2-CF(CF3)-O]- can also be present in `reverse' shape:
-O-[CF(CF3)-CF2-O]-
The C3F6ClO- end group is present in both normal CF3CFCl-CF2-O- and iso form: CF2Cl-CF(CF3)-O-.
Other end-groups in minor amount are CF3O-, CF2ClOand the ketone hydrate -CF2-C(OH)2-CF3.
Ref: Annex 1, 2 THIS INFORMATION IS CONFIDENTIAL
Ref: Annex 1
THIS INFORMATION IS CONFIDENTIAL
Main by-products are: - ketones (in hydrate form) -CF2-C(OH)2-CF3.
- -non-functional molecules (both end-groups like
C3F6ClO-; CF3O-; CF2ClO-
Ref: Annex 1
The active ingredient is nominally
C3F6ClO-[CF2-CF(CF3)-O]n-[CF(CF3)-O]m-CF2COOH where n ranges from 1 to 4 and m from 0 to 2.
Ref: Annex 2
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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1.3.11
molecular weight (Mw) and range:
Molecular Weight MW<300 content MW>750 content MW>800 content
Typical Composition
FLK7800
FLK7850
500-550 D
500-650 D
10% max
10% max
5% max
-
-
5% max
Ref: Annex 1,2
1.3.12 1.3.13
1.3.14 1.3.15 1.3.16 1.4 2. 2.1 2.1.1
purity (%):
The typical active ingredient levels are: -FLUOROLINK 7800= 80 5% -FLUOROLINK 7850= 79 5%
Ref: Annex 2
impurities (%):
The total levels of impurities are: -FLUOROLINK 7800= 20 5% -FLUOROLINK 7850= 21 5%
Main impurities are: - ketones (-CF2-C(OH)2-CF3 (present only in hydrate
form, in the acid-aqueous environment, 5-8%, acids and tensides titrations); - H2O (1-2%, determined by Karl Fisher titration) - -non-functional molecules (both end-groups like C3F6ClO-; CF3O-; CF2ClO- (1-2%); - residual HF (<0.1%, ion chromatography)) - MW < 300 max 10% (consisting of N1 (not detected at a detection limit of 100 ppm) and species like CF3OCF2COOH or CF2ClO-CF2COOH, determined by GC); - MW > 750 max. 5% (species N5 and higher, determined by GC)
Ref: Annex 2
spectroscopic data:
NMR spectrum is provided in the technical dossier
Ref: Annex 3
specifications:
None
other information:
-
polymer used as
NO
additive:
PHYSICAL AND CHEMICAL PROPERTIES OF SUBSTANCE
physical properties
melting point (C):
2.1.2 boiling point (C):
2.1.3
decomposition temperature (C):
Decomposition may start to occur at temperature exceeding 250 C; however, under normal processing
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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2.1.4
2.1.5
2.1.6 2.2 2.2.1
2.2.2 2.2.3
2.2.4 2.2.5
2.2.6
2.2.7 2.2.8 3. 3.1
conditions, evaporation will have preceded the possibility of decomposition.
Ref: Annex 4
solubility (g/l):
The solubility in water is below 5% w/w at T = 25 C. The substance is soluble in the following polar solvent: IPA, MEK, DPM (DiPropylenglycol monoMethylether)
octanol/water partition(log Po/w)
Data not available; information not relevant (migration is < 0.05 mg/kg of food, substance is not requested to be subject to Fat Reduction Factor).
other information related to lipophilicity:
No other information is submitted
chemical properties
nature:
. Ref: Annex 5
reactivity:
The substance is not reactive under the conditions described in section 3.
stability:
The substance is stable under the conditions described
in section 3.
Ref: Annex 4
hydrolysis:
The substance is not subject to hydrolysis
intentional decomposition/ transformation:
None
unintentional decomposition/ transformation product(s):
No decomposition/transformation has been observed under the conditions described in section 3.
interaction with food substances:
There are no known interactions with food substances.
other information:
No other information is submitted.
INTENDED APPLICATION OF SUBSTANCE
food contact material:
Fluorolink 7800 and 7850 are used in the manufacture of fluorinated polymers like:
These fluoropolymers are processed to produce a wide range of articles, like the following:
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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Parts for food processing equipment (fitting, valves);
Tubes, sheets, pipes; Tapes; Antistick coatings on cooking utensils All of these articles manufactured from these polymers and copolymers are for repeated use.
Fluorolink 7800
; 7850
.
EFSA question no. 4: A clear differentiation is needed between intended applications: which ones are for elastomers and which for non-elastomers?
The petition does not relate to fluoroelastomers but only to food contact materials that are covered by the definition of plastics.
Melt processable fluoropolymers and coating fluoropolymers mentioned in the present petition belong to the non-elastomer family. They are processed in order to produce a wide range of articles; - tubing, fittings, pipes and valves - films and antistick coatings on various food contact
articles. Finished articles are intended for repeated use.
3.2
technological function:
3.3
maximum process
temperature (C):
Ref: Annex 10
The substance is used as an emulsifier/dispersing agent during the polymerization process of fluoropolymers. Its presence ensures that the polymer to be synthesised forms a stable suspension of particles.
The typical temperatures in tubing extrusion and compression moulding are in the range 340380 C, up to 400 C. The maximum process temperature is encountered in coating applications; the coating is dried and then baked at temperatures up to 420 C for up to 10 minutes.
EFSA question no. 1: Information supporting the statement that the sample tested corresponds to a worst case situation: Can the substance quantitatively evaporate during compression moulding?
The sample tested for migration was
, a melt
processable TFE copolymer. Melt processable TFE
grades are considered to represent the worst case, i.e.
contain the highest amount of residual surfactant, if any.
Due to the processing temperature (lower) and the
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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thickness (higher) of melt processable grades, reduced evaporation of the surfactant in melt processable grades is expected when compared to coating grades. Furthermore, compression moulded articles can be considered the worst case vs the injection molded articles, the latter being processed at higher temperatures. Again, the lower molding temperature could result in a reduced evaporation of the surfactant.
Ref: Annex 10
3.4
maximum percentage in
The maximum content level, in polymerization recipe, is
formulation:
0.5 %.
the content of the surfactant is about 0.2% w/w of the full recipe; this content is equivalent to 0.5% w/w of the "solid" content. The level of the surfactant in the sample tested for migration is 0.5% w/w of the solid content
The resulting emulsion can be : - coagulated and the wet polymer is dried in a rotary kiln for 1h at 130-150 C;
Fluorolink 7850,
3.5
conditions of contact in
practice
3.5.1 3.5.2
contact food: time and temperature:
3.5.3 surface to volume ratio:
3.5.4 other information:
3.6
treatment of food
contact material prior to
use:
3.7
other uses:
In order to manufacture the final articles, the polymer has to be sintered at high temperature; this process results in a further reduction in the level of residual substance.
All types of foodstuffs
The maximum temperature of contact is experienced by coated cookware, which is used at temperature up to 230 C for usually up to 1 or 2 hours; there may be excursions up to 250 C for 15 minutes.
As a worst case the conventional surface to volume ratio of 6 dm2/kg is applicable. However many application will have lower surface to volume ratios.
All the articles manufactured from these fluoropolymers are for repeated use.
Cookware and bakeware are usually washed in hot soapy water before use; other articles, such as components of food processing machinery, are rinsed with hot water.
Lubricant powder grades containing Fluorolink may be
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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3.8 4. 4.1 4.1.1 4.1.2
4.1.3 4.2 4.2.1 4.2.2 4.2.3 4.2.4 4.3 5.
used as additives in a variety of polymers, which may be extruded and moulded into articles for contact with all types of foodstuffs, at all temperatures for repeated use. Lubricant powders are used to reduce friction and wear.
other information:
AUTHORISATION OF SUBSTANCE
EU countries
in Member States:
NO
notified as "new substance" in the
context of 6th Amendment of Directive 67/548/EEC:
Substance is a polymer according to 92/32/EC
other information:
-
non-EU countries
in USA:
NO
in Japan:
NO
in other countries:
NO
other information:
-
other information:
-
DATA ON MIGRATION OF SUBSTANCE
5.1
specific migration (SM):
5.2
overall migration (OM):
5.2.1 test sample:
5.2.2
treatment of sample prior to testing:
SM not determined; instead, the actual content of
Fluorolink 7850 was determined.
Ref: Annex 6
Overall migration determined.
Ref: Annex 6
Sheets of fluoropolymer
(
= propane, 1,1,1,2,2,3,3-heptafluoro-3-
[(trifluoroethenyl)oxy]-, polymer with tetrafluoroethene and
trifluoro(trifluoromethoxy)ethene)
The level of the surfactant used in the manufacture of the test sample is 0.5% w/w of the solid content.
In the migration test report the substance name is indicated as Fluorolink 7800:7850, while actually Fluorolink 7850 was tested. Fluorolink 7800 is a "sub-set" of Fluorolink 7850, therefore this last grade should be the "worst-case".
none
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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5.2.3 5.2.4 5.2.5 5.2.6
5.2.7
5.2.8 5.2.9
food simulant(s):
Iso-octane and 95% ethanol
contact mode:
Total immersion
contact time and temperature:
95% ethanol: 6 hr 60C Iso-octane: 4 hr 60C
surface to volume ratio:
Per test two sheets of approximately 13.5x13.5x0.04 cm were immersed in 100 ml food simulant resulting in a surface to volume ration of 3.484 dm/100 ml, taking one side into account.
test method:
After incubation period the samples were removed and after evaporating off the solvents under controlled conditions, the residues are estimated gravimetrically. The test was performed in duplicate. From the results the overall migration in mg/6 dm2 was determined.
other information:
-
results:
Results obtained for the overall migration are presented in table below. The total or overall migration in 95% ethanol and iso-octane are < 1 mg/6 dm2. Individual values are well below the established analytical error. Residues determined may be caused by some migration of substances or they may be just the result of the weighing error in the analytical procedure.
Overall migration from Fluoropolymer
Simulant
Test condition
95% ethanol
6 hr 60C
Iso-octane
4 hr 60C
Overall migration (mg/ 6 dm2) 0.27 0.68 Mean 0.48 0.45 0.95 Mean 0.7
5.3 Quantification and
identification of:
a)
migrating oligomers
and
b) reaction products derived
from monomers and starting
substances and additives
Determined. The residues obtained from experiments extracts with 95% were characterized using NMR.
the overall migration ethanol and iso-octane
Ref: Annex 6
EFSA question no. 2: Clarification on the procedure used for identification and quantification of migrating oligomers. - What in the procedure ensured that there is no loss of the substances to be analyzed during solvent evaporation?
The residue obtained under item 5.2.9 (overall migration)
was characterized and was obtained by concentrating the
migration extract under controlled conditions, i.e. by
solvent evaporation on a boiling water bath. This means
that no precautions were taken to ensure that no loss of
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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5.3.1 test sample:
the substances to be analyzed during solvent evaporation took place, and "only the non-volatile" oligomers/reaction products, if any, were taken into consideration.
In order to obtain additional data on the identification and quantification of migrating reaction product(s) or oligomer(s) of Fluorolink 7800:7850, including migration of any volatile substances, the migration study was repeated in 95% ethanol. The migration extract was analysed directly (i.e. without any concentration step) and after evaporation to dryness under milder conditions, for the presence of any Fluorolink 7800:7850 reaction product(s) and/or oligomer(s) using GC-MS and LC-MS.
Ref: Annex 11
- Why was 1H-NMR used, rather than 19F-NMR? LC-MS was used to determine the residual content of Fluorolink 7800:7850,
(in item 6), while 1H-NMR was used to find out if any other (non-fluoro containing) oligomer or reaction product of Fluorolink could be detected in the migration extracts.
Sheets of fluoropolymer
5.3.1.1 chemical composition:
5.3.1.2 physical composition: 5.3.1.3 density, melt flow index
of polymer: 5.3.1.4 dimensions of test
sample:
5.3.1.5 dimensions of test specimen
Sheets of fluoropolymer
Ref: Annex 11
= propane, 1,1,1,2,2,3,3-heptafluoro-3[(trifluoroethenyl)oxy]-, polymer with tetrafluoroethene and trifluoro(trifluoromethoxy)ethene
The level of the surfactant, Fluorolink 7850, in the test sample is 0.5% w/w of the solid content.
The sample tested was manufactured according the same process of the samples tested previously (TNO report V7054, October 2006)
the content of the surfactant is about 0.2% w/w of
the full recipe; this content is equivalent to 0.5% w/w of
the solid content.
Ref: Annex 11
Homogeneous material
Density: 2.12-2.17 Melt Flow Index = 2-5 g/10 m Measured at 372 C. with a load of 5 kg (ASTM D1238)
Sheets of approximately 13.5x13.5x0.04cm
Sheets of 13 x13 cm; thickness ca. 0.04 cm Ref: Annex 11
Per test two sheets of approximately 13.5x13.5x0.04 cm were immersed in 100 ml food simulant.
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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5.3.2 treatment of test sample prior to testing:
5.3.3
test food(s)/food simulant(s)/extraction solvent(s):
5.3.4 contact mode:
5.3.5
contact time and temperature:
5.3.6
surface to volume ratio in migration tests:
5.3.7 analytical method:
Per test two sheets of 13 x13 x 0.04 cm were immersed
in 100 ml food simulant
Ref: Annex 11
-
95% ethanol and iso-octane
95% ethanol
Ref: Annex 11
Total immersion
Total immersion
Ref: Annex 11
95% ethanol: 6 hr 60C Iso-octane: 4 hr 60C
95% ethanol: 6 hr 60C
Ref: Annex 11
3.484 dm/100 ml, taking one side into account.
3.38 dm /100 ml, taking one side into account Ref: Annex 11
The residue obtained under item 5.2.9 (overall migration) was characterized by NMR. Prior to NMR spectroscopy, the residue was dissolved in 1 ml deuterated chloroform (CDCl3) containing 0.05 % tetramethylsilane (TMS). The spectra were acquired by accumulation of 256 FIDs. Spectra were recorded using a spectral width of 8000 Hz. Chemical shifts of all spectra are expressed in ppm by reference to TMS (0.00 ppm). Resolution enhancement and noise reduction of the spectra was performed using an exponential window function with a line broadening of 0.3 Hz and a manual baseline correction was applied.
Per test, two sheets of fluoropolymer (one sheet is 13 cm x 13 cm, i.e. 1.69 dm per sheet or 3.38 dm for two sheets, taking one side into account) were cut into pieces of ca. 2x2 cm and transferred into a 250 ml Scott flask. An amount of 100 ml 95% ethanol (preheated at 60C) was added to the polymer sample. The flask was closed with a gas-tight cap and placed in an oven for 6 hours at 60C. After this period, the migration solution was cooled down and an aliquot of 0.5 ml of the 95% migration solution was injected directly for GC-MS and LC-MS analysis.
The remaining migration solution was gently evaporated to dryness at 60C under a nitrogen stream, redissolved in 0.5 ml 95% ethanol and injected for GC and LC-MS analysis.
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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5.3.8
detection/ determination limit:
5.3.9 recovery:
5.3.10 other information: 5.3.11 results:
For reference purposes, standard solutions of Fluorolink 7800:7850 were prepared in 95% ethanol at a level of 10 g/ml and 50 g/ml.
GC-MS conditions
Samples were injected on an Alltech AT 5ms column (30
m x 0.25 mm; film thickness 0.25 m); MS data were
collected in the scan mode (
).
LC-MS conditions: Blank, migration and standard solutions were analysed by Ion Trap- Mass Spectrometry (LC-IT-MS) in the ESI(+) and in the ESI (-) mode. 10 l of the solutions were directly injected (flow injection) in the system, using MeOH : ammonium acetate (5 mM) 1:1 (v/v) at a flow rate 300 l/min.
.
Not relevant
GC-MS: not established
The detection limit of the LC-MS method applied is set at
10 g/ml (
Fluorolink
7800:7850
).
Taking a surface to volume ratio of 3.38 dm/ 100 ml
this
corresponds to 9 g/6 dm or 9 g/kg food.
For the non-concentrated extract the detection limit is 1.8
mg/kg, see our comments in 5.3.11.
Not relevant
-
-
It appeared that the signals present in the 1H-NMR spectra of both, the fluoropolymer extracts and in their blanks, originate from compounds introduced during the extraction procedure and the NMR sample preparation; i.e. residual solvent (7.26 ppm), acetic acid (2.10 ppm_water (1.56 ppm), TMS (0.00 ppm). Due to the absence of protons in the fluoropolymer and monomers these are not visible for 1H-NMR. The signals present in the extract samples and absent in their blanks are assigned as proton containing migrants. Due to the low intensities en pure resolution of the signals further assignment was not possible. Final conclusion is that no significant peaks are detected that can be ascribed to reaction products of the fluoropolymer tested.
GC-MS analysis
Fluorolink 7800:7850
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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LC-MS analysis Fluorolink 7800:7850.
Fluorolink 7800:7850, .
Fluorolink 7800:7850 Fluorolink 7800:7850,
Fluorolink 7800:7850
.
In the sample extracts (both directly analysed and concentrated prior to analysis) no additional peaks were obtained compared to the spectra of blank 95% ethanol.
Fluorolink 7800:7850
Fluorolink
7800:7850
).
Taking a surface to volume ratio of 3.38 dm/ 100 ml
Fluorolink
7800:7850
is considered not
detectable, i.e. less than 9 g/6 dm or less than 9 g/kg
food.
The detection limit for direct injections is too high to detect small amounts of "volatile" components. However, in item 6 the loss of volatile components by using alkalized/non-alkalized extraction solvent was investigated. The extracts were directly injected, i.e. without any concentration step. No differences were
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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found for the alkalized/not alkalized extracts, which
means that no loss of migratable substances during
extraction was observed. The detection level was 20
g/kg polymer, which results in a worst case migration of
less than 1 g/kg food.
The experiments described in item 6 were measured in
the SIM mode, with significant lower detection limit, while
the 95% ethanol migration extracts were measured in the
scan mode (
.
It is considered that the alkalization will avoid evaporation
of substance containing the functional carboxylic group.
Substances, like decomposition products, that do not
contain the carboxylic group will not be influenced by the
alkalization. However decomposition products -if any-
that might have lost the polar carboxylic group are very
volatile. They will disappear, even faster than the
Fluorolink, during manufacturing of the polymer and/or
the final article.
As no differences were found in the spectra for the non-
concentrated and the concentrated ethanol migration
extract, it is concluded that concentrating the 95%
ethanol extract under the conditions applied does not
cause a loss of extracted substances as it was
demonstrated (see item 6) that no Fluorolink related
substances remain in the final FCM.
Ref: Annex 11
6.
DATA ON RESIDUAL CONTENT OF SUBSTANCE IN THE FOOD CONTACT MATERIAL
6.1
actual content:
6.2
substance:
6.3 6.3.1
test sample: chemical composition
6.3.2 6.3.3 6.3.4 6.3.5
physical composition
density, melt flow index of polymer
dimensions of test sample
dimensions of test specimen:
Actual content determined
Ref: Annex 6
In the report the substance name is indicated as Fluorolink 7800:7850, while Fluorolink 7850 has been used; Fluorolink 7800 is a "sub-set" of Fluorolink 7850, therefore this last grade should be the "worst-case".
Sheets of fluoropolymer
= propane, 1,1,1,2,2,3,3-heptafluoro-3[(trifluoroethenyl)oxy]-, polymer with tetrafluoroethene and trifluoro(trifluoromethoxy)ethene
The level of the surfactant used in the manufacture of the test sample is 0.5% w/w of the solid content.
Homogeneous material
Density 2.12-2.17 g/cm3
Sheets of approximately 13.5x13.5x0.04cm
The sheets of fluoropolymer were cut into pieces of ca. 1x3 cm. A test-sample of approximately 27 g is transferred to a conical flask of 100 ml.
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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6.4
treatment of sample:
6.5
test method:
The sample is refluxed for 8 hours with methanol/water (80/20; v/v). After the extraction an aliquot of the extract was transferred to a HPLC vial. The remaining extraction solvent was decanted and the extraction was repeated with a fresh amount of 50 ml methanol/water (80/20;v/v). From each of the first and second extracts 50 l was injected into the HPLC and analysed for containing Fluorolink 7800:7850 as described in 6.5. Using a new test specimen the extraction was repeated by using methanol/water (80/20) containing 0.1% ammonia. By addition of ammonia the less volatile Fluorolink 7800:7850 ammonium salt was formed and so the possibility of evaporation of the Fluorolink 7800:7850 during the extraction procedure was reduced.
The rationale of the procedure to determine the residual concentration of the substance. - Is methanol a swelling solvent for the polymer? - Why was an extraction solution like that not used for identification and quantification of oligomers?
Methanol/water (80/20) was used as extraction solvent for the determination of residual Fluorolink because Fluorolink is good soluble in the methanol/water mixture. In addition the test sample has a thickness of only 0.4 mm. Although swelling was not checked an extraction for 8 h at 80C was considered an exhaustive extraction. To check exhaustive extraction, the test sample was extracted a second time. In the first extract some small peaks (below the LOD) were detected, but in the second extract no peaks were found, it can be concluded that the conditions of extraction applied were adequate for the intended purpose, i.e. determination of the residual content of Fluorolink 7800:7850 in the polymer sample.
For the identification and quantification of oligomers, it was considered more appropriate to perform a migration experiment in a food simulant, i.e. 95% ethanol, instead of extraction with methanol/water. Performing a migration test is more close to any release in real foods, although it was noticed that condition of 6 h at 60C with 95% ethanol and extraction for 8 h at 80C with methanol/water most likely would not make a great difference in extraction quantities.
The extracts are analysed for the content of chlorofluoropolyether acids by LC-MS in the negative electrospray ionisation mode. Quantification is done by means of an external standard calibration.
6.5.1
detection/ determination limit:
6.5.2
precision of test method:
10,68 ng/ml, based on lowest calibration point. This corresponds to a residual content of 20 g/per kg fluoropolymer (= 10 ng/ml x 50 ml / 2.7 g).
Recovery and repeatability (SD of the recovery; n=3) of the method were for the standard addition to the sample material at the concentration level of 42.7 ng/ml: 99 7% for the extraction with methanol/water (80/20; v/v) and
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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6.5.3 6.5.4 6.6
recovery: other information: results:
101 8% for the extraction with methanol/water containing 0.1% of ammonia.
99-101%, see 6.5.2.
-
The Fluorolink 7800:7850
Fluorolink 7800:7850 :
f Fluorolink 7800:7850
6.7
calculated migration
(worst case):
7800:7850
Fluorolink .
7800:7850
Fluorolink
Conclusion: The residual content of Fluorolink 7800:7850 in the sample tested was not-detectable or <20 g/kg fluoropolymer.
The detection limit for the determination of Fluorolink 7800:7850 in samples of fluoropolymer was 20 g/kg.
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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6.8
residual content versus
specific migration:
From this result the worst case migration (M) of Fluorolink 7800:7850 to foodstuff can be calculated. Therefore the following formula has to be applied:
M=(Q*A*Ld*D)/1000
Assuming that:
Q= conc in mg/kg in fluoropolymer= 0.020 mg/kg, A= area of the food contact material in dm2, conventionally set at 600 cm2, Ld= thickness of food contact material = 0.04 cm and D=fluoropolymer density is 2.17 g/cm3
The worst case migration into foodstuff is M=(0.020*600*0.04*2.17)/1000=0.001 mg/kg or <1 g/kg into food.
-
7
MICROBIOLOGICAL PROPERTIES OF SUBSTANCE
7.1 Is the substance used as an
NO
anti-microbial agent?
8.
TOXICOLOGICAL DATA
8.1 8.1.1
Genotoxicity Gene mutation in bacteria:
Type of test: Ames Bacteria: S. typhimurium TA1535, TA98, TA100 & E. Coli WP2 uvrA
TA1537,
Year: 2006
GLP: YES
Test Substance: Fluorolink 7850
Dose Levels: Main Assay I & Main Assay II
ranging from 1.53 ug/plate to 5000 ug/plate
Method: the study was designed in compliance
with EEC Council Directive 2000/32, Annex 4D;
OECD 471; ICH S2A
Results: The test item does not induce reverse
mutation in both S. typhimurium and E. coli both
in absence and presence of metabolic activation
S9 Body responsible for the test: RTC - Research
Toxicology Centre Rome
Report number: RTC52400
Ref: Annex 7
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
19
8.1.2
In vitro mammalian cell gene mutation test:
8.1.3
In
vitro
mammalian
chromosome aberration test :
8.1.4 8.2
Other information: General toxicity
Type of test: Mutation in L5178Y TK+/- Mouse Lymphoma cells (Fluctuation method) Year: 2006 GLP: YES Test Substance: Fluorolink 7850 Dose Levels (ug/ml): Assay I (-S9) 125, 100, 80, 40, 20, 10, 5- Assay I (+S9) 150, 100, 75, 37.5, 18.8, 9.38 - Assay II (-S9) 160, 120, 80, 40, 20, 10 - Assay II (+S9) 120, 100, 83.3, 69.4, 57.9 Method: the study was designed in compliance with EEC Council Directive 2000/32, Annex 4E; OECD 476; ICH S2A, ICH S2B Results: Fluorolink 7850 does not induce mutation in mouse lymphoma L5178Y cells after in vitro treatment both in absence and presence of S9 metabolic activation Body responsible for the test: RTC - Research Toxicology Centre Rome Report number: RTC52410
Ref: Annex 8
Type of test: Chromosome aberration in Chinese Hamster Ovary cells in vitro Year: 2006 GLP: YES Test Substance: Fluorolink 7850 Dose Levels: Experiment I - 313, 156 and 78.1 ug/ml +/- S9; Experiment II - 300, 200, 133 ug/ml +/- S9 Method: the study was designed in compliance with EEC Council Directive 2000/32, Annex 4A; OECD 473 Results: Fluorolink 7850 does not induce chromosomal aberrations in CHO cells after in vitro treatment in the absence or presence of S9 metabolic activation Body responsible for the test: RTC - Research Toxicology Centre Rome Report number: RTC52420
Ref: Annex 9
8.2.1 8.2.2
8.2.3 8.2.4 8.3
Subchronic (90d) oral toxicity:
Chronic carcinogenicity:
toxicity/
Reproduction/teratogenicity:
Other information:
Metabolism
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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8.3.1 Absorption,
distribution,
biotransformation and excretion:
8.3.2 Accumulation in man:
8.3.3 Other information:
8.4
Miscellaneous
8.4.1 Effects on immune system:
8.4.2 Neurotoxicity:
8.4.3 Introduction on peroxisome proliferation:
8.4.4 Other information:
P-SDS of FLUOROLINK 7800/7850 CAS No. 329238-24-6
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LIST OF ANNEXES
Annex 1: Production process for FLK 7850 - Confidential information, P-SDS item 1.3.6, 1.3.8 1.3.9 and 1.3.11;
Annex 2: Analytical and Structural Characterization - Analytical report No. 60712, Bollate 24/01/2007; Confidential information, - Method of Analysis PF 29/151- PF30/83 and PF30/82 - P-SDS item 1.3.7, 1.3.11, 1.3.12 and 1.3.13;
Annex 3: NMR spectrum, P-SDS item 1.3.14;
Annex 4: TGA curve Fluorolink 7850 - 2.2.3;
, P-SDS item 2.1.3,
Annex 5: Determination of the Ka, P-SDS item 2.2.1;
Annex 6: TNO migration report V7054: Migration study of Fluorolink 7800:7850 - 6 October, 2006, P-SDS item 5 and 6;
Annex 7: RTC report no. 52400: Fluorolink 7850 - Bacterial Mutation Assay, 15 September 2006, P-SDS item 8.1.1;
Annex 8: RTC report no. 52410: Fluorolink 7850 - Mutations in L5178Y TK+/mouse lymphoma cells (fluctuations method), 13 December 2006, P-SDS item 8.1.2;
Annex 9: RTC report no. 52420: Fluorolink 7850 - Chromosome aberrations in Chinese Hamster Ovary cells in vitro, September 2006, P-SDS item 8.1.3.
Annex 10: Additional information provided by Solvay Solexis - Bollate 23/05/2008
Annex 11: TNO migration report V8128: Characterization of migrating oligomers and reaction products of Fluorolink 7800:7850 from a fluoropolymer sample - June 2008