Document 4aMmMZ1nE0xmgjrvzmOj1ZpR1

, organization for applied scientific CIVO research TldO-repor; ~- ac~p P o eo . 360 3700 A.: Ze .st Unecntseweg 40 Ze,st . The Netnenanas vnone - 31 34 04 5 2 z< . p. 1 13 ~~ 7 Report number A 88 .353/26060 2 Migration and extraction of emulsifiers from PTFE coated frying pan s '- : r . . tr_5 ' ssue may be reP r oeuceC a~ : o ou v .st : tv cr .n phct0,^.,= nt mc.olrm o, a - ~ o:ne means wanc,,t pe..nus wrme^ ;orsenl from. TN O Ju'.KrV:nc t : w e : or' lor ns:oectqn t e pan-es V ec q : nreestee is perm.net W. Case INS reDG r. waS Orahec unoe, Authors : N . de K rui j f M .A .H . RijIC L .A . Pranoto-Soetardhi H .A . Prins-Bod e Mstroypn Inc ncr.3 3 nC oDt.Sat .pn s c'r onVaa, ; :, a- C . ae suDreC to e,tner At the request of : t~ c .~~=z = C .~= . : ~ to, Resea :' Tr -, or Ine ee-a Du Pont de NeftlOULs zc~~e-t :-- ; -_- = xwee- ~e c~~ :,a:: ~,_~International S .A . 't,, eesea--oo~e :t Geneva, Switzerland Project number : B 86-0602 Approved by : R .H . de Vos Date : September 1988 Number of copies : 25 Number of pages : 43 Number of tables : 9 Number of annexes : 6 Number of figures : 7 ~~ ~r a''~ ~ ;; J r- ~ ,~~, ;,,,{,c~,e~ o 0 EID11216 0 ~~ p. 2 2- BACKGROUND We want C-8 to be on the positive list of substances that are allowed by the EC as additives to PTFE . Therefore, a toxicology file must be made . The extent of tox . testing depends on the result of a migration test into food simulants : water, 3i6 special olive oil . If 6 dm2 of PTFE surface is exposed to the food simulant and the final cone . is below 50 pg of C-8 per kg of simulant, only minor tox . testing is required . Between 50 Ng and 5 mg/kg more tests are needed . If > 5 mg --> many tests are needed . Extraction and migration tests were already done by TNO in 1979 and 1988, but gave unreliable results . CONCLUSIONS AND PATH FORWAR D 1 . The Azure A(= similar to Methylene Blue) method used by TNO sofar is not suitable for this purpose, because it is not specific to C-8, and other anionic surfactants are likely to be present . 2 . If we can prove that a worst case sample of PTFE corresponding to 6 dm2 area and thickness x mm does not contain more C-8 than 386 ppb, then we x can prove by calculation that at 100% migration we will stay below 50 pq of C-8 per kg of food simulant . We agreed that this is the first step to be tested . 3 . Dr Mitterberger will send to each party (DuPont, ICI, Dyneon) a 1 kg sample of 12 mm dia, 1 mm wallthickness FTFE tubing that has been sintered for 10 minutes . We all agree this is a representative worst-case material for food contact . Each party will do extraction tests with 954 ethanol C pH 9-10 and total reflux . Tests will be done 2 hours and 8 hours, with tube cut in pieces max . 70 mrn, preferably as fine as possible . Sample size 200 gram . DuPon t will also run CHC13 extractions in parallel . Each party will perform subsequent concentration and GC analysis in his own way, with which it has the most experience . We will send each other our results before end of January . 4 . Depending on the results, we will decide on fuitber action . This will be communicated on the next APME meeting in Brussels, on 24 February 1997 . 5 . The contribution of 3M consists of writing the technical file for the application with the EC authorities (Mr Cox - Antwerp) . EID751392 p. 3 A 88 .353 September Page 1988 2 SUMMARY Migration tests were carried out with frying pans coated with PTFE dispersion (PTFE - polytetrafluroethylene) put in contact with water or 3 % acetic acid for 90 minutes at 95 C or with fat simulant F03 307 for 90 minutes at 140 C or for 30 minutes at 200 C . The methanol-extractable amount of residual emulsifiers (ZONYL~ FSN-100, Serdox 2a1P 10 .5 and C8-emulsifier) in the PTFE coating was determined as well . The migration of non-ionic emulsifiers (ZRdYL FSN-100 and Serdox AIlNP 10 .5) into water or 3 % acetic acid (90 minutes at 95 C) or into f03 307 (90 niinutes at 140 C) was found to be 0 .001 or 0 .002 mg/dm2, which is of the order of magnitude of the detection limit . The migration value obtained for HB 307 (30 minutes at 200 C) is unreliable because of generation of interfering components during heating . The migration of C8-emulsifier into water and into 3 % acetic acid (90 niinutes at 95 C) was found to be 0 .005 and 0 .003 mg/dm2 respectively, which is of the order of magnitude of the detection limit . The values obtained for the migration of C8-emulsifier into HB 307 (90 minutes at 140 C or 30 minutes at 200 C) are unreliable due to the generation of interfering components during heating . The amount of methanol-extractable emulsifiers was found to be 0 .002 mg/dm2 for C8-emulsifier, 0 .002 mg/drn2 for ZQM FSN-100 and 0 .001 mg/dm2 for Serdox NNP 10 .5, which is of the order of magnitude of the detection limit . ~ C) o ~ E1D)1216 1 Du Pont's registered trademark p. 4 A 88 .353 September Page 1988 6 After extraction of the PTFE coating with methanol at 65 C the extractable amount of non-ionic emulsifier and of C8-emulsifier was determined with colorimetric methods of determination . A detailed description of the various experiments is given below . 2 .1 Sample materia l Frying pans coated with an aqueous PTFE dispersion, ZONYL* x-3551N', thickness 35-40 pm were provided by Du Pont de Nemours International S .A ., Geneva, Switzerland . It was stated that the PTFE dispersion contained non-ionic emulsifiers (ZONYL FSN-100 and Serdox NNP 10 .5) and an anionic emulsifier (C8-emulsifier) . Coated frying p-ns with a diameter of 20 cm on bottom level were used in the migration experiments . Coated frying pans with a diameter of 24 cm on bottom level were used in the extraction experiments . The non-ionic emulsifiers ZONYL FSN-100 (perfluorooctyl polyethoxylate) and Serdox NNP 10 .5 (nonylphenol polyethoxylate) and the anionic emulsifier C8-emulsifier (ammonium perfluorooctanoate), obtained by courtesy of Du Pont de Nemours International S .A ., Geneva, Switzerland, were used in the calibration and in the recovery experiments . 2 .2 Migration experiment s 2 .2 .1 Migration of non-ionic emulsifiers into aqueous food simulants A volume of 250 ml water or 250 ml 3%_acetic acid, heated to 95 C, was brought into a PTFE-coated pan . The total area of the PTFE coating in contact with the food simulant - bottom and side wall - was 3 .8 dm2 . Du Pont'6 registered trademark EID112162 0