Document 3Nm007rB20vyBo90Za0kBoMpE

f f *r%- BFGOODRICH CHEMICAL LIMITED PROJECT NO: 6980-2 ALTONA DATE: 20th October, 1980 EXTRACTION OF BISPHENOL A FROM FINISHED PVC PRODUCTS INTRODUCTION This work was initiated as an extension of Project No. 6980-1 in order to gain approval for the use of Bisphenol A (BPA) as a shortstop in the production of Poly (vinyl chloride) (PVC). Having determined the level of residual BPA in PVC resin, it was necessary to determine its extractability from food contact products. CONCLUSION The work showed that aqueous solvents did not extract a detectable amount of the BPA from the finished product. Fatty type solvent, heptane, extracted 17 >ug/square inch. Results are shown in Appendix II. EXPERIMENTAL 1. Introduction As there is no Australian Standard covering the presences of BPA in plastics used for food contact applications, the development of the extraction procedures was based on the American FDA method No 175-300, pages 505-510. Two formulations were tested, one representing rigid food packaging (E) such as bottles and the other (G) representing flexible food wrapping such as film. These formulations are shown in Appendix I. Each formulation was fluxed on a steam heated laboratory two roll mill. Plaques 15cm x 15cm x 0.125cm were prepared on a steam heated press. Small samples, 4cm x 4cm x 0.125cm, were then cut for the extraction tests. ../2 20814002 "T 2- - 2. Extraction FDA Method 175-300 specifies the following extraction media and conditions: Condition of use.Extractant and conditions(See table below) Type of food E. Room temperature filled and stored (no thermal treatment in the container) Rigid package Jl) Water, 120F, 24 hour (Simulating room temperature ! filling and storage) i2) n-Heptane, 70F, 30 min (Simulating room temperature filling and storage of fatty foods only) I, II, III, IV-A IV-B, VI-B III, IV-A, V, VII : j 1 G. Frozen storage (no thermal Water, 70Ff 24 hour treatment In the (Simulating frozen storage) container) Flexible package I, XI, III, IV-B, i VII Types of food I. Nonacid (pH above 5.0) aqueous products may contain salt or sugar or both and including oil-in-water emulsions of low or high-fat content. II. Acidic (pH 5.0 or below), aqueous products may contain salt or sugar or both, and including oil-in-water emulsions of low or high-fat content. III. Aqueous, acid or nonacid products containing free oil or fat; may contain salt and including water-in-oil emulsions of low or high fat content. IV. Dairy products and modifications: A. Water-in-oil emulsion, high or low fat. B. Oil-in-water emulsion, high or low fat. V. Low moisture fats and oils. VI. Beverages: A. Containing alcohol B. Nonalcoholic VII. Bakery products. VIII.Dry solids (no end test required). ../3 N) CD OC3O BFG06989 -3- 2. Extraction (cone) Four pieces of the prepared sample, totalling 36 sqin.in surface area, were placed in a jar to which had been added approximately 300ml of extracting solution. The jars were sealed with a screw lid, and placed in a water bath of the appropriate temperature. After the specified time, the jars were removed from the bath. The samples were then removed from the jars, and the solutions analysed for BPA as discussed later. 3. Analytical Method a) Equipment Used The analysis was carried out on a Hewlett Packard Gas Chromatograph fitted with an automatic sampler, and a flame ionization detector. Conditions used were as follows: Column: 6' x 1/8" stainless steel packed with 1Z OV-1 on Chromosorb G Column Temperature: 200C Carrier Gas; Nitrogen Carrier Gas flowrate: 10 cc/min Injection temperature: 300C Detection temperature: 300C Sample size: 3.2jxl b) Detection Limit The detection limit for the analysis was determined by analysing solutions of known BPA concentration. The concentrations used were: 0, 0.5, 1, 2, 5 ppm BPA. Chromatographs are shown in Figure 1. From these it can be seen that the limit of detection on the equipment available is lppm derivatised BPA* Conversion of this value to a limit of detection per area is shown below: 1 ppm * 1 ^ig/ml - 100 jug/100 ml (final solution volume) - 100 ^ig/36 sq in (area of sample) 2,7jig/sq in ../4 3FG06990 trU 0 frT 8 0 -4 - 3. Analytical Method (cont) c) Recovery Data Recovery data for the analyses was determined by spiking each extracting solvent with a known amount of BPA. The spiked aqueous solutions were extracted three times with 50ml benzene. The combined benzene extractants were then evaporated to dryness using a rotary evaporator. The residue was taken up in acetone, and then made up to 100ml in a volumetric flask using acetone. The spiked heptane was evaporated to dryness on a rotary evaporator and the residue taken up in acetone. This was then transferred to a volumetric flask and made up to 100ml using acetone. One millilitre aliquots of the acetone solutions was then derivatised with N,N bis (trimethyl silyl) acetamide and analysed by gas chromatography. Data for the aqueous solvents were obtained using a level of 4ppo and lOppm BPA in the extracting solvent. Data for the heptane solvent were obtained by adding an amount of BPA which would give a final solution of 5ppm BPA. The recovery data obtained were: Water: 4ppm - 98% lOppm -93% Heptane: 5 ppm - 75% Typical chromatograms are shown in Figure 2 for aqueous extraction and Figure 3 for heptane. Earlier work (Project 6980-1) showed that below 25ppm BPA, response of the gas chromatographic detector to the derivatized BPA is linear (Fig 2, project 6980-1). As a result of this, our analyses on recovery (and extractant) solutions were compared to a lOppm standard only. d) Analysis of extractant solutions After the specified extraction procedures had been carried out, the samples were removed from the solvent and these solvents were analysed as discussed above. Chromatograms obtained for analysis of extracting solutions are shown in figures 4 (water) and 5 (heptane). Results are given in Appendix II. N S 0 0 fcT8 0 GB:sc G. Brown ( SLpPrq 1 PPrf\ y ii 20814006 i bte*tC-3. N' ' isl A Tl Ci^l iiAl&cr K-i (VI jT" of 6 P- A . BFG06992 toff* = <*&% iltJbCT iO 9fr\ <t0*J61 3 Ql THI5>CPu c-^OOM^TCOj'^fN'.^^ <& `^'^CCi -n-*^ ^tcr CsT \s^f-?T~tL'\ e-v BFG06993 20814007 r JKJLL 20814008 TiPiGAl, fiTA^eo pk>. a BFG06994 FUmQHjE. Ard^ssii, &* -me; 6*r7V I NifeCi Vvi e^T^Ca-fV'JTS 20814009 BFG06995 iTMitw^fc S fii^ur. i->w tr.vi k.o vl <^'rc.feA8k(x*' cATftiNco Tt w 0814010 BFG06996 APPEN D I X I Formulations used to test extractability of BFA from PVC compounds Geon 103EP Kureha BTA III N Paraloid K120N Mark 465T Advastab CZlll DIOP Faraplex 662 Wax OP G.M.S. Stearic Acid Rigid Compound <E) phr 100 10 1 1.5 0.2 0.1 _ Flexible Compound (G) phr 100 - - 1.5 25 10 - 0.4 Formulation E represents a rigid food packaging product Formulation G represents a flexible food packaging product. 20814011 BFG06997 a 0 A P P E N D I X___ II TesC conditions and results for extraction studies of BPA from food contact PVC formulations Formulations used E G E Extraction conditions Water, 50C for 24 hours Water, 25C for 24 hours n-heptane, 25C for 30 minutes Level of BPA extracted ^2.7yug/sq in <2.7^ig/sq in 17 ^tig/sq in The formulations given In this report do not in any way constitute an individual endorsement of the additives suggested for use with our PVC resins or other products. Equivalent additives from ocher manufacturers may be used with similar effect. 2081401 BFG06998 0