GLOBAL and SPECIFIC MIGRATION OF POLYPROPYLENE AND POLYCARBONATE CONTAINERS. ARAVEN April 2009

Transcription

1 GLOBAL and SPECIFIC MIGRATION OF POLYPROPYLENE AND POLYCARBONATE CONTAINERS ARAVEN April 2009 Prof. Dra. Cristina Nerín de la Puerta Catedrática de Química Analítica Instituto de Investigación en Ingeniería de Aragón Centro Politécnico Superior de Ingenieros

2 Description According to the requirements of the Company ARAVEN, several PP and PC containers supplied by the Company were evaluated for being in direct contact with food. The European Directives 72/2002/EC, 19/2007/EC, 39/2008/EC and the Spanish RD 866/2008 and 103/2009 were taken into account. The global and specific migration tests were carried out on three independent replicates of each container and using the following food stimulants: 1. Simulant A: Distilled water 2. Simulant B: 3% (m/v) acetic acid in water 3. Simulant C: 10 % (V/V) ethanol in water 4. Simulant D:Isoctane and/or 95% (V/V) ethanol in water. Antioxidants, plastisizers and other organic compounds present in the stimulants after the migration tests were analyzed. The containers, caps and closure tights were also independently evaluated under the following experimental conditions: a) Global migration The materials were placed in contact with each stimulant for 2 hours at 70ºC and the stimulant was evaporated to dryness after the test. The remaining residue was gravimetrically analysed til constant weight.blank samples were simultaneously analyzed and the remaining residue was substracted from the final value obtained with the samples. b) Specific migration of Non volatile antioxidants, residual monomers and UV stabilizers Non volatile antioxidants, residual monomers and UV stabilizers commonly present in this type of plastics were analyzed by HPLC-UV at _=280 nm in each simulant after the migration test. The following standards were used for quantification: Chimassorb 81 Tinuvin P Irganox 1076 Tinuvin 326 Irgafos 168 Cyasorb UV 5411 BHT

3 Tinuvin 327 Irganox 1010 Cyasorb UV 24 Bisfenol A (BPA) And the detection limit was established at 2 mg/kg. According to the legislation the SML established for Bisphenol A is 0.6 mg/kg (See Table 1). Then, a GC-MS procedure was also optimized and applied to the stimulants to evaluate the BPA with a detection limit of 0.48 mg/kg. Table 1.- Specific migration limits of some migrants. Compound SML (mg/kg of simulant) Tinuvin Irganox Bisfenol A 0,6 Chimassorb 81 6 BHT 3 Tinuvin Cyasorb UV24 6 c) Specific migration of terephthalic acid, isophthalic acid and diethylenglicol According to the legislation the SML values are 30, 5 y 7,5 respectively for diethylenglicol, isophthalic acid and terephthalic acid. The simulants after the tests were analyzed by HPLC-MS. The detection limit was obtained at 0.5 mg/kg in the stimulant. d) Specific migration of plastisizers Phthalates present in the simulants after the tests were also analyzed by Solid Phase Microextraction (SPME) coupled to GC-MS. Diethylphthalate (DEP), dibutylphthalate (DBP) and bis(2-ethylhexylphthalate (DEHP) were used as standards for quantitative purposes in the range from 0 to 1.24 mg/kg in water (stimulant A) and the same using the other stimulants as

4 sample matrix for the calibration plots. Three independent replicates were analyzed. The quantification limits obtained were µg/g for DEP, µg/g for DBP y µg/g for DEHP. e) Screening of volatile compounds A screening of volatile compounds was carried out by SPME-GC-MS in stimulant A to check the likely presence of other migrants. f) Specific migration of butadiene Butadiene was also analyzed by HS-GC-MS in the stimulants after the test. The detection limit was 0,016 mg/kg ad the SML is 0.02 mg/kg.

5 Results Table 2 shows the results of global migration obtained. Table 2.- Global Migration in the simulants SAmple Simulant A(µg/g) Simulant B (µg/g) Simulant C (µg/g) Simulant D (µg/g) Polypropylene R1 < 0,01 < 0,01 < 0,01 < 0,01 R2 < 0,01 < 0,01 < 0,01 < 0,01 R3 < 0,01 < 0,01 < 0,01 < 0,01 R4 < 0,01 < 0,01 < 0,01 < 0,01 R5 < 0,01 < 0,01 < 0,01 < 0,01 Polycarbonate R1 < 0,01 < 0,01 < 0,01 < 0,01 R2 < 0,01 < 0,01 < 0,01 < 0,01 R3 < 0,01 < 0,01 < 0,01 < 0,01 R4 < 0,01 < 0,01 < 0,01 < 0,01 R5 < 0,01 < 0,01 < 0,01 < 0,01 The specific migration study showed in all cases values lower than 2 mg/kg for the antioxidants and the stabilizer. In the case of BPA the signal obtained was in all cases 30 times lower than that obtained for the standard of 0.48 mg/kg. The values obtained for diethylenglicol, isophthalic acid and terephthalic acid were in all cases lower than 0.5 mg/kg. Table 3 and 4 show the results of phthalates identified and quantified.

6 Table 3.- Phthalates obtained in Simulants A nd B. Sample Compound Simulant A (mg/kg) Simulant B (mg/kg) Polypropylene DEP < 0,079 DiBP < 0,075 < 0,075 DBP < 0,075 < 0,075 DEHP < 0,074 < 0,074 Polycarbonate DiBP < 0,075 < 0,075 DBP < 0,075 < 0,075 butyl-2-hexylphthalate - < 0,074 DEHP < 0,074 < 0,074 Table 4.- Phthalates obtained in Simulant C Sample Compound Simulant C (mg/kg) Polypropylene DiBP < 0,075 DBP < 0,075 DEHP < 0,074 9 phthalates < 0,074 Polycarbonate DiBP < 0,075 DBP < 0,075 DEHP < 0,074 9 phthalates < 0,074 The SML values in the legislation are shown in Table 5.-

7 Table 5.- SML values Compound CAS number SML (mg/kg in simulant) bencilbutyl phthalate bis(2-ethylhexylphthalate) ,5 dibutylphthalate ,3 Diésteres de ácido ftálico con alcoholes ramificados primarios, saturados C8-C10 más de 60% C In all cases the values obtained are well below the SML values. The results obtained from the screening of volatile compounds is shown in Tables 6, 7. Table 6.- Results of screening of volatile compounds in Simulant A Simulant A Polypropylene Polycarbonate Compound RT (min) Compound RT(min) Fenol [ ] 8,55 Fenol [ ] 8,54 Fenol [ ] 9,24 Fenol [ ] 9,24 Ftalato de diisobutilo 10,86 Ftalato de diisobutilo 10,84 Ftalato de dibutilo 11,56 Ftalato de dibutilo 11,57 Adipato (ester) [ ] 14,45 Ftalato de bis(2-etilhexilo) 15,64 Ftalato de bis(2-etilhexilo) 15,69 Indol (Skatole) [ ] 16,42 Indol (Skatole) [ ] 16,42

8 Table 7.- Results of screening of volatile compounds in Simulant B Simulant B Polypropylene Polycarbonate Compound RT(min) Compound RT (min) Fenol [ ] 8,53 Fenol [ ] 8,53 Ftalato de dietilo 9,20 Ftalato de dietilo 9,17 Ftalato de diisobutilo 10,86 Fenol [ ] 9,26 Ftalato de dibutilo 11,56 Ftalato de diisobutilo 10,85 Butil citrato 13,08 Ftalato de dibutilo 11,57 Butil citrato 13,52 Adipato (ester) [ ] 14,45 Indol (Skatole) [ ] 15,04 Indol (Skatole) [ ] 15,04 Ftalato de bis(2-etilhexilo) 15,65 Ftalato de bis(2-etilhexilo) 15,63 Indol (Skatole) [ ] 16,43 Indol (Skatole) [ ] 16,42 Table 8.- Results of screening of volatile compounds in Simulant C

9 Simulante C Polypropylene Polycarbonate Compound RT(min) Compound RT (min) Fenol [ ] 8,57 Fenol [ ] 8,53 Ftalato de diisobutilo 10,86 Fenol [ ] 9,25 Ftalato de dibutilo 11,54 Ftalato de diisobutilo 10,85 Adipato (ester) [ ] 14,46 Ftalato de dibutilo 11,54 Ftalato de bis(2-etilhexilo) 15,64 Palmitato de etilo (ester) [ ] 12,93 Ftalatos (9) 17,3-18,2 Adipato (ester) [ ] 14,45 Ftalato de bis(2-etilhexilo) 15,62 Indol (Skatole) [ ] 16,42 Ftalatos (9) 17,3-18,2 In all cases the values obtained were in the order ng/g in the stimulant. The analysis of Butadiene showed the values given in Table 9 Table 9.- Butadiene in the simulants Simulant A (mg/kg in the simulant) Butadiene < 0,016 Simulant B Butadiene (mg/kg in the simulant) < 0,016

10 Simulant C mg/kg in the simulant Butadiene <0,016 Simulant D mg/kg in the simulant Butadiene <0,016 CONCLUSIONS According to the results obtained the materials tested fullfil the EU legislation as food contact materials. Zaragoza, 15 th May, Prof. Dr. Cristina Nerín Catedrática de Química Analítica Directora del grupo GUIA Instituto de Investigación en Ingeniería de Aragón (I3A) Centro Politécnico Superior de Ingenieros María de Luna 3, Zaragoza, España Tel: ; Fax: