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Microwave heating causes rapid degradation of antioxidants in polypropylene packaging leading to greatly increased specific migration to food simulants as shown by ESI-MS and GC-MS
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymer Technology.ORCID iD: 0000-0002-7790-8987
2011 (English)In: Journal of Agricultural and Food Chemistry, ISSN 0021-8561, E-ISSN 1520-5118, Vol. 59, no 10, p. 5418-5427Article in journal (Refereed) Published
Abstract [en]

Microwave heating of commercial microwavable polypropylene packaging in contact with fatty food simulants caused significant antioxidant degradation and increased specific migration as shown by electrospray ionization-mass spectrometry (ESI-MS) and gas chromatography-mass spectrometry (GC-MS). Degradation of the antioxidants Irgafos 168 and Irganox 1010 was not detected during conventional heating of polypropylene packaging at the same temperature. The migration into aqueous food simulants was primarily restricted by the water solubility of the migrants. Using isooctane as fatty food simulant caused significant swelling and greatly enhanced overall migration values compared to the other fatty food simulant, 99.9% ethanol, or the aqueous food simulants 10% ethanol, 3% acetic acid, or water. ESI-MS spectra clearly reflected the overall migration values, and the number and amount of compounds detected decreased as the hydrophilicity of the food simulant increased. ESI-MS was shown to be an excellent tool for the analysis of semivolatile migrants and a good complement to GC-MS analysis of volatile migrants.

Place, publisher, year, edition, pages
2011. Vol. 59, no 10, p. 5418-5427
Keywords [en]
polypropylene, antioxidants, migration, food simulant, degradation
National Category
Polymer Chemistry Polymer Technologies
Identifiers
URN: urn:nbn:se:kth:diva-32077DOI: 10.1021/jf1048639ISI: 000290691300033Scopus ID: 2-s2.0-79957934168OAI: oai:DiVA.org:kth-32077DiVA, id: diva2:408570
Note
QC 20110613Available from: 2011-04-05 Created: 2011-04-05 Last updated: 2017-12-11Bibliographically approved
In thesis
1. Microwave heating effects on degradation and migration of additives from polypropylene packaging
Open this publication in new window or tab >>Microwave heating effects on degradation and migration of additives from polypropylene packaging
2011 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The effect of different food types, polymer qualities and microwaves on the overall and specific migration during microwave heating of plastic packaging was investigated to better understand the packaging-food interactions and the effect of microwaves on food packaging. This work focuses on the migration of chemical compounds to food simulants from commercially available polypropylene packages. Packages used were made of polypropylene homopolymer (PP), co-polymer (PP-C) and random co-polymer (PP-R). Polymers matrix changes were monitored by following possible changes in crystallinity after microwave heating. Antioxidants Irgafos 168 and Irganox 1010 were present in all the three PP packages. Other volatiles, primarily degradation products of antioxidants, were also detected and identified in the unaged packages. Significant antioxidant degradation took place during microwave heating of the packages in the fatty food simulants 90/10 isooctane/ethanol and ethanol resulting in the formation and migration of degradation products while no degradation of antioxidants was detected during conventional heating of the packages in the fatty food simulants. Antioxidant Irgafos 168 and Irganox 1010 migration rates were otherwise similar during microwave heating as during conventional heating to the fatty food simulants and antioxidant diffusion coefficients were similar to earlier established values obtained during conventional heating. Antioxidant migration rates from the three polymers to fatty food simulants differed largely with respect to PP type and increased with decreasing degree of crystallinity in the materials, PP-R showing the highest migration rate. Swelling in isooctane food simulant caused the antioxidant diffusion coefficients to increase by factors of 100-1000 at 80 ºC and decreased the temperature dependence of antioxidant migration. It also increased the overall migration to above established overall migration limits during both microwave and conventional heating. Electrospray ionization mass spectrometry (ESI-MS) was shown to be a valuable new tool for additive migration analysis of compounds not detectable by HPLC or GC-MS.

Abstract [sv]

Effekten av olika typer av mat, polymermaterial och mikrovågor på total och specifik migrering under mikrovågsvärmning av plastförpackningar undersöktes för att bättre förstå interaktioner mellan förpackningar och mat samt effekten av mikrovågor på förpackningarna. Denna licetiatavhandling behandlar migrering av ämnen till matsimulerande ämnen (food simulants) från vanliga matförpackningar av polypropen, inköpta från matvaruaffärer. Förpackningsmaterialen var polypropen homopolymer (PP), co-polymer (PP-C) och random co-polymer (PP-R). Genom att mäta kristallinitetsgrad i proven före och efter mikrovågsvärmning kunde eventuella förändringar orsakade av värming samt matsimulanterna detekteras. Antioxidanterna Irgafos 168 och Irganox 1010 fanns i samtliga tre förpackningar. Andra flyktiga ämnen, främst nedbrytningsprodukter från antioxidanterna, detekterades och identifierades i de oåldrade förpackningarna. Betydande nedbrytning av antioxidanter inträffade under mikrovågsvärmning av förpackningarna i de feta mat-simulanterna 90/10 isooktan/etanol och etanol, vilket resulterade i bildning och migrering av nedbrytningsprodukter medan ingen betydande nedbrytning av antioxidanter skedde under vanlig värmning i samma simulanter. Migreringshastigheter för antioxidanterna Irgafos 168 och Irganox 1010 var annars samma under mikrovågsvärmning som under vanlig värmning i 90/10 isooktan/etanol och etanol och diffusionskoefficienterna för antioxidanterna var likvärdiga med tidigare uppmätta värden under vanlig värmning. Skillnader i antioxidanternas migreringshastigheter var stora mellan de olika PP-typerna och ökade med minskad andel kristallin fas i materialen, PP-R visade därför högst migreringshastighet. Svällning i isooktan ökade diffusionskoefficienterna med faktorer på 100-1000 under 80 ºC och minskade migreringshastighetens temperaturberoende. Den ökade även global migrering till över satta gränsvärden under både mikrovågsvärmning och vanlig värmning. Elektrospray-joniserings-masspektrometri (ESI-MS) visade sig vara ett användbart verktyg för analys av migrerade högmolekylära ämnen vilka ej var detekterbara med HPLC eller GC-MS.

 



Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. p. 41
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2011:15
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-32078 (URN)978-91-7415-885-4 (ISBN)
Presentation
2011-04-01, V3, KTH, Teknikringen 76, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20110405Available from: 2011-04-05 Created: 2011-04-05 Last updated: 2011-04-26Bibliographically approved
2. Migration from plastic food packaging during microwave heating
Open this publication in new window or tab >>Migration from plastic food packaging during microwave heating
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Microwave heating of food has increased rapidly as a food processing technique. This increases the concern that chemicals could migrate from food packaging to food. The specific effect of microwave heating in contrast to conventional heating on overall and specific migration from common plastic food storage boxes was studied in this work. The purpose was especially to determine the interaction effects of different plastics in contact with different types of foods during microwave heating. The study focused on polycarbonate (PC), poly(ethylene terephthalate) (PET), polypropylene homo-polymer (PP), co-polymer (PP-C) and random co-polymer (PP-R) packages. The migration determinations were evaluated at controlled times and temperatures, using a MAE device. The migrants were analyzed by GC-MS and HPLC. ESI-MS was evaluated as a new tool for migration determinations. Food/food simulant absorption and changes in degree of crystallinity during heating were also followed.

Significant degradation of antioxidants Irgafos 168 and Irganox 1010 in PP packages occurred during microwave heating of the packages in food simulants containing ethanol, resulting in the formation of antioxidant degradation products. Degradation of PC by Fries chain rearrangement reaction leading to formation of 9,9-dimethylxanthene, and transesterification of PET leading to formation of diethyl terephthalate, were also observed after microwave heating the packages in ethanol and 90/10 isooctane/ethanol. These reactions were not observed during conventional heating of the packages at the same temperature, or after microwave heating of the packages in liquid food (coconut milk). The microwave heating also significantly increased the migration of cyclic oligomers from PET into ethanol and isooctane at 80 °C. Migration of compounds into coconut milk was slightly lower than calculated amounts using the EU mathematical model to predict migration of additives into foodstuffs. The results thus show that the use of ethanol as a fat food simulant during microwave heating can lead to a significant overestimation of migration as well as degradation of polymer or the incorporated additives.

Some other detected migrants were dimethylbenzaldehyde, 4-ethoxy-ethyl benzoate, benzophenone, m-tert-butyl phenol and 1-methylnaphthalene. All identified migrants with associated specific migration limit (SML) values migrated in significantly lower amounts than the SML values during 1 h of microwave heating at 80 °C. The antioxidant diffusion coefficients in PP and PP co-polymers showed larger relative differences than the corresponding degrees of crystallinity in the same polymers and PP-R showed by far the fastest migration of antioxidants.

Abstract [sv]

Mikrovågsuppvärmning av mat har ökat markant under de senaste åren. Detta ökar risken för att ämnen i plast migrerar från matförpackningar till mat. Den specifika effekten av mikrovågsvärmning i kontrast till konventionell värmning på total och specifik migrering från vanliga matförvaringslådor av plast studerades i denna avhandling. Syftet var i huvudsak att bestämma interaktionseffekter mellan olika typer av plaster och olika typer av mat under mikrovågsvärmning. Studien fokuserades på förpackningar av polykarbonat (PC), polyetentereftalat (PET), polypropylen homopolymer (PP), copolymer (PP-C) och random copolymer (PP-R). Migreringstesterna utfördes under kontrollerade tider och temperaturer genom att använda MAE. Migranterna analyserades med hjälp av GC-MS och HPLC. ESI-MS-analys utvärderades också som ny analysmetod för migreringstester. Absorption av mat- och matsimulanter samt förändringar i kristallinitetsgrad följdes också.

Signifikant nedbrytning av antioxidanterna Irgafos 168 och Irganox 1010 i PP-förpackningar inträffade under mikrovågsvärmning av förpackningarna i etanol-innehållande matsimulanter, vilket resulterade i bildning av nedbrytningsprodukter från antioxidanterna. Nedbrytning av PC genom en Fries omfördelningsreaktion, vilket orsakade bildning av 9,9-dimetylxanten, samt transesterifikation av PET, vilket orsakade bildning av dietyltereftalat, observerades också efter mikrovågsvärmning av förpackningarna i etanol och 90/10 isooktan/etanol. Dessa reaktioner observerades ej efter konventionell värmning av förpackningarna under samma temperatur och ej heller efter mikrovågsvärmning av förpackningarna i riktig mat (kokosmjölk). Mikrovågsvärmningen ökade också betydelsefullt migrering av cykliska oligomerer från PET till etanol och isooktan under 80 °C. Specifika ämnens migrering till kokosmjölk var alla något lägre än migreringsvärden beräknade m. h. a. EU's officiella matematiska modell för förutsägelse av migrering från matförpackningar till mat. Dessa resultat visar att användandet av etanol som matsimulant för fet mat under mikrovågsvärmning kan leda till betydande överestimering av migrering, samt nedbrytning av polymer och additiv i polymeren.

Andra detekterade migranter var till exempel dimetylbenzaldehyd, 4-etoxy-etylbenzoat, benzofenon, m-tertbutylfenol och 1-metylnaftalen. Alla identifierade migranter med tillhörande ‘specific migration limit’ (SML)-värden migrerade i betydelsefullt mindre mängder än ämnenas tillhörande SML-värden under 1 h mikrovågsvärmning under 80°C. Diffusionskoefficienterna för antioxidanterna i PP-förpackningarna visade större relativa skillnader än förpackningarnas motsvarande kristallinitetsgrader och migrering av antioxidanter var snabbast från PP-R.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. p. vi, 81
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:25
Keywords
migration, food packaging, microwave, degradation, food simulant, antioxidant
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-96078 (URN)978-91-7501-363-3 (ISBN)
Public defence
2012-06-08, K2, Teknikringen 28, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Formas, 2007-793
Note

QC 20120530

Available from: 2013-04-03 Created: 2012-05-30 Last updated: 2013-04-03Bibliographically approved

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