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Migration of a phenolic antioxidant from aluminium oxide-poly(ethylene-co- butyl acrylate) nanocomposites in aqueous media
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Polymeric Materials.
2013 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 98, no 2, 475-480 p.Article in journal (Refereed) Published
Abstract [en]

The migration of a phenolic antioxidant (Irganox 1010) from nanocomposites based on aluminium oxide (2-12 wt.%; uncoated or coated with aminopropyltriethoxysilane or octyltriethoxysilane) and poly(ethylene-co-butyl acrylate) (EBA) with 13 wt.% butyl acrylate nanocomposites in aqueous media (liquid water or air with 100%RH) at 90°C was studied. The concentration of effective antioxidant in the composites was assessed by the oxidation induction time (OIT) measured by DSC. The flat OIT-profiles through the materials showed that the migration was controlled by the boundary conditions. The boundary antioxidant loss rates to the different media were (in relative units): 1 (dry air; data reported earlier), 1.5-3 (humid air) and 4-10 (liquid water). OIT-profiles for two-layer sandwich samples (a pristine EBA layer and a nanocomposite layer containing 0.2 wt.% Irganox 1010) showed that the antioxidant diffusivity was lowest in the composites containing uncoated nanoparticles (which had the highest surface concentration of hydroxyl groups of all the studied nanoparticles). The presence of water in the composites had only a small effect on the diffusivity; it was 10-50% greater than in the dry systems.

Place, publisher, year, edition, pages
2013. Vol. 98, no 2, 475-480 p.
Keyword [en]
Aluminium oxide, Aqueous media, Irganox 1010, Nanocomposite, Poly(ethylene-co-butyl acrylate)
National Category
Polymer Chemistry
URN: urn:nbn:se:kth:diva-104726DOI: 10.1016/j.polymdegradstab.2012.12.016ISI: 000315131600001ScopusID: 2-s2.0-84872105956OAI: diva2:566795
Swedish Research Council, 621-2007-5095

QC 20130215. Updated from submitted to published.

Available from: 2012-11-09 Created: 2012-11-09 Last updated: 2013-03-22Bibliographically approved
In thesis
1. Preparation and long-term performance of poly(ethylene-co-butyl acrylate) nanocomposites and polyethylene
Open this publication in new window or tab >>Preparation and long-term performance of poly(ethylene-co-butyl acrylate) nanocomposites and polyethylene
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The current study discusses the preparation and long-term performance of polymer composites used for various purposes under different ageing conditions.

The first part deals with the preparation and characterization of polymer nanocomposites based on poly(ethylene-co-butyl acrylate) (EBA–13 and EBA–28 with 13 and 28 wt % butyl acrylate, respectively) and 2–12 wt % (0.5–3 vol %) of aluminum oxide nanoparticles (two types with different specific surface areas and different hydroxyl-group concentrations; uncoated and coated with, respectively, octyltriethoxysilane and aminopropyltriethoxysilane). The nanocomposite with EBA–13 showed better overall nanoparticle dispersion while EBA–28 resulted in poor dispersion, probably due to insufficiently high shear forces acting during extrusion mixing which were unable to break down nanoparticle agglomerates.

The activity of hindered phenolic antioxidant (0.2 wt%) in all EBA nanocomposites was assessed by determining the oxidation induction time using DSC. The composites containing uncoated aluminium oxide nanoparticles showed a much shorter initial OIT than the pristine polymer with the same initial concentration of antioxidant, indicating adsorption of antioxidant onto the nanoparticle surfaces. Composites containing coated nanoparticles showed a significantly smaller decrease in the initial OIT, suggesting the replacement of hydroxyl groups with organic silane tails, decreasing the concentration of available adsorption sites on the nanoparticle surfaces. The decrease in OIT with increasing ageing time in dry air at 90 °C of the nanocomposites was slower than

that of the unfilled pristine polymer, suggesting a slow release of antioxidant from adsorption sites.

The EBA nanocomposites exposed to liquid water at 90°C showed faster decrease of OIT than samples exposed to dry or humid air. The migration rate of antioxidant was controlled by the boundary conditions in the case of ageing in humid air and liquid water. The antioxidant diffusivity was lower for the composites containing uncoated ND than for the composites containing ND coated with octyltriethoxysilane or aminopropyltriethoxysilane.

The migration and chemical consumption of deltamethrin DM, (synthetic pyrethroid) and synergist piperonyl butoxide from molded polyethylene sheets was also studied. Deltamethrin and piperonyl butoxide are often used for food  storage and insect control purposes. DM showed no signs of crystallization and remained in a liquid state after being cooled to room temperature. Exposure of polyethylene compound sheets to liquid water (at 80 & 95 °C), caused degradation and hydrolysis of the ester bond in the DM, present in the prepared material, and generated species containing hydroxyl groups. Liquid chromatography and infrared spectroscopy showed a significant migration of the active species in liquid water, whereas in air at 80 °C (60 and 80 %RH) the loss of DM and PBO was negligible over 30 days.

The long-term performance of medium-density polyethylene stabilized with six different phenolic antioxidants (0.1 wt%) in aqueous chlorinated media at 70 °C was studied. The results were compared with data for previously studied solutions of antioxidants in squalane (a liquid, low molar mass analogue of polyethylene). A linear relationship was established between the time to reach antioxidant depletion in polyethylene tape samples and the time in squalane samples. Infrared spectroscopy and scanning electron microscopy of drawn samples revealed the onset of surface oxidation and surface embrittlement in tape samples exposed beyond the time for antioxidant depletion.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 57 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2012:44
Polymer nanocomposite, nanoparticles, aluminium oxide, poly(ethylene-co-butyl acrylate), long-term performance, ageing, antioxidant, OIT, aqueous media, silanization, irganox 1010, deltamethrin, piperonyl butoxide, chlorine dioxide, migration of stabilizer
National Category
Polymer Technologies
Research subject
SRA - Production
urn:nbn:se:kth:diva-104685 (URN)978-91-7501-491-3 (ISBN)
Public defence
2012-11-30, Entreplan (F3), Lindstedtsvägen 26, KTH, Stockholm, 13:00 (English)
Cable insulation materialsLoss of deltamethrin and pipronyl butoxide from polyethylenelong-term performance of polyethylene in chlorine dioxide water
Swedish Research CouncilXPRES - Initiative for excellence in production research

QC 20121109

Available from: 2012-11-09 Created: 2012-11-09 Last updated: 2013-04-19Bibliographically approved

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