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Migration and chemical consumption of deltamethrin and piperonyl butoxide from polyethylene 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.ORCID iD: 0000-0001-7944-4103
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: Polymers from Renewable Resources, ISSN 2041-2479, Vol. 4, no 1, 1-18 p.Article in journal (Refereed) Published
Abstract [en]

Deltamethrin (DM), an important insecticide (synthetic pyrethroid) together with synergist piperonyl butoxide (PBO), is used for food storage and insect control purposes. It is often impregnated in polymers for controlled and effective release of insecticide. The migration and chemical consumption of DM and PBO from moulded polyethylene sheets was studied. The thermal behaviour of pristine DM and the prepared polyethylene compound was studied by differential scanning calorimetry. DM did not crystallize and remained in a liquid state after cooling to room temperature. Evaporation rates and activation energies of evaporation were determined by thermogravimetry for pristine DM, PBO, a solution of DM and PBO and for the PE compound. Evaporation from the DM/PBO solution was greater than that predicted from the evaporation rates of the individual compounds, which suggested that the DM/PBO solution obeyed non-ideal solution properties. The migration of DM and PBO from the polyethylene was studied in liquid water at 80 and 95 °C and in air of different relative humidities (60 and 80%) at 80 °C. Exposure to liquid water caused degradation and hydrolysis of the ester bond in 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 the loss of DM and PBO in air at 80°C (60 and 80 %RH) was negligible over 30 days.

Place, publisher, year, edition, pages
2013. Vol. 4, no 1, 1-18 p.
Keyword [en]
Deltamethrin, Piperonyl butoxide., Polyethylene, Pyrethroids
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-104727Scopus ID: 2-s2.0-84876997302OAI: oai:DiVA.org:kth-104727DiVA: diva2:566799
Note

QC 20131125 Updated from submitted to published.

Available from: 2012-11-09 Created: 2012-11-09 Last updated: 2013-11-25Bibliographically 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.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:44
Keyword
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
Identifiers
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)
Opponent
Supervisors
Projects
Cable insulation materialsLoss of deltamethrin and pipronyl butoxide from polyethylenelong-term performance of polyethylene in chlorine dioxide water
Funder
Swedish Research CouncilXPRES - Initiative for excellence in production research
Note

QC 20121109

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

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