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Quality Assessment for the Improved Use of Recycled Styrenic Polymers: Application to packaging and electronic waste
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0003-3572-7798
2008 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

 Polymeric waste materials should be considered resources for the manufacture of new products through recycling processes, with a similar status as virgin fossil-based plastics and biopolymers from renewable resources. Several efforts can be done to achieve this qualitative quantum leap and introduce recycled products in the market with competitive performance. Detailed scientific knowledge about the degradation processes to which polymeric materials are subjected under their life cycle is important when discussing their further waste recovery possibilities and the performance of recycled plastic. The development of fast and reliable analytical methods for the quality assessment of recycled plastics is fundamental to guarantee their performance in new applications. Three key quality properties have been previously defined for this quality analysis: degree of mixing (composition), degree of degradation, and presence of low molecular weight compounds (degradation products, contaminants, additives).A dual experimental approach employing multiple processing and thermooxidation is proposed to model the life cycle of recycled high-impact polystyrene (HIPS) used in packaging applications, and in electrical and electronic equipment (E&E). Both reprocessing and thermo-oxidative degradation are responsible for coexistent physical and chemical effects (chain scission, crosslinking, apparition of oxidative moieties, polymeric chain rearrangements, and probably physical ageing) on the microstructure and morphology of polybutadiene (PB) and polystyrene (PS) phases; these effects ultimately influence the long-term stability, and the rheological and mechanical behaviour of HIPS. The PB phase has proved to be the initiation point of HIPS degradation throughout the life cycle. Thermo-oxidation seems to have more severe effects on HIPS properties; therefore, it can be concluded that previous service life may be the part of the life cycle with the greatest influence on the recycling possibilities and performance of HIPS recyclates in second-market applications.Different strategies are presented for the quality analysis of recycled styrenic polymers from packaging waste and electrical and electronic equipment. The results from the life cycle degradation simulation were compared with those obtained from real samples from a large-scale mechanical recycling plant. The presence and emission of low molecular weight compounds from recycled HIPS from packaging waste has been critically discussed using solvent and headspace extraction procedures. Special attention has been devoted to the determination of brominated flame retardants in recycled HIPS from electrical and electronic equipment using advanced extraction and chromatographic techniques, due to the legislative and environmental implications of these additives.

Place, publisher, year, edition, pages
Stockholm: KTH , 2008. , 57 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2008:63
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4895ISBN: 978-91-7415-112-1 (print)OAI: oai:DiVA.org:kth-4895DiVA: diva2:1802
Public defence
2008-10-09, F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100920Available from: 2008-09-25 Created: 2008-09-17 Last updated: 2010-09-20Bibliographically approved
List of papers
1. Degradation of recycled high-impact polystyrene. Simulation by reprocessing and thermo-oxidation
Open this publication in new window or tab >>Degradation of recycled high-impact polystyrene. Simulation by reprocessing and thermo-oxidation
2006 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 91, no 9, 2163-2170 p.Article in journal (Refereed) Published
Abstract [en]

 A simulation of the degradation of high-impact polystyrene (HIPS), occurring during service life and mechanical recycling, was performed by multiple processing and thermo-oxidative ageing. All samples were characterized by differential scanning calorimetry (DSC), melt mass-flow rate (MFR) measurements, tensile testing and infrared spectroscopy (FTIR). Multiple processing and thermo-oxidative ageing clearly alter the oxidative stability and the elongation at break of the materials. These changes observed at a macroscopic scale have been related to chemical alterations in the structure of HIPS. The polybutadiene phase was demonstrated to be the initiation point of the degradative processes induced by processing, service life and mechanical recycling. Thermo-oxidative degradation affects more severely the degree of degradation of the material, so it may be deduced that the changes occurring during service life of HIPS are the part of the life cycle that mostly affects its further recycling possibilities and performance in second-market applications.

Keyword
recycling, degree of degradation, high-impact polystyrene, reprocessing, thermo-oxidation
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-7224 (URN)10.1016/j.polymdegradstab.2006.01.007 (DOI)000238918200031 ()2-s2.0-33744510923 (Scopus ID)
Note
QC 20100907Available from: 2007-05-30 Created: 2007-05-30 Last updated: 2017-12-14Bibliographically approved
2. Changes in the microstructure and morphology of high-impact polystyrene subjected to multiple processing and thermo-oxidative degradation
Open this publication in new window or tab >>Changes in the microstructure and morphology of high-impact polystyrene subjected to multiple processing and thermo-oxidative degradation
2007 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 43, no 10, 4371-4381 p.Article in journal (Refereed) Published
Abstract [en]

Multiple processing and thermo-oxidation have been employed to simulate the degradative processes to which high-impact polystyrene (HIPS) is subjected during processing, service life, and mechanical recycling. A curve-fitting procedure has been proposed for the analysis of the individual bands corresponding to polybutadiene microstructure resulting from Raman spectroscopy. The analysis of the glass transition relaxations associated with the polybutadiene (PB) and polystyrene (PS) phases has been performed according to the free-volume theory. Both reprocessing and thermo-oxidative degradation are responsible for complex physical and chemical effects on the microstructure and morphology of PB and polystyrene PS phases, which ultimately affect the macroscopic performance of HIPS. Multiple processing affects PB microstructure and the free-volume parameter associated with the PS phase. Physical ageing of the PS phase predominates for shorter exposure to thermo-oxidation; after prolonged exposure, however, the chemical effects on the PB phase become significant and strongly influence the overall structure.

Keyword
high-impact polystyrene, degradation, Raman spectroscopy, dynamic-mechanical properties, polybutadiene microstructure
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-4891 (URN)10.1016/j.eurpolymj.2007.07.017 (DOI)000250386600031 ()2-s2.0-34748865085 (Scopus ID)
Note
QC 20100902Available from: 2008-09-17 Created: 2008-09-17 Last updated: 2017-12-13Bibliographically approved
3. Chromatographic pattern in recycled high-impact polystyrene (HIPS): Occurrence of low molecular weight compounds during the life cycle
Open this publication in new window or tab >>Chromatographic pattern in recycled high-impact polystyrene (HIPS): Occurrence of low molecular weight compounds during the life cycle
2010 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 95, no 2, 172-186 p.Article in journal (Refereed) Published
Abstract [en]

The analysis of the chromatographic pattern of virgin, reprocessed, thermo-oxidised, and recycled high-impact polystyrene (HIPS) proves to be a suitable and sensitive tool to assess the degree of degradation of HIPS during its first life and subsequent recycling. Different low molecular weight compounds, such as residues of polymerisation, degradation products, and additives have been identified and relatively quantified in HIPS, using microwave-assisted extraction and further analysis by gas chromatography-mass spectrometry (GC-MS). The release of residues of polymerisation has been proven to occur during reprocessing, thermo-oxidation, and in recycled samples, which may show the emissions of volatile and semi-volatile organic compounds during the life cycle of HIPS. A wide range of oxidised degradation products are formed during reprocessing and thermo-oxidation; these products can be identified as oxidised fragments of polystyrene (PS), oxidised fragments from polybutadiene (PB) phase, and oxidised fragments from the grafting points between the PS and PB phase. Real recycled HIPS samples may also contain contaminations and fragments from additives included in their original formulations; the presence of brominated fragments from flame retardants in electronic waste is here observed.

Keyword
Chromatographic pattern, High-impact polystyrene (HIPS), Degradation, Thermo-oxidation, Processing, Volatile organic compounds (VOCs), volatile organic-compounds, residual styrene monomer, gas-chromatography, long wavelengths, thermooxidative degradation, thermal polymerization, oxidative-degradation, expanded polystyrene, mass spectrometry, photo-oxidation
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-19230 (URN)10.1016/j.polymdegradstab.2009.11.033 (DOI)000274711100010 ()2-s2.0-73449117465 (Scopus ID)
Note
QC 20100525. Tidigare titel: Chromatographic pattern for mimicking the occurrence of volatiles and low molecular weight compounds in high-impact polystyrene during multiple processing and thermo-oxidationAvailable from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
4. Analytical strategies for the quality assessment of recycled high-impact polystyrene: A combination of thermal analysis, vibrational spectroscopy, and chromatography
Open this publication in new window or tab >>Analytical strategies for the quality assessment of recycled high-impact polystyrene: A combination of thermal analysis, vibrational spectroscopy, and chromatography
2007 (English)In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 604, no 1, 18-28 p.Article in journal (Refereed) Published
Abstract [en]

Various analytical techniques (thermal analysis, vibrational spectroscopy, and chromatographic analysis) were used in order to monitor the changes in polymeric properties of recycled high-impact polystyrene (HIPS) throughout mechanical recycling processes. Three key quality properties were defined and analysed; these were the degree of mixing (composition), the degree of degradation, and the presence of low molecular weight compounds. Polymeric contaminations of polyethylene (PE) and polypropylene (PP) were detected in some samples using differential scanning calorimetry (DSC). Vibrational spectroscopy showed the presence of oxidised parts of the polymeric chain and gave also an assessment of the microstructure of the polybutadiene phase in HIPS. The presence of low molecular weight compounds in the HIPS samples was demonstrated using microwave assisted extraction followed by gas chromatography mass spectrometry (GC-MS). Several volatile organic compounds (VOCs), residues from the polymerisation, additives, and contaminations were detected in the polymeric materials. Styrene was identified already in virgin HIPS; in addition, benzaldehyde, alpha-methylbenzenaldehyde, and acetophenone were detected in recycled HIPS. The presence of oxygenated derivates of styrene may be attributed to the oxidation of polystyrene (PS). Several styrene dimers were found in virgin and recycled HIPS; these are produced during polymerisation of styrene and retained in the polymeric matrix as polymerisation residues. The amount of these dimers was highest in virgin HIPS, which indicated that emission of these compounds may have occurred during the first lifetime of the products. This paper demonstrates that a combination of different analytical strategies is necessary to obtain a detailed understanding of the quality of recycled HIPS.

Keyword
recycling, quality analysis, high-impact polystyrene, degradation, thermal analysis, vibrational spectroscopy, chromatographic techniques
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-4892 (URN)10.1016/j.aca.2007.04.046 (DOI)000251293700004 ()2-s2.0-35648936956 (Scopus ID)
Note
QC 20100920Available from: 2008-09-17 Created: 2008-09-17 Last updated: 2017-12-13Bibliographically approved
5. Determination of volatiles and oxidated derivates of styrene released from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography - mass spectrometry
Open this publication in new window or tab >>Determination of volatiles and oxidated derivates of styrene released from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography - mass spectrometry
(English)Manuscript (preprint) (Other academic)
Keyword
Headspace solid-phase microextraction (SPME), volatiles, emissions from materials, polymers, high-impact polystyrene
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-24637 (URN)
Note
QC 20100920Available from: 2010-09-20 Created: 2010-09-20 Last updated: 2010-09-20Bibliographically approved
6. Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE)
Open this publication in new window or tab >>Microwave-assisted extraction for qualitative and quantitative determination of brominated flame retardants in styrenic plastic fractions from waste electrical and electronic equipment (WEEE)
2009 (English)In: Talanta: The International Journal of Pure and Applied Analytical Chemistry, ISSN 0039-9140, E-ISSN 1873-3573, Vol. 78, no 1, 33-39 p.Article in journal (Refereed) Published
Abstract [en]

A fast method for the determination of brominated flame retardants (BFRs) in styrenic polymers using microwave-assisted extraction (MAE) and liquid chromatography with UV detection (HPLC-UV) was developed. Different extraction parameters (extraction temperature and time, type of solvent, particle size) were first optimised for standard high-impact polystyrene (HIPS) samples containing known amounts of tetrabromobisphenol A (TBBPA) and decabromodiphenyl ether (Deca-BDE). Complete extraction of TBBPA was achieved using a combination of polar/non-polar solvent system (isopropanol/n-hexane) and high extraction temperatures (130 degrees C). Lower extraction yields were, however, obtained for Deca-BDE, due to its high molecular weight and its non-polar nature. The developed method was successfully applied to the screening of BFRs in standard plastic samples from waste electrical and electronic equipment (WEEE): TBBPA could be fully recovered, and Deca-BDE could be identified, together with minor order polybrominated diphenyl ether (PBDE) congeners.

Keyword
Microwave-assisted extraction, Brominated flame retardants, Polymers, HPLC-UV, accelerated solvent-extraction, organic-compounds, identification, samples, contaminants
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-18199 (URN)10.1016/j.talanta.2008.10.038 (DOI)000263634700004 ()2-s2.0-58549089176 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved
7. Analysis of brominated flame retardants in styrenic polymers: Comparison of the extraction efficiency of ultrasonication, microwave-assisted extraction and pressurised liquid extraction
Open this publication in new window or tab >>Analysis of brominated flame retardants in styrenic polymers: Comparison of the extraction efficiency of ultrasonication, microwave-assisted extraction and pressurised liquid extraction
Show others...
2008 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1196, no 1-2, 139-146 p.Article in journal (Refereed) Published
Abstract [en]

The extraction efficiency of pressurised liquid extraction (PLE), microwave-assisted extraction (MAE), and ultrasonic-assisted extraction (UAE) under different conditions has been compared for the recovery of the most commonly employed brominated flame retardants (BFRs) from styrenic polymeric Matrixes. A HPLC-MS/MS method has been proposed for the simultaneous separation and quantification of tetrabromobisphenol A (TBBPA), hexabromocyclododecane (HBCD) diastereomers, and decabromodiphenyl ether (deca-BDE) in the polymeric extracts. PLE results in complete extraction of TBBPA and HBCD (95-100% recovery), and intermediate recovery Fates for deca-BDE (50%). MAE, on the other hand, gives comparable performance to PLE for HBCD, but lower extraction yields for TBBPA and mainly deca-BDE. Ultrasonication, finally, offers relatively low extraction recoveries (10-50%). The proposed analytical procedures could be used for the effective identification and quantification of BFRs in styrenic plastics and for quality purposes in recycling facilities that deal with styrenic fractions from waste electrical and electronic equipment (WEEE).

Keyword
brominated flame retardants, TBBPA, HBCD, PBDEs, solvent extraction, polymers, HPLC-MS/MS
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-4893 (URN)10.1016/j.chroma.2008.05.001 (DOI)000257471600021 ()2-s2.0-45449097641 (Scopus ID)
Note
QC 20100830Available from: 2008-09-17 Created: 2008-09-17 Last updated: 2017-12-13Bibliographically approved
8. Quality concepts for the improved use of recycled polymeric materials: A review
Open this publication in new window or tab >>Quality concepts for the improved use of recycled polymeric materials: A review
2008 (English)In: Macromolecular materials and engineering (Print), ISSN 1438-7492, E-ISSN 1439-2054, Vol. 293, no 4, 274-297 p.Article, review/survey (Refereed) Published
Abstract [en]

Polymeric waste materials should be considered resources for the manufacture of new products through recycling processes, with a similar status to virgin fossil-based plastics and biopolymers from renewable resources. Several efforts can be made to achieve this qualitative quantum leap in plastics recycling, and consequently introduce recycled products, with competitive performance, to the market. Scientific knowledge about the degradation processes during the life cycle and the development of fast and reliable analytical methods for the quality assessment of reccycled plastics are fundamental to guarantee their performance in new applications. Different strategies - restabilisation, rebuilding, compatibilisation, and addition of elastomers and fillers can be used to upgrade the structure and properties of polymeric waste streams. This review discusses recent developments in the mechanical recycling of plastics, focusing on how to produce quality materials from waste streams and, thus, contribute to a sustainable management of resources and energy.

Keyword
degradation, mechanical recycling, quality analysis, reprocessing, upgrading, brominated flame retardants, high-density polyethylene, high-impact, polystyrene, electronic equipment weee, gas chromatography/mass, spectrometry, multicell imaging chemiluminescence, acrylonitrile-butadiene-styrene, postconsumer greenhouse films, solid-phase microextraction, commingled plastic wastes
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-17488 (URN)10.1002/mame.200700393 (DOI)000255430200002 ()2-s2.0-42949164514 (Scopus ID)
Note
QC 20100525Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

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