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Increased Onset Temperature of Expansion in Thermally Expandable Microspheres from Combination of Crosslinking Agents
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.ORCID iD: 0000-0002-8348-2273
2011 (English)In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 121, no 1, 369-375 p.Article in journal (Refereed) Published
Abstract [en]

Free-radical suspension polymerization was used to synthesize thermally expandable microspheres (TEMS) in which a poly(acrylonitrile-co-methacrylonitrile) shell encapsulates isooctane. TEMS were prepared with 1,4-butanediol dimethacrylate (BDDMA), in combination with 1,4-butanediol divinyl ether (BDDVE), diallyl carbonate (DAC), or allyl methacrylate, as crosslinkers. It was found that a significant increase in the onset temperature of expansion (T-start) could be obtained when a combination of BDDMA and BDDVE or DAC was used, compared to when only BDDMA was used as crosslinker. The expansion capacity of the TEMS was excellent when BDDMA and DAC were combined. One benefit of the increased T-start was demonstrated when poly(vinyl chloride)-plastisols containing TEMS could be cured at higher temperatures without premature expansion. The differences in expansion obtained with different combinations of crosslinkers originate from the difference in reactivity of the vinyl-functionalities of the crosslinkers, which regulate the incorporation of the crosslinker into the polymer and thereby, the mechanical properties of the microsphere shell.

Place, publisher, year, edition, pages
2011. Vol. 121, no 1, 369-375 p.
Keyword [en]
core-shell polymers, blowing agents, crosslinking, radical polymerization
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-11980DOI: 10.1002/app.33585ISI: 000289353700045ScopusID: 2-s2.0-79953705069OAI: diva2:291746
Swedish Research Council, 2003-4573Swedish Research Council, 2004-605
QC 20110211 Uppdaterad från Submitted till Published 20110509Available from: 2010-02-03 Created: 2010-02-03 Last updated: 2011-05-09Bibliographically approved
In thesis
1. Thermally Expandable Microspheres Prepared via Suspension Polymerization - Synthesis, Characterization, and Application
Open this publication in new window or tab >>Thermally Expandable Microspheres Prepared via Suspension Polymerization - Synthesis, Characterization, and Application
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Thermally expandable microspheres are polymeric core/shell particles in which a volatile hydrocarbon is encapsulated by a thermoplastic shell. When these microspheres are heated, they expand and increase their volume dramatically. This volume increase is retained upon cooling, leading to a density reduction from around 1100 kg m-3 to about 30 kg m-3. Since the development in the early 1970´s, microspheres have been used extensively by the industry as a foaming agent or light weight filler.

In this thesis, microspheres with a poly(acrylonitrile-co-methacrylonitrile) shell have been synthesized through free radical suspension polymerization. The microspheres have been characterized with respect to particle morphology and expansion properties in order to deepen the understanding of the microspheres.

It was found that the monomer feed ratio and the polymerization temperature are very important parameters with respect to the expansion properties. Excellent expansion could only be accomplished when polymerizing at 62 °C, with the acrylonitrile feed, fAN, being around 60 mol%, even though core/shell microspheres are formed over a much wider range of fAN. Furthermore, no expansion was achieved when polymerizing at 80 °C, even though no noticeable differences were found, compared to the corresponding sample polymerized at 62 °C.

It was also shown that the expansion properties can be modified by replacing the encapsulated hydrocarbon by another hydrocarbon with a different boiling point. Not only is the boiling point important, the structure of the hydrocarbon is also important. Isooctane which is highly branched was found to give superior expansion compared to linear or cyclic hydrocarbons having a similar boiling point.

Crosslinking of the polymer shell has proven to be very important for the expansion properties. Both the amount and the structure of the crosslinker are important parameters. Especially the maximum expansion can be improved by the crosslinking of the polymer shell. This originates in an increase in the shape persistence of the expanded microspheres at elevated temperatures. By the combination of crosslinkers that are incorporated separately into the polymer shell, the onset temperature of expansion can be increased significantly.

Finally, the surface of microspheres has been modified by grafting poly(glycidyl methacrylate) from the surface by ARGET ATRP. Given that the reaction conditions are appropriate, such modifications can be performed with only limited effects on the expansion properties of the microspheres.

Place, publisher, year, edition, pages
Stockholm: KTH, 2010. 54 p.
Trita-CHE-Report, ISSN 1654-1081 ; 2010:4
Thermally expandable microspheres
National Category
Polymer Chemistry
urn:nbn:se:kth:diva-11981 (URN)978-91-7415-542-6 (ISBN)
Public defence
2010-02-26, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Available from: 2010-02-04 Created: 2010-02-03 Last updated: 2010-04-28

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Jonsson, MagnusLarsson Kron, AnnaMalmström, Eva
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