Photoinitiated Bulk Polymerization of Liquid Crystalline Thiolene Monomers

The photoinitiated bulk polymerization of liquid crystalline thiolene monomers based on a phenyl benzoate core was investigated and the structure of the corresponding polymers analyzed. We show that polymerization occurs substantially in bulk, and can be initiated on demand by UV-irradiation. The li...

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Bibliographic Details
Published in:Macromolecules 2002-11, Vol.35 (24), p.8962-8968
Main Authors: Wilderbeek, Hans T. A, Goossens, J. (Han) G. P, Bastiaansen, Cees W. M, Broer, Dirk J
Format: Article
Language:English
Subjects:
Applied sciences
Exact sciences and technology
Physicochemistry of polymers
Polymerization
Polymers and radiations
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Summary:The photoinitiated bulk polymerization of liquid crystalline thiolene monomers based on a phenyl benzoate core was investigated and the structure of the corresponding polymers analyzed. We show that polymerization occurs substantially in bulk, and can be initiated on demand by UV-irradiation. The liquid crystalline thiolene polymers exhibit a nematic mesophase, and the molecular weight, molecular weight distribution and overall conversion are characteristic for polymers obtained by a step-growth polymerization. Using NMR spectroscopy, we show that anti-Markovnikov structures are predominantly formed, with a small fraction of the structures displaying different configurations that can be attributed to thiol olefin addition−cooxidation processes or to homopolymerization of the olefinic moiety. The conversions of the thiol and vinyl groups were monitored using time-resolved Raman spectroscopy and dissimilar partial reaction rates were observed.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma020916l