Kinetic Modeling of Radical Thiol–Ene Chemistry for Macromolecular Design: Importance of Side Reactions and Diffusional Limitations

The radical thiol–ene coupling of thiol-functionalized polystyrene (PS-SH) with dodecyl vinyl ether (DVE) and the polystyrene-b-poly(vinyl acetate) (PS-b-PVAc) polymer–polymer conjugation using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator are modeled to assess the importance of diffus...

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Bibliographic Details
Published inMacromolecules Vol. 46; no. 5; pp. 1732 - 1742
Main Authors Derboven, Pieter, D’hooge, Dagmar R, Stamenovic, Milan M, Espeel, Pieter, Marin, Guy B, Du Prez, Filip E, Reyniers, Marie-Françoise
Format Journal Article
LanguageEnglish
Published Washington, DC American Chemical Society 12.03.2013
Subjects
Applied sciences
Chemical modifications
Chemical reactions and properties
Exact sciences and technology
Grafting and modifications
Organic polymers
Physicochemistry of polymers
Polymers and radiations
End group
Photochemical reaction
Experimental study
Modeling
Free radical reaction
Chemical reaction kinetics
Kinetic model
Chemical modification
Side reaction
Vinyl acetate copolymer
Vinyl acetate polymer
Vinylic compound
Addition reaction
Diblock copolymer
Model reaction
Styrene polymer
Functional group
Styrene copolymer
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Summary:The radical thiol–ene coupling of thiol-functionalized polystyrene (PS-SH) with dodecyl vinyl ether (DVE) and the polystyrene-b-poly(vinyl acetate) (PS-b-PVAc) polymer–polymer conjugation using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator are modeled to assess the importance of diffusional limitations and side reactions. Intrinsic chemical rate coefficients are determined based on a kinetic study of the coupling of benzyl thiol (BT) and DVE. The addition and transfer reactions are chemically controlled, whereas diffusional limitations on termination slightly increase the coupling efficiency. Termination by recombination of carbon-centered radicals and addition of DMPA derived radicals to DVE are shown to be mainly responsible for the reduced coupling efficiency in case polymeric species are involved. The obtained results confirm the idea to disregard radical thiol–ene chemistry as a true member of the family of “click” chemistry techniques for polymer–polymer conjugation and show that the initial conditions have a significant impact on the coupling efficiency.
ISSN:0024-9297
1520-5835
DOI:10.1021/ma302619k