期刊
MACROMOLECULES
卷 46, 期 5, 页码 1732-1742出版社
AMER CHEMICAL SOC
DOI: 10.1021/ma302619k
关键词
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资金
- Flemish Government
- Belgian State, the Prime Minister's office [IAP/IUAP/PAI P7/05]
- European Science Foundation-Precision Polymer Materials (P2M) program
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 coupling efficiency. conditions have a significant impact on the
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