Poly(vinylidene chloride)-Based Amphiphilic Block Copolymers

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• 作者：Emilie Velasquez ; Ga毛lle Pembouong ; Jutta Rieger ; Fran莽ois Stoffelbach ; Olivier Boyron ; Bernadette Charleux ; Franck D鈥橝gosto ; Muriel Lansalot ; Pierre-Emmanuel Dufils ; J茅r么me Vinas
• 刊名：Macromolecules
• 出版年：2013
• 出版时间：February 12, 2013
• 年：2013
• 卷：46
• 期：3
• 页码：664-673
• 全文大小：491K
• 年卷期：v.46,no.3(February 12, 2013)
• ISSN：1520-5835

文摘

The controlled/living free-radical copolymerization of vinylidene chloride (VDC) with methyl acrylate (MeA) or acrylic acid (AA) was studied by the reversible addition鈥揻ragmentation chain transfer (RAFT) technique using a trithiocarbonate RAFT agent. The reactions were performed in 1,4-dioxane solution at 30 掳C and led to good control and high chain-end functionality. P(VDC-co-MeA)-b-PAA, PAA-b-P(VDC-co-MeA), and PAA-b-P(VDC-co-AA) amphiphilic block copolymers were then prepared in the same conditions, starting either from a hydrophobic P(VDC-co-MeA) macromolecular RAFT (macro-RAFT) agent or from a hydrophilic PAA one. The advantage of the first synthesis pathway relies on the very good transfer efficiency to trithiocarbonate-ended P(VDC-co-MeA) and on the rapid consumption of the latter even when low percentages (10 mol %) of MeA comonomer are incorporated in the macro-RAFT agent. In contrast, for the second approach a rapid consumption of the macro-RAFT agent is only reached with 30 mol % of MeA in the comonomer feed, whereas with 10 mol % of MeA the transfer constant was determined to be only close to 1. Finally, we demonstrated that PAA-b-P(VDC-co-AA) diblock copolymers might also be obtained with controlled features in a one-pot process.