Grafting onto a renewable unsaturated polyester via thiol-ene chemistry and cross-metathesis

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• 作者：Nicolai Kolb ; Michael A.R. Meier ; ^{m.a.r.meier@kit.edu} ;
• 关键词：Olefin cross-metathesis ; thiol&ndash ; ene ; Renewable polyester ; Methyl 10-undecenoate ; Malonate ; Passerini
• 刊名：European Polymer Journal
• 出版年：2013
• 出版时间：April, 2013
• 年：2013
• 卷：49
• 期：4
• 页码：843-852
• 全文大小：727 K

文摘

Methyl 10-undecenoate was modified to its corresponding malonate derivative by the reaction with sodium hydride in dimethyl carbonate. This malonate was then polymerized with 1,6-hexanediol, catalyzed by 1.0 mol % titanium (IV) isopropoxide, to a poly(malonate) bearing C₉ aliphatic side-chains with terminal double bonds. The double bonds of this poly(malonate) were used for grafting onto reactions by either ruthenium-catalyzed cross-metathesis reactions with acrylates or thiol-ene addition reactions. Several examples are shown for both methods. For the cross-metathesis reactions, 1.0 mol % Hoveyda-Grubbs 2nd generation (HG II) catalyst was used with 10.0 equivalents of the respective acrylate under bulk conditions at 40 ¡ãC. The thiol-ene additions were carried out with 1.0 equivalents of the respective thiol in THF with 5.0 mol % 2,2-Dimethoxy-2-phenylacetophenone (DMPA) under UV (365 nm) irradiation. Moreover, we have shown that a carboxylic acid group can be easily installed via thiol-ene addition and that the resulting polymer can be further modified by the Passerini three-component reaction with quantitative conversion.