Abstract α-(Chloromethyl)acryloyl cation, prepared from the corresponding acyl chloride and silver triflate, was used as an initiator for the living, cationic ring-opening polymerization of tetrahydrofuran. The α-end of the resulting poly(tetrahydrofuran) has an α-(chloromethyl)acrylate skeleton, which is an excellent substrate for nucleophilic conjugate substitution. In fact, treatment with a phenol resulted in a functionalized α-end. Moreover, 2-aminoethylanol and 2-mercaptoethanol afforded doubly functionalized polymers with two hydroxy groups at the α-ends via conjugate substitution and subsequent addition reactions. Since α-(chloromethyl)acrylate can be attacked by two equivalents of a nucleophile, it can function as a monomer in polycondensations with dithiols. Therefore, the α-(chloromethyl)acrylate chain end was subjected to polycondensation with 1,10-decandithiol in the presence of Bu 3 P, resulting in a graft copolymer. The above results suggest that the α-(chloromethyl)acryloyl cation is a functional initiator for incorporating a chain end reactive to a variety of nucleophiles for single and double end-functionalizations and the preparation of graft copolymers. Conjugate subst. allows single/double end-functionalization and graft copolymer synthesis.

中文翻译：

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通过共轭取代反应进行官能化和接枝共聚物合成的末端反应性聚（四氢呋喃）

摘要 由相应的酰氯和三氟甲磺酸银制备的 α-（氯甲基）丙烯酰阳离子用作四氢呋喃的活性阳离子开环聚合反应的引发剂。所得聚（四氢呋喃）的α-端具有α-（氯甲基）丙烯酸酯骨架，是亲核共轭取代的优良底物。事实上，用苯酚处理会产生一个功能化的 α-末端。此外，2-氨基乙醇和2-巯基乙醇通过共轭取代和随后的加成反应在α-端提供具有两个羟基的双官能化聚合物。由于 α-（氯甲基）丙烯酸酯可以被两当量的亲核试剂攻击，因此它可以在与二硫醇的缩聚反应中充当单体。所以，α-(氯甲基)丙烯酸酯链端在Bu 3 P存在下与1,10-癸二硫醇缩聚，得到接枝共聚物。上述结果表明，α-（氯甲基）丙烯酰基阳离子是一种功能性引发剂，可将链端与各种亲核试剂反应，用于单端和双端功能化以及接枝共聚物的制备。共轭物质。允许单/双末端官能化和接枝共聚物合成。