Steric and Electronic Effects in Cyclic Alkoxyamines—Synthesis and Applications as Regulators for Controlled/Living Radical Polymerization
作者:Christian Wetter、Johannes Gierlich、Christoph Alexander Knoop、Christoph Müller、Tobias Schulte、Armido Studer
DOI:10.1002/chem.200305427
日期:2004.3.5
trimethylsilyl(TMS)-diazomethane. The use of the new alkoxyamines as regulators/initiators for radical polymerization is discussed. Efficient controlled and living polymerization of styrene and n-butyl acrylate was obtained with the six-membered tetraethyl alkoxyamine 13. Controlled polymerizations can be conducted even at 90 degrees C. In addition, alkoxyamine 13 can be used for the preparation of AB diblock
描述了在烷氧基胺的α-N位置带有乙基的新的六元和七元环状烷氧基胺的合成。位阻六元环烷氧基胺合成的关键步骤是双膦酸酯1的Wadsworth-Horner-Emmons烯化反应。七元环烷氧基胺由相应的六元酮烷氧基胺通过与三甲基甲硅烷基环扩大而制得。 TMS)-重氮甲烷。讨论了使用新的烷氧基胺作为自由基聚合反应的调节剂/引发剂。用六元四乙基烷氧基胺13获得苯乙烯和丙烯酸正丁酯的有效的受控和活性聚合。即使在90℃下也可以进行受控的聚合。烷氧基胺13可用于制备具有窄多分散性的AB二嵌段和ABA三嵌段共聚物。讨论了较大的乙基取代环状烷氧基胺中N原子的α-位甲基对苯乙烯聚合反应(反应时间,PDI,CO键均相动力学)的影响。另外,还研究了新烷氧基胺的热分解。此外,描述了N,N-双甲硅烷基化的烷氧基胺的合成。甲硅烷基化的烷氧基胺不适合用作受控/活性自由基聚合的调节剂/引发剂。甲硅烷基化的烷氧基胺中的CO键比