Lee Bongjae F, Kade Matthew J, Chute Jerred A, Gupta Nalini, Campos Luis M, Fredrickson Glenn H, Kramer Edward J, Lynd Nathaniel A, Hawker Craig J
Materials Research Laboratory, University of California, Santa Barbara, CA, 93106.
J Polym Sci A Polym Chem. 2011 Oct 15;49(20):4498-4504. doi: 10.1002/pola.24891.
Allyl glycidyl ether, polymerized from potassium alkoxide/naphthalenide initiators under both neat and solution conditions was shown to be a highly-controlled process. In both cases, molar masses (10-100 kg/mol) were determined by the reaction stoichiometry, and low polydispersity indices (1.05-1.33) could be obtained with a full understanding of the dominant side reaction, isomerization of the allyl side chain, being developed. The degree of isomerization of allyl to cis-prop-1-enyl ether groups (0 - 10 % mol.) was not correlated to the molar mass or polydispersity of the polymer but was dictated by the polymerization temperature. This allows the extent of isomerization to be reduced to essentially zero under either melt or solution conditions at polymerization temperatures of less than 40 °C.
在纯态和溶液条件下,由醇钾/萘基引发剂聚合而成的烯丙基缩水甘油醚被证明是一个高度可控的过程。在这两种情况下,摩尔质量(10 - 100 kg/mol)由反应化学计量比确定,并且在充分理解主要副反应(烯丙基侧链异构化)的情况下,可以获得低多分散指数(1.05 - 1.33)。烯丙基异构化为顺式丙-1-烯基醚基团的异构化程度(0 - 10%摩尔)与聚合物的摩尔质量或多分散性无关,而是由聚合温度决定。这使得在聚合温度低于40°C的熔体或溶液条件下,异构化程度可基本降至零。