Allylidene Monomers: Anionically Polymerizable 1,1-Disubstituted 1,3-Diene Derivatives
Allylidene Monomers: Anionically Polymerizable 1,1-Disubstituted 1,3-Diene Derivatives
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DOI：
10.1021/acs.macromol.0c02103
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发表时间：
2020-11-24
期刊：
影响因子：
5.5
通讯作者：
Ishizone, Takashi
中科院分区：
文献类型：
--
作者：
Uchida, Satoshi;Togii, Kota;Ishizone, Takashi
一系列烯丙基单体，在1，1-位上具有取代基如二甲基（DMBd）、环己烷环（AC 6）、环庚烷环（AC 7）、2，2，5，5-四甲基环戊烷环（ATMC 5）和正庚烷（ABn）的1，3-丁二烯衍生物的阴离子聚合，在苯中在40 ℃下用sec-BuLi定量进行17-24小时，或在THF中在0或30 ℃下用sec-BuLi定量进行48-168小时。由具有环状结构的烯丙基单体得到的聚合物具有基于单体与引发剂之间的摩尔比的可预测的分子量和窄的分子量分布（M-w/M-n < 1.09）。基于H-1，C-13，DEPT 135，和HMQC NMR光谱的结果，所得聚合物的微观结构被发现是强烈依赖于取代基的体积。具有较小体积取代基的亚烯丙基单体如DMBd、AC 6和AC 7导致其中1，4-反式微结构占主导地位的聚合物。相比之下，在相同的聚合条件下，ATMC 5和ABn单体仅导致具有3，4-微结构的聚合物。聚合物表现出宽范围的玻璃化转变温度（-40至194摄氏度），这取决于所使用的单体的体积。
The anionic polymerizations of a series of allylidene monomers, 1,3-butadiene derivatives with substituents on the 1,1-position such as dimethyl (DMBd), cyclohexane ring (AC6), cycloheptane ring (AC7), 2,2,5,5-tetramethylcyclopentane ring (ATMC5), and bornane (ABn), proceeded quantitatively either in benzene at 40 degrees C with sec-BuLi for 17-24 h or in THF with sec-BuLi at 0 or 30 degrees C for 48-168 h. The obtained polymers from allylidene monomers possessing ring structures had predictable molecular weights based on the molar ratios between the monomer and the initiators and narrow molecular weight distributions (M-w/M-n < 1.09). Based on H-1, C-13, DEPT135, and HMQC NMR spectroscopy results, the microstructures of the resultant polymers were found to be strongly dependent on the bulkiness of the substituent. Allylidene monomers with less bulky substituents such as DMBd, AC6, and AC7 resulted in polymers wherein the 1,4-trans microstructure was predominant. In contrast, under the same polymerization conditions, ATMC5 and ABn monomers exclusively resulted in polymers with the 3,4-microstructure. The polymers exhibited a wide range of glass transition temperatures (-40 to 194 degrees C), which depended on the bulkiness of the monomer used.