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Synthesis of novel reactive polymers by allylboration polymerization

烯丙基硼化聚合合成新型反应性聚合物

基本信息

批准号：
07651085
负责人：
CHUJO Yoshiki
金额：
$ 1.41万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Novel boron-containing polymers were obtained by polyaddition between dicyano compounds and allylboranes such as triallylborane, trimethallylborane, and allyldialkylboranes.When polymerization between triallylborane and isophthalonitrile was carried out in bulk at 0ﾟC,the reaction mixture became homogeneous liquid within several minutes. After the reaction for 1 day, a glassy polymer was obtained. The molecular weight of the resulting polymer was estimated by GPC,from which M_n and M_w were found to be 14,000 and 25,700, respectively. The structure of the polymer was confirmed by ^1H-, ^<11>B-NMR,and IR analyzes. The air- as well as thermal stabilities of the obtained polymers were examined. Most part of the resulting boron-containing polymers became insoluble upon the storage even under the inert atmosphere. By heating the polymer around 140ﾟC,an irreversible chemical reaction (i.e., further allylboration reaction) took place and the polymer became insoluble accompanying its structura … More l change. Similarly to the polymers prepared by hydroboration polymerization of dicyano monomers, these polymers gave some residue after pyrolysis.Allylboration polymerization was also examined with trimethallylborane. When polymerizations of alpha, omega-dicyanoalkanes were carried out in bulk at ambient temperature, the allylboration reactions were completed instantly, but the molecular weights of the resulting polymers increased very slowly. The siow rate of polymerization in comparison with that of triallylborane was responsible for the slow dimerization of sterically hindered iminoboranes. In the case of aromatic dicyano monomers such as isophthalonitrile, the reaction with triallyborane produced oligomers as a results of the insufficient dimerization that could be clearly followed by its IR measurement. The structures of the obtained polymers were confirmed by their spectroscopic measurements. The boron-containing polymers from trimethallylborane were found to be somewhat stable in comparison with those obtained from triallylborane. Less

通过二氰基化合物与三烯丙基硼烷、三甲代烯丙基硼烷、烯丙基二烷基硼烷等烯丙基硼烷之间的加聚得到了新型含硼聚合物。当三烯丙基硼烷与间苯二甲腈在0℃下进行本体聚合时，反应混合物在几分钟内变成均匀液体。反应1天后，得到玻璃状聚合物。通过GPC估算所得聚合物的分子量，M_n和M_w分别为14,000和25,700。通过 1 H-、 11 B-NMR和IR分析证实了聚合物的结构。检查了所得聚合物的空气稳定性和热稳定性。即使在惰性气氛下储存，大部分所得含硼聚合物也变得不溶。将聚合物加热到140℃左右，发生不可逆的化学反应（即进一步烯丙基硼化反应），聚合物变得不溶，并伴随着结构的变化。与通过二氰基单体的硼氢化聚合制备的聚合物类似，这些聚合物在热解后产生一些残余物。还用三甲代烯基硼烷检验了烯丙基硼化聚合。当α，ω-二氰基烷烃在环境温度下进行本体聚合时，烯丙基硼化反应立即完成，但所得聚合物的分子量增加非常缓慢。与三烯基硼烷相比，聚合速率较慢，这是造成位阻亚氨基硼烷二聚缓慢的原因。在芳族二氰基单体如间苯二甲腈的情况下，由于二聚化不充分，与三硼烷的反应产生了低聚物，这可以通过红外测量清楚地看出。所得聚合物的结构通过光谱测量得到证实。发现由三甲代烯基硼烷获得的含硼聚合物与由三烯丙基硼烷获得的含硼聚合物相比有些稳定。较少的