镍催化转移缩聚合成全氟环丁基芳基醚聚合物

Synthesis of Perfluorocyclobutyl Aryl Ether-Containing Polymers via Kumada Catalyst-Tranfer Polycondensation

研究了通过镍催化转移缩聚的方法来合成全氟环丁基芳基醚聚合物.首先,我们以对溴苯酚和1,2-二溴四氟乙烷为起始原料,通过两步反应得到对溴三氟乙烯基芳基醚,进一步加热环化二聚得到单体1,2-二(4-溴苯氧基)六氟环丁烷.该二聚物再与异丙基格氏试剂发生镁交换反应,生成格氏试剂中间体,在催化剂Ni(dppe)Cl2的存在下发生镍催化转移缩聚生成聚合物.研究了反应时间、温度和单体投料比对催化缩聚反应的影响.

The synthesis of perfluorocyclobutyl aryl ether-based polymers via Kumada catalyst-tranfer polycondensation was studied.Firstly,1-bromo-4-（1,2,2-trifluorovinyloxy）benzene was prepared through two-step reaction using 4-bromophenol and 1,2-dibromo-1,1,2,2-tetrafluoroethane as starting materials.Then,2π ＋ 2π cycloaddition of 1-bromo-4-（1,2,2-trifluorovinyloxy）benzene yielded the dimer 4,4＇-（perfluorocyclobutane-1,2-diyl）bis（oxy）bis（bromobenzene）.Treatment of this dimer with i-PrMgCl gave an intermediate via a magnesium-bromine exchange reaction.Finally,polymerization of the intermediate was carried out using Ni（dppe）Cl2 as catalyst to yield polymer.Effect of reaction time and temperature as well as the feed ratio of the monomer to the catalyst on the polycondensation was also investigated.