Fe(Ⅲ)催化苯乙烯的AGET-ATRP法合成

AGET ATRP Synthesis of Styrene with FeCl_3/Triphenyl Phosphine as the Catalyst System

电子活化再生原子转移自由基聚合(AGET ATRP)是近年来原子转移自由基聚合(ATRP)发展的一种新的合成方法。文中选用FeCl3.6H2O为催化剂,三苯基磷(PPh3)为配体,抗坏血酸(AsAc)为还原剂,溴化苄(BzBr)为引发剂,采用AGET ATRP法在110℃用本体聚合的方式成功合成了分子量可控的聚苯乙烯。结果表明,其本体聚合优于溶液聚合;在110℃时,n(St)/n(BzBr)/n(FeCl3.6H2O)/n(PPh3)/n(AsAc)=100/1/1/3/0.5时,聚苯乙烯的-Mn,GPC=6371,且分子量分布较窄(PDI=1.36)。聚合过程表现出"活性"/可控聚合的特征。

Activators generated by electron transfer for atom transfer radical polymerization （AGET ATRP） is a new technique for conducting ATRP developed recently. In this work, an iron （III）-mediated AGET ATRP of styrene in bulk was carried out at 110℃, using oxidatively stable iron（liD chloride hexahydrate （FeCl3-6H20） as a catalyst, triphcnyl phosphine as a ligand, ascorbic acid as a reducing agent, and benzyl bromide as an initiator. The results indicate that the bulk polymerization of St is better than solution polymerization, when the polymerization procedure for the molar ratio is n （St）/n （BzBr）/n （ FeCl3· 6H2O）/n （PPh3）/n （AsAc） = 100/1/1/3/0.5 at 110 ℃ , the molecular weight value of the polymer Mn,GPC = 6371, and the distribution of molecular weight is narrow （PI）I = 1.36）. The polymerizations show the features of ＂living＂ /controlled free-radical polymerization.