醋酸乙烯酯可逆加成断裂链转移自由基细乳液聚合研究.pdf

醋酸乙烯酯可逆加成断裂链转移自由基细乳液聚合 蒋波，詹晓力，陈丰秋 （ 浙江大学 化学工程与生物工程学系, 浙江 杭州 310027 ） 摘要: 本文以黄原酸酯MPhSA 、MMSA 、MESA 、MiPSA 为链转移剂，考查了黄原酸酯结构对VAc 的RAFT 细乳液聚合的影响。实验发现不同结构黄原酸酯的实验聚合初期均存在不同程度的诱导期，诱导期 过后，单体转化率随时间线性增加，以MPhSA 为链转移剂的实验720min 聚合转化率最低，聚合300min 后 单体转化率几乎不变。不同结构的黄原酸酯都可以较好的调控 VAc 进行活性自由基聚合：产物分子量随转 化率线性增加，聚合初期产物分子量分布低于 1.2，随着转化率的增加，发生了向聚合物链转移副反应，造 成产物分子量分布加宽。 关键词: 黄原酸酯；可逆加成断裂链转移；细乳液 Xanthate-mediated controlled radical polymerization of vinyl acetate JIANG Bo, ZHAN Xiao-li, CHEN Feng-qiu (1. Department of Chemical and Biochemical Engineering, Zhejiang University, Hangzhou 310027) Abstract: The reversible addition fragmentation chain transfer radical miniemulsion polymerization of vinyl acetate (VAc) was carried out using four xanthates as the chain transfer agents. The results showed that inhibition period was founded at the beginning. After that, the conversion of VAc increased linearly with time, and kept constant after 300 min. The conversion of VAc mediated by MPhSA was lowest at 720 min. The polymerization of VAc mediated by different xanthates preceeded in controlled way: the number-average molecular weight of PVAc increased linearly with the conversion, the molucular weight distribution of PVAc was lower than 1.2 at low conversion. the molucular weight distribution was broad due to the chain transfer reaction to polymer. Keywords: Xanthate; Reversible Addition-Fragmentation Chain Transfer; Miniemulsion 醋酸乙烯酯（Vinyl Acetate ，VAc ）是一 为实施RAFT 细乳液聚合的理想方法。 种常见的单体，其聚合物聚醋酸乙烯酯 本文以黄原酸酯 MPhSA 、MMSA 、 （PVAc ）在粘结剂、涂料、生物医药领域应 MESA 、MiPSA 为链转移剂，进行了VAc 的 用广泛[1-2] ，所以实现VAc 的“活性”/可控 RAFT 细乳液聚合，考查了黄原酸酯结构对 聚合有很重要的意义。VAc 是一种非共轭单 VAc 的RAFT 细乳液聚合的影响。 体，它的自由基异常活泼，在聚合中容易发 1 实 验 生