含非共轭双键RAFT试剂的合成及与乙酸乙烯酯的共聚

以烯丙基胺、溴丙酰溴及黄原酸钾为原料,制备出含非共轭双键可逆加成-断裂链转移聚合(RAFT)试剂——N-烯丙基-(2-乙基黄原酸基)丙酰胺(NAPA)。研究了加料顺序、反应温度、溶剂等对NAPA产率的影响,获得了较优的合成条件,最终产率可达70%;红外光谱、核磁共振氢谱表明其化学结构与设计结构相符。以NAPA与乙酸乙烯酯(VAc)共聚,制备出具有支化结构的聚乙酸乙烯酯。采用称量法、核磁共振氢谱和凝胶渗透色谱法等手段研究了NAPA与VAc的共聚行为及共聚产物的结构,结果表明,NAPA与VAc共聚过程符合"活性"/可控自由基聚合特征;同时,在引发剂偶氮二异丁腈(AIBN)比例恒定的情况下,支化PVAc聚合物分子链上NAPA含量随着投料比NAPA/VAc的增加而增加。

Synthesis of Non-Conjugated Double Bonds RAFT Agent and the Copolymerization with Vinyl Acetate

The non-conjugated double bonds addition-fragmentation chain transfer polymerization (RAFT) agent N-allyl-(2-ethyl xanthogen) amide (NAPA)was synthesized using allylamine,bromopropionyl bromide and potassium xanthanate as raw materials.The effects of the order of addition,reaction temperature and solvent on the yield of NAPA were studied,and the final yield is 70 ％ under the optimum conditions.Infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H-NMR) show that the chemical structure is in accordance with the designed structure.Then,poly(vinyl acetate) with branched structure was obtained by copolymerizing NAPA as functional RAFT agent with vinyl acetate (VAc).The copolymerization behaviors of NAPA and vinyl VAc and the structure of the copolymer were studied by means of weighing method,1H-NMR and gel permeation chromatography (GPC).The results show that the copolymerization behaves of NAPA and Vac are consistent with the features of"living"/ controlled radical polymerization.What's more,in the case of initiator AIBN constant,the content of NAPA in the molecular chain of the branched PVAc polymer increases when the feed ratio of NAPA/VAc increases.