作　　者： ; ; ; ;

机构地区： 仲恺农业工程学院轻工食品学院

出　　处： 《高分子学报》 2010年第8期1035-1042,共8页

摘　　要： 设计并合成了一种新型含甲酰基同时又含β-蒎烯单元的新单体2-β-蒎氧基-5-乙烯基苯甲醛(POVB),选择苯基双硫代乙酸1-苯基乙酯(PEPDA)为RAFT试剂、以AIBN为引发剂、在60℃下THF中实现了POVB的"活性"/可控RAFT自由基聚合.单体浓度半对数ln([M]0/[M])与聚合时间符合线性关系,聚合过程呈现一级动力学特征;聚合物分子量(Mn)随单体转化率几乎线性增加,而且整个反应过程中分子量分布(Mw/Mn<1.2)保持在较窄的范围.1H-NMR的分析进一步证实了聚合物链的末端精细结构.此外,CD谱结果表明手性单元β-蒎烯基能赋予聚合物以光学活性. A new monomer 2-β-pinenyloxy-5-vinylbenzaldehyde （POVB ） containing both formyl and βPinene functional groups,was designed and prepared readily by the reaction of β-pinenyl-4methylbenzensulfonate with 2-hydroxy-5-vinylbenzaldehyde,and its structure was confirmed via elemental analysis,MS and NMR spectroscopy.The conventional radical polymerization of the new monomer POVB was investigated with AIBN in THF at 60℃ ,and the polymer with high molecular weight （Mn = 132100,Mw/Mn = 2.20,measured by GPC） was obtained at 68% conversion in 24 h,indicating the new monomer exhibited good polymerization activity.The thermal properties of the polymer were studied using TGA and DSC.The polymer exhibited good thermal stability until 320℃ ,and had a relatively high glass transition temperature （Tg ） at 130.6℃ due to its bulky substituents.Furthermore,the ＂living＂/controlled radical polymerization of POVB was successfully achieved using 2,2′-azobis（isobutyronitrile） as the initiator and 1-phenylethyl phenyldithioacetate （PEPDA） as the reversible addition-fragmentation chain transfer （RAFT） agent at 60℃ in tetrahydrofuran.Compared with 1-phenylethyl dithiobenzoate （PEDB ）,a much smaller retardation was observed using PEPDA as a RAFT agent.The polymerization followed first-order kinetics,the number-average molecular weight of the obtained polymers increased in direct proportion to the monomer conversion,and the molecular weight distribution was narrow （polydispersity index 1.2）.The chain and terminal structures of the obtained poly（POVB） were confirmed with the 1H-NMR analysis.Moreover,the circular dichroism （CD） spectra of the resulting polymers in THF solutions confirmed that poly（POVB）s were optically active.

关 键 词： 聚合 甲酰基 蒎烯 光学活性聚合物

领　　域： [化学工程]