中文摘要：

采用7Li-NMR对正丁基锂（n-BuLi）与不同摩尔比叔丁醇钾（t-BuOK）的混合物在四氢呋喃与环己烷溶液中的体系进行了分析.继而以1,1-二苯基己基锂作为引发剂,分别采用苯酚锂、叔丁醇钠以及t-BuOK作为副反应抑制剂,进行了甲基丙烯酸正丁酯（BMA）和甲基丙烯酸甲酯（MMA）的负离子嵌段共聚合,并用GPC、1H-NMR对聚合物的结构进行了表征.结果发现n-BuLi与t-BuOK会产生Li与K交换的反应,形成不具备引发活性的t-BuOLi,以及以K为反离子的活性种.其对MMA类极性单体嵌段聚合的副反应有着极为有效的抑制作用.过量的t-BuOK,将进一步提高对副反应的抑制作用.在体系中nt-BuOK/nn-BuL≥20后,即便聚合温度升高至40℃,BMA与MMA极性单体嵌段聚合的总产率也可达到100%,且分子量分布仅为1.40,呈单峰分布.实测的Mn与设定的Mn非常接近;采用1H-NMR实测的nMMA/nBMA也与原料十分接近.从而为MMA类极性单体嵌段聚合的工业化奠定了基础.

英文摘要：

7Li-NMR was used to characterize the mixed system of n-butyl lithium（ n-Bu Li） and potassium t-butoxide（ t-Bu Ok） with different molar ratios in THF and cyclohexane. The anionic block-copolymerization of butyl methacrylate（ BMA） and methyl methacrylate（ MMA） was initiated by 1,1-diphenyl hexyl lithium and using phenol lithium,sodium t-butoxide and t-Bu Ok as the side reaction inhibitors. GPC and1H-NMR were used to characterize the structure of the block copolymers. It was found that the exchange reaction of Li in n-Bu Li and K in t-Bu OK could be generated,in which the inactive lithium t-butoxide and active species with K as the counterion formed. The new species had admirable impact on inhibiting the side reaction in the anionic polymerization of the polar monomers,such as MMA. The surplus t-Bu OK in the system could further promote the inhibition effect. When the mole ratio of nt-Bu OK/ nn-Bu Liwas not lower than 20,the total yield of the block copolymerization of BMA and MMA could reach up to 100% and the molecular weight distribution was only1. 40 with unimodal distribution even when the copolymerization temperature was up to 40 ℃. Mndetermined by GPC well coincided with the calculated theoretically data. The value of nMMA/ nBMAin copolymer determined by1H-NMR was also well close to that of raw material. The results could lay an industrial foundation for the block copolymerization of polar monomers,such as MMA.