Zhang H, Ruckenstein E
Chemical Engineering Department, State University of New York at Buffalo, Amherst, New York 14260.
Macromolecules. 1998 Jul 28;31(15):4753-9. doi: 10.1021/ma9804996.
A tetrahydrofuran (THF) solution of the living poly(glycidyl methacrylate) (poly(GMA)) was prepared by the living anionic polymerization of GMA, using 1,1-diphenylhexyllithium (DPHL) as initiator, in the presence of LiCl ([LiCl]/[DPHL]0 = 3), at -45 degreesC. Upon introduction of a benzene solution of living polystyrene (poly(St)) into the above system at -30 degreesC, a very rapid coupling reaction between the epoxy groups of the living poly(GMA) and the propagating sites of the living poly(St) generated a graft copolymer containing a polar backbone and nonpolar side chains. When benzene solutions of living poly(St) and polyisoprene were sequentially transferred to the THF solution of living poly(GMA), a graft copolymer possessing two different nonpolar side chains was obtained. Further, a THF solution of the living block copolymer of methyl methacrylate (MMA) and GMA was prepared by the sequential anionic polymerization of the two monomers, at low temperatures. A block-graft copolymer having a poly(MMA-b-GMA) block backbone and poly(St) side chains was synthesized by reacting the living poly(St) with the epoxy groups of the above living block copolymer. In addition, when the poly(GMA) segment in poly(MMA-b-GMA) was short, a star-shaped copolymer containing a poly(MMA) arm and several poly(St) arms was obtained. GPC and 1H NMR measurements indicated that all the above copolymers possess high purity, designed molecular architectures, controlled molecular weights and narrow molecular weight distributions (Mw/Mn = 1.10-1.23).
以1,1 - 二苯基己基锂（DPHL）为引发剂，在LiCl（[LiCl]/[DPHL]0 = 3）存在下，于-45℃通过甲基丙烯酸缩水甘油酯（聚（GMA））的活性阴离子聚合制备了活性聚（甲基丙烯酸缩水甘油酯）（聚（GMA））的四氢呋喃（THF）溶液。在-30℃将活性聚苯乙烯（聚（St））的苯溶液引入上述体系时，活性聚（GMA）的环氧基团与活性聚（St）的增长链端之间发生非常快速的偶联反应，生成了一种含有极性主链和非极性侧链的接枝共聚物。当将活性聚（St）和聚异戊二烯的苯溶液依次转移到活性聚（GMA）的THF溶液中时，得到了具有两种不同非极性侧链的接枝共聚物。此外，通过两种单体在低温下的顺序阴离子聚合制备了甲基丙烯酸甲酯（MMA）和GMA的活性嵌段共聚物的THF溶液。通过使活性聚（St）与上述活性嵌段共聚物的环氧基团反应，合成了具有聚（MMA - b - GMA）嵌段主链和聚（St）侧链的嵌段接枝共聚物。另外，当聚（MMA - b - GMA）中的聚（GMA）链段较短时，得到了一种含有聚（MMA）臂和几个聚（St）臂的星形共聚物。凝胶渗透色谱（GPC）和1H核磁共振（1H NMR）测量表明，上述所有共聚物均具有高纯度、设计的分子结构、可控的分子量和窄的分子量分布（Mw/Mn = 1.10 - 1.23）。
