6-O-甲基丙烯酰基-D-吡喃半乳糖的水相原子转移自由聚合

合成了一种含半乳糖基团的水溶性单体6-O-甲基丙烯酰基-D-吡喃半乳糖(GMA)，详细考察了其在水相中的原子转移自由聚合（ATRP），并合成了分子量分布较窄的均聚物和共聚物。用1H-NMR和GPC对聚合物进行了表征。研究表明：当引发剂为2-溴丙酸甲酯（2-MBP），铜盐配合物为CuBr/2,2′-联吡啶时，聚合可控性较差，单体转化率较低；在聚合体系中加入适量溴化铜并同时采用甲醇和水的混合溶剂，可提高GMA的ATRP可控性；加入四甲基溴化铵，并改用N，N，N′,N″,N″-五甲基二亚乙基三胺(PMDETA)为配体，可有效抑制二价铜的水解，提高单体的转化率；用大分子引发剂和顺序加单体法可直接合成GMA的双亲水性两嵌段共聚物。

Aqueous Atom Transfer Radical Polymerization of 6-O-Methacryloyl-D-Galactopyranose

Water-soluble sugar monomer 6-O-methacryloyl-D-galactopyranose (GMA) was synthesized and its aqueous atom transfer radical polymerization (ATRP) was investigated. Narrow dispersed homopolymers and copolymers of GMA were synthesized and characterized by 1H-NMR and GPC. It has been revealed that the aqueous ATRP of GMA was fast but the monomer conversion was limited due to side reactions. The control of polymerization was improved by adding Cu(II) as a deactivator or methanol as a co solvent. The monomer conversion was increased using PMDETA as ligand and addition of N(CH3)+4Br- to control the hydrolysis of CuBr2. Double-hydrophilic block copolymers of GMA were directly obtained using ATRP macroinitiators or by-sequential monomer addition method.