Ishizu Koji, Satoh Junichiro, Sogabe Atsushi
Department of Organic Materials and Macromolecules, International Research Center of Macromolecular Science, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8552, Japan.
J Colloid Interface Sci. 2004 Jun 15;274(2):472-9. doi: 10.1016/j.jcis.2004.03.044.
Atom transfer radical polymerization (ATRP) was applied to the synthesis of AB-type brush-block-brush amphiphilic copolymers. The procedure included the following steps: (1). ATRP of methacryloyl-terminated poly(ethylene glycol methylether) macromonomer (PEG-MC) gave well-defined PEG brush macroinitiator, (2). subsequent ATRP of 2-hydroxyethyl methacrylate (HEMA) with this brush macroinitiator provided PEG brush-block-PHEMA (brush-block-coil) diblock copolymers, (3). esterification of the pendant hydroxy groups of PHEMA block with 2-bromoisobutyryl bromide yielded a block-type polyinitiator, brush-block-poly(2-(2-bromoisobutyryloxy)ethyl methacrylate) (PBIEM), (4). ATRP of HEMA using brush-block-PBIEM as polyinitiator provided AB-type brush-block-brush amphiphilic copolymers. Dilute-solution properties of such AB-type copolymer brushes were investigated by static and dynamic light scatterings. As a result, this copolymer exhibited a slightly ellipsoidal shape, i.e., Janus-type structure, in solution.
原子转移自由基聚合（ATRP）被应用于AB型刷-嵌段-刷两亲性共聚物的合成。该过程包括以下步骤：（1）. 甲基丙烯酰基封端的聚（乙二醇甲基醚）大分子单体（PEG-MC）的ATRP反应得到了结构明确的PEG刷状大分子引发剂；（2）. 用这种刷状大分子引发剂对甲基丙烯酸2-羟乙酯（HEMA）进行后续的ATRP反应，得到PEG刷-嵌段-PHEMA（刷-嵌段-无规线团）二嵌段共聚物；（3）. 用2-溴异丁酰溴对PHEMA嵌段的侧羟基进行酯化反应，得到一种嵌段型多引发剂，即刷-嵌段-聚（2-（2-溴异丁酰氧基）乙基甲基丙烯酸酯）（PBIEM）；（4）. 以刷-嵌段-PBIEM为多引发剂对HEMA进行ATRP反应，得到AB型刷-嵌段-刷两亲性共聚物。通过静态和动态光散射研究了这种AB型共聚物刷的稀溶液性质。结果表明，该共聚物在溶液中呈现出略微椭圆形的形状，即两面体型结构。
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