结合配位-插入开环聚合（CROP）及原子转移自由基聚合（ATRP）成功制备出一种两亲性新型四臂星型聚合物聚（ε-己内酯）-b-聚丙烯酸（PCL4-b-PAA4）。首先以季戊四醇为四官能团引发剂,辛酸亚锡Sn（Oct）2为催化剂,由ε-己内酯制备出分子量为8000、分子量分布为1.13的四臂星型聚（ε-己内酯）（PCL4）,其末端羟基与小分子2-溴异丁酰溴进行酯化反应,得到用于ATRP聚合的星型大分子引发剂（PCL-Br）4,然后引发丙烯酸叔丁酯（tBA）聚合,把得到的PCL4-b-Pt-BA4水解,得到目标产物PCL4-b-PAA4。水解3 h和6 h的样品通过凝胶渗透色谱（GPC）测试可知,分子量分布很窄,分别为1.31和1.40。用核磁共振（1H-NMR）和红外光谱（FT-IR）等手段,对中间及最终产物进行了详细表征。
A amphiphilic star-shaped copolymer poly（ε-caprolactone）4-b-poly（acrylic acid）4（PCL4-b-PAA4） was prepared by living polymerization.Firstly,PCL4 was synthesized by coordination-insertion ring-opening polymerization of ε-caprolactone（ε-CL） using pentaerythritol and stannous octoate（Sn（Oct）2） as initiator and catalyst-respectively.After the reaction of the hydroxyl groups of PCL4 with 2-bromoisobutyryl bromide,macroinitiator was used to initiate the polymerization of t-butyl acrylate by atom-transfer radical polymerization（ATRP）.Afterwards,the tert-butyl ester groups of the poly（tert-butyl acrylate）（PtBA） block were hydrolyzed by trifluoroacetic acid to obtain the copolymer PCL4-b-PAA4.The mass distribution of samples by gel permeation chromatography（GPC） test for hydrolysis of 3h and 6h is very narrow molecular,respectively,1.31 and 1.40.The final product and intermediates were characterized by nuclear magnetic resonance（NMR） and Fourier transform infrared spectrometry（FT-IR） in detail.
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