通过可逆加成-裂解链转移自由基聚合(RAFT)和活性阴离子开环聚合(ROP)方法合成了星型嵌段共聚物PEO4-b-PNIPAAm4。首先通过活性阴离子聚合合成了分子量为8000、分子量分布为1.1的四臂星型聚环氧乙烷(PEO4),PEO4的末端羟基和DDAT进行酯化反应,得到大分子RAFT引发剂。然后引发N-异丙基丙烯酸胺(NIPAAm)进行聚合反应,反应时间分别为0.16 h、0.33 h、0.66 h和1.0 h,得到了分子量分别为0.58×104、0.73×04、0.92×104、1.03×104,分子量分布为1.19、1.17、1.20和1.18的四种星型嵌段共聚物PEO4-b-PNIPAAm4。通过核磁共振(1H-NHR)和凝胶渗透色谱(GPC)对各步产物进行了表征。
a series of four-arm star-shaped block copolymers poly(ethylene oxide)-b-poly(N-isopropyl-acrylamide)(PEO4-b-PNIPAAm4) were synthesized by a combination of reversive addition-fragmentation chain transfer polymerization(RAFT) and anionic ring-opening polymeration(AROP).Firstly,the four-arm star-shaped PEO4 was prepared by AROP of EO.Then,PEO4 was esterified by reaction with S-1-dodecyl-S′-(α,α′-dimethyl-α″-acetic acid)trithio-carbonate)(DDAT),and then used as RAFT macroinitiator to initiate polymerization of NIPAAm.And a series of four-arm star-shaped copolymers PEO4-b-PNIPAAm4 were obtained.The structure and molecular weights of every segment of the star-shaped block copolymer were controllable,and the polydispersity was narrow.The final product and intermediate were characterized by 1H nuclear magnetic resonance spectrum(1H-NMR)and gel permeation in chromatography(GPC) in details.
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