PACMO-b-PVC-b-PACMO共聚物的合成和表征  

Synthesis and characterization of poly(N-acryloyl morpholine)-b-poly(vinyl chloride)-b-poly(N-acryloyl morpholine)copolymers

作　　者：韩剑鹏 包永忠[1,2] HAN Jian-peng;BAO Yong-zhong(State Key Laboratory of Chemical Engineering,College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310027,China;Institute of Zhejiang University-Quzhou,Quzhou 324000,China)

机构地区：[1]化学工程联合国家重点实验室浙江大学化学工程与生物工程学院,浙江杭州310027 [2]浙江大学衢州研究院,浙江衢州324000

出　　处：《高校化学工程学报》2021年第4期640-648,共9页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21676235)。

摘　　要：为拓展聚氯乙烯(PVC)嵌段共聚改性,以由单电子转移-蜕化链转移(SET-DT)活性自由基聚合制备的含活性碘末端的PVC(I-PVC-I)为大分子引发剂、Na2S2O4/NaHCO3为催化体系,进行丙烯酰吗啉SET-DT活性自由基溶液聚合,合成聚丙烯酰吗啉-b-聚氯乙烯-b-聚丙烯酰吗啉(PACMO-b-PVC-b-PACMO)共聚物,研究了丙烯酰吗啉聚合动力学、共聚物结构和表面特性。结果表明,在浓度相同的情况下,I-PVC-I分子量越大,嵌段共聚反应速率越大;PACMO-b-PVC-b-PACMO共聚物存在2个玻璃化转变区,随着PACMO质量分数的增加,对应2个转变区的玻璃化温度tg1和tg2均增加;聚合物溶度参数计算表明PVC和PACMO不相容,原子力显微镜观察旋涂膜发现PACMO-b-PVC-b-PACMO共聚物自组装形成“海-岛”结构,随着PVC质量分数的增加,“岛相”PVC逐渐增加直至聚并;随着PACMO质量分数增加,PACMO-b-PVC-b-PACMO共聚物薄膜与水的接触角变小,共聚物具有更好的亲水性。In order to extend the modification method of PVC by block copolymerization,poly(N-acryloyl morpholine)-b-poly(vinyl chloride)-b-poly(N-acryloyl morpholine)(PACMO-b-PVC-b-PACMO)copolymers were synthesized by single electron transfer-degenerative chain transfer(SET-DT)living radical polymerization(LRP)of N-acryloyl morpholine in solutions,using iodine terminated PVC(I-PVC-I)prepared by SET-DT LRP as initiators,and Na2S2O4/NaHCO3 as catalyst.The polymerization kinetics,structures and surface characters of copolymers were studied.The results show that the greater the molecular weight of the I-PVC-I initiator,the higher the reaction rate of block copolymerization at the same concentration.PACMO-b-PVC-b-PACMO copolymers had two glass transition regions,and the glass transition temperatures tg1 and tg2 of two regions increased with increase of the PACMO contents in copolymers.The calculation of polymer solubility parameters indicated that PVC block and PACMO block were incompatible.AFM observation on spin-coated copolymer films showed the self-assembly of PACMO-b-PVC-b-PACMO copolymers into"sea-island"structure,and domain size of PVC"island phase"was gradually increased with PVC content in copolymers until the coalescence of PVC phase.The contact angles between PACMO-b-PVC-b-PACMO copolymer films and water decreased with increase of PACMO contents in copolymer,indicating that the copolymers have better hydrophilicity.

关 键 词：活性自由基聚合 聚氯乙烯 聚丙烯酰吗啉 嵌段共聚物 

分 类 号：TQ325.3[化学工程—合成树脂塑料工业]