Synthesis of poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) multiblock terpolymers via a facile PROP method
Synthesis of poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) multiblock terpolymers via a facile PROP method
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通过简便的 PROP 方法合成聚对苯二甲酸丁二醇酯-嵌段-聚环氧乙烷-嵌段-聚环氧丙烷-嵌段-聚环氧乙烷多嵌段三元共聚物
DOI：
10.1016/j.polymer.2017.10.010
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发表时间：
2017-11
期刊：
影响因子：
4.6
通讯作者：
Li Christopher Y.
中科院分区：
文献类型：
--
作者：
Zhang Minzhi;Gu Jiali;Zhu Xiang;Gao Lingfeng;Li Xiaohong;Yang Xiaoming;Tu Yingfeng;Li Christopher Y.
采用原位级联缩聚-偶联开环聚合（PROP）方法合成了一系列三组分聚聚对苯二甲酸丁二醇酯环氧乙烷嵌段聚环氧丙烷嵌段聚环氧乙烷多嵌段三元共聚物（PBT-b-PEO-b-PPO-b-PEO-b-PBT）n，使用环状低聚（对苯二甲酸丁二醇酯）（COBT）作为单体和二羟基末端官能的PEO-b-PPO-b-PEO（EPE）作为大分子引发剂。用1H-1H gCOSY和1H-13 C gHSQC NMR对共聚物的结构进行了表征。通过对多嵌段链端、嵌段链端及各嵌段对应基团的归属，利用1HNMR谱定量估算了多嵌段三元共聚物及各嵌段的数均分子量。聚合动力学研究证实了PROP机理。对于结晶PBT和PEO链段，多嵌段三元共聚物是双结晶聚合物，其中PBT和PEO链段的熔点和结晶度分别随着相应的PBT和PEO含量而增加。PBT链段与PEO链段的共价连接导致两个嵌段的受限结晶环境，其中观察到PEO晶体的熔点的强烈抑制，其在EPE三嵌段含量为50%时变为无定形。TEM和SAXS结果表明，有趣的层状微相分离形态在这些多嵌段三元共聚物。
We present here the application of in situ cascade polycondensation-coupling ring-opening polymerization (PROP) method for the facile synthesis of a series of three-component poly(butylene terephthalate)-block-poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) multiblock terpolymers (PBT-b-PEO-b-PPO-b-PEO-b-PBT)n, using cyclic oligo(butylene terephthalate)s (COBTs) as monomers and dihydroxyl end-functional PEO-b-PPO-b-PEO (EPE) as macroinitiator. The structure details of these copolymers were characterized by1H-1H gCOSY and1H-13C gHSQC NMR spectra. With the assignment of multiblock chain ends, block segmental ends and corresponding groups for each segment, the number-average molecular weights for multiblock terpolymers and each block segment were estimated by the quantitative1H NMR spectra. Polymerization kinetics studies confirm the PROP mechanism. With crystalline PBT and PEO segments, the multiblock terpolymers are double-crystalline polymers, where the melting point and crystallinity of PBT and PEO segments increase with corresponding PBT and PEO content, respectively. The covalent linking of PBT segments with PEO segments leads to the confined crystallization environment for both blocks, where a strong depression on melting point of PEO crystals was observed, which becomes amorphous at an EPE triblock content of 50%. TEM and SAXS results show interesting lamella-like microphase separation morphologies in these multiblock terpolymers.
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影响因子：
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