超支化聚乙烯聚酯嵌段共聚物的制备与表征

温朝阳, 张志超, 韩双, 李盛宇

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塑料科技 ›› 2025, Vol. 53 ›› Issue (03) : 36-42. DOI: 10.15925/j.cnki.issn1005-3360.2025.03.007
理论与研究

超支化聚乙烯聚酯嵌段共聚物的制备与表征

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Synthesis and Characterization of Hyperbranched Polyethylene-b-Polyester Copolymers

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摘要

以2-巯基乙醇和超支化聚乙烯为原料，通过巯基-烯烃点击化学反应制备羟基功能化超支化聚乙烯（HBPE-OH）。以HBPE-OH作为引发剂，在有机碱1，5，7-三叠氮双环（4.4.0）癸-5-烯（TBD）或二正丁基镁（MgBu2）作用下可以开环聚合外消旋丙交酯以及ε-己内酯。结果表明：MgBu2/HBPE-OH催化体系的活性要高于TBD/HBPE-OH催化体系。生成的聚合物的核磁共振氢谱以及聚合物的凝胶渗透色谱（GPC）淋出曲线的单峰分布表明产物为超支化聚乙烯-聚丙交酯以及超支化聚乙烯-聚己内酯二元嵌段共聚物，聚合物的分子量分布较低。此外，以MgBu2/HBPE-OH催化剂制备超支化聚乙烯-聚丙交酯-聚己内酯三元嵌段共聚物，并通过核磁共振以及GPC对其结构进行表征。差示扫描量热法（DSC）表明所制备的嵌段共聚物的玻璃化转变温度和熔点随着聚酯链段长度的增加而变高。其中三元嵌段共聚物有两个熔点（200 ℃和224 ℃），玻璃化转变温度为136 ℃。

Abstract

Hydroxyl functionalized hyperbranched polyethylene (HBPE-OH) was prepared by thiol-ene click reaction between 2-mercaptoethanol and hyperbranched polyethylene. Using HBPE-OH as an initiator, racemic lactide and ε-caprolactone can be polymerized through ring opening polymerization using organic base 1,5,7-Triazabicylo[4.4.0]dec-5-ene (TBD) or di-n-butyl magnesium (MgBu2). It was found that the catalytic activity of the MgBu2/HBPE-OH catalytic system was higher than that of the TBD/HBPE-OH catalytic system. Thus, narrowly distributed (hyperbranched polyethylene)-b-(polylactide) and (hyperbranched polyethylene)-b-(polycaprolactone) block polymers were produced which were structurally characterized by 1H NMR spectroscopy and GPC. In addition, (hyperbranched polyethylene)-b-(polylactide)-b-(polycaprolactone) ternary block copolymers were prepared using a MgBu2/HBPE-OH catalyst and were characterized by nuclear magnetic resonance and GPC. The differential scanning calorimetry (DSC) characterization of the obtained block copolymer demonstrated that the glass transition temperature and melting point of the polymer increased with the increase of the length of the polyester chain segment. The ternary block copolymer has two melting points (200 ℃and 224 ℃) and a glass transition temperature of 136 ℃.

关键词

超支化聚乙烯 / 外消旋丙交酯 / ε-己内酯 / 开环聚合 / 嵌段共聚物

Key words

Hyperbranched polyethylene / Racemic lactide / ε-caprolactone / Ring opening polymerization / Block copolymers

中图分类号

O633.14

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温朝阳 , 张志超 , 韩双 , 等. 超支化聚乙烯聚酯嵌段共聚物的制备与表征. 塑料科技. 2025, 53(03): 36-42 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.03.007
WEN Zhaoyang, ZHANG Zhichao, HAN Shuang, et al. Synthesis and Characterization of Hyperbranched Polyethylene-b-Polyester Copolymers[J]. Plastics Science and Technology. 2025, 53(03): 36-42 https://doi.org/10.15925/j.cnki.issn1005-3360.2025.03.007

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基金

辽宁省自然科学基金引导项目(2019-ZD-0086)
辽宁省自然科学基金(2022-MS-293)
中国科学院长春应用化学研究所电分析化学国家重点实验室开放课题基金项目(SKLEAC202204)

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