Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization
Synthesis and characterization of functional polyethylene with regularly distributed thioester pendants via ring‐opening metathesis polymerization
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DOI：
10.1002/pola.28870
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发表时间：
2017-12
期刊：
影响因子：
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通讯作者：
Shaofei Song;Zhen Zhang;Xiaoyu Liu;Zhisheng Fu;Junting Xu;Zhiqiang Fan
中科院分区：
文献类型：
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作者：
Shaofei Song;Zhen Zhang;Xiaoyu Liu;Zhisheng Fu;Junting Xu;Zhiqiang Fan
采用钌基工业催化剂催化烷基环戊酯-3-烯碳硫酸酯开环复分解聚合（ROMP），并对ROMP产物（烷基=乙基、正丁基、正辛基和正十二基）进行加氢反应，合成了4种携带硫酯悬垂物的功能聚乙烯。在这些聚合物中，每五个亚甲基碳上的烷基硫酯基团沿主链精确分布。通过1H、13C NMR和GPC表征了聚合物的链结构、分子量和分子量分布。ROMP反应均达到了较高的单体转化率，并且ROMP产物的加氢是彻底的。通过DSC和TGA对聚合物的热转变和侧链结晶行为进行了研究和表征。这些聚合物的玻璃化转变温度和熔融温度都高于含有酯悬垂物的聚合物。TGA分析表明，含硫酯聚合物表现出中等的热稳定性，含硫聚合物表现出略低于不含硫聚合物的热稳定性。这一新的功能化聚乙烯家族可以作为乙烯-硫丙烯酸酯共聚物的模型，并作为新型功能材料得到应用。©2017 Wiley期刊公司j .变异较大。科学。A部分：Polym。化学，2017,55,4027-4036
Four kinds of functional polyethylene carrying thioester pendants were synthesized via ring-opening metathesis polymerization (ROMP) of alkyl cyclopent-3-enecarbothioate catalyzed by a ruthenium-based commercial catalyst and subsequent hydrogenation of the ROMP products (alkyl = ethyl, n-butyl, n-octyl, or n-dodecyl). In these polymers the pendant alkyl thioester groups are precisely distributed along the backbone on every five methylene carbons. Chain structure, molecular weight and molecular weight distribution of the polymers were characterized by 1H and 13C NMR, and GPC. The ROMP reactions all reached high monomer conversions, and hydrogenation of the ROMP products were exhaustive. Thermal transitions and side chain crystallization behaviors of the polymer were investigated and characterized by DSC and TGA. Glass transition temperature and melting temperature of these polymers were higher than the counterparts containing ester pendants. TGA analysis indicated that all the thioester-containing polymers exhibited moderate thermal stability, and the sulfur-containing polymers show slightly lower thermal stability than their counterparts without sulfur. The new family of functionalized polyethylenes could be used as models of ethylene-thioacrylate copolymers, and find applications as novel functional materials. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 4027–4036