官能化聚烯烃的进展和应用

doi:10.16085/j.issn.1000-6613.2021-1223

摘要/Abstract

摘要：

官能化聚烯烃是由聚烯烃改性后得到的产物，一般通过交联改性、共聚改性、固相力化学改性和接枝改性等方法制备，可应用于黏附、能源和封装等多重领域。基于聚烯烃高通量低成本的优势，聚烯烃接枝改性利用自由基反应直接向聚烯烃链上引入极性单体，较为经济便捷。聚烯烃接枝改性按反应条件的不同，又可分为溶液接枝、熔融接枝、辐射接枝、固相接枝和悬浮接枝。在接枝改性过程中，接枝率和接枝效率受多种因素影响，如聚烯烃型号、接枝单体、引发剂、共单体和反应条件等。本文综述了聚烯烃接枝改性不同接枝方法的研究进展，分析了各种接枝方法的优势和短板，并将接枝改性过程中的影响因素进行了总结。文章依据聚烯烃的可控自由基接枝改性和金属催化改性以及官能化聚烯烃的应用，展望了聚烯烃可控改性和官能化聚烯烃规模化生产。

关键词: 聚烯烃, 官能化聚合物, 接枝改性, 合金, 复合材料

Abstract:

Functionalized polyolefin is a modified product of polyolefin that can be applied to multiple fields, such as adhesion, energy and packaging. It is generally prepared by grafting, cross-linking, copolymerization, etc. Based on the large scale and low price of polyolefin, polyolefin grafting modification directly introduces the wide range of functional groups onto a polyolefin backbone by radical-induced grafting, which is the most economical and convenient. Due to the differences of reaction condition, polyolefin graft modification can be divided into solution grafting, melt grafting, irradiation grafting, solid phase grafting and suspension grafting. In the process of graft modification, the grafting degree and grafting efficiency are affected by many factors, such as polyolefin type, grafting monomer, initiator, comonomers and reaction conditions. This paper reviews the research progress of the grafting methods, the advantages and shortcomings of different grafting methods and analyzes the influence factors in the process of graft modification. According to the controllable free radical grafting modification and metal catalyzes modification of polyolefins, as well as the application of functionalized polyolefins, the controllable modification of functionalized polyolefins and large-scale production are prospected.

Key words: polyolefin, functional polymer, grafting modification, alloy, composite

中图分类号:

TQ325

余世勤, 赵鑫鹏, 郑艳, 严亮, 贾建洪, 余海斌. 官能化聚烯烃的进展和应用[J]. 化工进展, 2022, 41(5): 2487-2503.

YU Shiqin, ZHAO Xinpeng, ZHENG Yan, YAN Liang, JIA Jianhong, YU Haibin. Progess and application of functional polyolefin[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2487-2503.

图/表 10

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接枝方法	引发剂种类	溶剂	反应时间	反应温度	生产方式	成本	特点
溶液接枝	过氧化物类	大量	长	373~393K	间歇	较高	温度较低，接枝均匀，对环境污染
熔融接枝	过氧化物类	少量/无	短	433~483K	连续	低	反应快，无后处理
辐射接枝	芳基酮类	无	短	室温	间歇	高	接枝均匀，产物纯净
固相接枝	过氧化物类	少量/无	较长	373~413K	间歇	较低	表面接枝，反应温和
悬浮接枝	过氧化物类	少	较长	353~373K	间歇	较低	反应温和，接枝均匀

接枝方法	引发剂种类	溶剂	反应时间	反应温度	生产方式	成本	特点
溶液接枝	过氧化物类	大量	长	373~393K	间歇	较高	温度较低，接枝均匀，对环境污染
熔融接枝	过氧化物类	少量/无	短	433~483K	连续	低	反应快，无后处理
辐射接枝	芳基酮类	无	短	室温	间歇	高	接枝均匀，产物纯净
固相接枝	过氧化物类	少量/无	较长	373~413K	间歇	较低	表面接枝，反应温和
悬浮接枝	过氧化物类	少	较长	353~373K	间歇	较低	反应温和，接枝均匀

引发剂	半衰期（1h）/℃
过氧类
过氧化十二酰	80
过氧化苯甲酰	92
过氧化二异丙苯	128
过氧化二叔丁基	136
偶氮类
偶氮二异丁腈	79
偶氮二异庚腈	64
氢过氧类
异丙苯过氧化氢	193
叔丁基过氧化氢	199

引发剂	半衰期（1h）/℃
过氧类
过氧化十二酰	80
过氧化苯甲酰	92
过氧化二异丙苯	128
过氧化二叔丁基	136
偶氮类
偶氮二异丁腈	79
偶氮二异庚腈	64
氢过氧类
异丙苯过氧化氢	193
叔丁基过氧化氢	199

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