基于氯化聚丙烯的傅-克反应制备高熔点、高结晶度的改性PP-g-MAH

Preparation of Modified PP-g-MAH with High Melting Point and High Crystallinity Based on Friedel-Crafts Reaction of Chlorinated Polypropylene

摘要

本研究提出了一种高结晶度、高接枝率的马来酸酐接枝聚丙烯 (PP-g-MAH) 制备新策略。首先以高结晶度、低氯化度的氯化聚丙烯 (CPP) 为原料，利用碳氯键的反应活性，通过经典的傅-克 (Friedel-Crafts) 反应将甲苯接枝到聚丙烯主链上制备芳基化聚丙烯。然后，利用苄基自由基易于形成的特点，在较温和条件下引发马来酸酐（MAH）与苯乙烯（St）共聚，成功制备出MAH接枝率高达10.5%的高熔点、高结晶度的改性PP-g-MAH（熔点为152.4 ℃、结晶度为30.67%），解决了熔融法制备PP-g-MAH所带来的接枝率低和聚丙烯分子链规整性易被破坏的问题，为聚丙烯的高性能化应用提供了可能性。

Abstract

A novel strategy for preparing maleic anhydride-grafted polypropylene (PP-g-MAH) with high crystallinity and high grafting ratio was proposed. Using chlorinated polypropylene (CPP) with high crystallinity and low chlorination degree as the starting material, the reactive carbon-chlorine bonds were exploited to graft toluene onto the polypropylene backbone via the classic Friedel-Crafts reaction, yielding arylated polypropylene. Leveraging the facile formation of benzylic radicals, the copolymerization of maleic anhydride (MAH) and styrene (St) was subsequently initiated under mild conditions, successfully affording modified PP-g-MAH with a maximum MAH grafting ratio of up to 10.5%, a high melting point (152.4 ℃) and a high crystallinity (30.67%). This approach effectively addresses the issues of low grafting efficiency and compromised chain regularity associated with conventional melt-grafting methods, thereby paving the way for high-performance applications of polypropylene.

关键词

聚丙烯 / 氯化聚丙烯 / 傅-克反应 / 接枝改性 / 马来酸酐

Key words

polypropylene / chlorinated polypropylene / Friedel-Crafts reaction / graft modification / maleic anhydride

参考文献

[1] MADDAH H A . Polypropylene as a promising plastic: A review [J]. American Journal of Polymer Science, 2016, 6(1): 1-11.

[2] 康文倩, 马宗立, 高玉林, 王雄, 杨宝, 闫功臣 . 耐热聚丙烯专用料的结构与性能 [J]. 中国塑料, 2020, 34(7): 2-8.

[3] KANG W Q, MA Z L, GAO Y L, WANG X, YANG B, YAN G C . Structure and properties of heat—resistant polypropylene specialty material [J]. China Plastics, 2020, 34(7): 2-8.

[4] PENG Z G, LI C H, FENG Q, ZHENG Y . Research on surface modification of polypropylene fiber and its application evaluation in oil well cement [J]. Construction and Building Materials, 2024, 421: 135728.

[5] 傅和青, 黄洪, 陈焕钦 . 聚丙烯化学改性进展 [J]. 现代化工, 2003, 23(S1): 78-81.

[6] FU H Q, HUANG H, CHEN H Q . Research progress in chemical modification of polypropylene [J]. Modern Chemical Industry, 2003, 23(S1): 78-81.

[7] 张俊涛, 谢明, 段克尧, 蔡正国, 陈龙, 孙俊芬 . 聚丙烯/羟基化聚丙烯共混膜的增容 [J]. 功能高分子学报, 2023, 36(6): 554-560.

[8] ZHANG J T, XIE M, DUAN K Y, CAI Z G, CHEN L, SUN J F . Compatibilization of polypropylene/hydroxylated polypropylene blend membranes [J]. Journal of Functional Polymers, 2023, 36(6): 554-560.

[9] LIAN Z Y, XU Y Y, ZUO J, QIAN H, LUO Z W, WEI W J . Preparation of PP— g—(AA—MAH) fibers using suspension grafting and melt—blown spinning and its adsorption for aniline [J]. Polymers, 2020, 12(9): 1-18.

[10] 李朝, 贾元山 . 增容剂马来酸酐接枝聚丙烯接枝率的酸碱反滴定法测定误差分析 [J]. 中国塑料, 2023, 37(10): 77-84.

[11] LI C, JIA Y S . Error analysis of acid—base back titration method for determining grafting rate of maleic anhydride grafted polypropylene compatibilizer [J]. China Plastics, 2023, 37(10): 77-84.

[12] 于晓强, 王静媛, 李峰, 秦东奇, 徐冰, 汤心颐 . 马来酸酐接枝聚丙烯的等温结晶动力学研究 [J]. 高分子学报, 1998(1): 26-31.

[13] YU X Q, WANG J Y, LI F, QIN D Q, XU B, TANG X Y . Study on isothermal crystallization kinetics of maleic anhydride grafted polypropylene [J]. Acta Polymerica Sinica, 1998(1): 26-31.

[14] MITANI K, OGATA T, IWASAKI M . Chlorine distribution and structure—property relationship of chlorinated polypropylene [J]. Journal of Polymer Science: Polymer Chemistry Edition, 1974, 12(8): 1653-1669.

[15] 马向东, 刘大壮, 孙培勤 . 氯化聚丙烯接枝马来酸酐的合成研究 [J]. 涂料工业, 2007, 37(7): 29-31.

[16] MA X D, LIU D Z, SUN P Q . Study on synthesis of chlorinated polypropylene grafted with maleic anhydride [J]. Paint & Coatings Industry, 2007, 37(7): 29-31.

[17] 赵兴顺, 张军华, 郑朝晖, 潘毅, 朱珠, 丁晓斌, 彭宇行 . 溶液法马来酸酐接枝氯化聚丙烯的研究 [J]. 功能高分子学报, 2003, 16(1): 77-80.

[18] ZHAO X S, ZHANG J H, ZHENG Z H, PAN Y, ZHU Z, DING X B, PENG Y X . Study on maleic anhydride grafted chlorinated polypropylene by solution method [J]. Journal of Functional Polymers, 2003, 16(1): 77-80.

[19] LI T T, CUI Z Y, ZHANG Q F, QIN S H, HE B Q, LI J X . Synthesis of chlorinated polypropylene grafted poly(methyl methacrylate) using chlorinated polypropylene as macro—initiator via atom transfer radical polymerization and its application in lithium ion battery [J]. Materials Letters, 2016, 176(1): 64-67.

[20] HALOI D J, NASKAR K, SINGHA N K . Modification of chlorinated poly(propylene) via atom transfer radical graft copolymerization of 2—ethylhexyl acrylate: A brush—like graft copolymer [J]. Macromolecular Chemistry and Physics, 2011, 212(5): 478-484.

[21] ACIK G, ALTINKOK C, OLMEZ H, TASDELEN M A . Antibacterial film from chlorinated polypropylene via CuAAC click chemistry [J]. Progress in Organic Coatings, 2018, 125(1): 73-78.

[22] ACIK G, ALTINKOK C, TASDELEN M A . Synthesis and characterization of polypropylene—graft—poly(L—lactide) copolymers by CuAAC click chemistry [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2018, 56(22): 2595-2601.

[23] CHOI Y B, PARK O O . Preparation of sulfonated polypropylene and its dyeability: Thiol as a functionalization template of polypropylene [J]. Journal of Applied Polymer Science, 2008, 109(2): 736-748.

[24] FU X M, LIU X J, ZHANG C Y, LIU H, HU Y M, ZHANG X Q . Synthesis of propylene— co—styrenic monomer copolymers via arylation of chlorinated PP and their compatibilization for PP/PS blend [J]. Polymers, 2019, 11(1): 157-169.

[25] ZHANG H X, YAN X, HAN W, LIU C, CHEN Y J, XIA Y Y, CAI Z G, YOON K B, YANG J M . Fabrication of high—performance PP/graphene nanocomposites via Friedel—Crafts [J]. Journal of Inorganic and Organometallic Polymers and Materials, 2023, 33(2): 1156-1163.

[26] OLAH G A, REDDY V P, PRAKASH G K S . Friedel—Crafts reactions [J]. Kirk—Othmer Encyclopedia of Chemical Technology, 2004, 11: 1042-1081.

[27] ZHANG M, COLBY R H, MILNER S T, CHUNG T C M, HUANG T, DEGROOT W . Synthesis and characterization of maleic anhydride grafted polypropylene with a well—defined molecular structure [J]. Macromolecules, 2013, 46(11): 4313-4323.

[28] 刘敏, 刘大壮, 韦建国, 孙绍辉, 孙培勤 . 氯化聚丙烯与甲苯烷基化反应的研究 [J]. 郑州大学学报 (工学版), 2006, 27(1): 121-124.

[29] LIU M, LIU D Z, WEI J G, SUN S H, SUN P Q . Study on alkylation reaction of chlorinated polypropylene with toluene [J]. Journal of Zhengzhou University (Engineering Science Edition), 2006, 27(1): 121-124.

[30] 柯俊沐 . 酸碱滴定法测定马来酸酐接枝聚丙烯接枝率精度的影响因素研究 [J]. 中国塑料, 2023, 37(6): 16-20.

[31] KE J M . Study on factors affecting the accuracy of grafting rate determination of maleic anhydride grafted polypropylene by acid—base titration [J]. China Plastics, 2023, 37(6): 16-20.

基金资助

山东省自然科学基金面上项目(ZR2022ME154)

山东省重点研发计划项目（科技型中小企业创新能力提升工程项目）(2025TSGCCZZB0790)