低温等离子体诱发聚烯烃/有机单体原位聚合合金化及其结构与性能

In this project, the polyolefines (mainly one of polypropylene, and include polyethlene) as matrix resin were chosen. Low temperature plasma was produced using organic monomer (such as ethylene, styrene and acrylate etc.) and the compound of organic monomer with Ar, air and carbon dioxide. Low temperature plasma polymerization of ethlene was studied and the relation of the structure of polymers with the conditions of plasma formation, such as discharge voltage, gas flow rate and discharge mode (glow discharge and dielectric barrier discharge, DBD) were investigated. The plasma of ethylene-induced the modification of molten polypropylene and in-situ alloying of polypropylene in mixer (or double screw extruder) were observed. The relation of the structure and properies of alloys with reaction conditions (blending temperature, discharge voltage, gas flow rate and discharge mode) was studied; the modification of milten polyolefines/monomer in mixer (or double screw extruder) was studied by low temperature plasma of compound, and then modified polyolefines initiated the grafting copolymerization of the organic monomer onto polyolefines and homopolymerization of monomer to accomplish alloying of polyolefines in-situ, achieving high-performance and functionalization of the polyolefines. The relation of composition and structure of low plasma of organic monomer and compound with the conditions of plasma formation, such as discharge voltage, gas flow rate and discharge mode was studied. The structure and properties of the modified polyolefines of plasma were observed. The conditions of effect structure and properties on the modified polyolefines were investigated. The conditions, mechanism and kenitics of the formation of in-situ plasma-induced alloying of polyolefines with monomer under molten and mixing were studied and the formation and evolution of the structure of alloys under molten and mixing were investigated in-situ.

本项目以聚烯烃中的聚丙烯为基体树脂，兼顾聚乙烯。选择有机单体乙烯、丙烯、苯乙烯和丙烯酸酯等为等离子体介质，氩气、空气和二氧化碳等为无机等离子体介质，并与苯乙烯、丙烯酸酯组成有机/无机混合物(复合)等离子体。研究低温等离子体（有机等离子体和复合等离子体）与聚烯烃（聚丙烯或聚乙烯）熔体/单体（包括单体预聚体）在密炼机（或挤出机）中完成有机单体在聚烯烃上的接枝与接枝共聚，进而形成聚合物合金，实现聚烯烃的高性能与功能化。研究乙烯低温等离子体聚合、聚合物结构与等离子体形成条件[等离子体类型（辉光放电或介质阻挡放电，DBD）、放电电压、气体流量]和等离子体组成的关系；在密炼机中（或挤出机），研究乙烯等离子体诱发熔体聚丙烯改性和原位合金化。研究复合等离子体组成与等离子体形成条件（放电类型、放电电压、气体流量等）的关系；研究复合等离子体诱发聚烯烃聚合合金化过程中结构的形成与控制，合金结构与性能的关系。

本项目构建了等离子体发生器（介质阻挡放电和辉光放电）与密炼机的联合实验系统，实现了聚烯烃的在线改性与活化、原位诱发聚烯烃/单体的接枝共聚和聚烯烃/聚合物间的化学连接，实现了聚烯烃的高性能与功能化。探讨了不同等离子体介质（空气、氩气、CO2、乙烯，复合介质氩/乙烯和CO2/苯乙烯等）处理聚烯烃表面和聚烯烃熔体的结构与性能；研究了等离子体在线处理熔体聚丙烯(iPP)诱发iPP/苯乙烯（St）预聚体原位合金化和iPP/单体的原位接枝共聚；研究了iPP活性表面诱发单体的原位接枝共聚；讨论了等离子体诱发iPP/聚乙烯（PE）、iPP/乙丙橡胶（EPDM）原位大分子间的链接条件，对接枝共聚物和原位合金进行了结构与性能表征。.CO2等离子体处理熔体iPP，其熔体中的过氧化自由基含量高于等离子体处理iPP固体表面的自由基含量。为实现在线等离子体处理聚合物熔体进而原位诱发单体的接枝和聚合物/聚合物原位合金化（大分子连间的链接）提供了理论和实践依据。.等离子体处理的低密度聚乙烯（LDPE）表面可以诱发LDPE在熔融混炼过程中的交联。研究了影响交联的条件，讨论了其结构与性能。.乙烯等离子体处理的iPP表面可以诱发PPβ-晶的生成。样品再经混炼可提高iPP中β-晶的含量。.在联合实验系统中研究了CO2/St混合等离子体在线处理iPP熔体诱发iPP/苯乙烯预聚体（PSt）原位合金化，实现了iPP/PSt大分子间的链接（接枝）,其PSt在iPP上的接枝率可达3.5%。.在联合实验系统中还研究了iPP与乙烯基单体季戊四醇三丙烯酸酯（PETA）在线处理与的原位诱发PETA的接枝共聚。得到了聚丙烯长支链接枝物，其接枝率与过氧化物熔融法一致。.空气等离子体处理的iPP颗粒与PETA在密炼机中熔融共混接枝。同样得到了iPP-g-PETA接枝共聚物，其接枝率与过氧化物熔融法近似。.Ethylene/Ar复合等离子体处理iPP，其iPP表面不仅被活化，而且沉积了乙烯的聚合物。。活性iPP与LDPE共混实现了大分子之间的原位接枝反应，得到了聚合物金化，用X光小角分析的结果证明了这一结果。同样，CO2等离子体诱发iPP/EPDM原位形成大分子间的链接，得到了部分相容的聚合物共混物（合金）。