单茂钪催化月桂烯聚合的研究

发布时间：2018-01-03 23:08

  本文关键词：单茂钪催化月桂烯聚合的研究　出处：《大连理工大学》2016年硕士论文　论文类型：学位论文

  更多相关文章： 单茂钪 月桂烯 无规共聚物 立构可控

【摘要】：研发生物质单体月桂烯均聚合及其与烯烃共聚合的催化体系,掌握催化剂结构与反应性能的关系,合成结构可控的生物基新材料具有重要的理论和应用价值。本文系统研究了单茂钪催化月桂烯均聚合及其与烯烃共聚合时催化剂结构与性能的关系,发展了一类在月桂烯聚合中展现良好催化性能的单茂钪催化剂,实现了一系列立体结构丰富聚月桂烯均聚物及其与烯烃共聚物的合成。1.单茂钪催化剂配体结构对月桂烯聚合的活性和选择性有较大影响。配体空间位阻较大的单茂钪(C5Me4SiMe3)Sc(CH2SiMe3)2(THF) (Cp'ScTHF)和(C5Me4SiMe3)Sc(CH2C6H4 NMe2-o)2 (Cp'Sc)催化月桂烯均聚合活性和选择性相当(10～30 g polymer (mol of Sc)-1 h-1),获得以3,4-结构为主的聚月桂烯,聚月桂烯的玻璃化温度(Tg)为-46℃。配体空间位阻较小的单茂钪(C5H5)Sc(CH2C6H4 NMe2-o)2 (CpSc)催化月桂烯均聚合具有较高的催化活性(380 g polymer (mol of Sc)-1 h-1),获得以1,4-结构为主的聚月桂烯,1,4-选择性高达98%,聚月桂烯的玻璃化温度(Tg)为-70℃。通过改变月桂烯与催化剂当量比可实现对聚月桂烯分子量的有效调控,具有准活性聚合的特征。2.单茂钪实现了月桂烯与共轭烯烃的高效共聚合,获得了不同微观结构的共聚物。Cp'Sc和CpSc实现了月桂烯与丁二烯无规共聚合。Cp'Sc催化共聚合时月桂烯3,4-选择性达74%,丁二烯1,4-选择性达86%；CpSc催化共聚合时两单体的1,4-选择性达90%以上,获得的月桂烯/丁二烯无规共聚物的组成和分子量可通过改变两单体及催化剂的相对当量比实现,不同组成的无规共聚物的具有一个Tg(-60～95℃)。Cp'Sc和CpSc实现了月桂烯与苯乙烯的嵌段共聚合。Cp'Sc催化共聚合时月桂烯3,4-选择性达75%,聚苯乙烯嵌段为间规结构,获得嵌段共聚物具有Tg(-37℃)和%(250℃)；CpSc催化共聚合月桂烯1,4-选择性达97%,聚苯乙烯嵌段为无规结构,获得嵌段共聚物具有两个Tg(-63℃和94℃)；获得月桂烯/苯乙烯嵌段共聚物的组成可通过改变两单体当量比实现。3.单茂钪实现了月桂烯与乙烯的高效共聚合,获得了不同微结构的共聚物。单茂钪Cp'ScTHF催化月桂烯与乙烯共聚合获得月桂烯孤立插入的组成可控的无规共聚物,无规共聚物中月桂烯3,4-结构为58%、含量可在9～35 mol%间调控,共聚物具有Tg(-63～-55℃),当共聚物月桂烯含量小于21 mol%时具有Tm(108～133℃)；Cp'Sc催化月桂烯与乙烯共聚合获得组成可控的嵌段共聚物,嵌段共聚物中月桂烯以3,4-结构为74%、含量可在8～62 mol%间调控,共聚物具有毛(-50℃)和%(123℃)。
[Abstract]:To develop the catalytic system of isomerization of laurel and its copolymerization with olefin, and to master the relationship between catalyst structure and reaction performance. The synthesis of new biomaterials with controllable structure is of great theoretical and practical value. In this paper, the relationship between the structure and properties of monocentadienum-catalyzed isomerization of lauryl enes and its copolymerization with olefin has been systematically studied. A kind of monocene scandium catalyst with good catalytic performance in lauryl polymerization was developed. A series of solid structure rich polylauron homopolymers and their copolymers with olefins were synthesized. 1. The ligand structure of scandium monocene catalyst has a great influence on the activity and selectivity of lauryl polymerization. The space steric hindrance of the ligands is large. Scandium monopentadium (. C5Me4SiMe3scum (CH2SiMe3THF) and C5Me4SiMe3 (C5Me4SiMe3) and C5Me4SiMe3 (C5Me4SiMe3) and C5Me4SiMe3 (C5Me4SiMe3). The activity and selectivity of isomerization of laurene catalyzed by CH2C6H4 NMe2-o)2 were equal to 1030g polymer of scale. -1 h-1). Poly (lauryl) with the structure of 3 ~ 4 ~ (-) was obtained. The glass transition temperature of polylauronene was -46 鈩，

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