本文關(guān)鍵詞：單茂鈧催化月桂烯聚合的研究　出處：《大連理工大學(xué)》2016年碩士論文　論文類型：學(xué)位論文

  更多相關(guān)文章： 單茂鈧 月桂烯 無規(guī)共聚物 立構(gòu)可控

【摘要】：研發(fā)生物質(zhì)單體月桂烯均聚合及其與烯烴共聚合的催化體系,掌握催化劑結(jié)構(gòu)與反應(yīng)性能的關(guān)系,合成結(jié)構(gòu)可控的生物基新材料具有重要的理論和應(yīng)用價值。本文系統(tǒng)研究了單茂鈧催化月桂烯均聚合及其與烯烴共聚合時催化劑結(jié)構(gòu)與性能的關(guān)系,發(fā)展了一類在月桂烯聚合中展現(xiàn)良好催化性能的單茂鈧催化劑,實現(xiàn)了一系列立體結(jié)構(gòu)豐富聚月桂烯均聚物及其與烯烴共聚物的合成。1.單茂鈧催化劑配體結(jié)構(gòu)對月桂烯聚合的活性和選擇性有較大影響。配體空間位阻較大的單茂鈧(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選擇性相當(dāng)(10～30 g polymer (mol of Sc)-1 h-1),獲得以3,4-結(jié)構(gòu)為主的聚月桂烯,聚月桂烯的玻璃化溫度(Tg)為-46℃。配體空間位阻較小的單茂鈧(C5H5)Sc(CH2C6H4 NMe2-o)2 (CpSc)催化月桂烯均聚合具有較高的催化活性(380 g polymer (mol of Sc)-1 h-1),獲得以1,4-結(jié)構(gòu)為主的聚月桂烯,1,4-選擇性高達98%,聚月桂烯的玻璃化溫度(Tg)為-70℃。通過改變月桂烯與催化劑當(dāng)量比可實現(xiàn)對聚月桂烯分子量的有效調(diào)控,具有準(zhǔn)活性聚合的特征。2.單茂鈧實現(xiàn)了月桂烯與共軛烯烴的高效共聚合,獲得了不同微觀結(jié)構(gòu)的共聚物。Cp'Sc和CpSc實現(xiàn)了月桂烯與丁二烯無規(guī)共聚合。Cp'Sc催化共聚合時月桂烯3,4-選擇性達74%,丁二烯1,4-選擇性達86%；CpSc催化共聚合時兩單體的1,4-選擇性達90%以上,獲得的月桂烯/丁二烯無規(guī)共聚物的組成和分子量可通過改變兩單體及催化劑的相對當(dāng)量比實現(xiàn),不同組成的無規(guī)共聚物的具有一個Tg(-60～95℃)。Cp'Sc和CpSc實現(xiàn)了月桂烯與苯乙烯的嵌段共聚合。Cp'Sc催化共聚合時月桂烯3,4-選擇性達75%,聚苯乙烯嵌段為間規(guī)結(jié)構(gòu),獲得嵌段共聚物具有Tg(-37℃)和%(250℃)；CpSc催化共聚合月桂烯1,4-選擇性達97%,聚苯乙烯嵌段為無規(guī)結(jié)構(gòu),獲得嵌段共聚物具有兩個Tg(-63℃和94℃)；獲得月桂烯/苯乙烯嵌段共聚物的組成可通過改變兩單體當(dāng)量比實現(xiàn)。3.單茂鈧實現(xiàn)了月桂烯與乙烯的高效共聚合,獲得了不同微結(jié)構(gòu)的共聚物。單茂鈧Cp'ScTHF催化月桂烯與乙烯共聚合獲得月桂烯孤立插入的組成可控的無規(guī)共聚物,無規(guī)共聚物中月桂烯3,4-結(jié)構(gòu)為58%、含量可在9～35 mol%間調(diào)控,共聚物具有Tg(-63～-55℃),當(dāng)共聚物月桂烯含量小于21 mol%時具有Tm(108～133℃)；Cp'Sc催化月桂烯與乙烯共聚合獲得組成可控的嵌段共聚物,嵌段共聚物中月桂烯以3,4-結(jié)構(gòu)為74%、含量可在8～62 mol%間調(diào)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，

本文編號：1375984