用高活性和高热稳定性吡啶亚胺钛络合物催化异戊二烯聚合  

Polymerization of isoprene catalyzed by high active and thermo-stable iminopyridine-titanium complexes

作　　者：张君花[1] 匡佳 王亮 梁红文[1] 王庆刚 ZHNAG Jun-hua;KUANG Jia;WANG Liang;LIANG Hong-wen;WANG Qing-gang(Baling Petrochemical Co Ltd,SINOPEC,Yueyang 414000,China;Qingdao Institute of Bioenergy and Bioprocess Technology,Chinese Academy of Sciences,Qingdao 266100,China)

机构地区：[1]中国石化巴陵石油化工有限公司,湖南岳阳414000 [2]中国科学院青岛生物能源与过程研究所,山东青岛266100

出　　处：《合成橡胶工业》2022年第4期271-275,共5页China Synthetic Rubber Industry

摘　　要：合成了一系列分子结构明确的吡啶亚胺钛络合物,通过核磁共振波谱、X-射线单晶衍射和元素分析对络合物的结构进行了表征,并将该类络合物作为主催化剂,以抽干的甲基铝氧烷作为助催化剂进行了异戊二烯聚合。结果表明,取代基给电子能力较强的吡啶亚胺钛络合物表现出高催化活性[6.3×10^(4) g/(mol·h)]、高选择性(顺式-1,4-结构选择性74%)以及优异的热稳定性(聚合温度可达90℃);取代基位阻增加会明显降低络合物的催化活性及聚合物的分子量和顺式-1,4-结构的选择性。吡啶亚胺钛络合物的配体结构对催化活性的影响较大,但对聚合物结构选择性的影响较小。A series of well-defined iminopyridine-titanium complexes were prepared and characterized by nuclear magnetic resonance spectroscopy,X-ray diffraction analysis and elemental analysis.Isoprene polymerization was carried out by using those complexes as main catalyst and dried methylaluminoxane as cocatalyst.The results showed that the iminopyridine-titanium complexes with strong electron-donating group possessed high activity(up to 6.3×10^(4) g/(mol·h)),high cis-1,4-unit selectivity(up to 74%)and excellent thermo-stability(up to 90℃).The increased steric hindrance of substituent groups would significantly reduce the catalytic acti-vity,molecular weight and cis-1,4-unit selectivity.These results indicated that the ligand structure had more effects on activity than stereo-selectivity.

关 键 词：吡啶亚胺钛络合物 顺式聚异戊二烯 催化活性 选择性 热稳定性 

分 类 号：TQ333.3[化学工程—橡胶工业]