单茂钪催化非共轭双烯环化聚合及与乙烯共聚合的研究  

Cyclopolymerization of Non-conjugated α,ω-Dienes and Copolymerization with Ethylene by Scandium Complex

作　　者：郭方[1] 孟蕊[1] 史正海[1] 谭睿[1] 

机构地区：[1]大连理工大学化工学院高分子材料系精细化工国家重点实验室,大连116024

出　　处：《高分子学报》2014年第9期1219-1227,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号21204008);中国博士后科学基金(基金号2012M520614)资助项目

摘　　要：以(C5Me4SiMe3)Sc(CH2C6H4NMe2-o)2和[Ph3C][B(C6F5)4]组成的单茂钪催化体系催化非共轭双烯均聚合及与乙烯共聚合,考察了聚合条件及非共轭双烯结构对聚合活性、产物分子量和微结构的影响.单茂钪催化体系中,单体浓度、聚合温度、聚合溶剂以及烷基铝试剂对1,5-己二烯的聚合活性和选择性以及聚合产物的分子量和分子量分布均有较大影响.室温甲苯溶剂中,单茂钪可以催化1,5-己二烯,1,6-庚二烯,1,7-辛二烯,1,9-癸二烯四种非共轭双烯聚合获得相应的聚合物;除1,9-癸二烯聚合获得不溶的交联聚合物外,其它非共轭双烯聚合均获得可溶的环烯烃聚合物.1,5-己二烯聚合形成亚甲基-1,3-环戊基(MCPN)五元环和四元环开环形成的3-乙烯基四亚甲基(VTM)结构单元.1,6-庚二烯聚合完全环化形成亚甲基-1,3-环己基(MCHX)六元环和乙烯基-1,2-环戊基(ECPN)五元环结构单元,1,7-辛二烯聚合形成亚甲基-1,3-环庚基(MCHP)七元环结构单元和未环化的悬挂己烯(HEB)结构单元.室温1.01×105Pa乙烯压力下,单茂钪催化体系还可以快速催化非共轭双烯1,5-己二烯,1,6-庚二烯,1,7-辛二烯,1,9-癸二烯与乙烯共聚合,获得含有环状结构单元、悬挂双键结构单元和聚乙烯嵌段的无规共聚物.在单茂钪催化非共轭双烯均聚合及与乙烯共聚合中,非共轭双烯的链长直接影响了其聚合活性和选择性.The cyclopolymerization of non-conjugated α,ω-dienes such as 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene and 1,9-deeadiene and their copolymerization with ethylene by scandium complex [ （ C5 Me, SiMe3 ） Sc （ CH2 C6 H, NMe2-o ） 2/[ Ph3 C ] [ B （ C6 F5 ）4 ] ] have been examined. Polymerization conditions and the structure of non-conjugated α,ω-dienes have an important influence on the catalytic activity and selectivity,polymer products molecular weight and molecular weight distribution. Except for 1,9-deeadiene homopolymer which is an insoluble cross-linked polymer, the homopolymerization of 1,5-hexadiene, 1,6- heptadiene, and 1,7-octadiene has been achieved to affords soluble eyclopolymers materials. Under the optimum conditions, the homopolymerization of 1,5-hexadiene affords eyclopolymers containing methylene-1,3- cyclopentane （MCPN, 83% ） units and 3-vinyltetramethylene （VTM, 17% ） units. In the case of 1,6- heptadiene homopolymerization, a soluble cyclopolyolefin containing both six-member ring methylene-l, 3- cyelohexane （ MCHX, 91% ） units and five-member ring ethylene-1,2-cyclopentane （ ECPN, 9% ） units is obtained. However, the homopolymerization of 1,7-octadiene afford a homopolymer containing seven-member ring methylene-I, 3-cycloheptane （MCHP, 57% ） units and non-cyclic pendent double bond units （HEB, 43% ）. By use of this scandium catalyst, the copolymerization of non-conjugated a, o^-dienes such as 1,5- hexadiene,1,6-heptadiene,1,7-octadiene and 1,9-decadiene with ethylene （1.01 × 10 5 Pa） has also been achieved to afford relatively high molecular weight novel cyelocopolymer materials that contain polyethylene units,cyclic structure units or non-cyclic pendent double bond units. In the same eopolymerization conditions, 1,5-hexadiene and 1,6-heptadiene polymerization form cyclic structure units, while the 1,7-octadiene and 1,9-decadiene polymerization form non-cyclic pendent double bond units. The incorporation of 1,5-hexadiene or l ,6-hept

关 键 词：钪 非共轭双烯 乙烯 聚合 

分 类 号：O631.5[理学—高分子化学]