稀土催化乙烯与极性烯烃共聚合研究  

Copolymerization of Ethylene and Polar Vinyl Monomers by Rare-earth Metal Catalysts

作　　者：梁旦 姜洋 李世辉[1,2] 崔冬梅 Dan Liang;Yang Jiang;Shi-hui Li;Dong-mei Cui(State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022;School of Applied Chemistry and Engineering,University of Science and Technology of China,Hefei 230026)

机构地区：[1]中国科学院长春应用化学研究所高分子物理与化学国家重点实验室,长春130022 [2]中国科学技术大学应用化学与工程学院,合肥230026

出　　处：《高分子学报》2024年第11期1487-1494,共8页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号52073275,U23B6011,U21A20279,22331010)资助项目.

摘　　要：考察了(Flu-CH_(2)-Ph)Sc(CH_(2)SiMe_(3))_(2)(THF)(1)、(Flu-CH_(2)-C_(5)H_(4)N)Sc(CH_(2)SiMe_(3))_(2)(2)、(Flu-CH_(2)CH_(2)-NHC-C_(6)H_(2)Me_(3)-2,4,6)Sc(CH_(2)SiMe_(3))_(2)(3)、(Flu-CH_(2)CH_(2)-NHC-C_(6)H_(4)Me)Sc(CH_(2)SiMe_(3))_(2)(4)空间位阻大小不等的4种稀土催化剂,对乙烯与1.1倍摩尔量AliBu3保护的5-己烯-1-醇(M2)的共聚合行为.其中,催化剂1的催化活性最高,达到1.32×10^(6) g·mol_(Sc)^(-1)·h^(-1),但产生的是乙烯均聚物,催化剂2无催化活性,催化剂3和4的活性分别为0.38×10^(6)和1.24×10^(6) g·mol_(Sc)^(-1)·h^(-1),生成了M2插入率分别为0.7 mol%和1.8 mol%的共聚物.对不同烷烃链长间隔的极性烯烃单体,催化剂4对9碳烷烃间隔的10-十一烯-1-醇(M3)与乙烯共聚合活性最高(1.19×10^(7)g·mol_(Sc)^(-1)·h^(-1))、共聚能力最强(M3插入率为4.9 mol%).系统研究了极性单体M3浓度、聚合温度、乙烯压力等,对催化剂4催化乙烯与M3共聚合活性及其插入率的影响规律.通过NMR、GPC和DSC对所得的乙烯-极性烯烃共聚物进行了微观结构、热性能分析.The copolymerization of ethylene and 5-hexen-1-ol(M2)masked by 1.1 equivalents of AliBu3 is carried out by four rare-earth metal catalysts bearing different steric hindrances:(Flu-CH_(2)-Ph)Sc(CH_(2)-SiMe_(3))_(2)(THF)(1),(Flu-CH_(2)-C_(5)H_(4)N)Sc(CH_(2)SiMe_(3))_(2)(2),(Flu-CH_(2)CH_(2)-NHC-C_(6)H_(2)Me_(3)-2,4,6)Sc(CH_(2)SiMe_(3))_(2)(3),(Flu-CH_(2)CH_(2)-NHCC_(6)H_(4)Me)Sc(CH_(2)SiMe_(3))_(2)(4).Among them,complex 1 shows the highest catalytic activity(1.32×10^(6) g·mol_(Sc)^(-1)·h^(-1))but gives pure polyethylene without detectable M2 unit,and,in contrast,complex 2 is nearly inert.Under same conditions,the bulkier complex 3 shows moderate activity(0.38×10^(6) g·mol_(Sc)^(-1)·h^(-1))and low comonomer incorporation(0.7 mol%).On switching to the bulkiest complex 4,the copolymerization process is obviously promoted with a catalytic activity of 1.24×10^(6) g·mol_(Sc)^(-1)·h^(-1) and generates a copolymer with 1.8 mol%M2.For the polar vinyl monomers having different CH_(2) spacers between polar and vinyl groups,complex 4 exhibits the best catalytic performance for the copolymerization of ethylene with 10-undecene-1-ol with the highest catalytic activity(1.19×10^(7) g·mol_(Sc)^(-1)·h^(-1))and the strongest incorporation ability(4.9 mol%).The influence of reaction conditions such as comonomer concentration,polymerization temperature and ethylene pressures on the catalytic performance of complex 4 are screened.The microstructures and thermal properties of the resultant copolymers are well-characterized by nuclear magnetic resonance(NMR),gel permeation chromatography(GPC)and differential scanning calorimeter(DCS).

关 键 词：稀土 极性单体 共聚合 功能化聚烯烃 乙烯 

分 类 号：TQ325.1[化学工程—合成树脂塑料工业] TQ316.314