非均相聚合制备超高分子质量乙烯/十一烯醇共聚物
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摘要
与均相催化剂相比,负载型催化剂能够有效控制产物形态和聚合活性。以2,7-叔丁基芴基胺基二甲基钛[t-BuNSiMe_2(2,7-di-t-BuFlu)TiMe_2]为催化剂、改性甲基铝氧烷/二氧化硅(MMAO/SiO_2)为负载、乙烯和10-十一烯-1-醇为单体,制备了一系列超高分子质量乙烯/十一烯醇共聚物。研究结果表明:控制聚合活性在1000～2000 kg/(mol·h)时,可得到形态均一、稳定的超高分子质量聚乙烯共聚物颗粒,共单体插入率最高达5.3%;同时,共聚物有着不错的结晶度。
Compared to homogeneous catalyst,the supported catalyst can control morphology and polymerization activity effectively. The ultra-high molecular weight ethylene/10-undecene-1-ol copolymer was synthesized by using complexes t-BuNSiMe_2(2,7-di-t-BuFlu) TiMe_2 as the catalyst, modified methyaluminoxane/silica (MMAO/SiO_2) as the support. The results showed that the ethylene copolymer particles with uniform morphology were obtained with the insertion ratio up to 5.3%, where polymerization activity was 1000～2000 kg/(mol·h), and it's crystallinity was good.
Compared to homogeneous catalyst,the supported catalyst can control morphology and polymerization activity effectively. The ultra-high molecular weight ethylene/10-undecene-1-ol copolymer was synthesized by using complexes t-BuNSiMe_2(2,7-di-t-BuFlu) TiMe_2 as the catalyst, modified methyaluminoxane/silica (MMAO/SiO_2) as the support. The results showed that the ethylene copolymer particles with uniform morphology were obtained with the insertion ratio up to 5.3%, where polymerization activity was 1000～2000 kg/(mol·h), and it's crystallinity was good.
引文
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[3]杨敏,王路海,刘盘阁,等.紫外-可见光谱对β-二酮锆烯烃催化活性中心的研究[J].光谱学与光谱分析,2010(6):1566-1569.
[4]ZHANG He-xin,SHIN Young-jun,LEE Dong-ho,et al.Preparation of ultra high molecular weight polyethylene with MgCl2/TiCl4catalyst:effect of internal and external donor on molecular weight and molecular weight distribution[J].Polymer Bulletin,2011,66(5):627-35.
[5]KISHOR R,PADMANABHAN S,SARMA KR,et al.Correlation of arrhenius parameters for UHMWPE synthesis with ethylene solubility characteristics in different polymerization media[J].Journal of Applied Polymer Science,2011,122(4):2646-2652.
[6]TALEBI S,DUCHATEAU R,RASTOGI S,et al.Molar mass and molecular weight distribution determination of UHMWPE synthesized using a living homogeneous catalyst[J].Macromolecules,2010,43(6):2780-2788.
[7]KARBACH FF,MACKO T,DUCHATEAU R.Preparation of ethylene/1-hexene copolymers from ethylene using a fully silica-supported tandem catalyst system[J].Macromolecules,2016,49(4):1229-1241.
[8]许波,孙延杰,杜飞瀑,等.桥联环戊二烯金刚烷氨基二甲基钛配合物的合成及其催化丙烯聚合[J].应用化学,2015,32(9):1028-1032.
[9]袁浩波.改性UHMWPE的制备及其纤维性能研究[D].上海:东华大学,2017.
[10]马琼,GRUBBS Robert B,蔡正国.超高相对分子质量乙烯/1-十二烯共聚物的合成[J].合成纤维,2017,46(4):1-4.
[11]CAI Z,IKEDA T,AKITA M,et al.Substituent effects of tert-butyl groups on fluorenyl ligand in syndiospecific living polymerization of propylene with ansa-fluorenylamidodimethyltitanium complex[J].Macromolecules,2005,38(20):8135-8139.