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1.
Unmodified and SiCl4-modified spherical zirconia-supported methylaluminoxane were used as cocatalyst for propylene polymerization as well as ethylene/1-hexene copolymerization in combined with Me2Si(η3-C13H8)(η1-NtBu)TiMe2 (1) at 0 °C. The modification with SiCl4 improved the catalytic activity. The improvement was clearer in ethylene/1-hexene copolymerization than in propylene polymerization. The number average molecular weight (Mn) of polypropylenes increased linearly against the polymerization time regardless the cocatalyst used to give polymers with narrow molecular weight distribution (Mw/Mn < 1.32), indicating the living nature of the catalytic systems. Thus, propagation rate constant (kp) and the number of active centers (C*) were evaluated from Mn and the number of polymer-chains. When the zirconia was modified with SiCl4, the kp value decreased and the C* increased. The latter effect was more significant to enhance the catalytic activity.  相似文献   
2.
报道了3个β-羟亚胺配体(2,6-emPr2C6H3)N=C(Ph)CH2CH(Ph)OH(1a), (2,6-emPr2C6H3)N=C·(Ph)CH2C(Ph)2OH(1b)和(2,6-emPr2C6H3)N=C(Ph)CH2C(C12H8)OH(1c)及其二(β-羟亚胺)二氯化钛配合物[(2,6-emPr2C6H3)N=C(Ph)CH2CH(Ph)O]2TiCl2(2a), [(2,6-emPr2C6H3)N=C(Ph)CH2C(Ph)2O]2·TiCl2(2b)和[(2,6-emPr2C6H3)N=C(Ph)CH2C(C12H8)O]2TiCl2(2c)的合成, 并对其结构进行了表征. 在助催化剂甲基铝氧烷(MAO)作用下, 以化合物2b为主催化剂, 研究了Al/Ti摩尔比、 反应时间、 温度和聚合压力等对乙烯聚合的影响, 发现该催化体系在较宽的反应条件下均可得到很高分子量的聚乙烯, 熔点均在140℃左右. 以化合物2a~2c为主催化剂对乙烯进行催化聚合, 发现在β碳位上取代基的立体位阻对催化剂活性有很大影响. 当化合物2b上引入2个苯基取代基时, 催化剂显示出最佳催化活性.  相似文献   
3.
由五甲基单茂钛化合物Cp TiL3 和甲基铝氧烷 (MAO)组成的催化体系进行丁二烯聚合 .考察具有不同辅助配体L的主催化剂Cp TiL3 及外加三异丁基铝 (TIBA)对聚合的选择性 ;讨论了聚合温度、AlMAO Ti摩尔比和催化剂浓度对聚合反应的影响 .发现外加适量TIBA有助于提高催化活性 ,而且随着TIBA用量的增加聚丁二烯分子量增加 .结合钛氧化态分析 ,说明催化体系中Ti(Ⅲ )活性中心更有利于丁二烯聚合  相似文献   
4.
A series of unsymmetrical complexes of 2,3-bis(2-phenylphenyl)-butanediimine nickel(II) dibromide (complex 1), 1,4-bis(2-isopropyl-6-methylphenyl)-acenaphthenediimine nickel(II) dibromide (complex 2) and meso- and rac-1,4-bis (2,4-di-tert-butyl-6-methylphenyl)-acenaphthenediimine nickel(II) dibromide (meso-3 and rac-3) were synthesized and activated by methylaluminoxane (MAO) for ethylene polymerization. By 13C NMR characterization, meso- and rac-stereo-isomers were detected in the condensation products resulting from the reaction of unsym-substituted anilines with diketones. It was notable that meso- and rac-isomers in ligand 1 or ligand 2 could not be separated owing to their interconversion, however, meso- and rac-isomers in ligand 3 could be isolated and identified by X-ray diffraction and NMR analysis. At low polymerization temperatures, complex 1/MAO afforded polyethylene with bimodal molecular weight distribution, while complex 2/MAO prepared polyethylene with single-modal distribution. Moreover, by raising polymerization temperature or extending time of catalyst aging, bimodal molecular weight distribution polyethylene was also produced by complex 2/MAO. The hypothesis of bimodal molecular weight distribution polyethylene synthesized by unsymmetrical α-diimine nickel(II) complexes was supported that the molecular weight of polyethylene produced by rac-3/MAO was significantly higher than that produced by meso-3/MAO under identical polymerization conditions. A unique methodology to prepare polyethylene with bimodal molecular weight distribution was demonstrated.  相似文献   
5.
A sterically hindered metallocene catalyst, Cp ZrCl2 activated with methylaluminoxane (MAO), is found to polymerize ethene at temperatures up to 60° with a good propagation rate constant but low number of active sites, and with negligible β‐hydride elimination or β‐hydride transfer to monomer. Moreover, transmetalation to Al is found to be effectively irreversible for alkyl groups larger than Me. With the major mechanisms for chain transfer and termination suppressed, one might expect a living polymerization. The bulk polymerization of ethene was indeed found to be quasi‐living even when performed at well above room temperature, and furthermore provided rate constants which agreed remarkably well with those from the mass‐spectrometric study.  相似文献   
6.
杨敏  刘宾元 《高分子科学》2016,34(3):298-306
Tandem catalytic systems, consisting of ethylene bis(indenyl) zirconium dichloride with two different cocatalysts, alkylaluminum(diethylaluminium chloride or trialkylaluminum) and methylaluminoxane, were employed in preparing branched polyethylene from ethylene as sole monomer. The catalytic system rac-Et(Ind)2Zr Cl2/Al Et2Cl/MAO exhibited high incorporation(29.0/1000C). The oligomerization and copolymerization reaction conditions in the tandem catalytic system, as well as the different cocatalysts, have effects on the catalytic activity and the properties of the obtained polymer, such as melting temperature, crystallinity, molecular weight and molecular weight distribution. Moreover, the oligomerization reaction condition is the main factor in altering the properties and structures of polyethylene.  相似文献   
7.
用密度泛函理论对[(AlOMe)2]n、[(AlOMe)3]n和[(AlOMe)4]n (n=1~10)作为重复单元组成的甲基铝氧烷(MAO)纳米管进行了研究,计算了其所有体系的结合能和总能量.结果表明,[(AlOMe)3]n和[(AlOMe)4]n具有稳定的纳米管结构,在所有研究系统中n=3时具有最稳定的结构.考察发现,[(Al5O5)]n和[(Al7O7)]n两种结构的二聚体具有无规则、扭曲的结构,不能继续增长形成纳米管结构.  相似文献   
8.
β 二酮钛配合物/甲基铝氧烷催化体系用于苯乙烯的间规聚合许学翔谢光华(中国科学院化学研究所北京100080)关键词β 二酮钛配合物,苯乙烯,甲基铝氧烷,间规聚合苯乙烯聚合物可分为无规聚苯乙烯(a PS),等规聚苯乙烯(i PS),间规聚苯乙烯(s?..  相似文献   
9.
8 羟基喹啉钛配合物/甲基铝氧烷催化体系用于苯乙烯的间规聚合许学翔周鼐谢光华(中国科学院化学研究所北京100080)关键词8 羟基喹啉钛配合物,苯乙烯,甲基铝氧烷,间规聚合自日本学者Ishihara[1]发现单茂钛CpTiCl3在甲基铝氧烷(M...  相似文献   
10.
采用茂钛配合物五甲基茂基三(对氯苯氧基)钛[Cp- Ti(O- C6H4Cl -P)3]甲基铝氧烷(MAO)体系进行丙烯聚合反应,考察了聚合温度和Al- Ti摩尔比(nAl- nTi)对聚合活性和产物分子量的影响.研究发现在合适的聚合条件下,聚合初期产物的分子量随聚合时间线性增大,并保持较窄的分子量分布(Mw Mn=1.5~1.8),表现出准活性聚合的行为,而聚合物的GPC曲线呈双峰分布,表明聚合初期的体系存在多活性中心.另外,初步提出了衰减动力学方程以探讨聚合速率衰减期的丙烯聚合反应规律,求出了不同条件下丙烯聚合的衰减系数,从而可计算出衰减期内任一时间的丙烯聚合速率.  相似文献   
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