~(13)C-NMR研究高效载体催化剂丙烯立体定向聚合反应机理

<正> 自从用C-NMR技术对聚丙烯进行测定,得到了分辨力良好的聚丙烯甲基碳区域的核磁共振谱后,引起了聚丙烯研究者的极大兴趣,迅速开展了应用核磁共振技术来研究聚丙烯分子链的构型和立体定向聚合机理,众所周知,用不同催化剂体系进行丙烯聚合,得到的聚合物链结构不同,聚合机理也有所差别。Zambelli等认为用Ziegler-Natta型催化剂体系聚合得到的聚丙烯,其聚合机理属于催化剂活性中心控制的单活性中心模型。Yoshio Inoue等用TiCl_4/MgCl_2/C_6H_5COOC_2H_5-AlEt_3 催化剂体系进行丙烯聚合,     

丙烯聚合络合催化剂形成过程的研究

以倍半物为还原剂还原TiCl_4,经异戊醚络合处理,然后在TiCl_4己烷溶液中35℃条件下热处理,制得对丙烯聚合具有高活性和高定向度的络合催化剂。研究了制备过程中各步反应产物的组成和结构特征,并讨论了TiCl_3低温晶型转变机理。     

一种复合载体丙烯聚合催化剂的研究

采用SiO2-MgCl2复合载体制备了一种丙烯聚合催化剂,考察了SiO2活化条件、SiO2和MgCl2质量比和催化剂的不同制备工艺对催化剂性能的影响,通过对催化剂的氢调和聚合时间的试验,发现该催化剂用于催化丙烯聚合时,无需加入外给电子化合物就可以使树脂达到较高的等规指数。     

STUDIES ON TiCI4/Mg (OEt)_2/EB SUPPORTED CATALYSTS FOR PROPYLENE POLYMERIZATION

The supported catalysts for propylene polymerization were prepared by milling Mg (OEt)_2 with EB (ethylbenzoate) and treating with TiCl_4 solution. When TiCl_4/(Mg(OEt)_2/EB) (mol.) ratio was increased, decrease in contents of-OEt and Ti of the catalysts was observed, while the content of EB increased. It is proved by analyses of IR, X-ray and XPS that during co-milling Mg(OEt)_2 with EB no reactions have taken place. But after treatment with TiCl_4 solution, Mg(OEt)_2 converts into MgCl_2 and EB coordinates on the resulting MgCl_2 carrier, a surface complex forms.The activity of catalysts,isotacticity and vicosimetric molecular weight of polypropylene increase with the decrease of the content of ethoxyl group. The kinetic curves of propene polymerization obtained with present catalysts system display decay curves. It is found from the triad tacticity calculated from the expanded spectra of methyl carbon region that, ethoxyl group in catalyst has an effect on the configuration of polymer chain.     

NdCl_3/MgCl_2 BISUPPORTED CATALYST FOR OLEFIN POLYMERIZATION

The NdCl_3/MgCl_2 bisupported catalyst was prepared by using NdCl_3 ,MgCl_2, (CH_3)_2(CH_2)_2 OH and TiCl_4. It is shown that the structure of bisupported catalyst was different from those of either NdCl_3 or MgCl_2 single supported catalyst. A peculiar type of kinetic curve for ethylene polymerization was found.     

混合外给电子体环己基甲基二甲氧基硅烷/二苯基二氯硅烷对丙烯聚合的影响

The effect CMMS (cyclohexylmethyl dimethoxysilane/DPCS (diphenyl dichloridesilane) as electron donor on the polymerization of propene was discussed. The solvent polymerization of propene was carried out in 60 ℃ at 1. 04×10⁵ Pa. It was found that the catalyst activity has gone up by 20 per cent when CMMS/DPCS=1/3 under the given condition . The concentration of active titanium center (C) was determined with kinetic-molecular weight method. It turns out that the active titanium centers do not increase by using mixedelectron donor CMMS/DPCS as compare with CMMS as electron donor but can increase Kp by 20% In addition,average-chain length can be achieved in five minutes with CMMS/DPCS.So polymer isotacticity index does not change with the time of polymerization.     

α-烯烃聚合高效催化剂

自从50年代Ziegler-Natta催化剂问世,开拓了高分子合成的新领域以来,国外对烯烃配位聚合的研究非常活跃。经过30多年的发展,用Ziegler-Natta催化剂和配位聚合方法合成的各种聚烯烃树脂已成为当前世界上比例最大的高分子产品。近年来,由于催化剂制备技术和聚合工艺不断改进,聚烯烃工业得到迅速发展,而且催化     

MgBu_2/AlEt_2Cl为助催剂的钛催化剂上丙烯聚合动力学——Ⅰ.烷基金属浓度的影响

烯烃聚合催化剂种类繁多,改变金属离子或配位体能得到性能不同的烯烃聚合催化剂.可供选择的助催化剂主要有烷基铝,烷基氯化铝,铝氧烷和Cp_2MtMe化合物等(Mt=Ti,V,Zr,Hf).有实用价值的助催化剂只有烷基铝或烷基氯化铝.对丙烯聚合非载体钛系催化剂而言,AlEt_2Cl是较好的助催化剂,而对载体型MgCl_2/TiCl_4钛系催化剂,较好的助催化剂则是AlEt_3.如果将MgBu_2与AlEt_2Cl的混合物用     

给电子体在丙烯聚合MgCl_2载体催化剂体系中的作用

研究了不同给电子体分别作为内给电子体(D_(in))和外给电子体(D_(ex))对MgCl_2载体催化剂体系活性和定向性能的影响。还讨论了D_(in)和D_(ex)的搭配作用。烷氧基硅烷、苯甲酸乙酯(EB)、邻苯二甲酸二异丁酯(DIBP)和2,2,6,6-四甲基哌啶(TMP)用作Dex,可以明显改善聚丙烯的等规度,而同时使催化活性大大降低。EB、DIBP和TMP用作D_(in)的效果则各不相同。烷氧基硅烷等D_(ex)提高等规度的作用是由于它们选择性地使无规活性中心失活大大高于等规活性中心。适当的D_(in)和D_(ex)搭配,可以获得兼具高活性和高定向性能的催化剂体系。