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首页> 外文期刊>Journal of Polymer Science, Part A. Polymer Chemistry >Polymerizations of olefins and diolefins catalyzed by monocyclopentadienyltitanium complexes containing a (dimethylamino)ethyl substituent and comparison with ansa-zirconocene systems
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Polymerizations of olefins and diolefins catalyzed by monocyclopentadienyltitanium complexes containing a (dimethylamino)ethyl substituent and comparison with ansa-zirconocene systems

机译：含（二甲基氨基）乙基取代基的单环戊二烯基钛配合物催化的烯烃和二烯烃的聚合反应，以及与ansa-锆茂系统的比较

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摘要

{[2-(dimethylamino) ethyl]cyclopentadienyl} titanium trichloride ((CpTiCl3)-Ti-N, i) was activated with methylaluminoxane (MAO) to catalyze polymerizations of ethylene (E), propylene (P), ethylidene norbornene (ENB), vinylcyclohexene (VCH), and 1,4-hexadiene (HD). The dependence of homopolymerization activity (A) of 1/MAO on olefin concentration ([M](n)) is n = 2.0 +/- 0.5 for E and n = 1.8 +/- 0.2 for P. The value of n is 2.4 +/- 0.2 for CpTiCl3/MAO catalysis of ethylene polymerization; this system does not polymerize propylene. 1/MAO catalyzes HD polymerization at one-tenth of A(H) for l-hexene, probably because of chelation effects in the HD case. The copolymerization of E and P has reactivity ratios of r(E) = 6.4 and r(P) = 0.29 at 20 degrees C, and r(E)r(P) = 1.9, which suggests 1/MAO may be a multisite catalyst. The copolymerization activity of CpTiCl3/MAO is 50 times smaller than that of (CpTiCl3)-Ti-N/MAO. Terpolymerization of E/P/ENB has A of 10(5) g of polymer/(mel of Ti h), incorporates up to 14 mol % ( similar to 40 wt %) of ENB, and high MW's of 1 to 3 x 10(5). AU of these parameters are surprisingly insensitive to the ENB concentration. The E/P/VCH terpolymerization has comparable A value of (1.3 +/- 0.3) X 10(5) g/(mol of Ti h). The incorporation of VCH in terpolymer increases with increasing [VCH]. Terpolymerization with HD occurs at about one-third of the A of either ENB or VCH; the product HD-EPDM is low in molecular weight and contains less than 4% of HD. These terpolymerization results are compared with those obtained previously for three zirconocene precursors: rac-ethylenebis(1-eta(5)-indenyl)dichlorozirconium (6), rac-(dimethylsilylene)bis(1-eta(5)-indenyl)dichlorozirconium (7), and ethylenebis(9-eta(5)-fluorenyl) dichlorozirconium (8). The last compound is a particularly poor terpolymerization catalyst; it incorporates very Little VCH or HD and no ENB at all. 7/MAO is a better catalyst for E/P/VCH terpolymerization, while 6/MAO is superior in E/P/HD terpolymerization. (C) 1998 John Wiley & Sons, Inc. [References: 73]
机译：{[2-（二甲氨基）乙基]环戊二烯基}三氯化钛（（CpTiCl3）-Ti-N，i）用甲基铝氧烷（MAO）活化，以催化乙烯（E），丙烯（P），亚乙基降冰片烯（ENB）的聚合，乙烯基环己烯（VCH）和1,4-己二烯（HD）。 1 / MAO的均聚活性（A）对烯烃浓度（[M]（n））的依赖性对于E为n = 2.0 +/- 0.5，对于P为n = 1.8 +/- 0.2。n的值为2.4 CpTiCl3 / MAO催化的乙烯聚合反应为+/- 0.2;该系统不聚合丙烯。 1 / MAO催化1-己烯在A（H）的十分之一处催化HD聚合，这可能是由于HD情况下的螯合作用所致。 E和P的共聚反应在20摄氏度时的反应比为r（E）= 6.4和r（P）= 0.29，r（E）r（P）= 1.9，这表明1 / MAO可能是多位催化剂。 CpTiCl3 / MAO的共聚活性比（CpTiCl3）-Ti-N / MAO小50倍。 E / P / ENB的三元共聚物的A为10（5）g聚合物/（Ti h的熔融），掺入高达14 mol％（类似于40 wt％）的ENB，高分子量为1-3 x 10 （5）。所有这些参数都令人惊讶地对ENB浓度不敏感。 E / P / VCH三元聚合具有相当的A值（1.3 +/- 0.3）X 10（5）g /（Ti h摩尔）。 VCH在三元共聚物中的掺入量随[VCH]的增加而增加。与HD的三元聚合发生在ENB或VCH的A的大约三分之一处; HD-EPDM产品分子量低，且HD含量不足4％。将这些三元聚合结果与先前获得的三种锆茂前体的结果进行了比较：rac-乙烯双（1-eta（5）-茚基）二氯锆（6），rac-（二甲基亚甲硅烷基）双（1-eta（5）-茚基）二氯锆（ 7）和亚乙基双（9-eta（5）-芴基）二氯锆（8）。最后一种化合物是特别差的三元聚合催化剂。它集成了非常小的VCH或HD，完全没有ENB。 7 / MAO是E / P / VCH三元共聚物的较好催化剂，而6 / MAO在E / P / HD三元共聚物中是优良的。 （C）1998 John Wiley＆Sons，Inc. [参考：73]

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