公开(公告)号：US09266982B2

公开(公告)日：2016-02-23

申请号：US13991044

申请日：2011-12-01

申请人： Jun Liu ,  Mingfang Zheng ,  Weizhen Li ,  Haiying Zhang ,  Huaijie Wang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Hongfei Wu ,  Mingjun Xie ,  Chunhong Wu ,  Zhiguang Jia ,  Yanping Qi ,  Jilong Wang

发明人： Jun Liu ,  Mingfang Zheng ,  Weizhen Li ,  Haiying Zhang ,  Huaijie Wang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Hongfei Wu ,  Mingjun Xie ,  Chunhong Wu ,  Zhiguang Jia ,  Yanping Qi ,  Jilong Wang

IPC分类号： C07D471/04 ,  C07D211/70 ,  C07D211/82 ,  C07D213/46 ,  C08F110/02 ,  B01J31/18 ,  C07C2/32 ,  C07D213/127 ,  C07F15/02

CPC分类号： C08F110/02 ,  B01J31/183 ,  B01J2231/20 ,  B01J2531/0241 ,  B01J2531/842 ,  C07C2/32 ,  C07D213/127 ,  C07D471/04 ,  C07F15/025 ,  C07C11/02

摘要： Provided are a process for preparing an N ortho acyl substituted nitrogen-containing heterocyclic compound and an aminal iron (II) complex thereof, and the use of the complexes obtained by the process in an olefin oligomerization catalyst. The N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is for example 2-acyl-1,10-phenanthroline or 2,6-diacetyl pyridine as shown in formula b, and the N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is produced by a reaction of a precursor thereof in a substituted or unsubstituted nitrobenzene. Preferably the precursor shown in formula I in the present invention is produced by 1,10-phenanthroline reacting with trialkyl aluminum, or a halogenoalkyl aluminum RnAIXm, or a substituted or unsubstituted benzyl lithium Ph′CH2Li, followed by hydrolysis. The preparation method provided in the present invention has a few synthetic steps, an easy process, a low toxic effect, and reduces the preparation costs of the catalyst, and has a promising outlook in the industrial application.

摘要翻译： 提供了制备N-邻酰基取代的含氮杂环化合物和其亚胺铁（II）络合物的方法，以及通过该方法在烯烃低聚催化剂中获得的络合物的用途。 本发明中的N-邻酰基取代的含氮杂环化合物例如如式b所示的2-酰基-1,10-菲咯啉或2,6-二乙酰基吡啶，并且N-邻酰基取代的含氮杂环化合物 在本发明中通过其前体在取代或未取代的硝基苯中的反应来制备。 优选地，本发明中式I所示的前体是通过与三烷基铝或卤代烷基铝RnAIXm或取代或未取代的苄基锂Ph'CH2Li反应的1,10-菲咯啉然后水解制备的。 本发明提供的制备方法具有几个合成步骤，易操作，低毒性，降低催化剂的制备成本，在工业应用前景看好。

公开(公告)号：US20130267708A1

公开(公告)日：2013-10-10

申请号：US13991044

申请日：2011-12-01

申请人： Jun Liu ,  Mingfang Zheng ,  Weizhen Li ,  Haiying Zhang ,  Huaijie Wang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Hongfei Wu ,  Wingjun Xie ,  Chunhong Wu ,  Zhiguang Jia ,  Qi Yanping ,  Jilong Wang

发明人： Jun Liu ,  Mingfang Zheng ,  Weizhen Li ,  Haiying Zhang ,  Huaijie Wang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Hongfei Wu ,  Wingjun Xie ,  Chunhong Wu ,  Zhiguang Jia ,  Qi Yanping ,  Jilong Wang

IPC分类号： C08F110/02

CPC分类号： C08F110/02 ,  B01J31/183 ,  B01J2231/20 ,  B01J2531/0241 ,  B01J2531/842 ,  C07C2/32 ,  C07D213/127 ,  C07D471/04 ,  C07F15/025 ,  C07C11/02

摘要： Provided are a process for preparing an N ortho acyl substituted nitrogen-containing heterocyclic compound and an aminal iron (II) complex thereof, and the use of the complexes obtained by the process in an olefin oligomerization catalyst. The N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is for example 2-acyl-1,10-phenanthroline or 2,6-diacetyl pyridine as shown in formula b, and the N ortho acyl substituted nitrogen-containing heterocyclic compound in the present invention is produced by a reaction of a precursor thereof in a substituted or unsubstituted nitrobenzene. Preferably the precursor shown in formula I in the present invention is produced by 1,10-phenanthroline reacting with trialkyl aluminum, or a halogenoalkyl aluminum RnAlXm, or a substituted or unsubstituted benzyl lithium 2Li, followed by hydrolysis. The preparation method provided in the present invention has a few synthetic steps, an easy process, a low toxic effect, and reduces the preparation costs of the catalyst, and has a promising outlook in the industrial application.

摘要翻译： 提供了制备N-邻酰基取代的含氮杂环化合物和其亚胺铁（II）络合物的方法，以及通过该方法在烯烃低聚催化剂中获得的络合物的用途。 本发明中的N-邻酰基取代的含氮杂环化合物例如如式b所示的2-酰基-1,10-菲咯啉或2,6-二乙酰基吡啶，并且N-邻酰基取代的含氮杂环化合物 在本发明中通过其前体在取代或未取代的硝基苯中的反应来制备。 优选地，本发明中式I所示的前体是通过与三烷基铝或卤代烷基铝RnAlXm或取代或未取代的苄基锂2Li反应的1,10-菲咯啉然后水解制备的。 本发明提供的制备方法具有几个合成步骤，易操作，低毒性，降低催化剂的制备成本，在工业应用前景看好。

公开(公告)号：US20130018214A1

公开(公告)日：2013-01-17

申请号：US13637976

申请日：2011-03-30

申请人： Mingfang Zheng ,  Weizhen Li ,  Huaijie Wang ,  Jun Liu ,  Haiying Zhang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Jilong Wang ,  Hongfei Wu ,  Yuling Piao ,  Junlong Sui

发明人： Mingfang Zheng ,  Weizhen Li ,  Huaijie Wang ,  Jun Liu ,  Haiying Zhang ,  Yu Zhou ,  Tonglin Li ,  Lan Zhao ,  Jilong Wang ,  Hongfei Wu ,  Yuling Piao ,  Junlong Sui

IPC分类号： B01J31/12 ,  C07C2/26

CPC分类号： C08F10/02 ,  B01J31/143 ,  B01J31/183 ,  B01J2231/20 ,  B01J2531/842 ,  B01J2531/845 ,  B01J2531/847 ,  C07C2/32 ,  C07C2531/14 ,  C07C2531/22 ,  C08F110/02 ,  Y02P20/52 ,  C08F4/7042 ,  C08F2500/02 ,  C07C11/02 ,  C08F210/02

摘要： The present invention provides a catalyst composition for the ethylene oligomerization, which comprises 2-imino-1,10-phenanthroline coordinated iron (II), cobalt (II) or nickel (II) chloride as main catalyst and triethylaluminum as cocatalyst. The present invention also provides a process for oligomerization of ethylene is provided, wherein a catalyst composition comprising 2-imino-1,10-phenanthroline coordinated iron (II), cobalt (II) or nickel (II) chloride as main catalyst and triethylaluminum as cocatalyst is used, and the molar ratio of aluminum in the cocatalyst to central metal in the main catalyst ranges from 30 to less than 200. According to the present invention, another process for oligomerization of ethylene is also provided, wherein a catalyst composition comprising 2-imino-1,10-phenanthroline coordinated iron (II), cobalt (II) or nickel (II) chloride as main catalyst and triethylaluminum as cocatalyst is used, and the temperature of ethylene oligomerization ranges from −10 to 19° C. According to the present invention, the price of cocatalyst i.e. triethylaluminum, is low, just a fraction of that of methylaluminoxane, the amount of cocatalyst is therefore significantly reduced, with the catalytic activity is still acceptable, thus the cost of ethylene oligomerization is significantly reduced. In view of both the catalytic activity and the cost, the present invention is highly applicable in industry.

摘要翻译： 本发明提供了一种用于乙烯低聚的催化剂组合物，其包含2-亚氨基-1,10-菲咯啉配位的铁（II），钴（II）或氯化镍（II）作为主要催化剂，三乙基铝作为助催化剂。 本发明还提供了一种乙烯低聚方法，其中包含2-亚氨基-1,10-菲咯啉配位的铁（II），钴（II）或氯化镍（II）作为主要催化剂的催化剂组合物和三乙基铝作为 助催化剂，主催化剂中助催化剂与中心金属之间的铝的摩尔比为30至小于200.根据本发明，还提供了另一种乙烯低聚方法，其中催化剂组合物包含2 - 亚氨基-1,10-菲咯啉配位的铁（II），钴（II）或氯化镍（II）为主催化剂，三乙基铝为助催化剂，乙烯齐聚温度为-10〜19℃。 对于本发明，助催化剂即三乙基铝的价格低，仅仅是甲基铝氧烷的一部分，因此助催化剂的量显着降低，催化活性为 仍然是可接受的，因此乙烯低聚的成本显着降低。 鉴于催化活性和成本两方面，本发明在工业上是高度适用的。