权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Tandem catalysis using group 5 and 6 imido complexes and group 4 permethylindenyl catalysts

使用第 5 族和第 6 族亚氨基配合物和第 4 族全甲基茚基催化剂的串联催化

基本信息

批准号：
1811574
负责人：
金额：
--
依托单位：
University of Oxford
依托单位国家：
英国
项目类别：
Studentship
财政年份：
2016
资助国家：
英国
起止时间：
2016 至无数据
项目状态：
已结题

来源：
https://gtr.ukri.org/projects?ref=studentship-1811574
关键词：
Tandem catalysis using group imido

项目摘要

Complexes known as constrained geometry catalysts (CGC) of the form R2Si(C5R'4)(R''N)MX2 are of great interest for the synthesis of polyethylene; both industrially and scientifically. Furthermore, in recent years, the O'Hare group have synthesised a number of novel metallocenes based on group 4 permethylindenyl (I*) complexes for use as ethylene polymerisation catalysts.Ethylene oligomerisation, generating higher alpha-olefins from ethylene, is as the forefront of industrial research. This includes the Dimersol, Alphabutol and Phillips trimerisation processes. Work within the O'Hare group has shown that tungsten imido complexes to be extremely active and selective towards the ethylene dimerisation to 1-butene in both the solution and slurry phase. Recently niobium imido complexes of the form Nb(CHSiMe3)(NAr)(OC(CF3)3)(PMe3)2 (Figure 2(b)) were found to be active towards the ring opening metathesis polymerisation of norbornene.Tandem catalysis involves the cooperative action of two or more catalysts to afford a product that is not accessible by the individual catalyst alone. There have been a number of reported tandem catalytic systems reported in the literature, both in solution, and more recently in the heterogeneous phase. Karbach and co-workers developed a silica-supported system that allowed incorporation of 1-hexene into at polymer chain.Ethylene polymerisation catalysts - the aim of this part of the project is to synthesise new group 4 constrained geometry I* complexes of the general formula R12SB(R2N,I*)MX2 with intention of developing them into commercial viable ethylene polymerisation catalysts. Ethylene oligomerisation catalysts - the aims of this project include the synthesis of niobium and tantalum imido complexes of the form M(NAr)Cl3.THF, M(NAr)Me2Cl and the solid supported equivalents. These complexes will then be developed into commercially viable ethylene oligomerisation catalysts for higher alpha-olefins, in particular 1-octene or 1-butene with high selectivity.Tandem catalysis - the final aim is to simultaneously support both an ethylene polymerisation and an oligomerisation catalyst on a solid support, such as polymethylaluminoxane, in order to form LLDPE from a single ethylene feed source.This project falls within the EPSRC Physical Sciences research area. In particular this project focuses on catalysis with the aim to develop new catalysts for ethylene polymerisation and oligomerisation.

R2Si(C5R'4)(R''N)MX2 形式的配合物，即约束几何催化剂 (CGC)，对于聚乙烯的合成具有重要意义；无论是工业上还是科学上。此外，近年来，奥黑尔集团合成了许多基于第4族全甲基茚基（I*）配合物的新型茂金属，用作乙烯聚合催化剂。乙烯齐聚，从乙烯生成高级α-烯烃，是工业研究的前沿。这包括 Dimersol、Alphabutol 和 Phillips 三聚工艺。奥黑尔小组的工作表明，亚氨基钨配合物在溶液和浆料相中对乙烯二聚成 1-丁烯都具有极高的活性和选择性。最近发现 Nb(CHSiMe3)(NAr)(OC(CF3)3)(PMe3)2 (图 2(b)) 形式的铌亚氨基配合物对降冰片烯的开环易位聚合具有活性。串联催化涉及两种或多种催化剂的协同作用，以提供单独催化剂无法获得的产物。文献中已经报道了许多串联催化系统，无论是在溶液中，还是最近在多相中。 Karbach和同事开发了一种二氧化硅支撑的系统，可以将1-己烯掺入聚合物链中。乙烯聚合催化剂——该项目这部分的目的是合成通式R12SB(R2N,I*)MX2的新第4族约束几何I*配合物，旨在将其开发成商业上可行的乙烯聚合催化剂。乙烯低聚催化剂 - 该项目的目标包括合成 M(NAr)Cl3.THF、M(NAr)Me2Cl 形式的铌和钽亚氨基配合物以及固体负载的等效物。然后，这些配合物将被开发成商业上可行的乙烯低聚催化剂，用于高选择性的高级α-烯烃，特别是1-辛烯或1-丁烯。串联催化-最终目标是在固体载体（例如聚甲基铝氧烷）上同时负载乙烯聚合和低聚催化剂，以便由单一乙烯进料源。该项目属于 EPSRC 物理科学研究领域。该项目特别关注催化，旨在开发用于乙烯聚合和低聚的新型催化剂。