Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof

A dual-nuclear chromium catalyst, ethylene oligomerization technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve harsh reaction conditions, poor catalyst activity, product Low purity and other problems, to achieve the effect of low polymer product content, long catalyst life and high catalyst activity

Active Publication Date: 2016-02-24
TIANJIN UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] Chromium catalysts disclosed so far in scientific and patent literature for ethylene trimerization or tetramerization usually have one or more of the following drawbacks: ① low product purity; ② polymer formation, which leads to reactor blockage, difficulty in continuous long cycle ③ Poor catalyst activity and high co-catalyst cost; ④ Harsh reaction conditions and high pressure required, resulting in high input, maintenance and energy costs; ⑤ Sensitive to changes in co-catalyst quality

Method used

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  • Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof
  • Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof
  • Dual-core chromium catalyst for ethylene oligomerization and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] 1. Preparation of 1,4,7,10-tetrakis(diphenylphosphineamine)-1,4,7,10-tetraazacyclododecane ligand (C 56 h 56 N 4 P 4 )

[0033] The structure of the ligand 1,4,7,10-tetrakis(diphenylphosphineamine)-1,4,7,10-tetraazacyclododecane is shown in the following structural formula:

[0034]

[0035] The preparation method is as follows:

[0036] in the N 2 Add dehydrated dichloromethane (20mL), triethylamine (3.75mL), and diphenylphosphine chloride (1.326mL, 7.2mmol) into a fully replaced stirred 100mL reactor, cool to 0°C, and slowly 1,4,7,10-Tetraazacyclododecane (1.75 mmol) was added. After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying afforded the product (1.18 g, 74.2%).

[0037] 1 HNMR (400MHz, CDCl 3 ):d=2.935-2.951(m,16H,(CH 2 ) 2 ),7.132-7.249(m,40H,P(Ph) 2 ); 13 C{ 1 H}NMR (100MHz, CDCl 3 ):d=139.82, 139.68, 131.88, 131.68, 128.42-128.12, 77.33-76.70.31 PNMR (121MHz, CDCl 3 )δ: 66.496.

...

Embodiment 2

[0043] Same as Example 1, except that the addition amount of 1.4 mol / L MAO in toluene solution is 1.7 mL. (2.4 mmol), 70°C. The catalyst activity is 2.28×10 6 g oligomer / molCr h. The distribution of the oligomerization products is shown in Table 1.

Embodiment 3

[0045] 1. Preparation of 1,5,8,12-tetrakis(diphenylphosphineamine)-1,5,8,12-tetraazacyclotetradecane ligand (C 58 h 60 N 4 P 4 )

[0046] The structure of the ligand 1,5,8,12-tetrakis(diphenylphosphineamine)-1,5,8,12-tetraazacyclotetradecane is shown in the following structural formula:

[0047]

[0048] The preparation method is as follows:

[0049] Add dehydrated dichloromethane (20mL), triethylamine (3.75mL), diphenylphosphorous chloride (1.33mL, 7.2mmol) into a stirred 100mL reactor fully replaced by N2, and cool to 0 °C, 1,5,8,12-tetraazacyclododecane (1.75 mmol) was added slowly. After stirring for 30 minutes, the reaction was continued at room temperature for 12 hours. Filtration and drying gave the product (1.40 g, 85.5%).

[0050] 1 HNMR (400MHz, CDCl 3 ):d=1.436(s,4H,CH 2 ),2.711-2.728(d,8H,NCH 2 CH 2 CH 2 N),3.009-3.035(d,8H,NCH 2 CH 2 N),7.096-7.290(m,40H,P(Ph) 2 ); 13 C{ 1 H}NMR (100MHz, CDCl 3 ):d=139.52, 139.37, 132.08, 131.88, 128.41-128.12...

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Abstract

The invention relates to a dual-core chromium catalyst for ethylene oligomerization and a preparation method thereof; the dual-core chromium catalyst contains a transition metal chromium complex with a dual-core structure and an organic metal compound activator, the transition metal chromium complex with the dual-core structure is a compound having the general formula (I) defined in the specification, wherein R1, R2, R3 and R4 are connection groups and can be arbitrarily selected from alkyl, naphthenic group, aryl or heteroatomic groups containing O and S having a chain base structure with 1-6 atoms, R4, R5 and R6 are arbitrarily arene or alkane substituents, and CrX is CrCl2, CrCl3, Cr(acac)3, chromium 2-ethylhexanoate or Cr(CO)6. The catalyst has the catalytic activity of greater than 4.92*10<6> g polymerization product*mol<-1> Cr*h<-1>, and the selectivity of linear alpha-olefin in products is more than 98%. The catalyst composition has the characteristics of simple preparation method, high catalytic activity, and fewer C1-C4 alkanes and high-polymerized products in the products.

Description

technical field [0001] The invention belongs to the field of ethylene oligomerization catalysis, in particular to a binuclear chromium catalyst for ethylene oligomerization, a preparation method and its application in the preparation of linear alpha-olefins. Background technique [0002] Linear α-olefins are widely used in the fields of polyethylene comonomers, surfactant synthesis intermediates, plasticizer alcohols, synthetic lubricating oils and oil additives. In recent years, with the continuous development of the polyolefin industry, the worldwide demand for advanced linear α-olefins has grown rapidly. Ethylene oligomerization is the main method to prepare high-grade linear α-olefins. Through oligomerization, cheap ethylene can be converted into products with high added value. [0003] The use of transition metal complex homogeneous catalysts in the polymerization and oligomerization of olefins has always been paid attention to by people. Researchers are working hard t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07F11/00C07C2/36C07C11/02C07C11/107
CPCY02P20/52
Inventor 陈延辉姜涛张乐孟雪姣毕显佳
Owner TIANJIN UNIV OF SCI & TECH
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