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Asymmetric-structure diimine iron (II) catalyst containing nitrogen second-layer coordination space effect, and preparation method and application thereof

A steric effect, iron diimide technology, applied in the field of olefin polymerization, to achieve the effect of high selectivity, rich diversity, temperature-controlled polymerization performance

Active Publication Date: 2020-05-15
HEFEI UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, for N,N-bidete iron catalysts, there is little research on the formation of Fe–N weak metal bonds in the prior art, so when N,N-bidete iron catalysts are used for ethylene oligomerization, only oligomers can be obtained

Method used

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  • Asymmetric-structure diimine iron (II) catalyst containing nitrogen second-layer coordination space effect, and preparation method and application thereof
  • Asymmetric-structure diimine iron (II) catalyst containing nitrogen second-layer coordination space effect, and preparation method and application thereof
  • Asymmetric-structure diimine iron (II) catalyst containing nitrogen second-layer coordination space effect, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042] (1)[2,6-(C 5 h 10 N) 2 -C 6 h 3 N=C(Me)-C(Me)=N-(2,6- i PR 2 -C 6 h 3 )]FeCl 2 (N6- i Preparation of Pr-Fe)

[0043] Under nitrogen protection, add the ligand N6- to a 100 mL dry reaction tube iPr-L (0.49g, 1.0mmol), plus FeCl 2 (0.13g, 1.0mmol) and 25mL of dichloromethane, stirred and reacted at room temperature for 24h, filtered the suspension, and concentrated the obtained liquid (ie mother liquor) under vacuum, then added 20mL of n-hexane, crystallized blue crude The product, after removing the solvent, was washed twice with 15mL of n-hexane, and dried in vacuum to obtain 0.50g of iron (II) complex, which was named as N6- i Pr-Fe, yield 81%.

[0044] Anal.Calcd.for C 32 h 46 Cl 2 FeN 4 : C, 62.65; H, 7.56; N, 9.13; Found: C, 62.72; H, 7.48; N, 9.07.Ft-IR (KBr, cm -1 ):1649(v -C＝N- ).MALDI-TOF-MS(m / z) Calcd.for:C 32 h 46 ClFeN 4 :577.0798.Found:577.0805[M-Cl] +

[0045] Its reaction formula is as follows:

[0046]

[0047] (2) Ethylene pol...

Embodiment 2

[0073] (1)[2,6-(C 4 h 8 NO) 2 -C 6 h 3 N=C(Me)-C(Me)=N-(2,6- i PR 2 -C 6 h 3 )]FeCl 2 (NO- i Preparation of Pr-Fe)

[0074] Under the protection of nitrogen, add the ligand NO- i Pr-L (0.49g, 1.0mmol), plus FeCl 2 (0.13g, 1.0mmol) and 25mL of dichloromethane, stirred and reacted at room temperature for 24h, filtered the suspension, and concentrated the obtained liquid (ie mother liquor) under vacuum, then added 20mL of n-hexane, crystallized blue crude The product, after removing the solvent, was washed twice with 15mL of n-hexane, and dried in vacuum to obtain 0.47g of iron (II) complex, named as NO- i Pr-Fe, yield 77%.

[0075] Anal.Calcd.for C 30 h 42 Cl 2 FeN 4 o 2 : C, 58.36; H, 6.86; N, 9.07; Found: C, 58.14; H, 6.74; N, 9.12.Ft-IR (KBr, cm -1 ):1645(v -C＝N- ).MALDI-TOF-MS(m / z) Calcd.for:C30 h 42 ClFeN 4 o 2 :581.0724.Found:581.0781[M-Cl] +

[0076] Its reaction formula is as follows:

[0077]

[0078] (2) Ethylene polymerization

[0079] Re...

Embodiment 3

[0081] (1)[2,6-(C 4 h 8 N) 2 -C 6 h 3 N=C(Me)-C(Me)=N-(2,6- i PR 2 -C 6 h 3 )]FeCl 2 (N5- i Preparation of Pr-Fe)

[0082] Under nitrogen protection, add the ligand N5- to a 100 mL dry reaction tube i Pr-L (0.46g, 1.0mmol), plus FeCl 2 (0.13g, 1.0mmol) and 25mL of dichloromethane, stirred and reacted at room temperature for 24h, filtered the suspension, and concentrated the obtained liquid (ie mother liquor) under vacuum, then added 20mL of n-hexane, crystallized blue crude After removing the solvent, the product was washed twice with 15mL of n-hexane, and dried in vacuum to obtain 0.51g of iron (II) complex, which was named as N5- i Pr-Fe, 87% yield.

[0083] Anal.Calcd.for C 30 h 42 Cl 2 FeN 4 : C, 61.55; H, 7.23; N, 9.57; Found: C, 61.81; H, 7.47; N, 9.54.Ft-IR (KBr, cm -1 ):1647(v -C＝N- ).MALDI-TOF-MS(m / z):Calcd.for:C 30 h 42 ClFeN 4 :549.3473.Found:549.3457[M-Cl] + .

[0084] Its reaction formula is as follows:

[0085]

[0086] (2) Ethylene po...

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Abstract

The invention discloses an asymmetric-structure diimine iron (II) catalyst containing a nitrogen second-layer coordination space effect, relates to the technical field of olefin polymerization; the structural formula of the catalyst is shown in the specification. The invention also provides a preparation method of the asymmetric-structure diimine iron (II) catalyst containing the nitrogen second-layer coordination space effect and an application of the asymmetric-structure diimine iron (II) catalyst in ethylene polymerization; the diimine iron complex prepared by the preparation method introduces a group containing a nitrogen donor into the ortho-position of a unilateral imine nitrogen atom aromatic ring to form a weak Fe-N bond. The second-layer coordination space effect plays a key rolein controlling the ethylene polymerization process, and the catalytic performance depends on the catalyst structure and the polymerization temperature. Particularly, an o-piperidine-N-substituted catalytic system shows high catalytic activity in ethylene polymerization, and linear polyethylene with high molecular weight is generated. The catalyst with the second-layer coordination space effect hasgood potential application value in industrial production of polyolefin.

Description

technical field [0001] The invention relates to the technical field of olefin polymerization, in particular to an asymmetric structure diimide iron (II) catalyst with a nitrogen-containing second-layer coordination steric effect, a preparation method and an application. Background technique [0002] In the field of olefin polymerization, late-transition metal catalysts are a new generation of metal-organic catalysts with high activity. Since Brookhart and Gibson reported iron and cobalt catalysts of tridentate imine ligands (Small, B.L.; Brookhart, M.; Bennett, A.M.A. HighlyActive Iron and Cobalt Catalysts for the Polymerization of Ethylene.J.Am.Chem.Soc. 120,4049–4050), under the activation of the cocatalyst methylaluminoxane MAO, it has a very high activity in catalyzing ethylene polymerization. Over the past two decades, a large number of modified iron and cobalt catalysts for ethylene oligomerization and polymerization have been extensively studied. Many studies have s...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F110/02C08F4/70
CPCC08F110/02C08F4/7006
Inventor 李有桂夏卫领张瑞朱成峰吴祥
Owner HEFEI UNIV OF TECH