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4,4'-difluorobenzhydryl containing asymmetric alpha-diimine nickel complex, and intermediate, preparation method and application thereof

A technology of difluorobenzhydryl and nickel complexes, which is applied in the preparation of imino compounds, compounds containing elements of group 8/9/10/18 of the periodic table, nickel organic compounds, etc., which can solve the problem of not being able to prepare high molecular weight Polyethylene elastomer material and other issues

Inactive Publication Date: 2017-05-10
INST OF CHEM CHINESE ACAD OF SCI
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Problems solved by technology

[0011] In addition, the inventor's research group also designed and synthesized the 2-benzimidazole-1,10-phenanthroline nickel complex (shown in formula 7), whose catalytic activity for ethylene oligomerization reached 1.27×10 7 g·mol -1 h -1 (Eur.J.Inorg.Chem.2007,3816), which is significantly higher than other general complex catalysts to catalyze ethylene activity, but it cannot prepare polyethylene elastomer materials with high molecular weight and high degree of branching

Method used

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  • 4,4'-difluorobenzhydryl containing asymmetric alpha-diimine nickel complex, and intermediate, preparation method and application thereof
  • 4,4'-difluorobenzhydryl containing asymmetric alpha-diimine nickel complex, and intermediate, preparation method and application thereof
  • 4,4'-difluorobenzhydryl containing asymmetric alpha-diimine nickel complex, and intermediate, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0126] 2-(2,6-bis(4,4'-difluorobenzhydryl)-4-fluoroanilino)acenaphthylenone represented by formula (V) was prepared.

[0127] Add the amount of catalyst (1.25g) of p-toluenesulfonic acid was refluxed for 5h. The solvent was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:50, and the eluted fraction was detected through a thin-layer silica gel plate, and the developing solvent was petroleum ether and ethyl acetate The volume ratio of the ester was a mixed solvent of 10:1, the third fraction was collected, and an orange-yellow solid was obtained after removing the solvent. Yield: 67%. Melting point: 181-183°C.

[0128] The structural confirmation data are as follows:

[0129] FT-IR (KBr, cm -1 ):3025.9(w), 1722.6(m), 1649.9(m), 1595.3(m), 1491.5(m), 1446.6(m), 1274.4(w), 1026.4(m), 694.7(vs).

[0130] 1 H NMR (600MHz, CDCl 3 ,TMS):δ8.11(d,J=8.1Hz,1H,An–H),8.08(d...

Embodiment 2

[0135] 1-(2,6-dimethylaniline)-2-(2,6-bis(4,4'-difluorobenzhydryl)-4-fluoroaniline) acenaphthene[ L1], where R 1 is methyl, R 2 for hydrogen.

[0136] 2-(2,6-bis(4,4'-difluorobenzhydryl)-4-fluoroaniline)acenaphthylenone (1.36g, 2.0mmol) and 2,6-dimethylaniline (0.36g, 3.0 mmol) in toluene (100 mL) was added a catalytic amount of p-toluenesulfonic acid, heated to reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:50. The eluted fractions were examined through a thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to give an orange-yellow solid. Yield: 56%. Melting point: 197-199°C.

[0137] The structural confirmation data are as follows:

[0138] FT-IR (KBr, cm -1 ):3048(w),2924(w),1670(m),1642(m),1598(s),1505(vs),1224(vs),1157(s),1096(m),830(s ), 773(s).

[0139] 1 H NMR (600MHz, ...

Embodiment 3

[0144] 1-(2,6-diethylaniline)-2-(2,6-bis(4,4'-difluorobenzhydryl)-4-fluoroaniline) acenaphthene[ L2], where R 1 is ethyl, R 2 for hydrogen.

[0145] 2-(2,6-bis(4,4'-difluorobenzhydryl)-4-fluoroaniline)acenaphthylenone (1.00g, 1.47mmol) and 2,6-diethylaniline (0.33g, 2.21 mmol) in toluene (100 mL) was added a catalytic amount of p-toluenesulfonic acid, heated to reflux for 10 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of ethyl acetate and petroleum ether at a volume ratio of 1:50. The eluted fractions were examined through a thin-layer silica gel plate, the second fraction was collected, and the solvent was removed to give an orange-yellow solid. Yield: 39%. Melting point: 227-229°C.

[0146] The structural confirmation data are as follows:

[0147] FT-IR (KBr, cm -1 ):3057(w), 2968(w), 2931(w), 1662(m), 1639(m), 1597(s), 1505(vs), 1456(s), 1439(s), 1221(vs ), 1158(s), 1099(m), 830(s), 7...

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Abstract

The invention provides a 4,4'-difluorobenzhydryl containing asymmetric alpha-diimine nickel complex, and an intermediate, a preparation method and an application thereof. The nickel complex prepared by using the method provided by the invention has a single catalytic active center, can realize control of polymer molecular weight and branching degree by changing a ligand structure and polymerization conditions, and has the advantages of high catalytic activity, low cost, stable performance, etc. The preparation method has the advantages of mild conditions, short cycle and simple operation conditions. The nickel complex prepared by using the method provided by the invention can be used in a catalyst used for ethylene polymerization, and has the activity of catalyzing ethylene polymerization up to 2.20 * 10<7> g.mol<-1>(Ni).h<-1> under the condition of no oxygen; and the prepared polyethylene has a weight-average molecular weight Mw fluctuating in a range of (1.35-10.50) * 10<5> g.mol<-1> and molecular weight distribution in a range of 1.9 to 2.5. The nickel complex provided by the invention has good industrial application prospects.

Description

technical field [0001] The invention relates to the field of polymer material catalysis, in particular to an asymmetric α-diimine nickel complex containing 4,4'-difluorobenzhydryl, its intermediate, preparation method and application in catalyzing ethylene polymerization . Background technique [0002] As the fastest-growing, largest-yielding, and most widely-used synthetic resin—polyethylene, it is widely used in many fields such as industry, agriculture, military affairs, medical care, and daily life. The extensive development and application of polyethylene products is inseparable from the development of olefin polymerization catalysts. At present, industrialized polyethylene catalysts mainly include Ziegler-Natta type catalysts (DEPat 889229 (1953); IT Pat 536899 (1955) and IT Pat 545332 (1956); Chem.Rev., 2000, 100, 1169 and relevant Literature), Phillips type catalyst (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorga...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C07C251/20C07C249/02B01J31/22C08F110/02C08F4/70
CPCC07F15/045B01J31/22B01J2231/12B01J2531/0238B01J2531/847C07C249/02C08F110/02
Inventor 范琳琳王新鑫张亦琴杨文泓孙文华
Owner INST OF CHEM CHINESE ACAD OF SCI
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