Nitro-containing asymmetric α-diimine nickel complex for preparing ultra-high molecular weight polyethylene, intermediate, preparation method and use

A technology of nickel complexes and nickel diimides, applied to nickel organic compounds, compounds containing elements of group 8/9/10/18 of the periodic table, chemical instruments and methods, etc.

Active Publication Date: 2020-03-10
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0011] However, the catalytic performance of the above catalysts, as well as the conditions and efficiency of their preparation methods, still need to be further improved

Method used

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  • Nitro-containing asymmetric α-diimine nickel complex for preparing ultra-high molecular weight polyethylene, intermediate, preparation method and use
  • Nitro-containing asymmetric α-diimine nickel complex for preparing ultra-high molecular weight polyethylene, intermediate, preparation method and use
  • Nitro-containing asymmetric α-diimine nickel complex for preparing ultra-high molecular weight polyethylene, intermediate, preparation method and use

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0127] 2-(2,6-bis(benzhydryl)-4-nitroanilino)acenaphthenone represented by formula (V) was prepared.

[0128] Add catalyst amount (1.25g) of p- Toluenesulfonic acid, reflux reaction for 5h. The solvent was removed, and the residue was subjected to silica gel 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 the volume of petroleum ether and ethyl acetate. A mixed solvent with a ratio of 10:1, the third fraction was collected, and an orange-yellow solid was obtained after removal of the solvent. Yield: 70%.

[0129] The structural confirmation data are as follows:

[0130] 1 H NMR (400MHz, DMSO, TMS): δ8.32(d, J=8.8Hz, 1H), 8.18(d, J=6.8Hz, 1H), 7.86-7.82(m, 2H), 7.69-7.52(m ,3H),7.32(t,J=7.6Hz,1H),7.26-6.92(m,20H).

[0131] 13 C NMR (100MHz, CDCl 3 , TMS): δ189.1, 161.2, 154.1, 148.3, 144.3, 142.8, 141.0, 14...

Embodiment 2

[0133] 1-(2,6-dimethylaniline)-2-(2,6-bis(benzhydryl)-4-nitroaniline) acenaphthene [L1] shown in preparation formula (II), wherein R 1 is methyl, R 2 for hydrogen.

[0134] 2-(2,6-bis(benzhydryl)-4-nitroaniline)acenaphthylenone (0.98g, 1.55mmol) and 2,6-dimethylaniline (0.2g, 1.65mmol) in toluene (100mL ) into the solution, add a catalytic amount of p-toluenesulfonic acid, and heat to reflux for 10h. 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: 23%. Melting point: 162-164°C.

[0135] The structural confirmation data are as follows:

[0136] FT-IR (KBr, cm -1):3057(w), 1661(ν(C=N),w), 1589(w), 1494(m), 1467(s), 1408(w), 1294(vs), 1182(m), 1071 (m), 1027(m), ...

Embodiment 3

[0141] 1-(2,6-diethylaniline)-2-(2,6-bis(benzhydryl)-4-nitroaniline) acenaphthene [L2] shown in preparation formula (II), wherein R 1 is ethyl, R 2 for hydrogen.

[0142] 2-(2,6-bis(benzhydryl)-4-nitroaniline)acenaphthylenone (0.98g, 1.55mmol) and 2,6-diethylaniline (0.21g, 1.65mmol) in toluene (100mL ) into the solution, add a catalytic amount of p-toluenesulfonic acid, and heat to reflux for 10h. 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: 41%. Melting point: 170-172°C.

[0143] The structural confirmation data are as follows:

[0144] FT-IR (KBr, cm -1 ):3058(w), 2960(w), 1656(ν(C=N),w), 1587(w), 1498(m), 1470(m), 1447(s), 1340(m), 1290 (vs), 1184(m), 1...

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Abstract

The invention provides a nitryl asymmetric alpha-diimine nickel complex for preparation of ultrahigh-molecular-weight polyethylene and an intermediate, a preparation method and application of the nitryl asymmetric alpha-diimine nickel complex. The nickel complex has a single catalytic active center, regulation of polymer molecular weight and branching degrees can be realized through changing of aligand structure and polymerization conditions, and high catalytic activity, low cost, performance stability and the like are achieved. The preparation method is mild in condition, short in period andsimple in operation condition. The nickel complex can be applied to catalytic vinyl polymerization, the catalytic activity is up to 4.61*10<6>g mol<-1>(Ni) h<-1>, the weight-average molecular weightMw of prepared polyethylene fluctuates in a range of 8.2-32.8*10<5>g mol<-1>, molecular weight distribution is in a range of 1.8-2.8, the remarkable performance of polyethylene molecular weight control is achieved, and the nickel complex can be used for preparation of ultrahigh-molecular-weight polyethylene; obtained polyethylene is high in branching degree, the melt temperature Tm is in a range of 76.9-117.2 DEG C, and accordingly the polyethylene can be used as engineering plastic at a high environment temperature, and a promising industrial application potential is achieved.

Description

technical field [0001] The invention relates to the technical field of polyolefin catalysts, in particular to a nitro-containing asymmetric α-diimine nickel complex for preparing ultra-high molecular weight polyethylene, its intermediate, preparation method and application. Background technique [0002] As the fastest-growing, largest-yield, and most-used synthetic resin-polyethylene, it is widely used in many fields such as industry, agriculture, military, medical and health 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, Metalorganic Cat...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F15/04C07C251/20C08F10/02C08F110/02C08F4/70
CPCC07C251/20C07F15/045C08F10/02C08F110/02C08F4/7006C08F2500/01C08F2500/03Y02P20/52
Inventor 马艳平凯萨马穆德王新鑫孙文华
Owner INST OF CHEM CHINESE ACAD OF SCI
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