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Pyridinocycloheptane imine nickel complex catalyst, preparation method and application thereof

A complex and catalyst technology, which is applied in the production of nickel organic compounds and bulk chemicals, can solve the problems of restricting the development of basic research, poor thermal stability of complexes, and affecting the application of catalysts, and achieve high catalytic activity, narrow molecular weight distribution, The effect of a wide range of industrial application prospects

Active Publication Date: 2016-06-08
INST OF CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

However, as a new catalyst system, there are still some difficulties in basic research and constraints encountered in industrialization
First of all, since the rate of chain transfer termination increases with the increase of temperature, and the thermal stability of the complex itself is poor, this will inevitably affect the application of catalysts in industrial production; secondly, there are not many catalyst systems available for screening. , restricting the development of basic research

Method used

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  • Pyridinocycloheptane imine nickel complex catalyst, preparation method and application thereof
  • Pyridinocycloheptane imine nickel complex catalyst, preparation method and application thereof
  • Pyridinocycloheptane imine nickel complex catalyst, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0078] Embodiment 1, prepare the synthetic method of 5,6,7,8-tetrahydrocycloheptapyridin-9-one:

[0079] Add 8.03g (40.6mmol) formula II compound in 250ml stainless steel kettle, sodium acetate 3.83g (46.7mmol), 10% palladium carbon 0.80g, methyl alcohol 35ml, after hydrogen replacement three times, hydrogen pressure is added to 1.0MPa, magnetic force stirs, pass 60°C water bath, after 12 hours of reaction, the pressure gauge index did not drop, and the reaction was stopped. The reaction solution was filtered (suction filtration under reduced pressure) to obtain 6.30 g of solid. The solid is transferred to a 250ml jacketed bottle and added, dissolved with 70ml of dichloromethane, filtered to remove insoluble matter, and then 70ml of an aqueous solution of 10.08g (120mmol) sodium bicarbonate, 0.95g of potassium bromide (20mol%), and 0.95g of potassium bromide (20mol%) are added successively and 0.06 g of tetramethylpiperidine nitrogen oxide (1 mol%), mechanically stirred, and ...

Embodiment 2

[0083] Embodiment 2, the synthetic method of preparing (E)-2,6-diisopropyl-N-(5,6,7,8-tetrahydrocycloheptanepyridin-9-ene)aniline (L3, formula R in V 1 =i-Pr;R 2 = Compound of H):

[0084] In the compound (0.16g, 1mmol) shown in formula III and the chlorobenzene (20mL) solution of 2,6-diisopropylaniline (0.20g, 1.1mmol) shown in formula IV, add the p-toluenesulfonic acid catalyst of 30mg , stirred at 120° C. under reflux for 12 h, concentrated under reduced pressure, separated on a silica gel column, and eluted the target product with an eluent ratio of ethyl acetate:triethylamine:petroleum ether=1:1:50 to obtain 0.27g yellow oily substance, namely the pyridine enamine ligand compound L3 (wherein, R 1 is isopropyl, R 2 For hydrogen), the yield was 83.0%.

[0085] The structural confirmation data are as follows:

[0086] 1 H-NMR (400MHz; CDCl 3;TMS): δ8.66(d, J=4.4Hz, 1H, L3-Py-H), 8.54(d, J=4.4Hz, 1H, L3'-Py-H), 7.51(d, J=7.8 Hz,1H,L3-Py-H),7.34(d,J=6,8Hz,1H,L3'-Py-H)...

Embodiment 3

[0091] Example 3, the synthetic method for preparing (E)-2,6-dimethyl-N-(5,6,7,8-tetrahydrocycloheptanepyridin-9-ene)aniline (L1, formula V Middle R 1 = Me; R 2 = Compound of H):

[0092] Using the same method as in Example 1, only the 2,6-diisopropylaniline described in Example 1 was replaced by 2,6-dimethylaniline to obtain a yellow oily substance, which is pyridineenamine belonging to formula V Ligand compound L1 (wherein, R 1 = Me; R 2 =H), yield 75.0%.

[0093] The structural confirmation data are as follows:

[0094] 1 H-NMR (400MHz; CDCl 3 ;TMS): δ8.65(d, J=4.4Hz, 1H, L1-Py-H), 8.53(d, J=4.8Hz, 1H, L1'-Py-H), 7.51(d, J=7.8 Hz,1H,L1-Py-H),7.26(t,J=4.4Hz,1H,L1-Ar-H),7.15(t,J=4.8Hz,1H,L1'-Ar-H),7.12( d,J=5.2,2H,L1'-Ar-H),7.05(d,J=7.6Hz,2H,L1-Ar-H),6.92(t,J=7.8Hz,1H,L1-Py-H ), 6.15(s, 1H, L1'-NH), 4.56(t, J=6.8Hz, 1H, L1'-CH-), 2.87(t, J=6.0Hz, 2H, L1-CH 2 -),2.67(t,J=6.4Hz,2H,L1'-CH 2 -),2.35(s,6H,L1'-2xCH 3 ), 2.31(t, J=6.0Hz, 2H, L1-CH 2 -),2.16(s,6H,L1-2xC...

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Abstract

The invention discloses a pyridinocycloheptane imine nickel complex catalyst, a preparation method and application thereof. The structural formula of the complex is shown as formula I, wherein R1 is selected from methyl, ethyl or isopropyl, and R2 is selected from methyl or hydrogen. The preparation method consists of: under room temperature conditions, subjecting V-1 or V-2 shown ligand compound and NiCl2 or NiBr2 to complexation reaction in an organic solvent, thus obtaining a corresponding pyridinocycloheptane imine nickel complex shown as formula I. The invention designs and synthesizes the pyridinocycloheptane imine nickel complex, the series complex can well catalyze ethylene polymerization under the action of cocatalyst ethylaluminum sesquichloride or methylaluminoxane to obtain low molecular weight and narrow molecular weight distribution polyethylene, also has very high activity up to 7.80*10<6>g.mol<-1>(Ni).h<-1> respectively, thus having the potential for industrial application. (formula I).

Description

technical field [0001] The invention belongs to the field of complex catalysis, and in particular relates to a nickel pyridocycloheptaneimine complex and its preparation method and application. Background technique [0002] Polyolefins, also known as olefin polymers, are the most produced polymer products in the world. Since the industrial production of polyethylene in 1939, it has a history of more than 70 years. And the polyolefin industry has an output value of billions of dollars in the world every year. Among polyolefin products, linear α-olefins are widely used. Depending on the carbon number, they can be used as comonomers to produce linear low-density polyethylene, lubricants, plasticizers, and surfactants. In contrast, polyethylene wax (high degree of branching) is widely used because of its excellent cold resistance, heat resistance, chemical resistance and abrasion resistance. It can be directly added to polyolefin as an additive. It can increase the luster and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/04C08F10/02C08F4/70
CPCY02P20/52
Inventor 孙文华黄放胡信全孙泽林
Owner INST OF CHEM CHINESE ACAD OF SCI
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