Vinylene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof

An olefin catalyst and vinylidene technology, applied in chemical instruments and methods, nickel organic compounds, organic chemistry, etc., can solve the problems of inability to prepare high-molecular-weight, high-branched polyethylene, etc., and achieve reduced production costs and high activity , good thermal stability

Active Publication Date: 2018-05-08
ZHEJIANG UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

However, the catalyst still has the technical defect of being una

Method used

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  • Vinylene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof
  • Vinylene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof
  • Vinylene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation method and application thereof

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preparation example Construction

[0051] The preparation method of described vinylidene acenaphthylene (α-diimine) nickel olefin catalyst comprises the following steps:

[0052] 1) Compound C1 is obtained by diacylation of acenaphthene: using acenaphthene as a raw material and carbon disulfide as a solvent. Anhydrous aluminum bromide was added as a catalyst to obtain yellow solid acenaphthylenedione C1 under the condition of oxalyl bromide as an oxidizing agent.

[0053]

[0054] 2) compound C1 is subjected to bromination reaction to obtain compound C2: taking compound C1 obtained in step (1) as raw material, carbon tetrachloride as solvent, benzoyl peroxide as initiator, N-bromosuccinimide (NBS ) as brominating agent, compound C2 can be obtained by bromination reaction.

[0055]

[0056] 3) Compound C2 undergoes an elimination reaction to obtain compound C3: using compound C2 obtained in step (2) as a raw material, acetone as a solvent, and anhydrous potassium iodide as an initiator, acenaphthylenedion...

Embodiment 1

[0069] 2g (9.6mmol) C1 is added in the 500mL there-necked bottle that 250mL carbon tetrachloride is housed, N 2 Reflux at 85°C for 30min under protection, add 5.2g (30mmol) N-bromosuccinimide (NBS) and 200 mg benzoyl peroxide to the system, and continue to reflux the mixture at 85°C for 5h. After the reaction is over, filter while hot, and use 50mL hot CCl 4 After washing, the mixture obtained by washing was subjected to rotary evaporation, and the solvent carbon tetrachloride was removed to obtain a yellow solid, which was a mixture of product C2 and NBS. Purified by column chromatography with dichloromethane as the eluent, the total mass of product C2 was 2.311 g, and the yield was 65.57%.

[0070] 1 H-NMR (400MHz, CDCl 3 , δin ppm): 8.25 (dd, 2H, Ar-H), 7.91 (dd, 2H, Ar-H), 6.09 (s, 2H, CH).

[0071] Two, the preparation of compound C3

Embodiment 2

[0073] Dissolve 1.25g (34.2mmol) C2 in 100mL acetone under the protection of nitrogen, add the acetone solution into a 250mL three-necked flask, then add 7.5g (0.46mol) anhydrous potassium iodide to the three-necked flask, and at 60°C Reflux 4h. After the reaction was over, the mixture was cooled and poured into an aqueous solution of sodium thiosulfate, the mixture was extracted three times with chloroform, then washed three times with deionized water, and the red product C3 was obtained after rotary evaporation, with a yield of 0.960 g and a yield of 99.92% .

[0074] 1 H-NMR (400MHz, CDCl 3 , δin ppm): 8.26 (dd, 2H, Ar-H), 8.13 (dd, 2H, Ar-H), 7.69 (s, 2H, CH).

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Abstract

The invention relates to the field of olefin catalytic polymerization, and aims at providing a vinylene acenaphthene (alpha-diimine) nickel olefin catalyst, and preparation and an application thereof.The preparation comprises the typical synthetic steps: carrying out a diacylation reaction of acenaphthene to obtain a compound C1; carrying out a bromination reaction of the compound C1 and N-bromosuccinimide (NBS) to obtain a compound C2; carrying out an elimination reaction of the compound C2 to obtain a compound C3; carrying out ketone amine condensation reaction of the compound C3 with symmetric aniline, to obtain alpha-diimine ligands C4-C8; and under anhydrous and anaerobic conditions, complexing the alpha-diimine ligands C4-C8 with ethylene glycol dimethyl ether nickel dibromide to obtain a final product. The catalyst has higher activity and better thermal stability, and can catalyze ethylene with high activity at the temperature of greater than or equal to 60 DEG C to obtain high-molecular-weight hyperbranched polyethylene. Under the same polymerization conditions, ethylene can be catalyzed to polymerize to obtain branched polyethylene with higher molecular weight, so as to meet more application requirements. The cost of raw materials is low, the reaction yield is high and industrialized production can be achieved.

Description

technical field [0001] The invention relates to the field of catalytic polymerization of olefins, and specifically provides the preparation and application of a vinylidene acenaphthylene (α-diimine) nickel olefin catalyst. Background technique [0002] Polyolefin is a basic material related to the national economy and people's livelihood, and because of its excellent performance, variety of varieties, easy availability of raw materials and low price, it is widely used in various fields such as industry, agriculture and national defense. The development and application of new catalysts is one of the core driving forces to promote the progress and development of the polyolefin industry, and is the key to controlling the structure and performance of polyolefin materials. [0003] In recent decades, the study of functionalized and differentiated polyolefin materials obtained by coordination polymerization has received extensive attention. In 1995, the Brookhart research group f...

Claims

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Application Information

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IPC IPC(8): C08F10/00C08F4/70C08F110/02C08F110/06C07F15/04
CPCC07F15/045C08F10/00C08F110/02C08F110/06C08F4/7006C08F2500/01C07F15/04C08F4/70Y02P20/52
Inventor 傅智盛何峰范志强
Owner ZHEJIANG UNIV
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