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Chain walking catalysts, preparation method thereof, and application of catalysts in ethylene polymerization

A technology for catalyzing ethylene and catalysts, which is applied in the fields of catalyst synthesis and polymer synthesis. It can solve the problems of inability to form branched sequences and low branching numbers, and achieve high temperature resistance and high activity.

Pending Publication Date: 2020-10-02
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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Problems solved by technology

And because its branching number is too low, it is impossible to form an observable regular branching sequence

Method used

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  • Chain walking catalysts, preparation method thereof, and application of catalysts in ethylene polymerization
  • Chain walking catalysts, preparation method thereof, and application of catalysts in ethylene polymerization
  • Chain walking catalysts, preparation method thereof, and application of catalysts in ethylene polymerization

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preparation example Construction

[0039] The present invention also provides a preparation method of a chain walking catalyst, comprising:

[0040] A class of novel benzobarrelene pentadecene ligands described in general formula (II) and (DME)NiBr 2 (DME=ethylene glycol dimethyl ether) is dissolved in a solvent, the solvent is preferably dichloromethane or chloroform, and the resulting mixture is stirred at 20-50°C for 3-30 days, preferably 3-10 days, more preferably For 3-5 days, the solvent is preferably evaporated by rotary evaporation, recrystallized with n-hexane or ether and dichloromethane or chloroform, and the solid is separated by filtration, washed three times with hexane or ether and dried under vacuum to obtain a structural formula such as general formula (I) a class of transition metal catalysts. A class of novel benzobarrelene pentadecene ligands described in the general formula (II) and (DME) NiBr 2 The molar ratio is 1:1.

[0041]

[0042] According to the present invention, the general ...

Embodiment 1

[0047] Preparation of Example 1 Benzobarrelene Pentadecyl Nickel Dibromide (corresponding to 14 in Table 1)

[0048] The benzobarrelene pentadecene ligand (2.00g, 1.74mmol) and (DME)NiBr 2 (462 mg, 1.74 mmol) (DME = ethylene glycol dimethyl ether) mixture was stirred in 20 mL of dichloromethane at 25° C. for 72 hours. After the reaction was completed, the solvent was evaporated under reduced pressure to give a reddish-brown solid, which was then filtered and recrystallized from dichloromethane / hexane to give the pure compound as a reddish-brown solid (2.00 g, 82.10% yield). The single crystal diffraction pattern of the product prepared in Example 1 is as follows figure 1 shown. MALDI-TOF-MS spectrum such as figure 2 shown. Concrete reaction process is as follows:

[0049]

[0050] The catalyst synthesis methods used in Tables 1-5 are the same as those in Example 1 above, except that the ligand structures and yields are different, and the rest of the steps are the same...

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Abstract

The invention provides chain walking catalysts, a preparation method thereof, and application of the catalysts in ethylene polymerization, and belongs to the technical field of catalyst synthesis andpolymer synthesis. The structural formula of the catalysts is shown as a general formula (I). The invention also provides the preparation method of the chain walking catalysts. The preparation methodcomprises the following steps: dissolving novel benzobucene pentaptycene ligands shown in the general formula (II) and (DME)NiBr2 in a solvent, and stirring the obtained mixture at 20-50 DEG C for 3-30 days to obtain the chain walking catalysts with the structural formula shown in the general formula (I). The invention also provides the application of the chain walking catalysts in ethylene polymerization. The catalysts can adjust the branching type, the branching sequence and the branching number of the polymer to a certain extent.

Description

technical field [0001] The invention belongs to the technical field of catalyst synthesis and polymer synthesis, and specifically relates to a chain walking catalyst, a preparation method thereof and an application in ethylene polymerization. Background technique [0002] Since 1995, α-diimine post-transition metal (nickel) catalysts (J. Am. Chem. Soc. 1995, 117, 6414) have been developed as a class of very useful ethylene catalysts due to the unique chain walking mechanism. polymerization catalyst. For this type of catalyst, chain walking is its characteristic, but because the chain walking process is always accompanied by uncontrollable β-hydrogen elimination, it is the most difficult to control. For α-diimine post-transition metal (nickel) catalysts, as the external conditions such as temperature / pressure change, the branching sequence, branching type and branching number will change greatly, and the overall effect is that the temperature increases Or pressure reduction...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/02C08F110/02C08F4/70C07F15/04
CPCC08F10/02C08F110/02C07F15/045C08F4/7098C08F4/7006C08F2500/01C08F2500/10Y02P20/584
Inventor 简忠保张宇星
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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