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Silicon-based bridged polysubstituted indene-fluorene zirconium and hafnium complex and application thereof in olefin high-temperature polymerization

A technology for olefin polymerization and complexes, which is applied in the field of silicon-based bridged multi-substituted indene-fluorene zirconium and hafnium complexes and its high-temperature polymerization of olefins, which can solve the problems of decomposition and deactivation of catalyst active species, increased reactivity, loss of activity

Pending Publication Date: 2021-01-19
惠生(泰州)新材料科技有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] The application of bridged indene-fluorene metallocene catalysts in olefin polymerization has attracted extensive attention due to its easy structure modification. However, the current catalyst development work is mainly oriented to catalyze the polymerization or oligomerization of propylene and the homopolymerization of ethylene. The catalyst is generally at 0 ~80°C has ideal catalytic activity, and continuing to increase the degree of reaction usually leads to the decomposition and deactivation of the active species of the catalyst, resulting in a significant reduction in catalytic activity or even loss of activity
It is rare to report that this type of catalyst catalyzes the copolymerization of ethylene and other α-olefins under high temperature conditions and can obtain high molecular weight olefin copolymers with high activity

Method used

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  • Silicon-based bridged polysubstituted indene-fluorene zirconium and hafnium complex and application thereof in olefin high-temperature polymerization
  • Silicon-based bridged polysubstituted indene-fluorene zirconium and hafnium complex and application thereof in olefin high-temperature polymerization
  • Silicon-based bridged polysubstituted indene-fluorene zirconium and hafnium complex and application thereof in olefin high-temperature polymerization

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Experimental program
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preparation example Construction

[0051] The second aspect of the present invention provides the preparation method of the complex provided by the first aspect of the present invention, comprising:

[0052] 1) reacting the compound of formula II with an alkyl alkali metal compound to provide a dialkali metal salt of the compound of formula II;

[0053] 2) reacting a dialkali metal salt of a compound of formula II with a zirconium salt and / or a hafnium salt to provide a compound of formula I;

[0054]

[0055] In the step 1), those skilled in the art can select a suitable alkyl alkali metal compound for the above reaction, for example, the alkyl alkali metal compound can be methyllithium, n-butyllithium, tert-butyllithium, etc. one or a combination of more. The amount of the alkyl alkali metal compound is generally equivalent or excessive relative to the compound of formula II, for example, the molar ratio of the compound of formula II to the alkyl alkali metal compound can be 1:1~5, 1:1.8~2.2 , 1:1~1.5, 1...

Embodiment 1

[0078] Synthesis of zirconium complex C1

[0079] (1) Synthesis of Ligand Compound L1

[0080]

[0081] Under argon protection, weigh 5.43g (19.5mmol) of 2,7-di-tert-butylfluorene into a Schlenk bottle, add 30mL of ether and 10mL of tetrahydrofuran, and slowly add 9.8mL of n-butyllithium dropwise under ice-salt bath cooling ( 2.0M, 19.6mmol), after the dropping, naturally return to room temperature and stir for 24 hours to obtain the lithium salt of 2,7-di-tert-butylfluorene.

[0082] Under argon protection, weigh 4.03g (19.5mmol) of 3-benzylindene / 1-benzylindene into a Schlenk bottle, add 30mL of ether and 10mL of tetrahydrofuran, and slowly add n-butyllithium 9.8 mL (2.0M, 19.6mmol), after dropping, naturally return to room temperature and stir for 24 hours; through a constant pressure dropping funnel, slowly add 5.03g (39.0mmol) of dimethyldichlorosilane dropwise in an ice-water bath, and drop Afterwards, it was naturally raised to room temperature and continued to sti...

Embodiment 2

[0088] Synthesis of Hafnium Complex C25

[0089] Weigh 1.26g (2.3mmol) of ligand compound L1 in a Schlenk bottle under the protection of argon, add 40mL of ether to dissolve, slowly add 2.3mL of n-butyllithium (2.0M, 4.6mmol) dropwise at -78°C, drop After completion, naturally return to room temperature and stir for 24 hours; at -78°C, add 0.737g (2.3mmol) HfCl 4 ; Naturally rose to room temperature, the reaction system turned into a yellow turbid liquid, stirred and reacted for 48 hours. Remove the solvent in vacuo, add 50 mL of dry dichloromethane, stir for 2 hours and then centrifuge to obtain a red clear liquid, which is concentrated to saturation and recrystallized by adding n-hexane, and placed in a -20°C refrigerator for crystallization and separation to obtain 0.78 g of a yellow solid powder. rate of 42.9%.

[0090] Anal.Calcd.for C 39 h 44 Cl 2 SiHf: C, 59.28; H, 5.61. Found: C, 58.97; H, 5.72%.

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Abstract

The invention relates to the field of organic chemistry, in particular to a silicon-based bridged polysubstituted indenofluorene zirconium and hafnium complex and application thereof in olefin high-temperature polymerization. The invention provides a complex. The chemical structural formula of the complex is shown as a formula I in the specification. The silicon-based bridged polysubstituted indenofluorene zirconium and hafnium complex provided by the invention is an efficient catalyst, is stable in property, can catalyze olefin polymerization under a high-temperature condition, can easily obtain a polyolefin product with high molecular weight, can meet the requirements of industrial departments, and has a good industrialization prospect.

Description

technical field [0001] The invention relates to the field of organic chemistry, in particular to a silicon-based bridged multi-substituted indene-fluorene zirconium and hafnium complex and its application in high-temperature polymerization of olefins. Background technique [0002] The development of novel catalyst systems is at the heart of the olefin polymerization industry. In the middle of the last century, after the Ziegler-Natta heterogeneous catalytic body (Angew.Chem., 1955,67,541-547; Angew.Chem., 1956,68,393-403;) was established, Kaminsky et al. (Angew.Chem. Int.Ed.Engl.,1980,19,390-392; Makrkromol.Chem.Rapid.Commun.,1983,4,417-421.) Invented a homogeneous metallocene catalyst system, which is used to catalyze the coordination polymerization of ethylene and propylene On the one hand, it shows extremely high activity and surprising performance of a single active center, creating a new era of polymer synthesis science and polymer synthesis industry. This discovery ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F7/08C08F10/00C08F110/14C08F4/642C08F4/656
CPCC07F7/081C07F7/083C08F10/00C08F110/14
Inventor 张雷李东奇孙天旭
Owner 惠生(泰州)新材料科技有限公司
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