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Bridged metallocene Zr-tombarthite catalyst and preparation method thereof

A metallocene compound and rare earth technology, applied in the field of polyolefins, can solve the problems of residence, catalytic mechanism, and the structure-activity relationship between catalyst structure and catalytic activity without further research.

Inactive Publication Date: 2008-02-06
QILU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although many articles have been published in recent years, most of them stay on compound synthesis and molecular structure identification, while there is no further research on the catalytic mechanism, structure-activity relationship between catalyst structure and catalytic activity.

Method used

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  • Bridged metallocene Zr-tombarthite catalyst and preparation method thereof
  • Bridged metallocene Zr-tombarthite catalyst and preparation method thereof
  • Bridged metallocene Zr-tombarthite catalyst and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

preparation example Construction

[0032] The preparation method of compound (I) is as follows:

[0033] 1) Synthesis of ω-alkenyl epoxides

[0034] In organic solvents, the general formula is (wherein n is an integer of 1-10, preferably, n is an integer of 1-5; more preferably, n is 1, 3 or 5) of ω-diene and m-chloroperoxybenzoic acid in a molar ratio of 1: The ratio of 0.6 to 0.8 is reacted in an organic solvent, as shown in the following formula, to obtain 1,2-epoxy-alkyl ω-ene.

[0035]

[0036] The organic solvent is selected from dichloromethane, toluene, tetrahydrofuran.

[0037] 2)C 13 h 8 -R (R = alkenyl or substituted alkenyl) type of ligand synthetic synthesis method is shown in the following formula:

[0038]

[0039] Step 1) The obtained epoxide is reacted with an equimolar number of fluorene lithium to obtain the corresponding alcoholate, the reaction temperature is -90~-60°C, and the reaction time is 2-8 hours; then hydrolyzed to obtain 1-fluorene-ω- Alkyl-2-ols. Hydrolysis can be p...

Embodiment 1

[0061] Embodiment 1: the synthesis of binuclear catalyst A

[0062] Step 1: Synthesis of ω-alkenyl epoxides

[0063] 1,5-Hexadiene is reacted with m-chloroperoxybenzoic acid, as shown in the following formula, to obtain 1,2-epoxy-alkyl ω-ene epoxy compound.

[0064]

[0065] At room temperature, a solution of 13.75g (79.6mmol) m-chloroperbenzoic acid in 250ml dichloromethane was slowly dropped into a solution of 9g (110mmol) 1,5-hexadiene in 200ml dichloromethane, and the mixture was stirred overnight. The precipitate was removed by filtration, followed by 2M NaHCO 3 , 2N KOH and water, the organic layer was dried with anhydrous sodium sulfate, the solvent was removed in vacuo, and the residue was distilled to obtain an epoxy compound with a yield of 60-80%. The product was a colorless liquid, b.p.119-121°C.

[0066] 1 H NMR (CDCl3, 25°C): 5.68 (m, 1H, =CH), 4.83 (m, 1H, =CH 2 ), 4.83 (m, 1H, =CH 2 ), 2.73 (ABMX 2 , 1H, CH), 2.54 (ABM, 1H, CH 2 ), 2.27 (ABM, 1H, CH ...

Embodiment 2

[0077] The compound obtained in Example 2 undergoes a nucleophilic substitution reaction with indene lithium to obtain a C2 bridged ligand.

[0078]

[0079] At -78°C, 61mmol indene lithium in 100ml ether solution was mixed with 1-fluorene-hexa-5-diene-2-methanesulfonate, stirred for 24 hours, hydrolyzed with 50ml water, and the organic layer was washed with anhydrous sodium sulfate Dry and remove solvent in vacuo. The residue was dissolved with pentane and passed through a silica gel column. Crystallization in pentane at -18°C yield 40-50%. 6-(9-fluorene)-5-(1-indene)-1-hexene was obtained: GC: 2844s; MS: m / e362 (M + ); Its NMR data are as follows: 1 H NMR (CDCl 3 , 25°C): 7.71-7.23 (12H), 6.95 (m, 1H), 6.55 (m, 1H), 5.65 (m, 1H, =CH), 4.90 (m, 1H, =CH 2 ), 4.90 (m, 1H, =CH 2 ), 4.18(m), 3.95(m), 3.80(m, 1H, CH), 3.68(s), 3.56(s), 3.33(s, 1H, CH), 2.44(m, 1H, CH), 2.13 (m, 2H, CH 2 ), 1.85 (m, 2H, CH 2 ), 1.51 (m, 2H, CH 2 );

[0080] 13 C NMR (CDCl 3 , 25°C):...

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Abstract

The invention provides a heterodinuclear metallocene compound represented by the following structural formula, therein, M represents the lanthanon, R is chosen from methyl, ethyl, isopropyl, allyl (butyl-3-olefin), hexyl-5 olefin, octyl-7 olefin, cyclohexane or benzyl. The invention also provides the preparation process for the compound. The compound is coordinated with the alkyl aluminoxane (promoter) for olefin polymerization, has high polymerization reaction activity, and can obtain olefin polymerization products with the distribution of high molecular weight and wide molecular weight.

Description

technical field [0001] The invention belongs to the field of polyolefins, and relates to a catalyst for olefin polymerization, in particular to a bimetallic catalyst for the polymerization of ethylene and propylene. Background technique [0002] Metallocene catalysts have attracted extensive attention because of their single active center, and the catalyst activity, polymer stereoregularity, molecular weight and molecular weight distribution can be controlled by changing the ligand structure. Difficulties limit its industrialization process. People try to use composite catalysis (see KAMINSKY W, STEIGER R. Polymerization of olefins with homogeneous zirconocene / alumoxane catalysts, Polyhedron, 1988, 7(22-23): 2375-2381) or dual-core multi-nuclear catalysts (see Feng Zuofeng, Xie Jun, Chen Bin et al., Organic Chemistry, 2001, 21(1), 33-40) to improve the molecular weight distribution of polymers, since 1993 Jüngling (see Jüngling S, Mülhaupt R. Cooperative effects in binuclea...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F19/00C08F4/643C08F10/00
Inventor 班青
Owner QILU UNIV OF TECH
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