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Preparation method of cycloolefin copolymers

A cycloolefin copolymer, cyclopentadienyl technology, applied in the field of olefin polymerization, can solve the problem of low content of norbornene

Active Publication Date: 2012-10-03
CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the semi-metallocene complex CpM(R')X 2 (Cp=cyclocene or substituted cyclocene, M=early transition metal, X=halogen or alkyl, R′=OAr and other non-cyclocene substituents) are used in the preparation of cycloolefins, but the norbornene content in the resulting polymer is relatively low Low

Method used

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  • Preparation method of cycloolefin copolymers
  • Preparation method of cycloolefin copolymers
  • Preparation method of cycloolefin copolymers

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preparation example Construction

[0035] The present invention provides a method for preparing a cycloolefin copolymer, which includes the following steps: under the action of a semi-metallocene complex of the formula (I) structure and a co-catalyst, the norbornene and ethylene are polymerized, and the reaction pressure is 1~6atm to obtain cycloolefin copolymer.

[0036]

[0037] In formula (I), M is a pre-transition metal;

[0038] R is cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl or substituted fluorenyl;

[0039] X is halogen or alkyl;

[0040] R 1 And R 2 Respectively an alkyl group, a silyl group or an aryl group;

[0041] R 3 And R 4 Respectively alkyl or aryl;

[0042] E is an oxygen atom or a sulfur atom.

[0043] Wherein, the semi-metallocene complex is preferably prepared according to the following method:

[0044] A) Dissolve the (thio)phenol phosphine ligand of formula (II) in a solvent, which is an organic solvent well known to those skilled in the art, preferably te...

Embodiment 1

[0059] Example 1 Preparation of semi-metallocene complex A 1 ~A 7

[0060] A 1 :2-Silymethyl-6-diphenylphosphine-phenol-cyclopentadienyl titanium dichloride;

[0061] A 2 :2-tert-butyl-6-diphenylphosphine-phenol-cyclopentadienyl titanium dichloride;

[0062] A 3 :2,4-Di-tert-butyl-6-diphenylphosphine-phenol-cyclopentadienyl titanium dichloride;

[0063] A 4 :2-Silylmethyl-6-di-tert-butylphosphine-phenol-cyclopentadienyl titanium dichloride;

[0064] A 5 :2-Silylmethyl-6-diphenylphosphine-phenol-indenylcyclopentadienyl titanium dichloride;

[0065] A 6 : 2-Silymethyl-6-diphenylphosphine-phenol-fluorenylcyclopentadienyl titanium dichloride;

[0066] A 7 : 2-Silymethyl-6-di-tert-butylphosphine-phenol-indenylcyclopentadienyl titanium dichloride.

[0067] After adding 1mmol of non-clocene ligand 2-silylmethyl-6-diphenylphosphine-phenol and 15ml of THF to the reaction flask to dissolve, add 3mmol of NaH, stir at room temperature for 6h, filter to remove excess NaH, the resulting yellow The filt...

Embodiment 2

[0074] Example 2 Preparation of the semi-metallocene complex 2-silylmethyl-6-diphenylphosphine-thiophenol-fluorenylcyclopentadienyl titanium dichloride (B 1 )

[0075] Half metallocene complex B 1 The preparation method and A 1 The same, the difference is that the non-cylinder ligand is 2-silylmethyl-6-diphenylphosphine-thiophenol, and the single metallocene is fluorenylcyclopentadienyl titanium trichloride.

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Abstract

The invention provides a preparation method of cycloolefin copolymers. The preparation method comprises the steps of utilizing a half metallocene complex in a structure of a formula (I) as main catalysts, forming a salt ion active center after being acted with a cocatalyst, and thereby catalyzing the copolymerisation of ethylene and norbornene. On one hand, the existence of R in the half metallocene complex ensures the catalytic activity of a half metallocene system; the introduction of P, O or S atoms for the half metallocene complex improves the catalytic stability, therefore, the catalytic activity of the half metallocene complex is high; on the other hand, the introduction of aryloxy or aromatic sulfenyl further improves the charge properties and the space effects of a transition metal center, thereby being favorable for stabilizing a metal cation center; and the larger volume and an annual structure formed with the metal center also generate certain restriction to the spatial configuration of the half metallocene complex, therefore the generated cycloolefin copolymers through catalysis have high molecular weight, and at the same time, the method of the invention ensures that the content of the norbornene in the complex is high and can be regulated.

Description

Technical field [0001] The invention belongs to the technical field of olefin polymerization, and particularly relates to a preparation method of a cycloolefin copolymer. Background technique [0002] Norbornene homopolymer has the advantages of high temperature resistance, but because the glass transition temperature is too high, it is not conducive to processing, which limits its application and promotion; polyethylene is easy to process and shape, but it is very sensitive to chemical and mechanical effects. By copolymerizing norbornene and ethylene, a cycloolefin copolymer (COC) with excellent performance can be obtained, which not only has excellent heat stability, light resistance, moisture resistance, hydrolysis resistance and chemical resistance of polyolefin resin, but also No harmful gas is generated during incineration, and it also shows the characteristics of amorphous resin in terms of mechanical properties, flow characteristics, dimensional accuracy and other physica...

Claims

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Application Information

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IPC IPC(8): C08F232/08C08F210/02C08F4/6592C07F7/28C07F7/00
Inventor 刘靖宇唐小燕李彦国李悦生
Owner CHANGZHOU INST OF ENERGY STORAGE MATERIALS &DEVICES
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