Dicyclopentadiene-cyclopentene copolymer and preparation method thereof

A technology of cyclopentene copolymer and dicyclopentadiene, which is applied in the field of dicyclopentadiene-cyclopentadiene copolymer and its preparation, can solve the problems of high preparation cost, low production efficiency, long reaction time, etc., and achieve anti- Improved impact strength and bending performance, improved impact strength, and good material performance

Active Publication Date: 2016-10-05
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Though this method can obtain the better composite material of impact resistance, the preparation method of this material is more complicated, as will rubber be dissolved in the rubber solution of dicyclopentadiene in advance to prepare dicyclopentadiene, and solid rubber is in dicyclopentadiene The dissolution process in diene is slow and continuous production is difficult, resulting in low production efficiency
[0005] CN1084340C discloses a polydicyclopentadiene composite material and its preparation method. In the method, 0.1-2% of inorganic nano filler and 0-5% of auxiliary polymer particles are added to the feed liquid of polydicyclopentadiene before molding , although composite materials with good heat resistance, good surface finish, high impact resistance, and high flexural modulus can be obtained, this method requires a two-component composite catalyst, and flame retardants, Auxiliaries such as plasticizers, tackifiers, fillers, and pigments lead to complex preparation processes and high preparation costs, and the toughness and impact strength of the materials are average.
However, it needs to pre-dissolve the ethylene copolymer in dicyclopentadiene, and the preparation process is relatively complicated.
[0007] The disadvantage of the above methods is that the added elastomer material or filler and dicyclopentadiene are physically mixed and cannot be completely uniform.
[0008] Pang Deren etc. (Pang Deren, Zheng Yulian, Chen Wenqi, the novel rubber of cyclopentene and dicyclopentadiene copolymerization, I. the research of copolymerization law [J], synthetic rubber industry, 1981,4 (4): 288-292; Pang Deren, Chen Wenqi, A new type of rubber copolymerized with cyclopentene and dicyclopentadiene, II. The structural analysis and performance research of the copolymer [J], Synthetic Rubber Industry, 1981, 5 (4): 374-387) carried out cyclopentene Synthesis and performance research of new rubber copolymerized with dicyclopentadiene, wherein the content of dicyclopentadiene in the rubber material is 5-10%, to obtain a high elastic rubber material instead of engineering plastics, and the preparation method of the rubber material needs to adopt The solution polymerization method, the monomer concentration in the solution is about 20%, the reaction temperature is 0 ℃, the reaction time is long (about 2-3 hours), and the polymerization conversion rate is less than 87%, resulting in low reaction efficiency, complicated process, and polymerization The catalyst used in the reaction is different from the catalyst used in the preparation of polydicyclopentadiene engineering plastics
This document does not improve the performance of polydicyclopentadiene plastics

Method used

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  • Dicyclopentadiene-cyclopentene copolymer and preparation method thereof
  • Dicyclopentadiene-cyclopentene copolymer and preparation method thereof
  • Dicyclopentadiene-cyclopentene copolymer and preparation method thereof

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[0023] The present invention also provides a preparation method of dicyclopentadiene-cyclopentene copolymer, the method comprising: injecting solution A and solution B into a mold for reaction injection molding to obtain dicyclopentadiene-cyclopentene copolymer wherein, solution A contains a catalyst and a stabilizer, solution B contains an activator and a polymerization reaction time regulator, and at least one of solution A and solution B contains dicyclopentadiene, and at least one of solution A and solution B also contains Containing cyclopentene, the weight ratio of dicyclopentadiene to cyclopentene is 99-90:1-10; preferably, the weight ratio of dicyclopentadiene to cyclopentene is 98-94:2-6.

[0024] Reaction Injection Molding (RIM) is a method of injecting liquid monomers or low-viscosity copolymers directly into a mold for rapid polymerization. Short cycle, low energy consumption, low cost and good product quality.

[0025] In the presence of a catalyst, dicyclopentad...

Embodiment 1

[0046] This example is used to illustrate the preparation method of the dicyclopentadiene-cyclopentene copolymer provided by the present invention.

[0047] (1) Prepare solution A

[0048] Add catalyst bis(2,6 di-tert-butylphenoxy)tungsten tetrachloride 15g, dicyclopentadiene (dicyclopentadiene Purity>97%) 2750g, cyclopentene (cyclopentene purity greater than 99%) 250g and benzyl acetonitrile 0.075g, of which two (2,6 di-tert-butylphenoxy) tungsten tetrachloride: (dicyclopentadiene + cyclopentene): benzyl acetonitrile (weight ratio) = 1:200:0.005.

[0049] (2) Prepare Solution B

[0050] Add 18g of diethylaluminum chloride, 2g of diethylzinc, and 2000g of dicyclopentadiene (purity of dicyclopentadiene >97%) into tank B of the reaction injection molding machine at a temperature of 40±5°C and nitrogen protection and diethylene glycol dimethyl ether 300g. Wherein (diethylaluminum chloride+diethylzinc): dicyclopentadiene: diethylene glycol dimethyl ether (weight ratio) = 1:100...

Embodiment 2

[0058] This example is used to illustrate the preparation method of the dicyclopentadiene-cyclopentene copolymer provided by the present invention.

[0059] (1) Prepare solution A

[0060] Add catalyst bis(p-methylphenoxy)tungsten tetrachloride 15g, dicyclopentadiene (purity of dicyclopentadiene>97% ) 2950g, cyclopentene (cyclopentene purity greater than 99%) 50g and benzonitrile 0.15g; wherein two (p-methylphenoxy) tungsten tetrachloride: (dicyclopentadiene + cyclopentene): benzyl Formaldehyde (weight ratio)=1:200:0.01.

[0061] (2) Prepare Solution B

[0062] Add 9 g of diethyl aluminum chloride, 1 g of diethyl zinc, and 2000 g of dicyclopentadiene (purity of dicyclopentadiene >97%) into tank B of the reaction injection molding machine at a temperature of 40±5°C and nitrogen protection And diethylene glycol dibutyl ether 200g. Wherein (diethylaluminum chloride+diethylzinc): dicyclopentadiene: diethylene glycol dibutyl ether (weight ratio) = 1:200:20.

[0063] Where (dic...

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Abstract

The invention discloses a dicyclopentadiene-cyclopentene copolymer and a preparation method thereof. With the total weight of the copolymer as a reference, the copolymer contains 1-10wt% of cyclopentene structural units, and 90-99wt% of dicyclopentadiene structural units. The dicyclopentadiene-cyclopentene copolymer provided by the invention has high polymerization conversion rate. A prepared product has no odor, good heat resistance, and especially excellent impact resistance. With the preparation method, the impact resistance of the material is improved from approximately 100J/m of a prior polycyclopentene diene homopolymer material to 300-400J/m. The material can be used as various impact-resistant engineering materials.

Description

technical field [0001] The invention relates to a dicyclopentadiene-cyclopentene copolymer and a preparation method thereof. Background technique [0002] Polydicyclopentadiene (polydicyclopentadiene, English abbreviation PDCPD) is an engineering plastic with high impact resistance and high modulus obtained by polymerizing monomer dicyclopentadiene under the action of a catalyst. The monomer dicyclopentadiene is It is the largest by-product in petrochemical ethylene production. [0003] In 1985, the American Hercules Company and Goodrich Company jointly realized the industrialization of polydicyclopentadiene engineering plastics for the first time. Representative brands of polydicyclopentadiene engineering plastics include METTON jointly developed by Hercules and Teijin Co., Ltd., and TELENE and PENTAM series jointly developed by Goodrich and Zeon Corporation. Although polydicyclopentadiene engineering plastics have certain characteristics of heat resistance, creep resista...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F232/08C08F232/04C08F4/69
Inventor 贺小进王世朝张杰李传清王雪韩书亮李良杰
Owner CHINA PETROLEUM & CHEM CORP
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