阅读说明：本技术 一种耐高温高强度高透光新型环烯烃共聚物及其制备方法 (Novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer and preparation method thereof ) 是由 陈旭东 邓健文 甄智勇 于 2019-09-28 设计创作，主要内容包括：一种耐高温高强度高透光新型环烯烃共聚物及其制备方法,环烯烃共聚物包括以下重量份的原料：双环戊二烯35-65份、降冰片烯及其衍生物10-40份、苯类溶剂3-5份、酮类溶剂1-3份、醇类溶剂5-8份、高透明助剂10-15份、催化剂0.01-0.2份。制备步骤如下：除催化剂外将液体原料、透明助剂与5-10份溶剂混合均匀,制成A液；将催化剂与1-5份溶剂充分混合均匀,制成催化剂B液；将AB液按一定比例混合,在室温25℃左右搅拌均匀,AB液混合；将混合好的AB液倒入模具,放置45-80℃固化、脱模。本发明具有低密度、高强度、优异的耐温性能且工艺环保、简便、成本低廉特点。(A novel high-temperature-resistant high-strength high-light-transmission cycloolefin copolymer and a preparation method thereof are disclosed, wherein the cycloolefin copolymer comprises the following raw materials in parts by weight: 35-65 parts of dicyclopentadiene, 10-40 parts of norbornene and derivatives thereof, 3-5 parts of benzene solvents, 1-3 parts of ketone solvents, 5-8 parts of alcohol solvents, 10-15 parts of high-transparency auxiliaries and 0.01-0.2 part of catalysts. The preparation steps are as follows: uniformly mixing the liquid raw material, the transparent auxiliary agent and 5-10 parts of solvent except the catalyst to prepare solution A; fully and uniformly mixing the catalyst and 1-5 parts of solvent to prepare a catalyst B solution; mixing the AB liquid according to a certain proportion, stirring uniformly at room temperature of about 25 ℃, and mixing the AB liquid; pouring the mixed AB liquid into a mold, standing at 45-80 ℃ for curing, and demolding. The invention has the characteristics of low density, high strength, excellent temperature resistance, environment-friendly process, simplicity and low cost.)

1. The novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer is characterized by comprising the following raw materials in parts by weight: 35-65 parts of dicyclopentadiene, 10-40 parts of norbornene and derivatives thereof, 3-5 parts of benzene solvents, 1-3 parts of ketone solvents, 5-8 parts of alcohol solvents, 10-15 parts of high-transparency auxiliaries and 0.01-0.2 part of catalysts.

2. The novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance as claimed in claim 1, wherein the cyclic olefin polymer is prepared by copolymerizing dicyclopentadiene and norbornene, and comprises polydicyclopentadiene.

3. The novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance as claimed in claim 1, wherein the norbornene is 5-methyl-2-norbornene, 5, 6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene (PNB), norbornane dianhydride, 5-vinyl-2-norbornene, maleic anhydride derivative, styrene, olefin derivative, acrylic acid derivative, one or more of dienes, bicyclo [2.2.1] heptene derivatives, cyclopentene, cyclopentadiene, tetracyclododecene, 5-cyclohexyl-2-norbornene, 5-dimethyl-2-norbornene.

4. The novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance as claimed in claim 1, wherein the benzene solvent is one or more selected from cyclohexylbenzene, 1, 2-diphenylethane, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, dodecylbenzene, 1, 2, 4-trimethylbenzene, butylbenzene, p-methylisopropylbenzene, biphenyl, naphthalene, chlorobenzene and aniline.

5. The novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer as claimed in claim 1, wherein the alcoholic solvent is one or more of methanol, ethanol, propanol, butanol, isopropanol and neopentyl alcohol.

6. The novel cyclic olefin copolymer with high temperature resistance, high strength and high transmittance as claimed in claim 1, wherein the high transparency assistant is one or more of polymerization inhibitor, aging inhibitor, flame retardant, UV stabilizer, heat stabilizer and light stabilizer,

the polymerization inhibitor is one or more of hydroquinone, ethylene glycol dimethyl ether, diethylene glycol dibutyl ether, isopropyl ether, benzophenone, triphenylphosphine, tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol, p-benzoquinone and other polymerization inhibitors;

the aging resistant agent is selected from one or more of calcium sulfate, 2, 8-di-tert-butyl-4-methylphenol, an antioxidant lU1U, BASF 1010, p-tert-butylphenol, an antioxidant 168, tert-butylhydroquinone, aniline, 2-methylaniline and other aging resistant agents;

the flame retardant is selected from one or more of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, dibromomethane, trichlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethylbenzene, tetrabromobisphenol A and organic phosphorus-nitrogen polymer;

the anti-UV stabilizer is selected from one or more of UV-531, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-2908, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester, phenyl o-hydroxybenzoate and 2, 4-dihydroxybenzophenone.

7. The novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance as claimed in claim 1, wherein the catalyst is one or more of ruthenium carbene catalyst, platinum ruthenium carbene catalyst, palladium catalyst, osmium carbene catalyst, palladium acetate catalyst, rhodium carbonyl catalyst and triphenylphosphine rhodium carbonyl catalyst.

8. A method for preparing the novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance according to any one of claims 1 to 7, comprising the steps of:

the first step is as follows: preparing the solution A at normal temperature: uniformly mixing the liquid raw material, the transparent auxiliary agent and 5-10 parts of solvent except the catalyst;

the second step is that: preparation of a catalyst solution: fully and uniformly mixing the catalyst and 1-5 parts of solvent to prepare a solution B;

the third step: mixing the AB liquid according to a certain proportion, stirring uniformly at room temperature of about 25 ℃, and fully mixing the AB liquid;

the fourth step: pouring the mixed AB liquid into a mold, and standing at 45-80 ℃ for curing;

the fifth step: and (5) finishing curing and demolding.

Technical Field

The invention relates to a cycloolefin copolymer, in particular to a novel cycloolefin copolymer with high temperature resistance, high strength and high light transmittance and a preparation method thereof.

Background

With the call of new era, novel environment-friendly high-temperature-resistant and light-transmitting multifunctional materials are explored and pursued, and the high-temperature-resistant and light-transmitting materials can be widely applied to high-grade optical material application places such as temperature-resistant engine hoods, wind shields, exhibition halls and the like, and are wide in market demand.

At present, some reinforcing fillers such as particles or short fibers are mainly added into the temperature-resistant transparent material, so that the transparency of the material is reduced, the maximum light transmittance of the epoxy transparent material is less than 90%, the wear resistance of transparent PC is poor, and the weather resistance of transparent PS is poor, so that the application of the transparent PC in high-grade optical materials is influenced.

Disclosure of Invention

The invention aims to provide a novel high-temperature-resistant high-strength high-light-transmission cycloolefin copolymer and a preparation method thereof, which have the high-quality characteristics of low density, high strength, excellent heat resistance, environment-friendly and simple process, low cost and the like, improve the competitiveness of cycloolefin in the market, particularly polydicyclopentadiene and light-weight high-strength heat-resistant high-light-transmission plastic develop the wider neighborhood of the plastic in high-light-transmission materials, make up the defects of light-transmission PMMA and PC in the market, and solve the problems in the background art.

In order to achieve the purpose, the invention provides the following technical scheme: a novel high-temperature-resistant high-strength high-light-transmission cycloolefin copolymer comprises the following raw materials in parts by weight: 35-65 parts of dicyclopentadiene, 10-40 parts of norbornene and derivatives thereof, 3-5 parts of benzene solvents, 1-3 parts of ketone solvents, 5-8 parts of alcohol solvents, 10-15 parts of high-transparency auxiliaries and 0.01-0.2 part of catalysts.

Furthermore, the cycloolefin polymer is formed by copolymerizing dicyclopentadiene and norbornene, and comprises polydicyclopentadiene, wherein the purity of the polydicyclopentadiene is more than 70%, the transparency is 92% -96%, the polydicyclopentadiene can be used for a long time at 140 ℃ of 110-.

Further, the norbornene is 5-methyl-2-norbornene, 5, 6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, 5-ethylidene-2-norbornene (ENB), 5-propenyl-2-norbornene (PNB), norbornadic anhydride, 5-vinyl-2-norbornene, maleic anhydride derivatives, styrene, olefin derivatives, dienes, bicyclo [2.2.1] heptene derivatives, cyclopentene, cyclopentadiene, tetracyclododecene, 5-cyclohexyl-2-norbornene, 5-dimethyl-2-norbornene.

Further, the benzene solvent is one or more of cyclohexylbenzene, 1, 2-diphenylethane, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, dodecylbenzene, 1, 2, 4-trimethylbenzene, butylbenzene, p-methylisopropylbenzene, biphenyl, naphthalene, chlorobenzene and aniline.

Further, the alcohol solvent is one or more of methanol, ethanol, propanol, butanol, isopropanol and neopentyl alcohol.

The high-transparency additive is one or more of a polymerization inhibitor, an aging resistant agent, a flame retardant, an anti-UV stabilizer, a heat stabilizer and a light stabilizer, the transparency rate of the high-transparency additive is not less than 95%, wherein the polymerization inhibitor is one or more of hydroquinone, ethylene glycol dimethyl ether, diethylene glycol dibutyl ether, isopropyl ether, benzophenone, triphenylphosphine, tert-butyl catechol, 2, 6-di-tert-butyl-p-cresol, p-benzoquinone and other polymerization inhibitors;

the aging resistant agent is selected from one or more of calcium sulfate, 2, 8-di-tert-butyl-4-methylphenol, an antioxidant lU1U, BASF 1010, p-tert-butylphenol, an antioxidant 168, tert-butylhydroquinone, aniline, 2-methylaniline and other aging resistant agents;

the flame retardant is selected from one or more of tributyl phosphate, tri (2-ethylhexyl) phosphate, tri (2-chloroethyl) phosphate, tri (2, 3-dichloropropyl) phosphate, tri (2, 3-dibromopropyl) phosphate, dibromomethane, trichlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethylbenzene, tetrabromobisphenol A and organic phosphorus-nitrogen polymer;

the anti-UV stabilizer is selected from one or more of UV-531, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-2908, 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester, phenyl o-hydroxybenzoate and 2, 4-dihydroxybenzophenone.

Further, the catalyst comprises one or more of ruthenium carbene catalyst, platinum ruthenium carbene catalyst, palladium catalyst, osmium carbene catalyst, palladium acetate catalyst, rhodium carbonyl catalyst and triphenylphosphine rhodium carbonyl catalyst.

The invention also provides a preparation method of the novel high-temperature-resistant high-strength high-light-transmission cycloolefin copolymer, which comprises the following steps:

the first step is as follows: preparing the solution A at normal temperature: uniformly mixing the liquid raw material, the transparent auxiliary agent and 5-10 parts of solvent except the catalyst;

the second step is that: preparation of a catalyst solution: fully and uniformly mixing the catalyst and 1-5 parts of solvent to prepare a solution B;

thirdly, mixing the AB liquid according to a certain proportion, stirring evenly at room temperature of about 25 ℃, and fully mixing the AB liquid;

the fourth step: pouring the mixed AB liquid into a mold, and standing at 45-80 ℃ for curing;

the fifth step: and (5) finishing curing and demolding.

Compared with the prior art, the invention has the beneficial effects that:

the novel cyclic olefin copolymer is prepared by copolymerizing dicyclo norbornene and dicyclopentadiene, has the high-quality characteristics of low density, high strength, excellent temperature resistance, environment-friendly, simple and convenient process, low cost and the like, improves the competitiveness of cyclic olefin in the market, particularly polydicyclopentadiene, develops light-weight high-strength temperature-resistant high-light-transmission plastic, develops a wider neighborhood of the plastic in a high-light-transmission material, and makes up the defects of light-transmission PMMA and PC in the market.

Detailed Description

The following examples will explain the present invention in detail, but the present invention is not limited thereto. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.