CN110615867A - Novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer and preparation method thereof - Google Patents
Novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer and preparation method thereof Download PDFInfo
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- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
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Abstract
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.
Description
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.
Example 1
A novel high-temperature-resistant, high-strength and high-light-transmission cycloolefin copolymer and a preparation method thereof are prepared from the following raw materials in parts by weight:
60.7 percent of dicyclopentadiene, 12.6 percent of 5-dodecyl-2-norbornene, 6.9 percent of cyclopentene, 10 percent of 5-ethylidene-2-norbornane (ENB), 0.45 percent of 2, 6-di-tert-butyl-p-cresol, 0.03 percent of triphenylphosphine, 1680.5 percent of antioxidant, uv5310.5 percent, 0.8 percent of organophosphorus-nitrogen transparent flame retardant, 4 percent of toluene, 1 percent of acetone, 5 percent of neopentyl alcohol and 0.02 percent of ruthenium metal carbene catalyst. The preparation method comprises the following steps:
step one, fully mixing liquid raw materials of 5-dodecyl-2-norbornene, ENB and dicyclopentadiene at normal temperature; adding the antioxidant 168, uv531 and the organic phosphorus-nitrogen transparent flame retardant, and stirring until the solid particles are completely dissolved and uniformly dispersed; dissolving 2, 6-di-tert-butyl-p-cresol with acetone, pouring into the mixed solution, dissolving triphenylphosphine with half of toluene, pouring into the mixed solution, stirring, mixing, and vacuumizing to obtain solution A.
And secondly, dissolving the ruthenium metal carbene catalyst in the remaining 1/2 toluene at normal temperature, diluting and mixing uniformly by using neopentyl alcohol to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 95 percent.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
example 2
A novel high-temperature-resistant, high-strength and high-light-transmission cycloolefin copolymer and a preparation method thereof are prepared from the following raw materials in parts by weight:
35% of dicyclopentadiene, 13% of 5-ethyl-2-norbornene, 6.9% of cyclopentadiene, 10% of 5-propenyl-2-norbornene (PNB), 0.45% of ethylene glycol dimethyl ether, 0.03% of triphenylphosphine, 1680.5% of antioxidant, UV-29080.5%, 1% of tributyl phosphate flame retardant, 4% of xylene, 1% of butanone, 5% of methanol and 0.02% of platinum-ruthenium carbene catalyst. The preparation method comprises the following steps:
step one, fully mixing liquid raw materials of 5-ethyl-2-norbornene, PNB and dicyclopentadiene at normal temperature; adding the antioxidant 168, the UV-2908 and the tributyl phosphate flame retardant, and stirring until the solid particles are completely dissolved and uniformly dispersed; dissolving ethylene glycol dimethyl ether with butanone, pouring into the mixed solution, dissolving triphenylphosphine with half of xylene, pouring into the mixed solution, stirring, mixing, and vacuumizing to obtain solution A.
And secondly, dissolving the platinum ruthenium carbene catalyst in the remaining 1/2 dimethylbenzene at normal temperature, diluting with methanol and mixing uniformly to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 96%.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
example 3
A novel high-temperature-resistant, high-strength and high-light-transmission cycloolefin copolymer and a preparation method thereof are prepared from the following raw materials in parts by weight:
62% of dicyclopentadiene, 13.2% of 5-methyl-2-norbornene, 7.5% of cyclopentene, 12% of 5-ethylidene-2-norbornane (ENB), 0.52% of ethylene glycol dimethyl ether, 0.05% of p-benzoquinone, 1680.5% of antioxidant, 0.6% of 2-hydroxy-4-n-octoxy benzophenone, 0.8% of tris (2, 3-dibromopropyl) phosphate flame retardant, 3% of ethylbenzene, 3% of methyl butanone, 6% of isopropanol and 0.02% of palladium catalyst. The preparation method comprises the following steps:
step one, fully mixing liquid raw materials of 5-methyl-2-norbornene, ENB and dicyclopentadiene at normal temperature; adding an antioxidant 168, 2-hydroxy-4-n-octoxy benzophenone and a tris (2, 3-dibromopropyl) phosphate flame retardant, and stirring until solid particles are completely dissolved and uniformly dispersed; dissolving ethylene glycol dimethyl ether with methyl butanone, pouring into the mixed solution, dissolving p-benzoquinone with one half of ethylbenzene, pouring into the mixed solution, stirring, mixing, and vacuumizing to obtain solution A.
And secondly, dissolving the palladium catalyst in the remaining 1/2 ethylbenzene at normal temperature, diluting with isopropanol, and mixing uniformly to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 98 percent.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
example 4
A novel high-temperature-resistant, high-strength and high-light-transmission cycloolefin copolymer and a preparation method thereof are prepared from the following raw materials in parts by weight:
65% of dicyclopentadiene, 12.3% of 5-ethyl-2-norbornene, 6.8% of diene, 11% of 5-vinyl-2-norbornene, 0.48% of isopropyl ether, 0.06% of benzophenone, 0.5% of tert-butyl hydroquinone, 0.6% of phenyl o-hydroxybenzoate, 0.8% of octabromodiphenyl oxide flame retardant, 3% of 1, 2, 4-trimethylbenzene, 3% of methyl isobutyl ketone, 6% of neopentyl alcohol and 0.1% of osmium carbene catalyst. The preparation method comprises the following steps:
step one, fully mixing liquid raw materials of 5-methyl-2-norbornene, 11 percent of 5-vinyl-2-norbornene and dicyclopentadiene at normal temperature; adding tert-butyl hydroquinone, phenyl o-hydroxybenzoate and octabromodiphenyl oxide flame retardant, and stirring until solid particles are completely dissolved and uniformly dispersed; dissolving isopropyl ether with methyl isobutyl ketone, pouring into the mixed solution, dissolving benzophenone with half of 1, 2, 4-trimethylbenzene, pouring into the mixed solution, stirring, mixing, and vacuumizing to obtain solution A.
And secondly, dissolving the osmium carbene catalyst into the remaining 1, 2, 4-trimethylbenzene of 1/2 at normal temperature, diluting with neopentyl alcohol, and uniformly mixing to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 96%.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
example 5
A novel high-temperature-resistant, high-strength and high-light-transmission cycloolefin copolymer and a preparation method thereof are prepared from the following raw materials in parts by weight:
55% of dicyclopentadiene, 13.4% of 5-butyl-2-norbornene, 7.2% of tetracyclododecene, 12% of 5-propenyl-2-norbornene (PNB), 0.44% of diethylene glycol dibutyl ether, 0.06% of triphenylphosphine, 0.6% of antioxidant lU1U0.6, 0.6% of 2, 4-dihydroxy benzophenone, 0.8% of tetrabromobisphenol A flame retardant, 5% of propylbenzene, 2% of cyclopentanone, 8% of isopropanol and 0.15% of triphenylphosphine carbonyl rhodium catalyst. The preparation method comprises the following steps:
step one, fully mixing liquid raw materials of 5-butyl-2-norbornene, PNB and dicyclopentadiene at normal temperature; adding an antioxidant lU1U, 2, 4-dihydroxy benzophenone and tetrabromobisphenol A flame retardant, and stirring until solid particles are completely dissolved and uniformly dispersed; dissolving diethylene glycol dibutyl ether with cyclopentanone, pouring into the mixed solution, dissolving triphenylphosphine with half propyl benzene, pouring into the mixed solution, stirring, mixing, and vacuum-pumping to obtain solution A.
And secondly, dissolving the triphenylphosphine carbonyl rhodium catalyst in the residual 1/2 propylbenzene at normal temperature, diluting and mixing the solution with isopropanol uniformly to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 95 percent.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
comparative example 1
The cycloolefin copolymer and the preparation method thereof are prepared by the following raw materials by weight percentage:
55% of dicyclopentadiene, 0.44% of diethylene glycol dibutyl ether, 0.06% of triphenylphosphine, 0.6% of antioxidant lU1U0.6%, 0.8% of 2, 4-dihydroxy benzophenone, 0.8% of tetrabromobisphenol A flame retardant, 5% of propyl benzene, 2% of cyclopentanone, 8% of isopropanol and 0.15% of triphenylphosphine carbonyl rhodium catalyst. The preparation method comprises the following steps:
the preparation method comprises the following steps:
firstly, adding an antioxidant lU1U, 2, 4-dihydroxy benzophenone and tetrabromobisphenol A flame retardant into dicyclopentadiene at normal temperature, and stirring until solid particles are completely dissolved and uniformly dispersed; dissolving diethylene glycol dibutyl ether with cyclopentanone, pouring into the mixed solution, dissolving triphenylphosphine with half propyl benzene, pouring into the mixed solution, stirring, mixing, and vacuum-pumping to obtain solution A.
And secondly, dissolving the triphenylphosphine carbonyl rhodium catalyst in the residual 1/2 propylbenzene at normal temperature, diluting and mixing the solution with isopropanol uniformly to obtain solution B.
And thirdly, slowly adding the mixed solution B into the solution A at room temperature of about 25 ℃, stirring the solution A to uniformly mix the solution B in the solution A, and taking out after stirring for about 2 minutes. Putting into a vacuum box, vacuumizing, controlling the vacuum temperature to be not more than 35 ℃, taking out after about 10 minutes, and pouring into a mold.
And fourthly, heating the mould to 45 ℃ to enable the AB mixed solution to react and solidify within 10 minutes.
And fifthly, putting the completely cured product in an oven, raising the temperature from room temperature to 100 ℃ for 30min, raising the temperature to 30 ℃, raising the temperature to 210 in the same way, and then reducing the temperature by 15 ℃ every 15 min.
Sixthly, after the product is cooled, demoulding to obtain the plate with the transparency rate of 94 percent.
The product performance of the novel high temperature resistant, high strength and high light transmittance cyclic olefin copolymer prepared in this example was tested, and the results are as follows:
through the comparison of the product performance tests of the 5 examples and the comparative example 1, it can be found that the comparative example 1 has a performance standard obviously lower than that of the example of the invention because norbornene and derivatives thereof are not used, and the novel cyclic olefin copolymer of the invention is prepared by copolymerizing dicyclo norbornene and dicyclopentadiene, has a performance standard obviously superior to that of the comparative example 1, has the characteristics of high temperature resistance, light equal density, high strength and high toughness, has the light transmittance of more than 95 percent, resists 230 ℃ in extreme temperature, and can be well applied to the high temperature resistant light transmission field.
In summary, the following steps: the novel cyclic olefin copolymer is prepared by copolymerizing dicyclo norbornene and dicyclopentadiene, has the advantages of light weight, high strength, high modulus, high temperature resistance and high light transmittance, provides excellent performance for the cyclic olefin copolymer, gives a large competitive market, develops a wider neighborhood of plastics in high light transmittance materials, and makes up the defects of light transmittance PMMA and PC in the market.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910928874.6A CN110615867A (en) | 2019-09-28 | 2019-09-28 | Novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer and preparation method thereof |
| PCT/CN2020/094135 WO2021057074A1 (en) | 2019-09-28 | 2020-06-03 | Novel high-temperature-resistant high-strength high-light-transmittance cycloolefin copolymer and preparation method therefor |
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| CN201910928874.6A CN110615867A (en) | 2019-09-28 | 2019-09-28 | Novel high-temperature-resistant high-strength high-light-transmittance cyclic olefin copolymer and preparation method thereof |
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| CN114685716A (en) * | 2020-12-31 | 2022-07-01 | 江苏博睿光电股份有限公司 | Crosslinkable cycloolefin copolymer and preparation method and application thereof |
| CN115677932A (en) * | 2021-07-22 | 2023-02-03 | 财团法人工业技术研究院 | Copolymer, film composition comprising the same, and composite material |
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