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WO2021057074A1 - Nouveau copolymère de cyclooléfine à haute transmittance de la lumière, à haute résistance et résistant aux températures élevées et son procédé de préparation - Google Patents

Nouveau copolymère de cyclooléfine à haute transmittance de la lumière, à haute résistance et résistant aux températures élevées et son procédé de préparation Download PDF

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Publication number
WO2021057074A1
WO2021057074A1 PCT/CN2020/094135 CN2020094135W WO2021057074A1 WO 2021057074 A1 WO2021057074 A1 WO 2021057074A1 CN 2020094135 W CN2020094135 W CN 2020094135W WO 2021057074 A1 WO2021057074 A1 WO 2021057074A1
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Prior art keywords
norbornene
parts
catalyst
liquid
temperature
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PCT/CN2020/094135
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Chinese (zh)
Inventor
陈旭东
邓健文
甄智勇
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Guangdong Juhang Institute For Advanced Materials Co Ltd
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Guangdong Juhang Institute For Advanced Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F232/08—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 having condensed rings

Definitions

  • the invention relates to a cyclic olefin copolymer, in particular to a novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmission, and a preparation method thereof.
  • Temperature-resistant and high-light-transmitting materials can be widely used in temperature-resistant engine hoods, windshields, exhibition halls, and other high-end optical materials applications. , The market demand is extensive.
  • temperature-resistant and light-transmitting materials mainly add some reinforcing fillers, such as particles or short fibers, thereby reducing the transparency of the material.
  • the highest light transmittance of epoxy transparent materials is less than 90%, and the light-transmitting PC has poor wear resistance and transparency.
  • the poor weather resistance of optical PS affects the application in high-grade optical materials.
  • the purpose of the present invention is to provide a novel cycloolefin copolymer with high temperature resistance, high strength and high light transmission and a preparation method thereof, which has the advantages of low density, high strength, excellent temperature resistance, environmental protection, simplicity, and low cost.
  • cycloolefins especially polydicyclopentadiene, light-weight, high-strength, temperature-resistant and high-light-transmitting plastics have opened up a wider neighborhood of plastics in high-light-transmitting materials, and made up for the advantages of light-transmitting PMMA and PC.
  • the defects in the market are solved.
  • a new type of high temperature resistant, high strength and high light transmission cycloolefin copolymer includes the following parts by weight of raw materials: 35-65 parts of dicyclopentadiene, norbornene 10-40 parts of its derivatives, 3-5 parts of benzene solvents, 1-3 parts of ketone solvents, 5-8 parts of alcohol solvents, 10-15 parts of high transparency aids, 0.01-0.2 parts of catalysts.
  • the cycloolefin polymer is formed by the copolymerization of dicyclopentadiene and norbornene, including polydicyclopentadiene.
  • the purity of polydicyclopentadiene is greater than 70%, and the transparency is 92%-96%.
  • the pentadiene can be used for a long time at 110-140°, the maximum use temperature is as high as 230°, the elastic modulus of polydicyclopentadiene is 3.2GPa, the flexural modulus is 2.2GPa, and it has excellent strength.
  • 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 derivatives, styrene, olefin derivatives, dienes, Bicyclo[2.2.1]heptene derivatives, cyclopentene, cyclopentadiene, tetracyclododecene, 5-cyclohexyl-2-norbornene, 5,5-dimethyl-2-norbornene
  • the benzene solvent is cyclohexylbenzene, 1,2-diphenylethane, toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, dodecylbenzene, 1,2,4-triphenylene
  • cyclohexylbenzene 1,2-diphenylethane
  • toluene xylene
  • ethylbenzene diethylbenzene
  • propylbenzene propylbenzene
  • dodecylbenzene 1,2,4-triphenylene
  • 1,2,4-triphenylene One or more of toluene, butylbenzene, p-cymene, biphenyl, naphthalene, chlorobenzene, and aniline.
  • the alcohol solvent is one or more of methanol, ethanol, propanol, butanol, isopropanol, and neopentyl alcohol.
  • the high transparency auxiliary agent is one or more of polymerization inhibitor, anti-aging agent, flame retardant, anti-UV stabilizer, heat stabilizer, and light stabilizer.
  • the transparency rate of the high transparency auxiliary agent is ⁇ 95% of which,
  • the polymerization inhibitor is selected from hydroquinone, ethylene glycol dimethyl ether, diethylene glycol dibutyl ether, isopropyl ether, benzophenone, triphenylphosphine, tert-butylcatechol, 2,6 -One or more of polymerization inhibitors such as di-tert-butyl p-cresol and p-benzoquinone;
  • the anti-aging agent is selected from calcium sulfate, 2,8-di-tert-butyl-4-methylphenol, antioxidant 1U1U, BASF 1010, p-tert-butyl phenol, antioxidant 168, tert-butyl terephthalate
  • anti-aging agents such as phenol, aniline and 2-methylaniline;
  • the flame retardant is selected from the group consisting of tributyl phosphate, tris(2-ethylhexyl) phosphate, tris(2-chloroethyl) phosphate, tris(2,3-dichloropropyl) phosphate, tris(2-ethylhexyl) phosphate, (2,3-Dibromopropyl) ester, dibromomethane, chlorobromomethane, dichlorobromomethane, octabromodiphenyl oxide, pentabromoethylbenzene, tetrabromobisphenol A, organophosphorus-nitrogen polymer
  • tributyl phosphate tris(2-ethylhexyl) phosphate
  • tris(2-chloroethyl) phosphate tris(2,3-dichloropropyl) phosphate
  • tris(2-ethylhexyl) phosphate 2,3
  • the anti-UV stabilizer is selected from UV-531, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, UV-2908, 3,5-two One or more of n-hexadecyl tert-butyl-4-hydroxybenzoate, phenyl o-hydroxybenzoate, and 2,4-dihydroxybenzophenone.
  • the catalyst includes one or more of a ruthenium-based carbene catalyst, a platinum-ruthenium carbene catalyst, a palladium-based catalyst, an osmium-based carbene catalyst, a palladium acetate catalyst, a carbonyl rhodium catalyst, and a triphenylphosphine carbonyl rhodium catalyst.
  • the present invention also provides a method for preparing the novel cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance, which comprises the following steps:
  • Step 1 Prepare liquid A at room temperature: In addition to the catalyst, mix the liquid raw materials, transparency aid and 5-10 parts of solvent evenly;
  • the second step preparation of catalyst solution: fully mix the catalyst with 1-5 parts of solvent to make B solution;
  • the third step Mix AB liquid in a certain proportion, stir evenly at room temperature about 25°C, and mix AB liquid fully;
  • Step 4 pour the mixed AB liquid into the mold and place it at 45-80°C to cure;
  • the fifth step curing is completed and demoulding.
  • This new type of cyclic olefin copolymer with high temperature resistance, high strength and high light transmission and its preparation method is copolymerized with dicyclonorbornene and dicyclopentadiene, which has low density, high strength and excellent
  • the high-quality characteristics of temperature resistance, environmental protection, simplicity, and low cost have improved the competitiveness of cycloolefins in the market, especially polydicyclopentadiene.
  • It has also developed light-weight, high-strength, temperature-resistant, high-transparent plastics, and The plastics are in the wider neighborhood of high-transmittance materials, and the shortcomings of light-transmitting PMMA and PC in the market are made up.
  • a new type of high-temperature resistant, high-strength, high-light-transmitting cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to fully mix the liquid raw materials 5-dodecyl-2-norbornene, ENB and dicyclopentadiene at room temperature; add antioxidant 168, uv531, organic phosphorus-nitrogen transparent flame retardant and stir until The solid particles are completely dissolved and uniformly dispersed; 2,6-di-tert-butyl-p-cresol is dissolved in acetone and then poured into the mixed solution, and triphenylphosphine is dissolved in half of toluene and poured into the above mixed solution, stirring well After mixing uniformly, draw the vacuum to prepare liquid A.
  • the second step is to dissolve the ruthenium-based metal carbene catalyst in the remaining 1/2 toluene at room temperature, dilute and mix with neopentyl alcohol to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • the product is cooled, it is demoulded to obtain a board with a transparency rate of up to 95%.
  • a new type of high-temperature resistant, high-strength, high-light-transmitting cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to fully mix the liquid raw materials 5-ethyl-2-norbornene, PNB and dicyclopentadiene at room temperature; add antioxidant 168, UV-2908, and tributyl phosphate flame retardant and stir until solid The particles are completely dissolved and uniformly dispersed; after dissolving ethylene glycol dimethyl ether with methyl ethyl ketone, pour it into the mixed solution, dissolve triphenyl phosphine with one-half of xylene and pour into the above mixed solution, stir and mix well, The A liquid is ready when the vacuum is drawn.
  • the platinum ruthenium carbene catalyst was dissolved in the remaining 1/2 xylene at room temperature, diluted with methanol and mixed uniformly to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • demolding can obtain a plate with a transparency rate of up to 96%.
  • a new type of high-temperature resistant, high-strength, high-light-transmitting cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to fully mix the liquid raw materials 5-methyl-2-norbornene, ENB and dicyclopentadiene at room temperature; add antioxidant 168, 2-hydroxy-4-n-octyloxybenzophenone , Tris(2,3-dibromopropyl) phosphate flame retardant is stirred until the solid particles are completely dissolved and dispersed evenly; ethylene glycol dimethyl ether is dissolved in methyl butanone and poured into the mixed solution, and p-benzoquinone is used One-half of the ethylbenzene is dissolved and poured into the above mixed solution, stirred and mixed thoroughly, and then vacuum is drawn to prepare liquid A.
  • the palladium catalyst is dissolved in the remaining 1/2 ethylbenzene at room temperature, diluted with isopropanol and mixed uniformly to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • the sixth step after the product is cooled, it is demoulded to obtain a plate with a transparency rate of up to 98%.
  • a new type of high-temperature resistant, high-strength, high-light-transmitting cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to fully mix the liquid raw materials 5-methyl-2-norbornene and 11% 5-vinyl-2-norbornene with dicyclopentadiene at room temperature; add tert-butyl hydroquinone, Phenyl o-hydroxybenzoate and octabromodiphenyl oxide flame retardant are stirred until the solid particles are completely dissolved and evenly dispersed; the isopropyl ether is dissolved in methyl isobutyl ketone and poured into the mixture, and benzophenone is used in the mixture. One part of the 1,2,4-trimethylbenzene is dissolved and poured into the above mixed liquid. After stirring and mixing thoroughly, liquid A is prepared by drawing vacuum.
  • the second step is to dissolve the osmium-based carbene catalyst in the remaining 1/2 of 1,2,4-trimethylbenzene at room temperature, dilute with neopentyl alcohol and mix uniformly to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • demolding can obtain a plate with a transparency rate of up to 96%.
  • a new type of high-temperature resistant, high-strength, high-light-transmitting cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to fully mix the liquid raw materials 5-butyl-2-norbornene, PNB and dicyclopentadiene at room temperature; add antioxidants 1U1U, 2,4-dihydroxybenzophenone, and tetrabromobis Phenol
  • a flame retardant is stirred until the solid particles are completely dissolved and evenly dispersed; Diethylene glycol dibutyl ether is dissolved in cyclopentanone and poured into the mixed solution, and triphenylphosphine is dissolved in half of the propylbenzene and then poured into the mixture.
  • the A liquid is prepared by drawing the vacuum.
  • the triphenylphosphine carbonyl rhodium catalyst is dissolved in the remaining 1/2 propylbenzene at room temperature, diluted with isopropanol and mixed uniformly to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • the product is cooled, it is demoulded to obtain a board with a transparency rate of up to 95%.
  • Cyclic olefin copolymer and its preparation method are prepared from the following raw materials in weight fraction:
  • the first step is to add antioxidant 1U1U, 2,4-dihydroxybenzophenone, and tetrabromobisphenol A flame retardant to dicyclopentadiene at room temperature and stir until the solid particles are completely dissolved and dispersed evenly;
  • Dibutyl alcohol is dissolved in cyclopentanone and poured into the mixed solution.
  • Triphenylphosphine is dissolved in one-half of propylbenzene and poured into the above mixed solution. After stirring and mixing thoroughly, the vacuum is drawn to prepare liquid A.
  • the triphenylphosphine carbonyl rhodium catalyst is dissolved in the remaining 1/2 propylbenzene at room temperature, diluted with isopropanol and mixed uniformly to obtain liquid B.
  • the third step at room temperature about 25 °C, slowly add the well-mixed solution B to the solution A, while stirring the solution A so that the solution B is evenly mixed in the solution A, stirring for about 2 minutes to take out. Put it into the vacuum box to extract the vacuum, control the vacuum temperature not to exceed 35°C, take it out in about 10 minutes, and pour it into the mold.
  • the mold is heated to 45°C to make the AB mixture react and solidify within 10 minutes.
  • the cured product is placed in an oven, and the temperature is increased from room temperature to 100° for 30 minutes and then increased by 30°. In the same way, the temperature is increased to 210, and then the temperature is decreased by 15° every 15 minutes.
  • the product is cooled, it is demoulded to obtain a board with a transparency rate of up to 94%.
  • Comparative Example 1 does not use norbornene and its derivatives, its performance standards are significantly lower than those of the examples of the present invention. Because the invented new cycloolefin copolymer is copolymerized with dicyclonorbornene and dicyclopentadiene, its performance standard is significantly better than that of Comparative Example 1. It has the characteristics of high temperature resistance, light constant density, high strength and high toughness. , The light transmittance reaches more than 95%, and the extreme temperature resistance is 230°C, which can be well applied in the field of high temperature resistance and light transmission.
  • this new type of cyclic olefin copolymer with high temperature resistance, high strength and high light transmittance and its preparation method is made by copolymerization of dicyclonorbornene and dicyclopentadiene, which has light weight and high strength.
  • High modulus, high temperature resistance, high light transmittance, which provides excellent performance for cycloolefin copolymers gives a great competitive market, opens up a wider neighborhood of plastics in high light transmittance materials, and makes up for light transmittance The defects of PMMA and PC in the market.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un nouveau copolymère de cyclooléfine à haute transmittance de la lumière, à haute résistance et résistant à des températures élevées, et son procédé de préparation. Le copolymère de cyclooléfine comprend les matières premières suivantes en parties en poids: 35 à 65 parties de dicyclopentadiène, 10 à 40 parties de norbornène et leurs dérivés, 3 à 5 parties d'un solvant benzène, 1 à 3 parties d'un solvant cétone, 5 à 8 parties d'un solvant alcoolique, 10 à 15 parties d'un agent auxiliaire à haute transparence, et 0,01 à 0,2 partie d'un catalyseur. Le procédé de préparation comprend les étapes suivantes consistant à: en plus du catalyseur, mélanger uniformément un matériau liquide, un agent auxiliaire transparent et 5 à 10 parties du solvant pour préparer une solution A; mélanger complètement et uniformément le catalyseur avec 1 à 5 parties d'un solvant pour préparer une solution de catalyseur B; mélanger le liquide A et le liquide B selon une certaine proportion, agiter uniformément la solution mélangée à la température ambiante d'environ 25 °C, et mélanger le liquide A et le liquide B; verser le liquide AB mélangé dans un moule, effectuer un traitement de base pour mouler le mélange à 45-80 °C, et démouler le produit moulé. La présente invention présente les caractéristiques de procédé simple et pratique, de faible densité, de haute résistance, d'une excellente résistance à la température, d'un environnement respectueux de l'environnement, et de faible coût.
PCT/CN2020/094135 2019-09-28 2020-06-03 Nouveau copolymère de cyclooléfine à haute transmittance de la lumière, à haute résistance et résistant aux températures élevées et son procédé de préparation Ceased WO2021057074A1 (fr)

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CN201910928874.6 2019-09-28
CN201910928874.6A CN110615867A (zh) 2019-09-28 2019-09-28 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

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CN111777701B (zh) * 2020-06-16 2022-07-22 派迈新材料(成都)有限责任公司 一种树脂组合物在制备绝缘基板或覆铜箔层压板中的用途
CN114685716B (zh) * 2020-12-31 2024-02-02 江苏博睿光电股份有限公司 一种可交联环烯烃共聚物及其制备方法和应用
TW202504937A (zh) * 2021-07-22 2025-02-01 財團法人工業技術研究院 共聚物
CN114350073B (zh) * 2022-01-11 2023-04-25 广东德冠包装材料有限公司 一种bopp消光料及其制备方法和bopp消光膜
CN115850897B (zh) * 2022-12-27 2024-07-09 上海中化科技有限公司 树脂组合物、纤维增强树脂基复合材料及其制备方法

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WO2009154879A2 (fr) * 2008-06-20 2009-12-23 3M Innovative Properties Company Moules polymères et articles fabriqués à partir de ceux-ci
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CN106432617A (zh) * 2015-08-07 2017-02-22 现代自动车株式会社 用于制备轻质透明复合材料的组合物、制备复合材料的方法以及由此制备的复合材料
CN105199290A (zh) * 2015-08-24 2015-12-30 克琴新材料科技（上海）有限公司 一种聚双环戊二烯复合材料及其单料反应注射成型工艺
CN110615867A (zh) * 2019-09-28 2019-12-27 广东聚航新材料研究院有限公司 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

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