CN118420818A - Cycloolefin copolymer, preparation method and application thereof in virtual reality level head-mounted display - Google Patents
Cycloolefin copolymer, preparation method and application thereof in virtual reality level head-mounted display Download PDFInfo
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
- G02B27/01—Head-up displays
- G02B27/017—Head mounted
- G02B27/0172—Head mounted characterised by optical features
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Abstract
The invention relates to the technical field of high molecular compounds obtained by only using carbon-carbon unsaturated bond reaction, and particularly discloses a cycloolefin copolymer, a preparation method and application thereof in a virtual reality level head-mounted display. The invention takes solvent as medium, takes norbornene, spirofluorenyl alkene monomer and ethylene as polymerization monomer, and carries out polymerization reaction under the existence of catalyst to obtain the cycloolefin copolymer. The cycloolefin copolymer has high transparency and excellent refractive index and mechanical property, so that the application range of the polymer is widened.
Description
Technical Field
The invention relates to the technical field of high molecular compounds obtained by using only carbon-carbon unsaturated bond reaction, in particular to a cycloolefin copolymer, a preparation method and application thereof in a virtual reality level head-mounted display.
Background
Cycloolefin copolymers are a class of amorphous polymers which are formed by the copolymerization of ethylene or alpha-olefins with cycloolefins. It has many outstanding excellent properties such as high light transmittance, high chemical stability, high thermal stability, low birefringence, low density, low hygroscopicity, low dielectric loss, etc. Cycloolefin copolymers are widely used in the field of optical devices, such as: mobile phone lenses, security lenses, vehicle-mounted lenses, video cameras, camera lenses, printer lenses, terahertz lenses, AR/VR, HUD, specular reflectors, light guide panels, light control panels and reflective films of liquid crystal displays, flakes for liquid crystal backgrounds, optical discs, optical fibers and the like. Compared to other fields, such as: in the fields of packaging and medical treatment, the application of the cycloolefin copolymer in the optical field has the highest requirements on various properties of the material. Compared with the traditional optical glass, the optical-grade cycloolefin copolymer material has the advantages of light weight and strong plasticity, so that the material becomes the first choice material for preparing optical elements.
Compared with PMMA (polymethyl methacrylate), the cycloolefin copolymer material has comparable optical properties and has heat resistance higher than PC (polycarbonate), and also has more excellent dimensional stability than PMMA and PC, and the like. Therefore, cycloolefin copolymer materials are preferable materials for optical lenses such as mobile phones, AR/VR, and the like, and besides lenses, film materials made of cycloolefin copolymers can be used for various screens such as display polarizers in electronic products.
CN202011549213.1 relates to the field of cycloolefin copolymers, more specifically, the invention relates to a cycloolefin copolymer and a preparation method thereof, the structural units of the cycloolefin copolymer are (a) and (b) and/or the glass transition temperature of the cycloolefin copolymer is 100-400 ℃, and the number average molecular weight is 1000-10000000; the molecular weight distribution is 1.1-3.5. The invention adopts the copolymerization of styrene monomer and cycloolefin monomer to prepare cycloolefin copolymer, the activity of the polymerization system is high, the structure and the characteristics of the polymer, such as molecular weight, molecular weight distribution, cycloolefin content, glass transition temperature and the like, can be adjusted in a large range, meanwhile, the number average molecular weight of cycloolefin can reach the industrial application requirement, and in addition, the method for preparing cycloolefin copolymer is suitable for the industrial production condition and the processing and forming method of the polymer at present.
CN201510705169.1 provides a cycloolefin copolymer which has a structure shown in a formula I, wherein in the formula I, x is more than or equal to 240 and less than or equal to 480, and y is more than or equal to 30 and less than or equal to 150. The cycloolefin copolymer provided by the invention has good thermal stability and mechanical property, and in addition, the cycloolefin copolymer provided by the invention has adjustable molecular weight and good transparency. Experimental results show that the glass transition temperature of the cycloolefin copolymer provided by the invention is 137.9-221.5 ℃, the thermal loss weight of 10% exceeds 320 ℃, the tensile strength is 43-50 MPa, the tensile modulus is 2300MPa-3000 MPa, the elongation at break is 2.2-8.6%, the number average molecular weight of the cycloolefin copolymer provided by the invention is 180 kg/mol-370 kg/mol, and the light transmittance of the cycloolefin copolymer provided by the invention is more than 90%.
In recent years, the field of Virtual Reality (VR) has been developed faster in recent years, and is considered as a next generation computing platform, a head-mounted display in a display form has high requirements on optical performance, and a glass lens is a common scheme, but has the requirements of light weight and cost reduction as a consumer electronics grade product, so that the glass lens provides a better development opportunity for optical plastics. The cycloolefin copolymer is used as an AR/VR optical lens, and is also effective in achieving light and thin AR/VR devices and providing beneficial optical properties. However, the conventional cycloolefin copolymers have problems of insufficient refractive index and transparency, and it is difficult to satisfy the requirements as optical lenses.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to provide a cycloolefin copolymer, a preparation method and an application thereof in a virtual reality level head mounted display.
A high refractive index is critical for the optics, which can be made thinner as the refractive index of the material is higher, which not only means that the improvement in performance can also be achieved for the purpose of light-weight materials, which is important for the role of the virtual reality level head mounted display. In the invention, the inventor obtains the cycloolefin copolymer by introducing aromatic groups with high molar refractive index into spirofluorene-based vinyl monomers and polymerizing the cycloolefin copolymer with norbornene and ethylene, and the free volume fraction around the fluorene part provides high solubility and processability because the fluorene part faces to the polymer main chain vertically, and in terms of optical properties, the polarization anisotropy can be counteracted by the multi-structure, and the spirofluorene part of the vertically oriented polymer main chain can counteract the high refractive index in the stretching direction, thereby reducing the polarization anisotropy, realizing low birefringence and high refractive index, and achieving high transmittance. Due to the influence of the high refractive group, the high refractive cycloolefin copolymer with certain toughness is obtained, and the larger steric hindrance and the stronger rigid structure of the spirofluorenyl can bring about the improvement of mechanical properties, so that the performance of the cycloolefin copolymer is further improved.
In order to achieve the above object, the present invention provides a process for preparing a cycloolefin copolymer, comprising the steps of:
Mixing norbornene and spirofluorenyl alkene monomer with solvent under nitrogen atmosphere, heating
Adding the mixed solution of the mixed catalyst and solvent, introducing ethylene to the pressure of 0.1-0.2 MPa, stirring for 1-2 h, stopping heating, injecting ethanol acidified by hydrochloric acid to stop reaction, washing the product, filtering, and drying in vacuum to obtain the cycloolefin copolymer.
Further, the concentration of norbornene is 0.2-1 mol/L.
Further, the concentration of the spirofluorenyl alkene monomer is 0.1 to 0.5mol/L.
Further, the molar ratio of the catalyst to norbornene is 1:1-10.
Further, the solvent is one of n-hexane, cyclohexane, cyclopentane, methylcyclohexane, benzene, toluene and xylene.
Further, the heating temperature range is 70-80 ℃.
Further, the catalyst is a metallocene, and may be one of Cp2ZrCl2、(Ind)2ZrCl2、rac-[Et(Ind)2]ZrCl2、rac-[Et(Ind-H4)2]ZrCl2.
Further, the catalyst also includes an aluminoxane compound, which can be methylaluminoxane or modified methylaluminoxane.
Preferably, the molar ratio of the metallocene to the norbornene is 1:1000-4000, and the molar ratio of the metallocene to the aluminoxane compound is 1:500.
The preparation method of the spirofluorenyl alkene monomer comprises the following steps:
X1, adding 10-20 parts by weight of p-toluenesulfonyl chloride and 0.1-0.5 part by weight of 4-dimethylaminopyridine into 60-80 parts by weight of pyridine, mixing to obtain a solution A, and adding 2-8 parts by weight of 5-norbornene-2-endo, 3-endo-dimethanol into 10-20 parts by weight of pyridine to obtain a solution B; adding the solution A into the solution B, cooling to 0-5 ℃ and stirring for 12-18 h, concentrating after stirring, removing the solvent, extracting the residue by chloroform, washing with water and brine, and drying for the next step;
X2, adding 10-20 parts by weight of 2, 7-bis (phenylmethyl) -9H-fluorene into 20-50 parts by weight of tetrahydrofuran, uniformly mixing, then dropwise adding 50-100 parts by weight of n-hexane solution of n-butyllithium at the temperature of-80 to-70 ℃, and continuously stirring at the temperature of-80 to-70 ℃ for 1-2 hours after the dropwise adding is finished to obtain a mixture C; adding 10-20 parts by weight of the product obtained in the step X1 into 100-200 parts by weight of tetrahydrofuran, and uniformly mixing to obtain a solution D; dropwise adding the solution D into the mixture C at the temperature of-80 to-70 ℃, heating to room temperature after the dropwise adding is finished, stirring for 10-20 h, extracting with chloroform to obtain an organic phase, and then washing, drying and concentrating to obtain the spirofluorenyl alkene monomer.
The invention also provides the cycloolefin copolymer prepared by the method and the application of the cycloolefin copolymer in the virtual reality level head-mounted display.
The invention has the beneficial effects that:
The invention takes solvent as medium, takes norbornene, spirofluorenyl alkene monomer and ethylene as polymerization monomer, and carries out polymerization reaction under the existence of catalyst to obtain the cycloolefin copolymer. The cycloolefin copolymer has high transparency and excellent refractive index and mechanical property, so that the application range of the polymer is widened.
Detailed Description
2,7-Bis (phenylmethyl) -9H-fluorene, 2,7-bis (phenylmethyl) -9H-fluorene, CAS number: 578766-02-6.
2-Phenyl-9H-fluorene, CAS number: 28065-98-7.
N-hexane solution of n-butyllithium, 1.6mol/L.
Rac- [ Et (Ind) 2]ZrCl2, witco.
Comparative example 1 a process for preparing a cycloolefin copolymer comprising the steps of:
Norbornene and 5-norbornene-2-methanol are mixed with toluene under nitrogen atmosphere, the concentration of the norbornene is 0.8mol/L, the concentration of the 5-norbornene-2-methanol is 0.2mol/L, the mixture of rac- [ Et (Ind) 2]ZrCl2, methylaluminoxane and toluene is heated to 80 ℃, the mixed solution of rac- [ Et (Ind) 2]ZrCl2 and norbornene is 1:3000, the molar ratio of rac- [ Et (Ind) 2]ZrCl2 and methylaluminoxane is 1:500, ethylene is introduced to the pressure of 0.1MPa, the stirring is stopped for 2h, the reaction is stopped by injecting ethanol acidified by hydrochloric acid, and the product is washed, filtered and dried in vacuum to obtain the cycloolefin copolymer.
Example 1 a process for the preparation of a cyclic olefin copolymer comprising the steps of:
norbornene and spirofluorenyl alkene monomer are mixed with toluene under nitrogen atmosphere, the concentration of the norbornene is 0.8mol/L, the concentration of the spirofluorenyl alkene monomer is 0.2mol/L, the mixture of rac- [ Et (Ind) 2]ZrCl2, methylaluminoxane and toluene is heated to 80 ℃, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to norbornene is 1:3000, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to methylaluminoxane is 1:500, ethylene is introduced to the pressure of 0.1MPa, the stirring is stopped for 2 hours, the reaction is stopped by injecting ethanol acidified by hydrochloric acid, and the cycloolefin copolymer is obtained after washing and suction filtration and vacuum drying.
The preparation method of the spirofluorenyl alkene monomer comprises the following steps:
X1, adding 15g of p-toluenesulfonyl chloride and 0.3g of 4-dimethylaminopyridine into 70mL of pyridine, mixing to obtain a solution A, and adding 5-norbornene-2-endo, 3-endo-dimethanol and 5g of 5-endo-dimethanol into 15mL of pyridine to obtain a solution B; adding the solution A into the solution B, cooling to 0 ℃ and stirring for 16 hours, concentrating after stirring is finished to remove the solvent, extracting the residue by chloroform, washing with water and brine, and drying for the next step;
X2, adding 16g of 2, 7-bis (phenylmethyl) -9H-fluorene into 40mL of tetrahydrofuran, uniformly mixing, dropwise adding 65mL of n-hexane solution of n-butyllithium at-76 ℃, and continuously stirring at-76 ℃ for 2 hours after the dropwise adding is finished to obtain a mixture C; adding 12g of the product obtained in the step X1 into 150mL of tetrahydrofuran, and uniformly mixing to obtain a solution D; dropping the solution D into the mixture C at-76 ℃, heating to room temperature after dropping, stirring for 16h, extracting with chloroform to obtain an organic phase, washing with water, drying, and concentrating to obtain spirofluorenyl alkene monomer.
Example 2a process for the preparation of a cyclic olefin copolymer comprising the steps of:
norbornene and spirofluorenyl alkene monomer are mixed with toluene under nitrogen atmosphere, the concentration of the norbornene is 0.8mol/L, the concentration of the spirofluorenyl alkene monomer is 0.2mol/L, the mixture of rac- [ Et (Ind) 2]ZrCl2, methylaluminoxane and toluene is heated to 80 ℃, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to norbornene is 1:3000, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to methylaluminoxane is 1:500, ethylene is introduced to the pressure of 0.1MPa, the stirring is stopped for 2 hours, the reaction is stopped by injecting ethanol acidified by hydrochloric acid, and the cycloolefin copolymer is obtained after washing and suction filtration and vacuum drying.
The preparation method of the spirofluorenyl alkene monomer comprises the following steps:
X1, adding 15g of p-toluenesulfonyl chloride and 0.3g of 4-dimethylaminopyridine into 70mL of pyridine, mixing to obtain a solution A, and adding 5-norbornene-2-endo, 3-endo-dimethanol and 5g of 5-endo-dimethanol into 15mL of pyridine to obtain a solution B; adding the solution A into the solution B, cooling to 0 ℃ and stirring for 16 hours, concentrating after stirring is finished to remove the solvent, extracting the residue by chloroform, washing with water and brine, and drying for the next step;
X2, adding 12g of 2-phenyl-9H-fluorene into 40mL of tetrahydrofuran, uniformly mixing, dropwise adding 65mL of n-hexane solution of n-butyllithium at-76 ℃, and continuously stirring at-76 ℃ for 2H after the dropwise adding is finished to obtain a mixture C; adding 12g of the product obtained in the step X1 into 150mL of tetrahydrofuran, and uniformly mixing to obtain a solution D; dropping the solution D into the mixture C at-76 ℃, heating to room temperature after dropping, stirring for 16h, extracting with chloroform to obtain an organic phase, washing with water, drying, and concentrating to obtain spirofluorenyl alkene monomer.
Example 3a process for the preparation of a cyclic olefin copolymer comprising the steps of:
norbornene and spirofluorenyl alkene monomer are mixed with toluene under nitrogen atmosphere, the concentration of the norbornene is 0.8mol/L, the concentration of the spirofluorenyl alkene monomer is 0.2mol/L, the mixture of rac- [ Et (Ind) 2]ZrCl2, methylaluminoxane and toluene is heated to 80 ℃, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to norbornene is 1:3000, the mol ratio of rac- [ Et (Ind) 2]ZrCl2 to methylaluminoxane is 1:500, ethylene is introduced to the pressure of 0.1MPa, the stirring is stopped for 2 hours, the reaction is stopped by injecting ethanol acidified by hydrochloric acid, and the cycloolefin copolymer is obtained after washing and suction filtration and vacuum drying.
The preparation method of the spirofluorenyl alkene monomer comprises the following steps:
X1, adding 15g of p-toluenesulfonyl chloride and 0.3g of 4-dimethylaminopyridine into 70mL of pyridine, mixing to obtain a solution A, and adding 5-norbornene-2-endo, 3-endo-dimethanol and 5g of 5-endo-dimethanol into 15mL of pyridine to obtain a solution B; adding the solution A into the solution B, cooling to 0 ℃ and stirring for 16 hours, concentrating after stirring is finished to remove the solvent, extracting the residue by chloroform, washing with water and brine, and drying for the next step;
X2, adding 8g of fluorene into 40mL of tetrahydrofuran, uniformly mixing, then dropwise adding 65mL of n-hexane solution of n-butyllithium at the temperature of minus 76 ℃, and continuously stirring at the temperature of minus 76 ℃ for 2 hours after the dropwise adding is finished to obtain a mixture C; adding 12g of the product obtained in the step X1 into 150mL of tetrahydrofuran, and uniformly mixing to obtain a solution D; dropping the solution D into the mixture C at-76 ℃, heating to room temperature after dropping, stirring for 16h, extracting with chloroform to obtain an organic phase, washing with water, drying, and concentrating to obtain spirofluorenyl alkene monomer.
Example 4 the same as in example 1, the only difference being that the concentration of the spirofluorenyl alkene monomer was 0.1mol/L.
Example 5 the same as example 1, the only difference being that the concentration of the spirofluorenyl alkene monomer was 0.3mol/L.
Test examples the cycloolefin copolymers prepared in the control examples and examples were tested for light transmittance, refractive index and elongation at break. The light transmittance is measured by an ultraviolet-visible spectrophotometer, and the measurement wavelength is 400-800 nm. The refractive index was measured by the Beckline method using an Abbe refractometer, and the measurement wavelength was 623nm. Elongation at break is described in GB/T1040.1-2018 determination of tensile Properties of plastics part 1: the general rule is that the spline clamp distance is 20.0mm, the test speed is 5mm/min, and each sample is tested 5 times to obtain the average value.
TABLE 1 Performance test of cycloolefin copolymers
| Experimental protocol | Transmittance/% | Refractive index | Elongation at break/% |
| Comparative example 1 | 90.8 | 1.522 | 5.2 |
| Example 1 | 93.1 | 1.581 | 8.1 |
| Example 2 | 91.2 | 1.543 | 6.9 |
| Example 3 | 90.1 | 1.529 | 6.3 |
| Example 4 | 91.5 | 1.542 | 7.0 |
| Example 5 | 92.2 | 1.576 | 6.8 |
As can be seen from comparison of comparative example 1 and examples, the cycloolefin copolymer synthesized from the spirofluorenyl vinyl monomer has better optical and mechanical properties, probably because in the examples, the cycloolefin copolymer is obtained by introducing an aromatic group having a high molar refractive index into the spirofluorenyl vinyl monomer and then polymerizing with norbornene and ethylene, since the fluorene portion is oriented perpendicularly to the polymer main chain, the free volume fraction around the fluorene portion provides high solubility and processability, and in terms of optical properties, polarization anisotropy can be offset by a card structure, and the spirofluorene portion oriented perpendicularly to the polymer main chain can offset the high refractive index in the stretching direction, thereby reducing polarization anisotropy, realizing low birefringence and high refraction, and thus achieving high transmittance. Due to the influence of the high refractive group, the high refractive cycloolefin copolymer with certain toughness is obtained, and the larger steric hindrance and the stronger rigid structure of the spirofluorenyl can bring about the improvement of mechanical properties, so that the performance of the cycloolefin copolymer is further improved. In example 1, the (2, 7-bis (phenylmethyl) -9H-fluorene used in combination of the spirofluorenyl alkene monomers had more aromatic rings and larger molecular weight and steric hindrance than those of examples 2 to 3, so that the optical properties and mechanical properties were better than those of examples 2 to 3, and because the mechanical properties were improved and then reduced when the concentration of the added spirofluorenyl alkene monomers was increased, the properties of example 1 were better than those of examples 4 to 5.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. A process for producing a cycloolefin copolymer, which comprises the steps of:
Mixing norbornene and spirofluorenyl alkene monomer with solvent under nitrogen atmosphere, heating
Adding the mixed solution of the mixed catalyst and solvent, introducing ethylene to the pressure of 0.1-0.2 MPa, stirring for 1-2 h, stopping heating, injecting ethanol acidified by hydrochloric acid to stop reaction, washing the product, filtering, and drying in vacuum to obtain the cycloolefin copolymer.
2. The method for producing a cycloolefin copolymer according to claim 1, characterized in that the norbornene concentration is 0.2 to 1mol/L.
3. The method for producing a cycloolefin copolymer according to claim 1, characterized in that the concentration of the spirofluorenyl olefin monomer is 0.1 to 0.5mol/L.
4. The process for preparing a cycloolefin copolymer according to claim 1, characterized in that the molar ratio of the catalyst to norbornene is 1:110.
5. The method for preparing a cycloolefin copolymer according to claim 1, wherein the solvent is one of n-hexane, cyclohexane, cyclopentane, methylcyclohexane, benzene, toluene, and xylene.
6. The method for producing a cycloolefin copolymer according to claim 1, characterized in that the heating temperature is in the range of 70 to 80 ℃.
7. The process for preparing cycloolefin copolymer according to claim 1, wherein the catalyst is a metallocene which is one of Cp2ZrCl2、(Ind)2ZrCl2、rac-[Et(Ind)2]ZrCl2、rac-[Et(Ind-H4)2]ZrCl2; the catalyst further comprises an aluminoxane compound, which can be methylaluminoxane or modified methylaluminoxane; the molar ratio of the metallocene to the norbornene is 1:1000-4000, and the molar ratio of the metallocene to the aluminoxane compound is 1:500.
8. The process for preparing a cycloolefin copolymer according to claim 1, characterized in that the process for preparing a spirofluorenyl olefin monomer comprises the steps of:
X1, adding 10-20 parts by weight of p-toluenesulfonyl chloride and 0.1-0.5 part by weight of 4-dimethylaminopyridine into 60-80 parts by weight of pyridine, mixing to obtain a solution A, and adding 2-8 parts by weight of 5-norbornene-2-endo, 3-endo-dimethanol into 10-20 parts by weight of pyridine to obtain a solution B; adding the solution A into the solution B, cooling to 0-5 ℃ and stirring for 12-18 h, concentrating after stirring, removing the solvent, extracting the residue by chloroform, washing with water and brine, and drying for the next step;
X2, adding 10-20 parts by weight of 2, 7-bis (phenylmethyl) -9H-fluorene into 20-50 parts by weight of tetrahydrofuran, uniformly mixing, then dropwise adding 50-100 parts by weight of n-hexane solution of n-butyllithium at the temperature of-80 to-70 ℃, and continuously stirring at the temperature of-80 to-70 ℃ for 1-2 hours after the dropwise adding is finished to obtain a mixture C; adding 10-20 parts by weight of the product obtained in the step X1 into 100-200 parts by weight of tetrahydrofuran, and uniformly mixing to obtain a solution D; dropwise adding the solution D into the mixture C at the temperature of-80 to-70 ℃, heating to room temperature after the dropwise adding is finished, stirring for 10-20 h, extracting with chloroform to obtain an organic phase, and then washing, drying and concentrating to obtain the spirofluorenyl alkene monomer.
9. Cycloolefin copolymer, characterized in that it is prepared by the process according to any of claims 1 to 8.
10. Use of the cyclic olefin copolymer according to claim 9 in a virtual reality level head mounted display.
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| CN101125901A (en) * | 2007-09-11 | 2008-02-20 | 浙江大学 | A kind of cyclic olefin copolymer and preparation method thereof |
| WO2015137446A1 (en) * | 2014-03-13 | 2015-09-17 | 富士フイルム株式会社 | Liquid crystal display device |
| CN105524217A (en) * | 2016-01-21 | 2016-04-27 | 浙江大学 | Bimodal molecular weight distributed cycloolefin copolymer and preparation method thereof |
| CN115028763A (en) * | 2022-07-28 | 2022-09-09 | 中国科学院长春应用化学研究所 | A kind of cycloolefin copolymer and preparation method thereof |
| CN116217772A (en) * | 2023-01-10 | 2023-06-06 | 中国科学院长春应用化学研究所 | A kind of cyclic olefin copolymer and preparation method thereof |
| US20230312786A1 (en) * | 2020-07-31 | 2023-10-05 | Polyplastics Co., Ltd. | Production method for cyclic olefin copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125901A (en) * | 2007-09-11 | 2008-02-20 | 浙江大学 | A kind of cyclic olefin copolymer and preparation method thereof |
| WO2015137446A1 (en) * | 2014-03-13 | 2015-09-17 | 富士フイルム株式会社 | Liquid crystal display device |
| CN105524217A (en) * | 2016-01-21 | 2016-04-27 | 浙江大学 | Bimodal molecular weight distributed cycloolefin copolymer and preparation method thereof |
| US20230312786A1 (en) * | 2020-07-31 | 2023-10-05 | Polyplastics Co., Ltd. | Production method for cyclic olefin copolymer |
| CN115028763A (en) * | 2022-07-28 | 2022-09-09 | 中国科学院长春应用化学研究所 | A kind of cycloolefin copolymer and preparation method thereof |
| CN116217772A (en) * | 2023-01-10 | 2023-06-06 | 中国科学院长春应用化学研究所 | A kind of cyclic olefin copolymer and preparation method thereof |
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