Pure hydrocarbon cycloolefin polymer with high refractive index as well as preparation method and application of pure hydrocarbon cycloolefin polymer

Abstract

The invention discloses a high-refraction cycloolefin polymer as well as a preparation method and application thereof, and belongs to the technical field of polymer preparation. A cycloolefin monomer is subjected to a polymerization reaction in an inert solvent in the presence of a catalyst, then a polymerization reaction product is subjected to a hydrogenation reaction, and the pure-hydrocarbon high-refractive-index cycloolefin polymer is obtained. The cycloolefin polymer has excellent refractive index, heat resistance, light transmittance and low hygroscopicity, and can be widely applied to the field of transparent optical materials such as optical lenses and polarizing films, the field of medical instruments such as pre-filling needles and pipettes, and the field of 5G / 6G low-dielectric communication materials.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer preparation, and in particular relates to a pure hydrocarbon high-refractive index cycloolefin polymer and a preparation method and application thereof. Background Art

[0002] Cycloolefin polymer (COP) is a non-crystalline high value-added thermoplastic engineering plastic obtained by hydrogenating a polymer obtained by ring-opening metathesis polymerization (ROMP) of norbornene cycloolefin monomers. COP contains a highly hindered cyclic alkane structure and has good transparency, excellent optical properties, excellent heat resistance, chemical stability, melt fluidity, biocompatibility, dimensional stability and resistance to chemical corrosion. It is widely used in optics, electronic parts, biomedicine and other fields.

[0003] As a very promising optical material, COP has been widely used in the manufacture of various optical lenses / lenses, car light lenses, display films, 5G antenna receiving covers, large LCD light guide materials, optical speakers, polygonal mirrors, protective films for corneal plates, etc. Currently, commercial COP materials have good optical properties and are mainly used in the fields of optics and medical materials. However, the refractive index of this type of cyclic olefin copolymer is fixed at 1.53-1.55, and the inability to further increase the refractive index limits the application of this type of cyclic olefin copolymer.

[0004] In recent years, due to the rapid development of optoelectronic device manufacturing technology, cycloolefin polymer resins with higher refractive index, high Abbe number and small birefringence when made into optical components are needed to improve the design freedom of optical components such as optical lenses. In addition, increasing the refractive index of COP is conducive to reducing the thickness of optical lenses, and pure hydrocarbon cycloolefin polymers (COP) are conducive to maintaining their extremely low water absorption and preventing lens deformation.

[0005] Existing cycloolefin polymers (COP) cannot have high light transmittance, heat resistance, low birefringence and hygroscopicity, excellent fluidity, formability and dimensional stability while having a high refractive index. Existing authorized patents (CN114651026B) and patent applications (CN116675809A) can achieve refractive indices of pure hydrocarbon COP of 1.63 and 1.65 respectively, but the ultra-high refractive index of 1.70 has not been broken through so far. Improving the refractive index of cycloolefin polymers (COP) can greatly expand its scope of use. Providing low hygroscopicity and high refractive COP is also an important direction of current research. It is of great significance to develop innovative high-performance COP materials. Summary of the invention

[0006] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.

[0007] In view of this, in view of the problems existing in the prior art, the purpose of the present invention is to provide a cycloolefin polymer having high refractive index, high heat resistance and low hygroscopicity, and a preparation method and application thereof. The cycloolefin polymer of the present invention has other excellent properties while having a high refractive index, and its highest glass transition temperature is 282°C, and its highest refractive index can reach 1.720, while maintaining a high light transmittance of 95.3%, and extremely low water absorption (<0.01%), and can further prepare a cycloolefin polymer resin material with high refractive index and high toughness.

[0008] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0009] Therefore, the object of the present invention is to overcome the deficiencies in the prior art and provide a pure hydrocarbon high refractive index cycloolefin polymer.

[0010] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0011] The polymer has a structure as shown in Formula I,

[0012]

[0013] Where, 3≥m≥0, 5000≥x≥0, 5000≥y≥0;

[0014] R 1 and R 2 R is independently selected from hydrogen, monosubstituted or disubstituted diphenylamino, carbazolyl, diphenyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, chrysene, fluorine, chlorine, bromine, iodine, phenyl or phenyl derivatives, 1 and R 2 Can form a ring with the carbon it is in;

[0015] R 3 It is selected from independently hydrogen or a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0016] As a preferred embodiment of the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: 1≥m≥0, 3000≥x≥0, 3000≥y≥0.

[0017] As a preferred embodiment of the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the structural formula of the cycloolefin polymer as shown in Formula I includes one of Formulas a to l;

[0018]

[0019] As a preferred embodiment of the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the cycloolefin polymer has a light transmittance of >88%, a refractive index of 1.5586-1.7203, a glass transition temperature of 30-282°C, a weight average molecular weight of 56-806 kg / mol, and a molecular weight of 1.22-2.91.

[0020] The purpose of the present invention is to overcome the deficiencies in the prior art and provide a method for preparing a pure hydrocarbon high refractive index cycloolefin polymer.

[0021] In order to solve the above technical problems, the present invention provides the following technical solutions, including:

[0022] The cycloolefin monomer represented by formula II and the cycloolefin monomer represented by formula III are used as polymerization monomers, and a ring-opening metathesis polymerization reaction is carried out in an inert solvent under the action of a catalyst;

[0023] The polymerization product is subjected to hydrogenation reaction with a hydrogen source to obtain a cycloolefin polymer of the compound represented by formula I;

[0024]

[0025] Where, 1≥m≥0;

[0026] R 1 and R 2 R is independently selected from hydrogen, monosubstituted or disubstituted diphenylamino, carbazolyl, diphenyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, chrysene, fluorine, chlorine, bromine, iodine, phenyl or phenyl derivatives, 1 and R 2 Can form a ring with the carbon it is in;

[0027] R 3 It is selected from independently hydrogen or a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

[0028] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: the cycloolefin monomer having the structure shown in Formula II includes one of Formulas 1 to 12;

[0029]

[0030] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the cycloolefin monomer having the structure shown in formula III includes norbornene (NB), tetracyclododecene (TCD), 5-butyl-2-norbornene (NBB), 5-hexyl-2-norbornene (NBH), 9-butyl-2-tetracyclododecene (TCDB) or 9-hexyl-2-tetracyclododecene (TCDH), 5-norbornene-2-carboxaldehyde, 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid ethyl ester, 5-norbornene-2-carboxylic acid tert-butyl ester, 5-norbornene-2-methylamine, 2-cyano-5-norbornene, and 2-acetyl-5-norbornene.

[0031] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the inert solvent comprises one or more of hydrocarbon compounds, halogenated hydrocarbon compounds, cyclic hydrocarbon compounds or aromatic hydrocarbon compounds.

[0032] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the inert solvent includes any one or more of cyclopentane, hexane, cyclohexane, decane, isododecane, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform or tetrahydrofuran.

[0033] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the inert solvent comprises any one or more of benzene, toluene, dichloromethane, cyclohexane or tetrahydrofuran.

[0034] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the inert solvent is most preferably dichloromethane.

[0035] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the catalyst comprises one or more of a multi-component tungsten catalyst, a molybdenum catalyst, a Grubbs series catalyst, and a Schrock series catalyst.

[0036] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the Grubbs series catalyst includes the first generation Grubbs catalyst, the second generation Grubbs catalyst and the third generation Grubbs catalyst.

[0037] As a preferred solution of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the Grubbs series catalyst is most preferably a third generation Grubbs catalyst.

[0038] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the molar ratio of the cycloolefin monomer having the structure shown in formula II to the cycloolefin monomer having the structure shown in formula III is 1:0-25.

[0039] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the molar ratio of the cycloolefin monomer having the structure shown in formula II to the cycloolefin monomer having the structure shown in formula III is 1:0-15.

[0040] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the molar ratio of the cycloolefin monomer having the structure shown in formula II to the cycloolefin monomer having the structure shown in formula III is 1:0-10.

[0041] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the ratio of the total mole number of the cycloolefin monomer having the structure shown in Formula II and the cycloolefin monomer having the structure shown in Formula III to the mole number of the catalyst is 100 to 3000:1

[0042] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the ratio of the total mole number of the cycloolefin monomer having the structure shown in Formula II and the cycloolefin monomer having the structure shown in Formula III to the mole number of the catalyst is 100 to 2000:1.

[0043] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the ratio of the total mole number of the cycloolefin monomer having the structure shown in Formula II and the cycloolefin monomer having the structure shown in Formula III to the mole number of the catalyst is 200 to 1600:1.

[0044] As a preferred solution of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: the polymerization reaction, wherein the reaction temperature is -20 to 50°C, and the reaction time is 5 to 240 minutes.

[0045] As a preferred solution of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: the polymerization reaction, wherein the reaction temperature is -10 to 30°C, and the reaction time is 30 to 120 minutes.

[0046] As a preferred solution of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: the polymerization reaction, wherein the reaction temperature is 0-5°C, the reaction time is 50-70min.

[0047] As a preferred scheme of the preparation method of the pure hydrocarbon high-refractive index cycloolefin polymer of the present invention, wherein: after the polymerization reaction is completed, the present invention preferably terminates the polymerization reaction by stopping stirring to obtain a polymerization reaction solution; the polymerization reaction solution and a precipitant are mixed to obtain a precipitated product; the precipitated product is filtered, washed, and dried to obtain a polymerization reaction product.

[0048] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: the reagent for washing the precipitated product is preferably acetone. In the present invention, the number of times the precipitated product is washed is preferably 2 to 4 times, more preferably 3 times. In the present invention, the method for drying the precipitated product is preferably vacuum drying. In the present invention, the temperature for drying the precipitated product is preferably 20°C to 50°C, more preferably 25°C to 45°C, and most preferably 40°C. In the present invention, the drying time of the precipitated product is preferably 12h to 24h, more preferably 16h to 20h, and most preferably 18h.

[0049] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the hydrogenation reaction is preferably carried out under the condition of protective gas, and the protective gas is preferably nitrogen.

[0050] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, the hydrogen source comprises a homogeneous catalyst p-toluenesulfonyl hydrazide and the heterogeneous catalyst is a diatomaceous earth supported nickel catalyst. In the present invention, when the hydrogen source is a hydrazine compound, the present invention preferably performs a hydrogenation reaction according to the following method to prepare the cycloolefin polymer: the polymerization product and the hydrazine compound are subjected to a hydrogenation reaction in a solvent to obtain the cycloolefin polymer.

[0051] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: in the present invention, the ratio of the molar number of double bonds in the polymerization product to the molar number of hydrazine compounds is preferably 1: (3 to 6), more preferably 1: (4 to 5). In the present invention, the hydrogenation reaction solvent is preferably toluene. The present invention has no special restrictions on the amount of the hydrogenation reaction solvent, and the solvent used can provide a liquid environment for the above-mentioned hydrogenation reaction. In the present invention, the reaction temperature when the polymerization product and the hydrazine compound are hydrogenated is preferably 110°C to 150°C, more preferably 120°C to 140°C, and most preferably 130°C. In the present invention, the reaction time when the polymerization product and the hydrazine compound are hydrogenated is preferably 12h to 20h, more preferably 13h to 16h.

[0052] As a preferred embodiment of the method for preparing the pure hydrocarbon high refractive index cycloolefin polymer of the present invention, wherein: after the hydrogenation reaction is completed, the present invention preferably mixes the obtained hydrogenation reaction product with ethanol, and filters, washes and dries the obtained mixed product to obtain the cycloolefin polymer. In the present invention, the purity of the ethanol is preferably 97% to 99%. The present invention has no special restrictions on the methods of filtering, washing and drying the mixed product, and the technical schemes of filtering, washing and drying well known to those skilled in the art can be adopted. In the present invention, the drying method of the mixed product is preferably vacuum drying. In the present invention, the drying time of the mixed product is preferably 12h to 24h, more preferably 16h to 20h. In the present invention, the drying temperature of the mixed product is preferably 40°C to 70°C, more preferably 50°C to 65°C, and most preferably 60°C.

[0053] Beneficial effects of the present invention:

[0054] The cycloolefin polymer prepared by the present invention has other excellent properties while having a high refractive index. Its highest glass transition temperature is 282° C., and its highest refractive index can reach 1.720. At the same time, it maintains a high light transmittance of 95.3% and an extremely low water absorption rate (<0.01%). Further, a cycloolefin polymer resin material with a high refractive index and high toughness can be prepared. BRIEF DESCRIPTION OF THE DRAWINGS

[0055] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work. Among them:

[0056] Figure 1 This is a visible light transmission curve spectrum of the cycloolefin polymer of Example 2 of the present invention.

[0057] Figure 2 The cycloolefin polymer of Example 12 of the present invention 13 C-NMR spectrum.

[0058] Figure 3 The cycloolefin polymer of Example 12 of the present invention 1 H-NMR spectrum.

[0059] Figure 4 This is a tensile fracture curve spectrum of the cycloolefin polymer of Example 19 of the present invention. DETAILED DESCRIPTION

[0060] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0061] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0062] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor is it a separate or selective embodiment that is mutually exclusive with other embodiments.

[0063] The substances and their English abbreviations in the present invention are as follows:

[0064] Norbornene (NB), tetracyclododecene (TCD), 5-butyl-2-norbornene (NBB), 5-hexyl-2-norbornene (NBH), 9-butyl-2-tetracyclododecene (TCDB) or 9-hexyl-2-tetracyclododecene (TCDH), cycloolefin polymer (COP).

[0065] The raw materials used in the present invention are all commercially available unless otherwise specified.

[0066] The cycloolefin polymer prepared in the embodiment of the present invention was subjected to structural identification and performance testing, and the specific process is as follows:

[0067] NMR spectroscopy refers to the 1 H and 13 C NMR spectra were measured by Varian Unity-400 NMR spectrometer at 25°C, TMS was used as internal standard, and deuterated chloroform was used as solvent (high temperature 110°C, deuterated tetrachloroethane was used as solvent).

[0068] Differential thermal analysis (DSC) refers to the glass transition temperature of the polymer measured by a Perkin-Elmer Pyris 1 DSC differential scanning calorimeter with a heating and cooling rate of 20°C / min and a second scan.

[0069] Gel Permeation Chromatography (GPC) refers to the determination of the molecular weight and molecular weight distribution index of a polymer by a Waters 1525 gel permeation chromatograph; an RI-Laser detector is used, the solvent is trichlorobenzene, the test temperature is 150°C, the flow rate is 1.0 mL / min, and PL EasiCal PS-1 is used as the standard sample.

[0070] Thermogravimetric analysis (TGA) was performed using a Perkin-Elmer Pyris 1 instrument.

[0071] The refractive index was measured at 20° C. using an Abbe refractometer (DR-M4, Atago Co. Ltd., Tokyo, Japan) without using a contact liquid.

[0072] The light transmittance was measured using a Shimadzu UV-3600 ultraviolet-visible-near infrared spectrophotometer at a wavelength of 400 to 800 nm.

[0073] The mechanical properties of the cycloolefin polymers tested on an INSTRON 1121, Canton, MA instrument are tested according to the standard of GB / T1040-1992 "Test Method for Tensile Properties of Plastics", with a sample clamping distance of 20.0 mm and a test rate of 5 mm / min. Each sample is tested at least 5 times to ensure the reliability of the data.

[0074] The present invention adopts a product weighing method to test the polymerization conversion rate of the polymerization reaction described in the above technical solution.

[0075] The water absorption rate was determined by preparing samples with a thickness of 1 to 3 mm and immersing them in water at 23°C for 24 hours according to the conditions specified in ASTM-D 570. The water absorption rate was determined by measuring the change in the mass of the samples.

[0076] Example 1

[0077] This embodiment provides a method for preparing a pure carbon-hydrogen high-refractive index cycloolefin polymer, specifically:

[0078] 1) Ring-opening metathesis polymerization: Add 1.0 mmol of monomer 1 having a structure of formula II (i.e., the cycloolefin monomer shown in formula 1 of claim 6) and 0.0 mmol of cycloolefin monomer (NBH) having a structure of formula III (the molar ratio of the cycloolefin monomers shown in formula II to III is 1:0) to a polymerization reaction bottle in a glove box, and add 38 mL of dichloromethane to fully dissolve under stirring. Then, 5.0 μmol of catalyst G3 is dissolved in 2 mL of dichloromethane and injected into the polymerization system through a syringe (the molar ratio of the cycloolefin monomer to the catalyst is 200), and the polymerization temperature is maintained at 0°C, and the polymerization reaction is carried out for 60 minutes. After the polymerization reaction is completed, the obtained polymerization reaction solution is poured into an acetone solution to obtain a precipitated product; the precipitated product is filtered and washed with acetone 3 times, and dried in a vacuum oven at 40°C to constant weight to obtain a polymerization reaction product.

[0079] 2) Hydrogenation reaction: under nitrogen, the above polymerization product and 4 to 6 times the molar equivalent of p-toluenesulfonyl hydrazide, 4 to 6 times the molar equivalent of tri-n-propylamine, and an appropriate amount of toluene are added to a reaction bottle and refluxed for 16 hours. After the reaction is completed and the temperature is lowered, the reaction solution is injected into a large amount of ethanol to precipitate a polymer, which is dried in a vacuum oven at 60°C to constant weight to obtain a pure hydrocarbon high refractive index cycloolefin polymer.

[0080] Example 2

[0081] The difference between this embodiment and embodiment 1 is that the amount of the cycloolefin monomer (NBH) added to adjust the structure of formula III is 1.0 mmol, and the amount of the catalyst G3 added is 10.0 μmol, that is, the molar ratio of the cycloolefin monomers represented by formula II and formula III is 1:1, and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0082] Figure 1 This is a visible light transmission curve spectrum of the cycloolefin polymer of Example 2 of the present invention.

[0083] Example 3

[0084] The difference between this embodiment and embodiment 1 is that the monomer having the structure of formula II is adjusted to monomer 3 (ie, the cycloolefin monomer shown in formula 3 in claim 6), and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0085] Example 4

[0086] The difference between this embodiment and embodiment 2 is that the monomer having the structure of formula II is adjusted to monomer 3 (ie, the cycloolefin monomer shown in formula 3 in claim 6), and the rest of the preparation process is the same as that of embodiment 2 to obtain a cycloolefin polymer.

[0087] Example 5

[0088] The difference between this embodiment and embodiment 1 is that the monomer having the structure of formula II is adjusted to monomer 5 (ie, the cycloolefin monomer shown by formula 5 in claim 6), and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0089] Example 6

[0090] The difference between this embodiment and embodiment 2 is that the monomer having the structure of formula II is adjusted to monomer 5 (ie, the cycloolefin monomer shown by formula 5 in claim 6), and the rest of the preparation process is the same as that of embodiment 2 to obtain a cycloolefin polymer.

[0091] Example 7

[0092] The difference between this embodiment and embodiment 1 is that the monomer having the structure of formula II is adjusted to monomer 7 (ie, the cycloolefin monomer shown by formula 7 in claim 6), and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0093] Example 8

[0094] The difference between this embodiment and embodiment 2 is that the monomer having the structure of formula II is adjusted to monomer 7 (ie, the cycloolefin monomer shown by formula 7 in claim 6), and the rest of the preparation process is the same as that of embodiment 2 to obtain a cycloolefin polymer.

[0095] Example 9

[0096] The difference between this embodiment and embodiment 1 is that the monomer having the structure of formula II is adjusted to monomer 8 (ie, the cycloolefin monomer shown by formula 8 in claim 6), and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0097] Example 10

[0098] The difference between this embodiment and embodiment 2 is that the monomer having the structure of formula II is adjusted to monomer 8 (ie, the cycloolefin monomer shown by formula 8 in claim 6), and the rest of the preparation process is the same as that of embodiment 2 to obtain a cycloolefin polymer.

[0099] Embodiment 11

[0100] The difference between this embodiment and embodiment 1 is that the monomer having the structure of formula II is adjusted to monomer 9 (ie, the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 1 to obtain a cycloolefin polymer.

[0101] Example 12

[0102] The difference between this embodiment and embodiment 2 is that the monomer having the structure of formula II is adjusted to monomer 9 (ie, the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 2 to obtain a cycloolefin polymer.

[0103] Figure 2 The cycloolefin polymer of Example 12 of the present invention 13 C-NMR spectrum. Figure 3 The cycloolefin polymer of Example 12 of the present invention 1 H-NMR spectrum.

[0104] Embodiment 13

[0105] The difference between this embodiment and embodiment 3 is that the addition amount of the cycloolefin monomer 3 of the structure of formula II is adjusted to 2.0 mmol, and the addition amount of the catalyst G3 is adjusted to 1.25 μmol, that is, the molar ratio of the cycloolefin monomer to the catalyst is 1600, and the rest of the preparation process is the same as that of embodiment 3 to obtain a cycloolefin polymer.

[0106] Embodiment 14

[0107] The difference between this embodiment and embodiment 13 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 13 to obtain a cycloolefin polymer.

[0108] Embodiment 15

[0109] The difference between this embodiment and embodiment 3 is that the amount of the cycloolefin monomer (NBH) added to adjust the structure of formula III is 3.0 mmol, and the amount of the catalyst G3 added is 2.5 μmol, that is, the molar ratio of the cycloolefin monomers represented by formula II and formula III is 1:3, and the rest of the preparation process is the same as that of embodiment 3 to obtain a cycloolefin polymer.

[0110] Example 16

[0111] The difference between this embodiment and embodiment 15 is that the addition amount of the cycloolefin monomer 3 of the structure of formula II is adjusted to 3.0 mmol, and the addition amount of the cycloolefin monomer (NBH) of the structure of formula III is adjusted to 1.0 mmol, that is, the molar ratio of the cycloolefin monomers represented by formula II and formula III is 1:0.67, and the rest of the preparation process is the same as that of embodiment 15 to obtain a cycloolefin polymer.

[0112] Embodiment 17

[0113] The difference between this embodiment and embodiment 15 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 15 to obtain a cycloolefin polymer.

[0114] Embodiment 18

[0115] The difference between this embodiment and embodiment 16 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 16 to obtain a cycloolefin polymer.

[0116] Embodiment 19

[0117] The difference between this embodiment and embodiment 15 is that the added amount of the cycloolefin monomer 3 of the structure of formula II is adjusted to 2.0 mmol, and the added amount of the cycloolefin monomer (NBH) of the structure of formula III is adjusted to 2.0 mmol, that is, the molar ratio of the cycloolefin monomers represented by formula II and formula III is 1:1, and the rest of the preparation process is the same as that of embodiment 15 to obtain a cycloolefin polymer.

[0118] Figure 4 This is a tensile fracture curve spectrum of the cycloolefin polymer of Example 19 of the present invention.

[0119] Embodiment 20

[0120] The difference between this embodiment and embodiment 19 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 19 to obtain a cycloolefin polymer.

[0121] Embodiment 21

[0122] The difference between this embodiment and embodiment 19 is that the type of the cycloolefin monomer of the structure of formula III is adjusted to NB, and the rest of the preparation process is the same as that of embodiment 19 to obtain a cycloolefin polymer.

[0123] Embodiment 22

[0124] The difference between this embodiment and embodiment 16 is that the type of the cycloolefin monomer of the structure of formula III is adjusted to NB, and the rest of the preparation process is the same as that of embodiment 16 to obtain a cycloolefin polymer.

[0125] Embodiment 23

[0126] The difference between this embodiment and embodiment 21 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 21 to obtain a cycloolefin polymer.

[0127] Embodiment 24

[0128] The difference between this embodiment and embodiment 22 is that the monomer having the structure of formula II is adjusted to monomer 9 (i.e., the cycloolefin monomer shown by formula 9 in claim 6), and the rest of the preparation process is the same as that of embodiment 22 to obtain a cycloolefin polymer.

[0129] Comparative Example 1

[0130] Commercially available Zeonex product.

[0131] The structures of Examples 1 to 24 were identified and tested for performance. The results are shown in the following table.

[0132] Table 1

[0133]

[0134] It can be seen from the data in Table 1 that by regulating the ratio of the catalyst to the cycloolefin monomer in the catalytic system, the compound having the structure of Formula II or Formula III can be subjected to ring-opening metathesis polymerization, and the conversion rate can reach 99% without gel. Under the condition of the hydrogenation agent, the ring-opening metathesis polymerization product is completely hydrogenated, and the obtained cycloolefin polymer has a weight average molecular weight of 56kg / mol to 806kg / mol, a molecular weight distribution of 1.22 to 2.91, and a glass transition temperature of 30°C to 282°C.

[0135] The properties of some of the above-mentioned cycloolefin polymers were characterized, and the results are shown in Table 2 below.

[0136] Table 2

[0137]

[0138] As shown in Table 2, the type and molar ratio of the cycloolefin monomers of formula II and III affect the optical and thermal properties of the obtained cycloolefin polymer. When the molar ratio of cycloolefin monomer 3 to norbornene NB is 1:1, a cycloolefin polymer with a weight average molecular weight of 312,000, a glass transition temperature of 121°C, and a refractive index of 1.6362 can be obtained. The experimental results show that the transmittance of the prepared cycloolefin polymers is greater than 89%. By adjusting the type and ratio of the copolymerized cycloolefin monomers, a cycloolefin polymer with a refractive index of 1.5586 to 1.7203 can be obtained, and the hygroscopicity is low, which proves that the material has certain advantages in the application of optics.

[0139] As can be seen from the above embodiments, the present invention uses cycloolefin monomers having structures of formula II and III as polymerization monomers in an inert solvent, performs polymerization reaction in the presence of a G3 catalyst in an inert solvent, and then performs hydrogenation reaction on the polymerization product and a hydrogen source to obtain a cycloolefin polymer having a structure of formula I. The polymerization reaction has a high conversion rate, and the molecular weight and glass transition temperature of the obtained cycloolefin copolymer are controllable. In the present invention, since R1 and R2 in the structure of formula II are introduced into the cycloolefin monomer, the refractive index of the cycloolefin copolymer resin can be increased, and the pure hydrocarbon characteristics of the structures of formula II and formula III make the corresponding cycloolefin polymer have extremely low water absorption.

[0140] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A pure hydrocarbon high refractive index cycloolefin polymer, characterized in that: The polymer has a structure as shown in Formula I, Where, 3≥m≥0, 5000≥x≥0, 5000≥y≥0; R1 and R2 are independently selected from hydrogen, monosubstituted or disubstituted diphenylamino, carbazolyl, diphenyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, chrysene, fluorine, chlorine, bromine, iodine, phenyl or phenyl derivatives, and R1 and R2 may form a ring with the carbon where they are located; R3 is independently selected from hydrogen or a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

2. The pure hydrocarbon high refractive index cycloolefin polymer according to claim 1, characterized in that: Said 1≥m≥0, 3000≥x≥0, 3000≥y≥0.

3. The pure hydrocarbon high refractive index cycloolefin polymer according to claim 1, characterized in that: The structural formula of the cycloolefin polymer as shown in Formula I includes one of Formulas a to l; 4. The pure hydrocarbon high refractive index cycloolefin polymer according to claim 1, characterized in that: The cycloolefin polymer has a light transmittance of more than 88%, a refractive index of 1.5586-1.7203, a glass transition temperature of 30-282° C., a weight average molecular weight of 56-806 kg / mol, and a molecular weight of 1.22-2.

91.

5. The method for preparing a pure hydrocarbon high refractive index cycloolefin polymer according to any one of claims 1 to 4, characterized in that: include, The cycloolefin monomer represented by formula II and the cycloolefin monomer represented by formula III are used as polymerization monomers, and a ring-opening metathesis polymerization reaction is carried out in an inert solvent under the action of a catalyst; The polymerization product is subjected to hydrogenation reaction with a hydrogen source to obtain a cycloolefin polymer of the compound represented by formula I; Where, 1≥m≥0; R1 and R2 are independently selected from hydrogen, monosubstituted or disubstituted diphenylamino, carbazolyl, diphenyl, fluorenyl, biphenyl, naphthyl, pyrenyl, anthracenyl, phenanthrenyl, acenaphthenyl, chrysene, fluorine, chlorine, bromine, iodine, phenyl or phenyl derivatives, and R1 and R2 may form a ring with the carbon atoms on which they are located; R3 is independently selected from hydrogen or a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms.

6. The method for preparing a pure hydrocarbon high refractive index cycloolefin polymer as claimed in claim 5, characterized in that: The cycloolefin monomer having the structure shown in Formula II includes one of Formulas 1 to 12; 7. The method for preparing a pure hydrocarbon high refractive index cycloolefin polymer as claimed in claim 5, characterized in that: The cycloolefin monomer having the structure shown in formula III includes one of norbornene, tetracyclododecene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 9-butyl-2-tetracyclododecene or 9-hexyl-2-tetracyclododecene, 5-norbornene-2-carboxaldehyde, 5-norbornene-2-methanol, 5-norbornene-2-carboxylic acid, 5-norbornene-2-carboxylic acid methyl ester, 5-norbornene-2-carboxylic acid ethyl ester, 5-norbornene-2-carboxylic acid tert-butyl ester, 5-norbornene-2-methylamine, 2-cyano-5-norbornene, and 2-acetyl-5-norbornene.

8. The method for preparing a pure hydrocarbon high refractive index cycloolefin polymer as claimed in claim 5, characterized in that: The catalyst for the polymerization reaction includes one or more of a multi-component tungsten catalyst, a molybdenum catalyst, a Grubbs series catalyst, and a Schrock series catalyst; The inert solvent includes one or more of hydrocarbon compounds, halogenated hydrocarbon compounds, cyclic hydrocarbon compounds or aromatic hydrocarbon compounds; The molar ratio of the cycloolefin monomer having the structure shown in formula II to the cycloolefin monomer having the structure shown in formula III is 1:0-25; The ratio of the total mole number of the cycloolefin monomer having the structure shown in formula II and the cycloolefin monomer having the structure shown in formula III to the mole number of the catalyst is 100 to 3000:1; The reaction temperature of the polymerization reaction is -20 to 50° C., and the reaction time is 5 to 240 minutes.

9. The method for preparing a pure hydrocarbon high refractive index cycloolefin polymer as claimed in claim 5, characterized in that: The hydrogen source includes a hydrazine compound, a palladium-carbon catalyst or a diatomaceous earth-supported nickel catalyst; The ratio of the molar number of double bonds in the polymerization product to the molar number of the hydrogen source is 1:3-6; The reaction temperature of the hydrogenation reaction is 110-150° C., and the reaction time is 12-20 hours.

10. Use of the pure hydrocarbon high refractive index cycloolefin polymer according to any one of claims 1 to 4 in the fields of optical materials, medical devices, and low dielectric communication materials.

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