Hydrogenated cycloolefin polymer and preparation method thereof

Abstract

The invention provides a preparation method of a hydrogenated cycloolefin polymer, which comprises the following steps: reacting a cycloolefin polymer with hydrogen in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain the hydrogenated cycloolefin polymer, the hydrogenation auxiliary agent is selected from one or more of aliphatic dibasic acid esters, phthalate esters and benzene polyacid esters. Compared with the prior art, in the presence of the hydrogenation catalyst and the hydrogenation auxiliary agent, the cycloolefin polymer and the hydrogen are subjected to hydrogenation reaction, and an induced dipole is induced in the adjacent cycloolefin polymer through the hydrogenation auxiliary agent molecule with an inherent dipole; the molecular attraction between the induced dipole and the inherent dipole destroys the entanglement of the original molecular chain, and the friction force between the cycloolefin polymer molecules is reduced, so that the viscosity between the polymers is reduced, and the mass transfer effect of the reaction is improved; meanwhile, intramolecular electron conjugation can be inhibited, double bonds in molecules in the hydrogenation process can be damaged more easily, the hydrogenation efficiency is improved, and then the production efficiency is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and more specifically to a hydrogenated cycloolefin polymer and a preparation method thereof. Background Art

[0002] In recent years, cyclic olefin copolymers have attracted much attention due to their high light transmittance, high Abbe number, and excellent heat resistance as thermoplastic transparent resins. Cyclic olefin polymer materials are widely used in optical lenses, medical bag materials, optical films and other material fields. Among them, cyclic olefin ring-opening metathesis polymerization hydrogenated polymer (COP) has better processing performance, optical properties, weather resistance and dimensional stability than other cyclic olefin copolymers, and can be used in AR / VR lenses, HUD curved mirrors, high-end functional films and other fields.

[0003] However, since the solubility of the hydrogenated polymer in the solvent has decreased significantly, the concentration cannot be increased during the hydrogenation reaction. For example, the mass percentage concentration of the aromatic polymer solution in patent CN117820517A is 5-30%, and the mass of the cycloolefin monomer used in patent CN115850581B accounts for 5-30% of the solvent mass. Too low monomer concentration leads to low production efficiency, and too high monomer concentration leads to high viscosity of the solution after polymerization, which is not conducive to the next hydrogenation reaction. Therefore, the production efficiency of cycloolefin industrialization is greatly limited, and the cost of solvent removal is increased, which limits its wide application. Summary of the invention

[0004] In view of this, the present invention aims at the problem that the concentration of hydrogenated cycloolefin polymer cannot be increased, and provides a hydrogenated cycloolefin polymer and a preparation method thereof. In the presence of a hydrogenation catalyst and a hydrogenation aid, the cycloolefin polymer and hydrogen are reacted, and an induced dipole is induced in the adjacent cycloolefin polymer by the hydrogenation aid molecule with an inherent dipole, so that the molecular attraction between the induced dipole and the inherent dipole destroys the entanglement of the original molecular chain, reduces the friction between the cycloolefin polymer molecules, reduces the viscosity between the polymers, and increases the mass transfer effect of the reaction; at the same time, the intramolecular electron conjugation can be suppressed, so that the double bonds in the molecules in the hydrogenation process are more easily destroyed, the hydrogenation efficiency is improved, and then the production efficiency is improved.

[0005] The present invention provides a method for preparing a hydrogenated cycloolefin polymer, comprising the following steps:

[0006] The cycloolefin polymer and hydrogen are reacted in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain a hydrogenated cycloolefin polymer;

[0007] The hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalic acid esters, and benzene polyesters.

[0008] Preferably, the cycloolefin polymer is a copolymer formed by ring-opening and polymerization of cycloolefin monomers; the structure of the cycloolefin polymer is shown in Formula 1, wherein the mass ratio of the three repeating units I, II, and III is (50-100): (50-150): (10-200);

[0009]

[0010] In Formula 1, the R side groups in the structural unit III are independently selected from one or more of the following groups:

[0011]

[0012] Preferably, the hydrogenation catalyst is one or more of a heterogeneous palladium-based supported catalyst, a platinum-based supported catalyst, and a nickel-based supported catalyst.

[0013] Preferably, the amount of the hydrogenation catalyst added is 1% to 30% of the mass of the cycloolefin polymer.

[0014] Preferably, the hydrogenation aid is one or more of dioctyl adipate, dibutyl phthalate, dipentyl phthalate, diisooctyl phthalate, dioctyl (2-ethylhexyl) 4,5-epoxytetrahydrophthalate, and tri (2-ethylhexyl) trimellitate.

[0015] Preferably, the amount of the hydrogenation aid added is 10 ppm to 10000 ppm of the mass of the cycloolefin polymer.

[0016] Preferably, the hydrogen pressure of the reaction is 0.1 MPa to 20 MPa.

[0017] Preferably, the reaction temperature is 10°C to 500°C, and the reaction time is 0.1h to 60h.

[0018] The present invention also provides a hydrogenated cycloolefin polymer, which is prepared by the preparation method described in the above technical solution.

[0019] Preferably, the hydrogenated cycloolefin polymer has a weight average molecular weight of 10,000 g / mol to 100,000 g / mol, a tensile strength of ≥60 MPa, a Tg of 120° C. to 150° C., a light transmittance of 95% to 99%, a refractive index of ≥1.52, a haze of <2%, a water absorption of ≤0.1%, and residual metal ions of <1 ppm.

[0020] The present invention provides a method for preparing a hydrogenated cycloolefin polymer, comprising the following steps: reacting a cycloolefin polymer with hydrogen in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain a hydrogenated cycloolefin polymer; the hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalic acid esters, and benzene polyacid esters. Compared with the prior art, the present invention allows the cycloolefin polymer and hydrogen to undergo a hydrogenation reaction in the presence of a hydrogenation catalyst and a hydrogenation aid, and induces an induced dipole in the adjacent cycloolefin polymer through the hydrogenation aid molecule with an inherent dipole, so that the molecular attraction between the induced dipole and the inherent dipole destroys the entanglement of the original molecular chain, reduces the friction between the molecules of the cycloolefin polymer, reduces the viscosity between the polymers, and increases the mass transfer effect of the reaction; at the same time, it can inhibit the intramolecular electron conjugation, so that the double bonds in the molecules in the hydrogenation process are more easily destroyed, improve the hydrogenation efficiency, and thus improve the production efficiency. DETAILED DESCRIPTION

[0021] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] The present invention provides a method for preparing a hydrogenated cycloolefin polymer, comprising the following steps:

[0023] The cycloolefin polymer and hydrogen are reacted in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain a hydrogenated cycloolefin polymer;

[0024] The hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalic acid esters, and benzene polyesters.

[0025] The invention provides a preparation method of a cycloolefin hydrogenated ring-opening polymer and a polymer material. The preparation method comprises the following steps: reacting a cycloolefin polymer with hydrogen in the presence of a hydrogenation catalyst and a hydrogenation aid, hydrogenating double bonds in the cycloolefin polymer, and obtaining a hydrogenated cycloolefin polymer.

[0026] In the present invention, the cycloolefin polymer is preferably a copolymer formed by polymerization of cycloolefin monomers after ring opening; the structure of the cycloolefin polymer is shown in Formula 1, wherein the mass ratio of the three repeating units I, II, and III is preferably (50-100): (50-150): (10-200);

[0027]

[0028] In Formula 1, the R side groups in the structural unit III are independently selected from one or more of the following groups:

[0029]

[0030]

[0031] The present invention has no particular limitation on the sources of the cycloolefin polymer and hydrogen, and any commercially available product or self-made product known to those skilled in the art may be used.

[0032] In the present invention, the hydrogenation catalyst is preferably one or more of a heterogeneous palladium-based supported catalyst, a platinum-based supported catalyst, and a nickel-based supported catalyst. The present invention has no particular limitation on the source of the hydrogenation catalyst, and commercially available products known to those skilled in the art may be used.

[0033] In the present invention, the amount of the hydrogenation catalyst added is preferably 1% to 30% of the mass of the cycloolefin polymer, more preferably 1% to 10%.

[0034] In the present invention, the hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalates, and benzene polyesters, preferably dioctyl adipate, dibutyl phthalate, dipentyl phthalate, diisooctyl phthalate, dioctyl (2-ethylhexyl) 4,5-epoxytetrahydrophthalate, and tri (2-ethylhexyl) trimellitate. The present invention has no particular restrictions on the source of the hydrogenation aid, and commercially available products known to those skilled in the art can be used.

[0035] In the present invention, the amount of the hydrogenation aid added is preferably 10 ppm to 10000 ppm, more preferably 100 ppm to 5000 ppm, based on the mass of the cycloolefin polymer.

[0036] In the present invention, the hydrogen pressure of the reaction is preferably 0.1 MPa to 20 MPa, more preferably 0.1 MPa to 15 MPa, and even more preferably 0.1 MPa to 10 MPa.

[0037] In the present invention, the reaction temperature is preferably 10°C to 500°C, more preferably 50°C to 300°C, and even more preferably 100°C to 200°C; the reaction time is preferably 0.1h to 60h, more preferably 0.1h to 20h, and even more preferably 0.1h to 10h.

[0038] The preparation method provided by the present invention selects specific raw materials and cooperates with specific process steps to achieve overall good interaction, so that the double bonds in the molecules in the hydrogenation process are more easily destroyed, the hydrogenation efficiency is improved, and then the production efficiency is improved, while the solvent removal cost is reduced, and the application prospect is broad.

[0039] The present invention also provides a hydrogenated cycloolefin polymer, which is prepared by the preparation method described in the above technical solution.

[0040] In the present invention, the weight average molecular weight of the hydrogenated cycloolefin polymer is preferably 10000 g / mol to 100000 g / mol, the tensile strength is preferably ≥60 MPa, the Tg is preferably 120°C to 150°C, the transmittance is preferably 95% to 99%, the refractive index is preferably ≥1.52, the haze is preferably <2%, the water absorption is preferably ≤0.1%, and the metal ion residue is preferably <1 ppm.

[0041] The present invention provides a method for preparing a hydrogenated cycloolefin polymer, comprising the following steps: reacting a cycloolefin polymer with hydrogen in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain a hydrogenated cycloolefin polymer; the hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalic acid esters, and benzene polyacid esters. Compared with the prior art, the present invention allows the cycloolefin polymer and hydrogen to undergo a hydrogenation reaction in the presence of a hydrogenation catalyst and a hydrogenation aid, and induces an induced dipole in the adjacent cycloolefin polymer through the hydrogenation aid molecule with an inherent dipole, so that the molecular attraction between the induced dipole and the inherent dipole destroys the entanglement of the original molecular chain, reduces the friction between the molecules of the cycloolefin polymer, reduces the viscosity between the polymers, and increases the mass transfer effect of the reaction; at the same time, it can inhibit the intramolecular electron conjugation, so that the double bonds in the molecules in the hydrogenation process are more easily destroyed, improve the hydrogenation efficiency, and thus improve the production efficiency.

[0042] In order to further illustrate the present invention, the following examples are provided for detailed description.

[0043] In the following embodiments:

[0044] The molecular weight and PDI of hydrogenated cycloolefin polymers were tested by high temperature GPC, with the test instrument: Agilent 1260 Infinity, mobile phase: 1,2,4-trichlorobenzene, chromatographic column: PLgel Olexis, test flow rate 1.0 ml / min. The polymer concentration was 1 mg / mL.

[0045] The glass transition temperature of hydrogenated cycloolefin polymers was measured by differential scanning calorimetry.

[0046] Differential scanning calorimeter: METTLER DSC-3; carrier gas: nitrogen;

[0047] The tensile strength and elongation at break of the obtained cycloolefin copolymer and its hydride materials were tested in accordance with GB / T 1040.1-2018 at a test temperature of 23°C;

[0048] The viscosity of the sample during hydrogenation was tested by an online viscosity tester, the testing instrument was Heimerson: XL7-HT;

[0049] The polymer hydrogenation rate was tested by high temperature nuclear magnetic hydrogen spectrum, the testing instrument was Bruker Ascend TM400, and the solvent was deuterated o-dichlorobenzene.

[0050] The calculation method of hydrogenation rate is

[0051]

[0052] Synthesis example 1

[0053] 136g (1mol) of o-aminobenzoic acid, 500ml of tetrahydrofuran, 200g (1.65mol) of isoamyl nitrite and 0.5g (3mmol) of trichloroacetic acid were stirred at 0°C for reaction for 2h and then filtered. The obtained solid product was added to a 500ml reactor, and 130g (1.88mol) of dicyclopentadiene was added. The mixture was heated to 130°C under air isolation and stirring for reaction. After reaction for 30 minutes, the temperature was lowered, and the unreacted dicyclopentadiene was removed by distillation to obtain 92g of a monomer having a side group of R1 in the structural formula III.

[0054] Synthesis example 2

[0055] 253.1 g (0.6 mol) of 1,2-bis(dibromomethyl)benzene, 630 mL of norbornadiene, 2400 mL of dimethylformamide, and 633 g of sodium iodide were reacted at an internal temperature of 65°C for 4 hours. The mixture was extracted with ethyl acetate / water and the organic layer was taken out. The volatiles were dried with magnesium sulfate, filtered, and evaporated. The residue was subjected to column chromatography and distilled with hexane. The concentrated residue was crystallized with ethyl acetate / hexane to obtain 92 g of a monomer having a side group of R2 in the structural formula III.

[0056] Synthesis example 3

[0057] 264 g (2 mol) of dicyclopentadiene and 174 g (1.5 mol) of indene were added into a reaction kettle, and the system was replaced by nitrogen. The mixture was then heated in a closed state with stirring at 180°C for 2 h. After completion, the reaction mixture was filtered and the product was subjected to vacuum distillation to remove unreacted cyclopentene and dicyclopentadiene. The fraction distilled at 100°C to 130°C was taken to obtain 204 g of a monomer having a side group of R3 in the structural formula III.

[0058] Dicyclopentadiene, tetracyclododecene and monomers containing different side groups in the synthesis example are subjected to ring-opening heterotopic polymerization according to the proportions in Table 1, wherein the polymerization method is not particularly limited. For example, the monomers in Synthesis Example 1 can be subjected to ring-opening polymerization with dicyclopentadiene and tetracyclododecene in the presence of a polymerization catalyst, and the polymerization form and catalyst used are not particularly limited: bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, etc. can be performed, and the ring-opening polymerization reaction is usually carried out in an organic solvent. The organic solvent is not particularly limited as long as it does not affect the polymerization reaction and dissolves or disperses the obtained polymer under specified conditions.

[0059] More specifically, the organic solvent can be selected from: aliphatic hydrocarbons such as pentane, hexane, and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, cyclopentane, cyclohex ...

[0060] Octane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene and other halogenated aromatic hydrocarbons; nitromethane, nitrobenzene, acetonitrile and other nitrogen-containing hydrocarbon solvents; diethyl ether, tetrahydrofuran and other ether solvents; anisole, phenethyl ether and other aromatic ether solvents, etc. Among these, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents and aromatic ether solvents commonly used in industry are preferred.

[0061] The polymerization temperature is not particularly limited, and is generally -100 to 150° C., preferably -50 to 120° C. If the temperature is lower than -100° C., the polymerization rate is slow, and if the temperature is higher than 150° C., the activity of the catalyst may be reduced. By selecting the polymerization temperature within the above range, the polymerization rate, molecular weight, etc. can be adjusted.

[0062] The polymerization time is not particularly limited, and is, for example, 1 minute to 100 hours. In addition, the polymerization is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0063] Table 1

[0064]

[0065] The monomer unit compositions of the polymers in Examples 1 to 5 are shown in Table 1.

[0066] Example 1

[0067] 200 g of the polymer to be hydrogenated (Mw=20342 g / mol, 50 wt%) was added to 200 g of toluene solution, and 30 mg (1000 ppm) of dioctyl adipate as a hydrogenation aid and 3 g (10%) of 5 wt% palladium carbon (Shaanxi Ruike) as a catalyst were added. The mixture was reacted at 160°C and a hydrogen pressure of 5 MPa for 2 hours. During the reaction, hydrogen was continuously added to maintain the reaction pressure of the system stable. After the reaction, the reaction liquid was filtered to remove the catalyst, and the resulting solution was rotary evaporated and vacuum dried for 24 hours to obtain a white flaky polymer A1.

[0068] The concentration of the polymer solution was changed only by changing the mass of the toluene solution, and different concentrations were verified. The concentrations of different samples and the hydrogenation rates are shown in Table 2 below.

[0069] Table 2

[0070] sample Polymer concentration (wt%) Hydrogenation rate A1 50 ＞99％ A2 5 ＞99％ A3 15 ＞99％ A4 25 ＞99％ A5 60 ＞99％

[0071] Example 2

[0072] 30 g of the polymer to be hydrogenated (Mw = 20000 g / mol) was added to 270 g of cyclohexane solution (10 wt%), and 9 mg (300 ppm) of dibutyl phthalate as a hydrogenation aid, 5 wt% of platinum alumina as a catalyst (100 m 2 / g, 100nm) 6g (20%), reacted at 180℃ and hydrogen pressure 3MPa for 1 hour, during which hydrogen was continuously added to maintain the reaction pressure of the system stable. After the reaction, the reaction liquid was filtered to remove the catalyst, and the obtained solution was rotary evaporated and vacuum dried for 24h to obtain white flaky polymer B1.

[0073] The concentration of the polymer solution was changed only by changing the mass of the cyclohexane solution, and different concentration verifications were performed. The concentrations of different samples and the hydrogenation rates are shown in Table 3 below.

[0074] Table 3

[0075] sample Polymer concentration (wt%) Hydrogenation rate B1 50 ＞99％ B2 5 ＞99％ B3 15 ＞99％ B4 25 ＞99％ B5 60 ＞99％

[0076] Example 3

[0077] Take 30g of the polymer to be hydrogenated (Mw = 30000g / mol) and add it to 70g of chlorobenzene solution (30wt%), add 60mg (2000ppm) of hydrogenation aid 330, catalyst 3wt% palladium / calcium carbonate (200m 2 / g, 80nm) 15g (50%), reacted at 100°C and a hydrogen pressure of 10MPa for 4 hours, during which hydrogen was continuously added to maintain a stable reaction pressure of the system. After the reaction, the reaction liquid was filtered to remove the catalyst, and the resulting solution was rotary evaporated and vacuum dried for 24h to obtain a white flaky polymer C1.

[0078] The concentration of the polymer solution was changed only by changing the mass of the cyclohexane solution, and different concentration verifications were performed. The concentrations of different samples and the hydrogenation rates are shown in Table 4 below.

[0079] Table 4

[0080] sample Polymer concentration (wt%) Hydrogenation rate C1 50 ＞99％ C2 5 ＞99％ C3 15 ＞99％ C4 25 ＞99％ C5 60 ＞99％

[0081] Example 4

[0082] Take 30g of the polymer to be hydrogenated (Mw = 30000g / mol) and add it to 70g of chlorobenzene solution (30wt%), add 60mg (2000ppm) of hydrogenation aid 330, catalyst 3wt% palladium / calcium carbonate (200m 2 / g, 80nm) 15g (50%), reacted at 100°C and a hydrogen pressure of 10MPa for 4 hours, during which hydrogen was continuously added to maintain the reaction pressure of the system stable. After the reaction, the reaction liquid was filtered to remove the catalyst, and the resulting solution was rotary evaporated and vacuum dried for 24h to obtain a white flaky polymer D1.

[0083] The concentration of the polymer solution was changed only by changing the mass of the cyclohexane solution, and different concentration verifications were performed. The concentrations of different samples and the hydrogenation rates are shown in Table 5 below.

[0084] Table 5

[0085] sample Polymer concentration (wt%) Hydrogenation rate D1 50 ＞99％ D2 5 ＞99％ D3 15 ＞99％ D4 25 ＞99％ D5 60 ＞99％

[0086] Example 5

[0087] Take 30g of the polymer to be hydrogenated (Mw = 30000g / mol) and add it to 70g of chlorobenzene solution (30wt%), add 60mg (2000ppm) of hydrogenation aid 330, catalyst 3wt% palladium / calcium carbonate (200m 2 / g, 80nm) 15g (50%), reacted at 100°C and a hydrogen pressure of 10MPa for 4 hours, during which hydrogen was continuously added to maintain the reaction pressure of the system stable. After the reaction, the reaction liquid was filtered to remove the catalyst, and the resulting solution was rotary evaporated and vacuum dried for 24h to obtain a white flaky polymer E1.

[0088] The concentration of the polymer solution was changed only by changing the mass of the cyclohexane solution, and different concentration verifications were performed. The concentrations of different samples and the hydrogenation rates are shown in Table 6 below.

[0089] Table 6

[0090] sample Polymer concentration (wt%) Hydrogenation rate E1 50 ＞99％ E2 5 ＞99％ E3 15 ＞99％ E4 25 ＞99％ E5 60 ＞99％

[0091] Comparative Example 1

[0092] Except for not adding the hydrogenation aid, other conditions are the same as those in Example 1. Similarly, the concentration of the polymer solution is changed by changing the mass of the toluene solution, and verification at different concentrations is performed. The concentrations and hydrogenation rates of different samples are shown in Table 7 below.

[0093] Table 7

[0094]

[0095]

[0096] Comparative Example 2

[0097] Except for not adding hydrogenation aid, other conditions are the same as those in Example 2. Similarly, the concentration of the polymer solution is changed by changing the mass of the cyclohexane solution, and different concentrations are verified. The concentrations and hydrogenation rates of different samples are shown in Table 8 below.

[0098] Table 8

[0099] sample Polymer concentration (wt%) Hydrogenation rate B1* 50 -(Viscosity is too high and cannot react normally) B2* 5 ＞99％ B3* 15 95％ B4* 25 78％ B5* 60 -(The amount of double bonds is too high to be integrated)

[0100] Compared with the example, except that the hydrogenation aid is not added, other conditions are the same; it can be seen that the hydrogenation effect in the comparative example is quite different from that in the example. The addition of the hydrogenation aid can effectively increase the concentration in the hydrogenation process and improve the equipment utilization rate in the production process.

[0101] Table 9

[0102] sample A1 B1 C1 D1 E1 A1* B1* System viscosity / cps 6870 7720 7550 8930 5800 113000 Over range (>150000)

[0103] At the same time, the addition of hydrogenation aids can reduce the viscosity of the reaction system, reduce the difficulty of subsequent processing, and reduce processing costs.

[0104] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing a hydrogenated cycloolefin polymer, characterized in that: The following steps are involved: The cycloolefin polymer and hydrogen are reacted in the presence of a hydrogenation catalyst and a hydrogenation aid to obtain a hydrogenated cycloolefin polymer; The hydrogenation aid is selected from one or more of aliphatic dibasic acid esters, phthalic acid esters, and benzene polyesters.

2. The preparation method according to claim 1, characterized in that: The cycloolefin polymer is a copolymer formed by polymerization of cycloolefin monomers after ring opening; the structure of the cycloolefin polymer is shown in Formula 1, wherein the mass ratio of the three repeating units I, II, and III is (50-100): (50-150): (10-200); In Formula 1, the R side groups in the structural unit III are independently selected from one or more of the following groups:

3. The preparation method according to claim 1, characterized in that: The hydrogenation catalyst is one or more of a heterogeneous palladium-based supported catalyst, a platinum-based supported catalyst, and a nickel-based supported catalyst.

4. The preparation method according to claim 1, characterized in that: The amount of the hydrogenation catalyst added is 1% to 30% of the mass of the cycloolefin polymer.

5. The preparation method according to claim 1, characterized in that: The hydrogenation aid is one or more of dioctyl adipate, dibutyl phthalate, dipentyl phthalate, diisooctyl phthalate, dioctyl (2-ethylhexyl) 4,5-epoxytetrahydrophthalate, and tri (2-ethylhexyl) trimellitate.

6. The preparation method according to claim 1, characterized in that: The amount of the hydrogenation aid added is 10 ppm to 10000 ppm of the mass of the cycloolefin polymer.

7. The preparation method according to claim 1, characterized in that: The hydrogen pressure of the reaction is 0.1 MPa to 20 MPa.

8. The preparation method according to claim 1, characterized in that: The reaction temperature is 10°C to 500°C, and the reaction time is 0.1h to 60h.

9. A hydrogenated cycloolefin polymer, characterized in that The preparation method is described in any one of claims 1 to 8.

10. The hydrogenated cycloolefin polymer according to claim 9, characterized in that The hydrogenated cycloolefin polymer has a weight average molecular weight of 10000 g / mol to 100000 g / mol, a tensile strength of ≥60 MPa, a Tg of 120° C. to 150° C., a light transmittance of 95% to 99%, a refractive index of ≥1.52, a haze of <2%, a water absorption of ≤0.1%, and a metal ion residue of <1 ppm.

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