CN103951787A - Cycloolefin copolymer and preparation method thereof - Google Patents

Abstract

The present invention provides a cycloolefin copolymer, which has a structure shown in formula I. In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150. The cycloolefin copolymer provided by the invention has good heat resistance and mechanical properties at the same time. Experimental results show that the cycloolefin copolymer provided by the present invention has a glass transition temperature of 160°C to 201°C and has good heat resistance; its tensile strength is 32MPa to 35MPa, and its tensile modulus is 1450MPa to 1750MPa. The elongation rate is 2.1% to 2.9%, and it has good mechanical properties. In addition, the cycloolefin copolymer provided by the invention also has better transparency. Experimental results show that the light transmittance of the cycloolefin copolymer provided by the invention is greater than 85%.

Description

A kind of cyclic olefin copolymer and preparation method thereof

technical field

The invention relates to the technical field of copolymers, in particular to a cycloolefin copolymer and a preparation method thereof.

Background technique

Cyclic olefin copolymers are a class of high value-added thermoplastic engineering plastics polymerized from cyclic olefins. This copolymer has high transparency, low dielectric constant, excellent heat resistance, chemical resistance, and melt flow. Good resistance, barrier property and dimensional stability. Therefore, cycloolefin copolymers can be widely used in the manufacture of various optical, information, electrical, and medical materials.

The heat resistance of cycloolefin copolymers is an important property of this material. In some high-temperature environments, if the heat resistance of the cycloolefin copolymer is poor, the cycloolefin copolymer will undergo dimensional changes such as distortion and deformation, which will directly affect the optical properties and properties of the cycloolefin copolymer. mechanical properties. Therefore, improving the heat resistance of cyclic olefin copolymers can greatly expand the scope of use of cyclic olefin copolymers. An important index to measure the heat resistance of cycloolefin copolymers is the glass transition temperature of cycloolefin copolymers. The glass transition temperature is the temperature at which the copolymer changes from glass state to rubber state. At the transition temperature, the copolymer will undergo serious deformation and its mechanical properties will be greatly reduced, which will have an extremely adverse effect on the application of copolymer materials. Therefore, increasing the glass transition temperature of the copolymer can effectively improve the heat resistance of the copolymer.

There are two methods for synthesizing cyclic olefin copolymers: one is the chain polymerization of ethylene and norbornene monomers, and the other is ring-opening metathesis polymerization (ROMP) and hydrogenation of norbornene monomers. . Utilize the commercialized cyclic olefin copolymer that ROMP method gains at present, such as trade mark is and The cyclic olefin copolymer has good mechanical properties, but the glass transition temperature of this cyclic olefin copolymer is low, such as and The glass transition temperature is only 140°C, The glass transition temperature of the cyclic olefin copolymer is 170 ° C, so the heat resistance of this cycloolefin copolymer is poor.

A cycloolefin copolymer with a higher glass transition temperature can be prepared by chain polymerization of ethylene and norbornene monomers. The cyclic olefin copolymer, but the molecular chain rigidity of this cyclic olefin copolymer is stronger, and the elongation at break of the cyclic olefin copolymer is poor, so the mechanical properties of this cyclic olefin copolymer are poor.

The cyclic olefin copolymers provided by the prior art cannot have good heat resistance and mechanical properties at the same time.

Contents of the invention

In view of this, the object of the present invention is to provide a cyclic olefin copolymer, which has good heat resistance and mechanical properties at the same time.

The present invention provides a kind of cyclic olefin copolymer, has the structure shown in formula I:

In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150.

Preferably, in the formula I, 230≤x≤320, 40≤y≤86.

The present invention provides a kind of preparation method of cycloolefin copolymer described in above-mentioned technical scheme, comprises the following steps:

1), under the action of a catalyst, a compound having a structure shown in formula II and a compound having a structure shown in formula III are polymerized in a solvent to obtain a polymerized reaction product;

2), hydrogenating the polymerization reaction product and a hydrogen source to obtain a cycloolefin copolymer;

Preferably, the catalyst is a carbene catalyst.

Preferably, the catalyst is a ruthenium carbene compound.

Preferably, the ratio of the total moles of the compound having the structure shown in formula II to the compound having the structure shown in formula III to the moles of the catalyst is (300-500):1;

The molar ratio of the compound having the structure shown in formula II to the compound having the structure shown in formula III is (0.5-2):1.

Preferably, the temperature of the polymerization reaction in the step 1) is 0°C to 50°C;

The time for the polymerization reaction in the step 1) is 5 minutes to 60 minutes.

Preferably, the hydrogen source in step 2) is a hydrazine compound.

Preferably, the ratio of the number of moles of double bonds of the polymerization reaction product in the step 2) to the number of moles of hydrazine compounds is 1:(3-6).

Preferably, the temperature of the hydrogenation reaction in step 2) is 110°C to 150°C;

The hydrogenation reaction time in the step 2) is 12 hours to 24 hours.

The present invention provides a cycloolefin copolymer, which has a structure shown in formula I. In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150. The cycloolefin copolymer provided by the invention has good heat resistance and mechanical properties at the same time. Experimental results show that the cycloolefin copolymer provided by the present invention has a glass transition temperature of 160°C to 201°C and has good heat resistance; its tensile strength is 32MPa to 35MPa, and its tensile modulus is 1450MPa to 1750MPa. The elongation rate is 2.1% to 2.9%, and it has good mechanical properties. In addition, the cycloolefin copolymer provided by the invention also has better transparency. Experimental results show that the light transmittance of the cycloolefin copolymer provided by the invention is greater than 85%.

Description of drawings

Fig. 1 is the carbon nuclear magnetic resonance spectrogram of the cycloolefin copolymer that the embodiment of the present invention 3 obtains;

Fig. 2 is the proton nuclear magnetic resonance spectrogram of the polymerization reaction product that the embodiment of the present invention 3 obtains and cycloolefin copolymer;

Fig. 3 is the gel permeation chromatogram of the polymerization reaction product that the embodiment of the present invention 3 obtains and cycloolefin copolymer;

Fig. 4 is the differential scanning calorimetry curve of the cycloolefin copolymer that embodiment 3～embodiment 6 of the present invention obtains;

Fig. 5 is the thermogravimetric curve of the cycloolefin copolymer that embodiment 3～embodiment 6 of the present invention obtains;

Fig. 6 shows the light transmittance of cycloolefin copolymers obtained in Examples 3 to 6 of the present invention.

Detailed ways

The present invention provides a kind of cyclic olefin copolymer, has the structure shown in formula I:

In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150.

In the present invention, preferably, 230≤x≤320; more preferably, 256≤x≤310. In the present invention, preferably, 40≤y≤86; more preferably, 50≤y≤80. The cycloolefin copolymer provided by the invention has good heat resistance and mechanical properties at the same time. In addition, the cycloolefin copolymer provided by the invention also has better transparency.

The present invention provides a kind of preparation method of cycloolefin copolymer described in above-mentioned technical scheme, comprises the following steps:

1), under the action of a catalyst, a compound having a structure shown in formula II and a compound having a structure shown in formula III are polymerized in a solvent to obtain a polymerized reaction product;

2), hydrogenating the polymerization reaction product and a hydrogen source to obtain a cycloolefin copolymer;

In the present invention, preferably, the compound having the structure shown in formula II, the compound having the structure shown in formula III and a solvent are mixed, and a catalyst is added to the obtained mixture for polymerization reaction to obtain a polymerization reaction product. In the present invention, the compound having the structure represented by formula II, the compound having the structure represented by formula III and the solvent are preferably mixed under the condition of stirring. In the present invention, there is no special limitation on the stirring method during mixing, and the stirring technical solution well known to those skilled in the art can be adopted. In the present invention, the stirring time during the mixing is preferably 5 minutes to 15 minutes, more preferably 8 minutes to 12 minutes, and most preferably 10 minutes.

The present invention preferably carries out the polymerization reaction under dry, oxygen-free conditions. In the present invention, the polymerization reaction can be carried out in a Braun glove box, or can be carried out under the protection of nitrogen using standard Schlenk techniques. In the present invention, the polymerization reaction is preferably carried out under the condition of stirring. The present invention has no special limitation on the stirring method of the polymerization reaction, and the stirring technical solution well known to those skilled in the art can be used.

In the present invention, the temperature of the polymerization reaction is preferably 0°C to 50°C, more preferably 10°C to 40°C, and most preferably 20°C to 30°C.

In the present invention, the transparency of the prepared cycloolefin copolymer can be controlled by controlling the time of the polymerization reaction. In the present invention, the reaction rate of the compound with the structure shown in the formula II is greater than the reaction rate of the compound with the structure shown in the formula III, and controlling the time of the polymerization reaction can make the compound with the structure shown in the formula III incompletely polymerized , There are fewer compounds with the structure shown in the formula III in the cycloolefin copolymer obtained, and the fewer compounds with the structure shown in the formula III in the cycloolefin copolymer obtained in the present invention, the better the transparency of the cycloolefin copolymer. In the present invention, the time for the polymerization reaction is preferably 5 min to 60 min, more preferably 10 min to 50 min, and most preferably 10 min to 30 min.

In the present invention, the catalyst is preferably a carbene catalyst, more preferably a ruthenium carbene compound, most preferably a compound having a structure shown in formula IV:

In formula IV, L is preferably PCy ₃ ; X is preferably Cl, Br or I; R ₁ is preferably H, Ph or CH ₂ CH ₃ ; R is preferably Cy, Cp or Ph. In the present invention, X in the formula IV is more preferably Cl; R ₁ is more preferably Ph; R is more preferably Cy. In the present invention, the catalyst is most preferably a compound having a structure shown in formula V:

In the present invention, a carbene catalyst is preferably used to catalyze the polymerization reaction. This catalyst has high activity and good polymerization tolerance, so that the present invention does not need to add a co-catalyst in the process of preparing the cycloolefin copolymer.

In the present invention, the catalyst is preferably a catalyst solution. In the present invention, the solvent in the catalyst solution is preferably a hydrocarbon compound, a halogenated hydrocarbon compound, a cyclic hydrocarbon compound or an aromatic compound; more preferably cyclopentane, hexane, cyclohexane, decane, Isododecane, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform or tetrahydrofuran; most preferably benzene, toluene, dichloromethane, cyclohexane or tetrahydrofuran. In the present invention, there is no special limitation on the source of the solvent in the catalyst solution, and the above-mentioned solvents known to those skilled in the art can be used, which can be purchased from the market.

In the present invention, the molar concentration of the catalyst solution is preferably 2.5 μmol/mL-4.5 μmol/mL, more preferably 3 μmol/mL-4 μmol/mL, most preferably 3.3 μmol/mL-3.7 μmol/mL. In order to fully dissolve the catalyst in the solvent of the catalyst solution, the present invention preferably mixes the catalyst and the solvent of the catalyst solution under ultrasonic conditions to obtain a catalyst solution. The present invention has no special limitation on the ultrasonic method, and the ultrasonic technical solution well known to those skilled in the art can be used. In the present invention, the ultrasonic time is preferably 2 minutes to 5 minutes, more preferably 3 minutes to 4 minutes.

In the present invention, there is no special limitation on the source of the catalyst, and it can be prepared by the above-mentioned catalyst preparation methods well known to those skilled in the art. In the present invention, the preparation method of the compound having the structure shown in formula V is preferably:

React phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine in an organic solvent to obtain a compound having the structure shown in formula V.

In the present invention, it is more preferred to mix phenyldiazomethane, organic solvent and dichlorotris(triphenylphosphine)ruthenium, and add tricyclohexylphosphine to the obtained mixture for reaction to obtain the compound having the structure shown in formula V. In the present invention, the temperature at which the phenyldiazomethane, organic solvent and dichlorotris(triphenylphosphine)ruthenium are mixed is preferably -80°C to -50°C, more preferably -78°C to -55°C , most preferably -75°C to -65°C. In the present invention, the temperature for adding tricyclohexylphosphine is preferably -70°C to -50°C, more preferably -60°C to -55°C. In the present invention, the reaction of phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine is preferably carried out under the protection of nitrogen. In the present invention, the reaction of phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine is preferably carried out under the condition of stirring. In the present invention, there is no special limitation on the reaction and stirring method of the phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine, and the stirring technical solution well known to those skilled in the art can be adopted.

In the present invention, the reaction temperature of the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably -80°C to 30°C, more preferably -78°C to 25°C , most preferably -70°C to 20°C. In the present invention, the reaction time of the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably 30 minutes to 50 minutes, more preferably 35 minutes to 45 minutes, most preferably Preferably it is 40 minutes.

The present invention has no special limitation on the source of the phenyldiazomethane, which can be purchased from the market, or can be prepared by the preparation method of phenyldiazomethane well known to those skilled in the art. In the present invention, the preparation method of said phenyldiazomethane is preferably:

Benzaldehyde-p-toluenesulfonylhydrazone, sodium methoxide and triethylene glycol are synthesized to obtain phenyldiazomethane.

In the present invention, the synthesis reaction is preferably carried out under the condition of a water bath. In the present invention, the temperature of the synthesis reaction is preferably 50°C to 70°C, more preferably 55°C to 65°C, most preferably 60°C. In the present invention, the synthesis reaction time is preferably 0.5 hours to 1.5 hours, more preferably 1 hour. In the present invention, the mass ratio of the benzaldehyde-p-toluenesulfonylhydrazone, sodium methylate and triethylene glycol is preferably 1:(2～3):(25～35), more preferably 1 :(2.4～2.9):(27～32), most preferably 1:2.8:25. The present invention has no special limitation on the sources of the benzaldehyde-p-toluenesulfonylhydrazone, sodium methoxide and triethylene glycol, which can be purchased from the market.

After the synthesis reaction is completed, in the present invention, the methanol in the obtained synthesis reaction solution is preferably removed to obtain a synthesis reaction product; the synthesis reaction product is extracted and dried to obtain phenyldiazomethane. The present invention has no special limitation on the method for removing methanol. In the embodiments of the present invention, a mechanical pump can be used to extract the methanol in the synthesis reaction solution. In the present invention, the synthesis reaction product is preferably first extracted with n-pentane, and then the obtained first extracted product is subjected to a second extraction with an aqueous sodium chloride solution. In the present invention, the aqueous sodium chloride solution is preferably a saturated aqueous sodium chloride solution. In the present invention, the method for drying the synthetic reaction product is preferably spin drying. In the present invention, the drying temperature of the synthesis reaction product is preferably -35°C to -45°C, more preferably -40°C.

In the present invention, the phenyldiazomethane is preferably a pentane solution of phenyldiazomethane. In the present invention, the mass concentration of the pentane solution of phenyldiazomethane is preferably 90 mg/mL-100 mg/mL, more preferably 94 mg/mL-98 mg/mL.

The present invention has no special limitation on the source of the dichlorotris(triphenylphosphine)ruthenium, which can be purchased from the market.

In the present invention, the tricyclohexylphosphine is preferably a dichloromethane solution of tricyclohexylphosphine. In the present invention, the mass concentration of the dichloromethane solution of tricyclohexylphosphine is preferably 0.06g/mL-0.07g/mL, more preferably 0.064g/mL-0.068g/mL. In the present invention, there is no special limitation on the source of the tricyclohexylphosphine, which can be purchased from the market.

In the present invention, the mass ratio of the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably 1:(3～6):(1～3.5), more preferably 1:(4-5):(2-3), most preferably 1:4.6:2.6.

In the present invention, the organic solvent is preferably dichloromethane. The present invention has no special limitation on the amount of the organic solvent used, as long as the organic solvent can provide a liquid environment for the reaction of the above-mentioned phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine. In order to exclude the air in the organic solvent, the present invention preferably performs liquid nitrogen freeze-thaw treatment on the organic solvent. In the present invention, the number of times of the liquid nitrogen freezing-thawing treatment is preferably 3 times. The present invention has no special limitation on the liquid nitrogen freeze-thaw treatment method, and the technical scheme of liquid nitrogen freeze-thaw treatment well-known to those skilled in the art can be adopted. The present invention can carry out liquid nitrogen freeze-thaw treatment to described organic solvent according to following method:

The organic solvent is packed into a Schlenk bottle, and the Schlenk bottle is put into liquid nitrogen to freeze;

The organic solvent in the Schlenk bottle was thawed after vacuumizing the frozen Schlenk bottle.

In the present invention, air bubbles escape during the process of thawing the organic solvent, thereby removing the air in the organic solvent.

After the phenyldiazomethane, dichlorotri(triphenylphosphine) ruthenium and tricyclohexylphosphine should be completed, the present invention preferably obtains phenyldiazomethane, dichlorotri(triphenylphosphine) The reaction solution of ruthenium and tricyclohexylphosphine was filtered, dissolved, concentrated, precipitated, washed and dried to obtain a compound with the structure shown in formula V. The present invention has no special limitation on the methods of filtering, dissolving, concentrating, precipitating, washing and drying, and the technical solutions of filtering, dissolving, concentrating, precipitating, washing and drying well known to those skilled in the art can be adopted. In the present invention, the precipitation reagent is preferably methanol. In the present invention, the reagents for washing after the precipitation of the reaction solution of phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine are preferably methanol and acetone. In the present invention, the method for drying the reaction solution of phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine is preferably vacuum drying. In the present invention, the drying time of the reaction solution of phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine is preferably 2 hours to 4 hours, more preferably 3 hours.

In the present invention, there is no special limitation on the source of the compound having the structure shown in Formula II, and it can be prepared by a method well known to those skilled in the art for preparing the compound having the structure shown in Formula II. In the present invention, the preparation method of the compound having the structure shown in formula II is preferably:

React norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol to obtain a compound having the structure shown in formula II.

In the present invention, the reaction of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably carried out under vacuum conditions. In the present invention, the reaction of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably carried out under the condition of protective gas. In the present invention, the protective gas in the reaction of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably nitrogen. In the present invention, the reaction temperature of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably 160°C to 200°C, more preferably 170°C to 190°C, most preferably 180°C ℃. In the present invention, the reaction time of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably 25 hours to 35 hours, more preferably 28 hours to 32 hours.

In the present invention, the molar ratio of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably (1500～2000):(260～300):1, more preferably (1600 ~1800):(270~295):1, most preferably (1700~1760):(284~290):1. In the present invention, there is no special limitation on the sources of the norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol, which can be purchased from the market.

After the reaction of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is completed, the present invention preferably obtains norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol The reaction product was cooled, allowed to stand, filtered and washed to obtain a compound with the structure shown in formula II. The method of cooling, standing, filtering and washing is not particularly limited in the present invention, and the technical solutions of cooling, standing, filtering and washing well known to those skilled in the art can be adopted. In the present invention, the cooling temperature is preferably 20°C to 30°C, more preferably 24°C to 28°C. In the present invention, the standing time is preferably 10 hours to 16 hours, more preferably 12 hours to 14 hours. In the present invention, the reagent for washing the reaction product of norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol is preferably n-hexane.

In the present invention, there is no special limitation on the source of the compound having the structure shown in formula III, which can be purchased from the market.

In the present invention, the type and source of the solvent for the polymerization reaction are consistent with the type and source of the solvent in the above catalyst solution, and will not be repeated here. In the present invention, the solvent for the polymerization reaction may be the same as or different from the solvent in the catalyst solution described in the above technical solution.

In the present invention, the glass transition temperature of the prepared cycloolefin copolymer can be controlled by controlling the amount of the raw materials used in the polymerization reaction. The more compounds having the structure shown in formula II in the cycloolefin copolymer prepared by the present invention, the higher the glass transition temperature of the cycloolefin copolymer. In the present invention, the ratio of the total moles of the compound having the structure shown in formula II to the moles of the compound having the structure shown in formula III to the moles of the catalyst is preferably (300～500):1, more preferably (350～ 450):1, most preferably (380-420):1. In the present invention, the molar ratio of the compound having the structure represented by formula II to the compound having the structure represented by formula III is preferably (0.5-2):1, more preferably (0.5-1.5):1.

In the present invention, there is no special limitation on the amount of solvent used in the polymerization reaction, and the amount of solvent used in the polymerization reaction known to those skilled in the art can be used. In the present invention, the mass ratio of the compound having the structure represented by formula II to the polymerization solvent is preferably 1:(20-30), more preferably 1:(24-28).

After the polymerization reaction is completed, the present invention preferably uses a terminator to terminate the polymerization reaction to obtain a polymerization reaction solution; mix the polymerization reaction solution with a precipitating agent to obtain a precipitated product; filter, wash, and dry the precipitated product, A polymerized reaction product is obtained.

The present invention has no special limitation on the type and source of the terminator, and the terminator used in the preparation of cycloolefin copolymers well known to those skilled in the art can be used, which can be purchased from the market. In the present invention, the terminator is preferably vinyl ether. In the present invention, the molar ratio of the terminator to the catalyst is preferably (100-500):1, more preferably (200-400):1, most preferably 300:1. In the present invention, the time for terminating the polymerization reaction is preferably 20 minutes to 40 minutes, more preferably 25 minutes to 35 minutes, most preferably 30 minutes.

After obtaining the polymerization reaction solution, the present invention preferably mixes the polymerization reaction solution and a precipitating agent to obtain a precipitation product. In the present invention, there is no special limitation on the type of precipitating agent for precipitating the polymerization reaction solution, and the precipitating agent well known to those skilled in the art for the preparation of cycloolefin copolymers can be used. In the present invention, the precipitating agent for precipitating the polymerization reaction solution is preferably methanol, more preferably anhydrous methanol. In the present invention, the mixing temperature of the polymerization reaction solution and the precipitation agent is preferably -10°C to 0°C, more preferably -8°C to -5°C.

After obtaining the precipitated product, in the present invention, the precipitated product is preferably filtered, washed, and dried to obtain a polymerization reaction product. The present invention has no special limitation on the method of filtering, washing and drying the precipitated product, and the technical solution of filtering, washing and drying well known to those skilled in the art can be adopted. In the present invention, the reagent for washing the precipitated product is preferably acetone. In the present invention, the number of washings of the precipitated product 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 drying temperature of the precipitation product is preferably 20°C-40°C, more preferably 25°C-35°C, most preferably 30°C. In the present invention, the drying time of the precipitated product is preferably 12 hours to 24 hours, more preferably 16 hours to 20 hours, most preferably 18 hours.

After the polymerization reaction product is obtained, the present invention performs hydrogenation reaction on the polymerization reaction product and a hydrogen source to obtain a cycloolefin copolymer. In the present invention, the hydrogenation reaction is preferably carried out under the condition of protective gas. In the present invention, the protective gas for the hydrogenation reaction is preferably nitrogen. The method of the hydrogenation reaction in the present invention has no special limitation, and the hydrogenation reaction technical solution well known to those skilled in the art can be adopted.

The present invention has no special limitation on the type of the hydrogen source, and the hydrogen source is preferably hydrogen gas or a hydrazine compound, more preferably a hydrazine compound, most preferably p-toluenesulfonyl hydrazide.

In the present invention, when the hydrogen source is a hydrazine compound, the present invention preferably carries out a hydrogenation reaction according to the following method to prepare a cycloolefin copolymer:

The polymerization reaction product and the hydrazine compound are subjected to a hydrogenation reaction in a solvent to obtain a cycloolefin copolymer.

In the present invention, the ratio of the number of moles of double bonds in the polymerization reaction product to the number of moles of hydrazine compounds is preferably 1:(3-6), more preferably 1:(4-5). In the present invention, the hydrogenation reaction solvent is preferably toluene. In the present invention, there is no special limitation on the amount of solvent used in the hydrogenation reaction, as long as the solvent used can provide a liquid environment for the hydrogenation reaction. In the present invention, the reaction temperature of the hydrogenation reaction between the polymerization reaction product and the hydrazine compound is preferably 120°C-140°C, more preferably 125°C-135°C, most preferably 130°C. In the present invention, the reaction time for the hydrogenation reaction between the polymerization reaction product and the hydrazine compound is preferably 12 hours to 24 hours, more preferably 14 hours to 20 hours.

In order to prevent the cross-linking reaction during the hydrogenation reaction between the above-mentioned polymerization product and the hydrazine compound, the reaction raw materials for the hydrogenation reaction between the polymerization reaction product and the hydrazine compound preferably further include a free radical scavenger. The present invention has no special limitation on the type and source of the free radical scavenger, and the free radical scavenger known to those skilled in the art can be used, which can be purchased from the market. In the present invention, the free radical scavenger is preferably 2,6-di-tert-butyl-4-methylphenol. In the present invention, there is no special limitation on the amount of the free radical scavenger, and the amount of the free radical scavenger known to those skilled in the art can be used. In the present invention, the usage amount of the free radical scavenger is preferably 0.05 eqv-3 eqv relative to the mole number of the catalyst described in the above technical solution.

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 a cycloolefin copolymer. In the present invention, the purity of the ethanol is preferably 97%-99%. The present invention has no special limitation on the method of filtering, washing and drying the mixed product, and the technical solution 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 12 hours to 24 hours, more preferably 16 hours to 20 hours. In the present invention, the drying temperature of the mixed product is preferably 40°C-70°C, more preferably 50°C-65°C, most preferably 60°C.

After the cyclic olefin copolymer is prepared, the present invention carries out carbon nuclear magnetic resonance spectrum detection and proton nuclear magnetic resonance spectrum detection on the cycloolefin copolymer obtained, and the detection method of the carbon nuclear magnetic resonance spectrum detection and proton nuclear magnetic resonance spectrum detection is Varian Unity -400 nuclear magnetic resonance spectrometer was measured at 25°C, tetramethylsilane (TMS) was used as internal standard, and deuterated chloroform was used as solvent. The detection result shows that the cycloolefin copolymer provided by the present invention has the structure shown in formula I. The present invention calculates according to the content of the structure compound shown in formula II in the cycloolefin copolymer obtained by formula VI:

The compound with the structure shown in formula II mol%=(I _3.9～4.3 /I _5.42 )×100% formula VI,

In the formula VI, I _3.9-4.3 is the peak area of the chemical shift of 3.9-4.3 in the proton nuclear magnetic resonance spectrum, and I _5.42 is the peak area of the chemical shift of 5.42 in the proton nuclear magnetic resonance spectrum. The calculation result shows that the molar content of the compound having the structure shown in formula II in the cycloolefin copolymer provided by the present invention is 75%-91%.

The present invention adopts the glass transition temperature of the cycloolefin copolymer obtained by differential thermal analysis and thermogravimetric testing, and the detection method is to adopt Perkin-ElmerPyris1DSC differential scanning calorimeter to carry out differential thermal analysis and measurement, and the rate of heating and cooling is 10 °C/min, perform a second scan. Thermal weight loss was measured using a Perkin-Elmer Pyris 1 instrument. The test results show that the cycloolefin copolymer provided by the present invention has a glass transition temperature of 160° C. to 201° C., and has good thermal stability.

The mechanical property of the cycloolefin copolymer that the present invention tests on INSTRON1121, Canton, MA instrument is tested according to the standard of GB/T1040-1992 "Plastic Tensile Properties Test Method", the specimen clamp distance is 20.0mm, and the test speed 5mm/min, each sample is tested at least 8 times to ensure the reliability of the data. The test results show that the cycloolefin copolymer provided by the invention has a tensile strength of 32MPa-35MPa, a tensile modulus of 1450MPa-1750MPa, and an elongation at break of 2.1%-2.9%.

In the present invention, a Shimadzu UV-3600 ultraviolet-visible-near-infrared spectrophotometer is used to test the transparency of the obtained cycloolefin copolymer, and the test wavelength is 400nm to 800nm. The test result is that the light transmittance of the cycloolefin copolymer obtained in the present invention is greater than 85%.

The present invention adopts the molecular weight distribution and the number average molecular weight of the cyclic olefin copolymer that the gel permeation chromatography test obtains, and detection method is to adopt waters152 type gel permeation chromatography to measure; Adopt RI-Laser detector to detect; Detection solvent is tetrahydrofuran, detects The temperature was 35°C; the flow rate of the mobile phase was 1.0 mL/min, and PL EasiCal PS-1 was used as the standard sample. The test results show that the molecular weight distribution of the cycloolefin copolymer provided by the present invention is 1.20-1.52, and the number-average molecular weight is 6.5×10 ⁴ g/mol-10.5×10 ⁴ g/mol.

The present invention provides a cycloolefin copolymer, which has a structure shown in formula I. In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150. The cycloolefin copolymer provided by the invention has good heat resistance and mechanical properties at the same time. In addition, the cycloolefin copolymer provided by the invention also has better transparency.

In order to further understand the present invention, the cyclic olefin copolymer provided by the present invention and its preparation method are described in detail below in conjunction with the examples, but it should be understood that these descriptions are only to further illustrate the characteristics and advantages of the present invention, and they cannot be interpreted as an explanation of the present invention. Limitation of the protection scope of the invention.

The reaction materials used in the following examples of the present invention are commercially available.

Example 1

Add 800 mL of norbornadiene, 230 grams of anthracene and 1 gram of 2,6-di-tert-butyl-p-cresol in sequence to a 2-liter stainless steel autoclave, and repeatedly vacuumize the autoclave 3 times Nitrogen filling operation: the autoclave was heated to 180° C., and the contents in the autoclave were reacted for 30 hours under stirring conditions.

After the reaction, the obtained reaction product was cooled to 25° C., left to stand for 12 hours and then filtered. The obtained filtered product was washed twice with n-hexane to obtain 260 g of the product. The yield of the product prepared by the method provided in Example 1 of the present invention was 75%.

The product obtained above was subjected to proton nuclear magnetic resonance spectrum detection and carbon nuclear magnetic resonance spectrum detection, and the detection result was that the product obtained in Example 1 of the present invention was a compound having the structure shown in formula II.

Example 2

Add 4.96 grams of benzaldehyde-p-toluenesulfonylhydrazone, 1.75 grams of sodium methoxide and 40 mL of triethylene glycol in a 100 mL single-necked bottle, and place the single-necked bottle in a water bath at 60 ° C for 1 hours of synthesis.

After the synthesis reaction is completed, the methanol in the obtained synthesis reaction solution is extracted by a water pump to obtain a synthesis reaction product; the synthesis reaction product is extracted with n-pentane in ice water and then extracted with a saturated NaCl aqueous solution, and the The obtained extracted product was spin-dried to obtain phenyldiazomethane; the yield of said phenyldiazomethane was 50%.

Add 4.0 grams of dichlorotris(triphenylphosphine) ruthenium to a 250mL branch bottle, feed nitrogen to replace the air in the branch bottle, inject 40mL into the branch bottle and freeze it three times with liquid nitrogen - melted dichloromethane; place the check flask in a cold bath at -78°C, and add a pentane solution of phenyldiazomethane with a mass concentration of 98.5mg/mL at -50°C under stirring Mix 10mL, the phenyldiazomethane in the pentane solution of phenyldiazomethane is the phenyldiazomethane prepared above; stir the obtained mixture at -70°C for 10min, then add 40mL, -50°C A dichloromethane solution of tricyclohexylphosphine with a mass concentration of 0.064 g/mL was reacted at 25° C. for 30 min.

After the reaction is finished, the obtained reaction solution is filtered to remove insoluble matter, the filtered reaction solution is concentrated to 10 mL and then filtered again, and 100 mL of methanol is added to the obtained filtered product through three times of liquid nitrogen freezing-thawing for precipitation , the obtained precipitate was first washed three times with methanol, then washed twice with acetone, and the washed precipitate was vacuum-dried for 3 hours to obtain 2.1 g of the product. The yield of the product prepared by the method provided in Example 2 of the present invention was 81%.

The product obtained above was subjected to proton nuclear magnetic resonance spectrum detection and carbon nuclear magnetic resonance spectrum detection, and the detection results showed that the product obtained in Example 2 of the present invention was a compound having the structure shown in formula V.

Example 3

Add 1 g of the compound having the structure shown in Formula II prepared in Example 1 and 0.41 g of the compound having the structure shown in Formula III and 15 mL of dichloromethane into the dry polymerization reaction bottle at 25 ° C, stir and mix for 10 min, Obtain the mixture; add 15.2mg of the compound having the structure shown in formula V prepared in Example 2 to the small ampoule, then add 5mL of dichloromethane to the small ampoule and carry out ultrasonic treatment for 3min, so that the compound having the formula V The compound of the shown structure is fully dissolved in dichloromethane to obtain a compound solution with the structure shown in formula V; under stirring conditions, the compound solution with the structure shown in formula V is added to the above-mentioned polymerization reaction bottle to carry out 15min polymerization reaction;

After the completion of the polymerization reaction, add vinyl ethyl ether of 300 eqv relative to the molar number of the compound shown in formula V to the above-mentioned polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization The reaction solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.03 g of a polymerized reaction product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 3 of the present invention was 72.8%.

In the dry polymerization reaction bottle, add 0.8g of the above-mentioned polymerization reaction product, 6.6g of p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl relative to the molar number of 1eqv of the compound represented by the above formula V Base-4-methylphenol (BHT) and 40mL of toluene were refluxed and stirred for 16 hours at 130°C to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300mL of 98% ethanol , after the obtained mixed product was filtered and drained, it was dissolved again at 130° C. for 30 minutes with 40 mL of toluene, and the dissolved solution was added to 300 mL of ethanol with a purity of 98%, and the obtained mixed product was put into a vacuum oven at Drying was carried out at 60°C for 12 hours to obtain 0.72 g of a cycloolefin copolymer. The hydrogenation reaction method provided in Example 3 of the present invention obtained a cycloolefin copolymer with a yield of 90.0%.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 3 of the present invention was detected by carbon nuclear magnetic resonance spectrum and proton nuclear magnetic resonance spectrum. Cycloolefin copolymer carbon nuclear magnetic resonance spectrogram, as can be seen from Fig. 1, the cycloolefin copolymer that the embodiment of the present invention 3 obtains has the structure shown in formula I, and x is 285 in formula I, and y is 50, and the embodiment of the present invention 3 The structure of the obtained cycloolefin copolymer is clear.

Fig. 2 is the proton nuclear magnetic resonance spectrum figure of the polymerization reaction product that the embodiment of the present invention 3 obtains and cycloolefin copolymer, and curve 1 is the proton nuclear magnetic resonance spectrum of the polymerization reaction product that the embodiment of the present invention 3 obtains in Fig. 2, and curve 2 is The hydrogen nuclear magnetic resonance spectrum of the cycloolefin copolymer obtained in Example 3 of the present invention can be seen from FIG. 3 , the double bond peak of the polymerization reaction product obtained in Example 3 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better. Calculated according to the above formula VI, the molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 3 of the present invention is 86.96%.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 3 of the present invention is subjected to gel permeation chromatography test, and the test results are shown in Figure 3, and Figure 3 shows the polymerization reaction product and cycloolefin copolymer obtained in Example 3 of the present invention The gel permeation chromatogram of product, in Fig. 3, curve 1 is the gel permeation chromatography of the polymerization reaction product that the embodiment of the present invention 3 obtains, and curve 2 is the gel permeation chromatography of the cycloolefin copolymer that the embodiment of the present invention 3 obtains, As can be seen from Figure 3, the peak shape of the polymerization reaction product obtained in Example 3 of the present invention remains unchanged after the hydrogenation reaction, and the hydrodynamic volume does not change much; it can be known by gel permeation chromatography that the cycloolefin obtained in Example 3 of the present invention The molecular weight distribution of the copolymer was 1.35, and the number average molecular weight was 8.42×10 ⁴ g/mol.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 3 of the present invention was tested by differential thermal analysis. The test results are shown in Figure 4, and Figure 4 shows the cycloolefin obtained in Example 3 to Example 6 of the present invention The differential scanning calorimetry curve of the copolymer, in Fig. 4, curve 2 is the differential scanning calorimetry curve of the cycloolefin copolymer obtained in Example 3 of the present invention, as can be seen from Fig. 4, the cycloolefin copolymer obtained in Example 3 of the present invention It has no melting temperature and is in an amorphous state. The cycloolefin copolymer obtained in Example 3 of the present invention has a glass transition temperature of 171.9°C. According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 3 of the present invention was tested by thermogravimetric method, and the test results are shown in Figure 5, and Figure 5 shows the cycloolefin copolymer obtained in Example 3 to Example 6 of the present invention Curve 1 in Fig. 5 is the thermogravimetric curve of the cycloolefin copolymer obtained in Example 3 of the present invention, as can be seen from Fig. 5, the decomposition rate of the cycloolefin copolymer obtained in Example 3 of the present invention at 350°C 10%, with good thermal stability.

Test the mechanical properties of the cyclic olefin copolymer obtained in the embodiment of the present invention 3 according to the method described in the above-mentioned technical scheme, the test result is that the elongation at break of the cyclic olefin copolymer obtained in the embodiment 3 of the present invention is 2.9%, and the tensile strength is 33.0MPa, the tensile modulus is 1450MPa.

Test the transparency of the cycloolefin copolymer obtained in Example 3 of the present invention according to the method described in the above technical solution, and the test results are shown in Figure 6, and Figure 6 shows the transparency of the cycloolefin copolymer obtained in Example 3 to Example 6 of the present invention Light transmittance. Curve 1 in FIG. 6 is the light transmittance of the cycloolefin copolymer obtained in Example 3 of the present invention. It can be seen from FIG. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 3 of the present invention is >85%.

Example 4

Add 1 g of the compound having the structure shown in Formula II prepared in Example 1 and 0.82 g of the compound having the structure shown in Formula III and 15 mL of dichloromethane into the dry polymerization reaction flask at 25° C., stir and mix for 10 min, Obtain the mixture; add 22.9mg of the compound with the structure shown in the formula V prepared in Example 2 to the small ampoule, then add 5mL of dichloromethane to the small ampoule and carry out ultrasonic treatment for 3min, so that the compound with the formula V The compound with the structure shown in V is fully dissolved in dichloromethane to obtain a compound solution with the structure shown in Formula V; under stirring conditions, add the compound solution with the structure shown in Formula V into the above-mentioned polymerization reaction bottle Carry out the polymerization reaction of 15min;

After the completion of the polymerization reaction, add vinyl ethyl ether of 300 eqv relative to the molar number of the compound shown in formula V to the above polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization reaction The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.12 g of a polymerization reaction product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 4 of the present invention is 61.6%.

In the dry polymerization reaction bottle, add 0.8g of the above-mentioned polymerization reaction product, 7.8g of p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl with respect to the molar number of 0.05eqv of the above-mentioned compound having the structure shown in formula V Base-4-methylphenol (BHT) and 40mL of toluene were refluxed and stirred for 16 hours at 130°C to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300mL of 98% ethanol , after the obtained mixed product was filtered and drained, it was dissolved again at 130° C. for 30 minutes with 40 mL of toluene, and the dissolved solution was added to 300 mL of ethanol with a purity of 98%, and the obtained mixed product was put into a vacuum oven at Drying was carried out at 60° C. for 12 hours to obtain 0.75 g of a cycloolefin copolymer. The yield of the cycloolefin copolymer obtained by the hydrogenation reaction method provided in Example 4 of the present invention was 91.5%.

According to the method described in Example 3, the structure of the cycloolefin copolymer obtained in Example 4 of the present invention is detected. The detection result is that the cycloolefin copolymer obtained in Example 4 of the present invention has a structure shown in Formula I, where x in Formula I is 260, y is 86, calculated according to the above formula VI, the molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 4 of the present invention is 75.19%.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 4 of the present invention is subjected to gel permeation chromatography test, and the test result shows that the molecular weight distribution of the cycloolefin copolymer obtained in Example 4 of the present invention is 1.26, and the number average molecular weight is 6.54 ×10 ⁴ g/mol.

According to the method described in the above-mentioned technical scheme, the cycloolefin copolymer obtained in Example 4 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4. Curve 1 in Figure 4 is the cycloolefin copolymer obtained in Example 4 of the present invention. According to the differential scanning calorimetry curve of the compound, it can be seen from Figure 4 that the glass transition temperature of the cycloolefin copolymer obtained in Example 4 of the present invention is 160.8°C. According to the method described in the above-mentioned technical scheme, the cycloolefin copolymer obtained in Example 4 of the present invention is tested by thermogravimetric method, and the test results are as shown in Figure 5. Curve 2 in Figure 5 is the cycloolefin copolymer obtained in Example 4 of the present invention. From the thermogravimetric curve, it can be seen from Figure 5 that the cycloolefin copolymer obtained in Example 4 of the present invention has better thermal stability.

Test the mechanical properties of the cyclic olefin copolymer obtained in Example 4 of the present invention according to the method described in the above-mentioned technical scheme. The test result shows that the elongation at break of the cyclic olefin copolymer obtained in Example 4 of the present invention is 2.9%, and the tensile strength is 32.9MPa, the tensile modulus is 1670MPa.

Test the transparency of the cycloolefin copolymer obtained in Example 4 of the present invention according to the method described in the above-mentioned technical scheme. The test results are as shown in Figure 6. Curve 3 in Figure 6 is the transparency of the cycloolefin copolymer obtained in Example 4 of the present invention. As for the light rate, it can be seen from FIG. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 4 of the present invention is >85%.

Example 5

Add 1 g of the compound having the structure shown in Formula II prepared in Example 1 and 0.205 g of the compound having the structure shown in Formula III and 20 mL of dichloromethane into the dry polymerization reaction bottle at 25 ° C, and stir and mix for 10 min. Obtain the mixture; add 11.4mg of the compound with the structure shown in the formula V prepared in Example 2 to the small ampoule, then add 5mL of dichloromethane to the small ampoule and carry out ultrasonic treatment for 3min, so that the compound with the formula V The compound with the structure shown in V is fully dissolved in dichloromethane to obtain a compound solution with the structure shown in Formula V; under stirring conditions, add the compound solution with the structure shown in Formula V into the above-mentioned polymerization reaction bottle Carry out the polymerization reaction of 15min;

After the completion of the polymerization reaction, add vinyl ethyl ether of 300 eqv relative to the molar number of the compound shown in formula V to the above polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization reaction The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.06 g of a polymerization reaction product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 5 of the present invention was 87.5%.

In the dry polymerization reaction flask, add 0.8 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl - 4-Methylphenol (BHT) and 40mL of toluene were refluxed and stirred at 130°C for 16 hours to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300mL of ethanol with a purity of 98%, After the obtained mixed product was filtered and drained, it was re-dissolved at 130° C. for 30 minutes with 40 mL of toluene, and the dissolved solution was added to 300 mL of ethanol with a purity of 98%, and the obtained mixed product was put into a vacuum oven at 60 It was dried at °C for 12 hours to obtain 0.73 g of a cycloolefin copolymer. The yield of the cycloolefin copolymer obtained by the hydrogenation reaction method provided in Example 5 of the present invention was 90.1%.

According to the method described in Example 3, the structure of the cycloolefin copolymer obtained in Example 5 of the present invention is detected. The detection result is that the cycloolefin copolymer obtained in Example 5 of the present invention has a structure shown in Formula I, and x in Formula I is 310, y is 52, calculated according to the above formula VI, the molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 5 of the present invention is 90.09%.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 5 of the present invention was subjected to gel permeation chromatography test, and the test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 5 of the present invention was 1.26, and the number average molecular weight was 7.01. ×10 ⁴ g/mol.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 5 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4. Curve 3 in Figure 4 is the cycloolefin copolymer obtained in Example 5 of the present invention According to the differential scanning calorimetry curve of the compound, it can be seen from Fig. 4 that the glass transition temperature of the cycloolefin copolymer obtained in Example 5 of the present invention is 195.2°C. According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 5 of the present invention is tested by thermogravimetric method, and the test results are as shown in Figure 5. Curve 3 in Figure 5 is the cycloolefin copolymer obtained in Example 5 of the present invention. From the thermogravimetric curve, it can be seen from Figure 5 that the cycloolefin copolymer obtained in Example 5 of the present invention has better thermal stability.

Test the mechanical properties of the cycloolefin copolymer obtained in Example 5 of the present invention according to the method described in the above-mentioned technical scheme. The test result shows that the elongation at break of the cycloolefin copolymer obtained in Example 5 of the present invention is 2.1%, and the tensile strength is 32.5MPa, the tensile modulus is 1520MPa.

Test the transparency of the cycloolefin copolymer obtained in Example 5 of the present invention according to the method described in the above-mentioned technical scheme, and the test results are as shown in Figure 6, and curve 2 in Figure 6 is the transparency of the cycloolefin copolymer obtained in Example 5 of the present invention As for the light rate, it can be seen from Fig. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 5 of the present invention is >85%.

Example 6

Add 1 g of the compound having the structure shown in formula II prepared in Example 1 and 0.205 g of the compound having the structure shown in formula III and 25 mL of dichloromethane into the dry polymerization reaction bottle at 25 ° C, stir and mix for 10 min, Obtain the mixture; add 11.4mg of the compound with the structure shown in the formula V prepared in Example 2 to the small ampoule, then add 5mL of dichloromethane to the small ampoule and carry out ultrasonic treatment for 3min, so that the compound with the formula V The compound with the structure shown in V is fully dissolved in dichloromethane to obtain a compound solution with the structure shown in Formula V; under stirring conditions, add the compound solution with the structure shown in Formula V into the above-mentioned polymerization reaction bottle Carry out the polymerization reaction of 20min;

After the completion of the polymerization reaction, add vinyl ethyl ether of 100 eqv relative to the molar number of the compound shown in formula V to the above polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization reaction The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.08 g of a polymerization reaction product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 6 of the present invention was 89.5%.

In the dry polymerization reaction flask, add 0.8 g of the above polymerization reaction product, 8.0 g of p-toluenesulfonyl hydrazide, 2,6-di-tert-butyl - 4-Methylphenol (BHT) and 40mL of toluene were refluxed and stirred at 130°C for 14 hours to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300mL of ethanol with a purity of 98%, After the obtained mixed product was filtered and drained, it was re-dissolved at 130° C. for 30 minutes with 40 mL of toluene, and the dissolved solution was added to 300 mL of ethanol with a purity of 98%, and the obtained mixed product was put into a vacuum oven at 60 It was dried at °C for 12 hours to obtain 0.74 g of a cycloolefin copolymer. The yield of the cycloolefin copolymer obtained by the hydrogenation reaction method provided in Example 5 of the present invention was 90.1%.

According to the method described in Example 3, the structure of the cycloolefin copolymer obtained in Example 6 of the present invention is detected. The detection result is that the cycloolefin copolymer obtained in Example 6 of the present invention has a structure shown in Formula I, where x in Formula I is 230, y is 25, calculated according to the above formula VI, the molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 6 of the present invention is 90.91%.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 6 of the present invention was subjected to gel permeation chromatography test, and the test result showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 6 of the present invention was 1.52, and the number average molecular weight was 10.5 ×10 ⁴ g/mol.

According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 6 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4. Curve 4 in Figure 4 is the cycloolefin copolymer obtained in Example 6 of the present invention According to the differential scanning calorimetry curve of the compound, it can be seen from Fig. 4 that the glass transition temperature of the cycloolefin copolymer obtained in Example 6 of the present invention is 201.3°C. According to the method described in the above technical scheme, the cycloolefin copolymer obtained in Example 6 of the present invention is tested by thermogravimetric method, and the test results are shown in Figure 5. Curve 4 in Figure 5 is the cycloolefin copolymer obtained in Example 6 of the present invention. From the thermogravimetric curve, it can be seen from Figure 5 that the cycloolefin copolymer obtained in Example 6 of the present invention has better thermal stability.

Test the mechanical properties of the cyclic olefin copolymer obtained in Example 6 of the present invention according to the method described in the above-mentioned technical scheme. The test result shows that the elongation at break of the cyclic olefin copolymer obtained in Example 6 of the present invention is 2.3%, and the tensile strength is 32MPa, the tensile modulus is 1580MPa.

Test the transparency of the cycloolefin copolymer obtained in Example 6 of the present invention according to the method described in the above-mentioned technical scheme, the test results are as shown in Figure 6, and curve 4 in Figure 6 is the transparency of the cycloolefin copolymer obtained in Example 6 of the present invention As for the light rate, it can be seen from FIG. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 6 of the present invention is greater than 85%.

Example 7

Add 1g of the compound having the structure shown in formula II prepared in Example 1 and 0.82g of the compound having the structure shown in formula III and 25mL of hexane to the dry polymerization reaction bottle at 0°C, stir and mix for 10min to obtain Mixture; add 36.4mg of the compound with the structure shown in formula V prepared in Example 2 to the small ampoule, then add 5mL of toluene to the small ampoule and carry out ultrasonic treatment for 3min, so that the compound with the structure shown in formula V The compound of the structure is fully dissolved in toluene to obtain a compound solution having the structure shown in Formula V; under stirring conditions, the compound solution having the structure shown in Formula V is added to the above-mentioned polymerization reaction bottle for 5 minutes of polymerization reaction ;

After the completion of the polymerization reaction, add vinyl ethyl ether of 300 eqv relative to the molar number of the compound shown in formula V to the above polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization reaction The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.08 g of a polymerization reaction product.

The autoclave was pre-dried under vacuum conditions for 5 hours, and 1 g of the above-prepared polymerization reaction product, 300 mL of cyclohexane, and 0.5 g of Pd/Al ₂ O ₃ catalyst were added to the autoclave, and the The autoclave was pumped and ventilated three times, and then 30 MPa of hydrogen gas was filled into the autoclave, and hydrogenation reaction was carried out at 130°C for 24 hours, and the obtained hydrogenation reaction solution was filtered to recover the Pd/Al ₂ O ₃ catalyst therein , to obtain a hydrogenation reaction product; the hydrogenation reaction product was poured into ethanol for precipitation, and the obtained precipitated product was filtered and then put into a vacuum oven and dried at 60° C. for 12 hours to obtain 0.92 g of cycloolefin copolymer.

According to the method described in Example 3, the structure and properties of the cycloolefin copolymer obtained in Example 7 of the present invention are tested. The test result is that the cycloolefin copolymer obtained in Example 7 of the present invention has a structure shown in formula I, and in formula I x is 320 and y is 53. The molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 7 of the present invention is 88.45%, and the glass transition temperature of the cycloolefin copolymer obtained in Example 7 of the present invention is At 186.3°C, the molecular weight distribution of the cycloolefin copolymer obtained in Example 7 of the present invention was 1.46, and the number average molecular weight was 6.48×10 ⁴ g/mol. The elongation at break of the cycloolefin copolymer obtained in Example 7 of the present invention is 2.8%, the tensile strength is 35 MPa, and the tensile modulus is 1750 MPa. The light transmittance of the cycloolefin copolymer obtained in Example 7 of the present invention is >85%. The cycloolefin copolymer obtained in Example 7 of the present invention has relatively high glass transition temperature, mechanical properties and transparency.

Example 8

Add 1 g of the compound having the structure shown in formula II prepared in Example 1 and 0.205 g of the compound having the structure shown in formula III and 25 mL of benzene into the dry polymerization reaction bottle at 50 ° C, stir and mix for 10 min to obtain a mixture Add 3.34mg of the compound with the structure shown in formula V prepared in Example 2 to the small ampoule, then add 5mL of cyclohexane to the small ampoule and carry out 3min ultrasonic treatment, so that the compound with the structure shown in formula V Fully dissolve the compound with the structure shown in cyclohexane to obtain a compound solution with the structure shown in Formula V; under stirring conditions, add the compound solution with the structure shown in Formula V into the above-mentioned polymerization reaction bottle for 60min polymerization reaction;

After the completion of the polymerization reaction, add vinyl ethyl ether of 300 eqv relative to the molar number of the compound shown in formula V to the above polymerization reaction bottle under stirring conditions to terminate the polymerization reaction; after 30 minutes, the obtained polymerization reaction The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed three times with acetone, and dried in a vacuum oven at 40° C. for 12 hours to obtain 1.10 g of a polymerization reaction product.

In a dry polymerization reaction flask, add 0.8 g of the above polymerization reaction product, 8.0 g of p-toluenesulfonyl hydrazide and 40 mL of toluene in sequence, and reflux and stir at 150° C. for 20 hours to carry out the hydrogenation reaction to obtain the hydrogenation reaction product; The above hydrogenation reaction product was added dropwise to 300mL of ethanol with a purity of 98%. After the obtained mixed product was filtered and drained, it was re-dissolved with 40mL of toluene at 130°C for 30 minutes, and the dissolved solution was added to 300mL of ethanol with a purity of In 98% ethanol, the obtained mixed product was dried in a vacuum oven at 60° C. for 12 hours to obtain 1.05 g of cycloolefin copolymer.

According to the method described in Example 3, the structure and properties of the cycloolefin copolymer obtained in Example 8 of the present invention are tested. The test result is that the cycloolefin copolymer obtained in Example 8 of the present invention has a structure shown in formula I, in formula I x is 256 and y is 40. The molar content of the compound having the structure shown in formula II in the cycloolefin copolymer obtained in Example 8 of the present invention is 86.51%, and the glass transition temperature of the cycloolefin copolymer obtained in Example 8 of the present invention is At 175°C, the molecular weight distribution of the cycloolefin copolymer obtained in Example 8 of the present invention was 1.38, and the number average molecular weight was 7.56×10 ⁴ g/mol. The elongation at break of the cycloolefin copolymer obtained in Example 8 of the present invention is 2.6%, the tensile strength is 33.5 MPa, and the tensile modulus is 1580 MPa. The light transmittance of the cycloolefin copolymer obtained in Example 8 of the present invention is >85%. The cycloolefin copolymer obtained in Example 8 of the present invention has relatively high glass transition temperature, mechanical properties and transparency.

It can be seen from the above examples that the present invention provides a cycloolefin copolymer having the structure shown in formula I, where x and y are the degree of polymerization, 100≤x≤350, 25≤y≤150. The cycloolefin copolymer provided by the invention has good heat resistance and mechanical properties at the same time. In addition, the cycloolefin copolymer provided by the invention also has better transparency.

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention. Various modifications to these embodiments will be readily 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 invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. A cycloolefin copolymer has a structure shown in formula I: In formula I, x and y are degrees of polymerization, 100≤x≤350, 25≤y≤150. 2. The cycloolefin copolymer according to claim 1, characterized in that, in the formula I, 230≤x≤320, 40≤y≤86. 3. a preparation method of cycloolefin copolymer described in claim 1 or 2, comprises the following steps: 1), under the action of a catalyst, a compound having a structure shown in formula II and a compound having a structure shown in formula III are polymerized in a solvent to obtain a polymerized reaction product; 2), hydrogenating the polymerization reaction product and a hydrogen source to obtain a cycloolefin copolymer; 4. The method according to claim 3, characterized in that the catalyst is a carbene catalyst. 5. The method according to claim 3, characterized in that, the catalyst is a ruthenium carbene compound. 6. The method according to claim 3, characterized in that, the compound with the structure shown in formula II and the ratio of the total moles of the compound with the structure shown in formula III and the moles of the catalyst are (300～500 ):1; The molar ratio of the compound having the structure shown in formula II to the compound having the structure shown in formula III is (0.5-2):1. 7. The method according to claim 3, characterized in that, the temperature of the polymerization reaction in the step 1) is 0°C to 50°C; The time for the polymerization reaction in the step 1) is 5 minutes to 60 minutes. 8. The method according to claim 3, characterized in that, the hydrogen source in the step 2) is a hydrazine compound. 9. The method according to claim 8, characterized in that the ratio of the number of moles of the double bond of the polymerization reaction product in the step 2) to the number of moles of the hydrazine compound is 1:(3-6). 10. The method according to claim 8, characterized in that, the temperature of the hydrogenation reaction in the step 2) is 110° C. to 150° C.; The hydrogenation reaction time in the step 2) is 12 hours to 24 hours.