WO2015176588A1

WO2015176588A1 - Cycloolefin copolymer and preparation method therefor

Info

Publication number: WO2015176588A1
Application number: PCT/CN2015/076621
Authority: WO
Inventors: 李悦生; 李彦国; 杨继兴; 崔磊; 王永霞; 穆红亮
Original assignee: 中国科学院长春应用化学研究所
Priority date: 2014-05-21
Filing date: 2015-04-15
Publication date: 2015-11-26
Also published as: JP2017515943A

Abstract

A cycloolefin copolymer has a structure represented by formula I, II, III or IV, wherein in the formula I, 100≤x≤350, 25≤y≤150; in the formula II, 300≤z≤1000; in the formula III, 180≤m≤430, 40≤n≤220; and in the formula IV, 250≤i≤500, 20≤j≤144. The present invention provides a method for preparing a cycloolefin copolymer. The method comprises: under the effect of a catalyst, a first compound and a second compound are subjected to polymerization reaction in a solvent to obtain a polymerization reaction product; and the polymerization reaction product and a hydrogen source are subjected to hydrogenation reaction to obtain a cycloolefin copolymer, wherein the first compound has a structure represented by formula 1, and the second compound has a structure represented by formula 1, 2, 3 or 4. The cycloolefin copolymer provided by the present invention has good thermal resistance and mechanical performance.

Description

Cyclic olefin copolymer and preparation method thereof

This application is submitted to the Chinese Patent Office on May 21, 2014, the application number is 201410216491.3, the invention name is "a cyclic olefin copolymer and its preparation method"; the application number is 201410216477.3, the invention name is "a cyclic olefin copolymerization" And its preparation method"; application number is 201410216438.3, the invention name is "a cyclic olefin copolymer and its preparation method"; the application number is 201410216495.1, the invention name is "a cyclic olefin copolymer and its preparation method" The priority of the patent application, the entire contents of which is incorporated herein by reference.

Technical field

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

Background technique

The cyclic olefin copolymer is a kind of high value-added thermoplastic engineering plastic which is polymerized from a cyclic olefin. The copolymer has high transparency, low dielectric constant, excellent heat resistance, chemical resistance, and melt flow. Good properties, barrier properties and dimensional stability. Therefore, the cyclic olefin copolymer can be widely applied to the manufacture of various optical, information, electrical, and medical materials.

The heat resistance of cyclic olefin copolymers is an important property of such materials. In some higher temperature environments, if the heat resistance of the cyclic olefin copolymer is poor, the cyclic olefin copolymer will undergo dimensional changes such as distortion and deformation, thereby directly affecting the optical properties of the cyclic olefin copolymer and Mechanical properties. Therefore, increasing the heat resistance of the cyclic olefin copolymer greatly expands the range of use of the cyclic olefin copolymer. An important indicator for measuring the heat resistance of a cyclic olefin copolymer is the glass transition temperature of a cyclic olefin copolymer. The glass transition temperature is the temperature at which the copolymer transitions from a glassy state to a rubbery state. When the ambient temperature approaches or reaches the vitrification of the copolymer. At the transition temperature, the copolymer undergoes more severe deformation and the mechanical properties are greatly reduced, which has a very adverse effect on the application of the copolymer material. Therefore, increasing the glass transition temperature of the copolymer can effectively improve the heat resistance of the copolymer.

There are two methods for synthesizing a cyclic olefin copolymer: one is a chain polymerization of ethylene and a norbornene monomer, and the other is a ring-opening metathesis polymerization (ROMP) of a norbornene monomer and hydrogenation. . Commercially available cyclic olefin copolymers currently obtained by the ROMP method, such as the commercial brand number

with

The cyclic olefin copolymer has good mechanical properties, but the cyclic olefin copolymer has a low glass transition temperature, such as

with

The glass transition temperature is only 140 ° C,

The glass transition temperature is 170 ° C, and thus the cyclic olefin copolymer is inferior in heat resistance.

A cyclic olefin copolymer having a higher glass transition temperature can be prepared by a chain polymerization method of ethylene and a norbornene monomer, such as a commercial brand number

The cyclic olefin copolymer, but the cyclic olefin copolymer has a strong molecular chain rigidity, and the cyclic olefin copolymer has a poor elongation at break, so the mechanical properties of the cyclic olefin copolymer are poor.

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

Summary of the invention

In view of the above, an object of the present invention is to provide a cyclic olefin copolymer, and the cyclic olefin copolymer provided by the present invention has both good heat resistance and mechanical properties.

The present invention provides a cyclic olefin copolymer having the structure of Formula I, Formula II, Formula III or Formula IV:

In formula I, 100≤x≤350, 25≤y≤150;

In Formula II, 300 ≤ z ≤ 1000;

In Formula III, 180 ≤ m ≤ 430, 40 ≤ n ≤ 220;

In Formula IV, 250 ≤ i ≤ 500, and 20 ≤ j ≤ 144.

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

In the formula II, 400≤z≤700;

In the formula III, 240≤m≤410, 80≤n≤170;

In the formula IV, 325 ≤ i ≤ 475, and 30 ≤ j ≤ 125.

The invention provides a preparation method of a cyclic olefin copolymer, comprising the following steps:

1), under the action of a catalyst, the first compound and the second compound are polymerized in a solvent to obtain a polymerization reaction product;

2) hydrogenating the polymerization reaction product and the hydrogen source to obtain a cyclic olefin copolymer;

The first compound has the structure shown in Formula 1:

The second compound has the structure shown in Formula 1, Formula 2, Formula 3 or Formula 4:

Preferably, the catalyst is a carbene type catalyst.

Preferably, the catalyst is a quinone carbene compound.

Preferably, the ratio of the total number of moles of the first compound and the second compound to the number of moles of the catalyst is (270 to 1000): 1;

The molar ratio of the first compound to the second compound is (0.5 to 19):1.

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

The polymerization reaction time in the step 1) is from 5 minutes to 180 minutes.

Preferably, the hydrogen source in the step 2) is an anthraquinone compound.

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

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

The hydrogenation reaction in the step 2) is carried out for a period of from 12 hours to 24 hours.

The cyclic olefin copolymer provided by the invention has both good heat resistance and mechanical properties. The experimental results show that the cyclic olefin copolymer provided by the invention has a glass transition temperature of 125 ° C to 224 ° C and has good heat resistance; the tensile strength is 21 MPa to 55 MPa, and the tensile modulus is 1000 MPa to 1950 MPa. The elongation is 1.7% to 4.9%, and has good mechanical properties. Further, the cyclic olefin copolymer provided by the present invention also has good transparency. The experimental results show that the cycloolefin copolymer provided by the present invention has a light transmittance of >85%.

DRAWINGS

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below. Obviously, the drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can obtain other drawings according to the provided drawings without any creative work.

1 is a nuclear magnetic resonance spectrum of a product obtained in Example 1 of the present invention;

2 is a nuclear magnetic resonance hydrogen ( ¹ H) spectrum of the product obtained in Example 2 of the present invention;

Figure 3 is a nuclear magnetic resonance phosphorus ( ^31P ) spectrum of the product obtained in Example 2 of the present invention;

Figure 4 is a nuclear magnetic resonance carbon spectrum of the cyclic olefin copolymer obtained in Example 3 of the present invention;

Figure 5 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 3 of the present invention;

Figure 6 is a gel permeation chromatogram of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 3 of the present invention;

Figure 7 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Examples 3 to 6 of the present invention;

Figure 8 is a thermogravimetric curve of the cyclic olefin copolymer obtained in Examples 3 to 6 of the present invention;

Figure 9 is a light transmittance of the cyclic olefin copolymer obtained in Examples 3 to 6 of the present invention;

Figure 10 is a nuclear magnetic resonance carbon spectrum of the cyclic olefin copolymer obtained in Example 9 of the present invention;

Figure 11 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 9 of the present invention;

Figure 12 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Examples 9 to 11 of the present invention;

Figure 13 is a thermogravimetric curve of a cyclic olefin copolymer obtained in Example 9 of the present invention;

Figure 14 is a light transmittance of the cyclic olefin copolymer obtained in Example 9 of the present invention;

Figure 15 is a nuclear magnetic resonance spectrum of the product obtained in Example 15 of the present invention;

Figure 16 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 16 of the present invention;

Figure 17 is a graph showing the reactivity ratio of a compound having a structure represented by Formula 1 and a compound having a structure represented by Formula 3 in the preparation of a cyclic olefin copolymer according to Examples 16 to 20 of the present invention;

Figure 18 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 16 of the present invention;

Figure 19 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 17 of the present invention;

Figure 20 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 18 of the present invention;

Figure 21 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 19 of the present invention;

Figure 22 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 20 of the present invention;

Figure 23 is a graph showing the relationship between the glass transition temperature of the cyclic olefin copolymer obtained in Examples 16 to 20 and Example 14 of the present invention and the content of the compound having the formula 1 in the cyclic olefin copolymer;

Figure 24 is a graph showing the thermogravimetric curves of the cyclic olefin copolymer obtained in Examples 16 to 20 of the present invention;

Figure 25 is a graph showing the thermogravimetric curves of the cyclic olefin copolymer obtained in Examples 16 to 20 of the present invention;

Figure 26 is a light transmittance of the cyclic olefin copolymer obtained in Example 16, Example 18 and Example 20 of the present invention;

Figure 27 is a nuclear magnetic resonance spectrum of the product obtained in Example 23 of the present invention;

Figure 28 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 24 of the present invention;

Figure 29 is a graph showing the reactivity ratio of a compound having a structure represented by Formula 1 and a compound having a structure of Formula 4 in the preparation of a cyclic olefin copolymer according to Examples 24 to 29 of the present invention;

Figure 30 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 24 of the present invention;

Figure 31 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 25 of the present invention;

Figure 32 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 26 of the present invention;

Figure 33 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 27 of the present invention;

Figure 34 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 28 of the present invention;

Figure 35 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 29 of the present invention;

Figure 36 is a thermogravimetric curve of a cyclic olefin copolymer obtained in Example 28 of the present invention;

Figure 37 is a graph showing the relationship between the glass transition temperature of the cyclic olefin copolymer obtained in Examples 24 to 29 and Example 14 of the present invention and the content of the compound having the formula 1 in the cyclic olefin copolymer;

38 is a light transmittance of a cycloolefin copolymer obtained in Examples 24 to 28 of the present invention.

detailed description

The technical solutions in the embodiments of the present invention are clearly and completely described below. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.

In formula I, 100≤x≤350, 25≤y≤150;

In Formula II, 300 ≤ z ≤ 1000;

In Formula III, 180 ≤ m ≤ 430, 40 ≤ n ≤ 220;

In Formula IV, 250 ≤ i ≤ 500, and 20 ≤ j ≤ 144.

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. In the present invention, preferably, 400 ≤ z ≤ 700; more preferably, 500 ≤ z ≤ 600. In the present invention, preferably, 240 ≤ m ≤ 410; more preferably, 280 ≤ m ≤ 360. In the present invention, preferably, 80 ≤ n ≤ 170; more preferably, 90 ≤ n ≤ 160. In the present invention, preferably, 325 ≤ i ≤ 475; more preferably, 336 ≤ i ≤ 420. In the present invention, preferably, 30 ≤ j ≤ 125; more preferably, 50 ≤ j ≤ 100.

The cyclic olefin copolymer provided by the invention has both good heat resistance and mechanical properties. Further, the cyclic olefin copolymer provided by the present invention also has good transparency.

The invention provides a preparation method of the cyclic olefin copolymer of the above technical solution, comprising the following steps:

The first compound has the structure shown in Formula 1:

In the present invention, the first compound, the second compound and the solvent are preferably mixed, and a catalyst is added to the obtained mixture to carry out a polymerization reaction to obtain a polymerization reaction product. The present invention preferably mixes the first compound, the second compound and the solvent under stirring. The method of the present invention for mixing during mixing is not particularly limited, and a stirring technique known to those skilled in the art may be employed. In the present invention, the stirring time during mixing is preferably from 5 minutes to 15 minutes, more preferably 8 minutes. The clock is ~12 minutes, most preferably 10 minutes.

The present invention preferably carries out the polymerization under dry, anaerobic conditions. In the present invention, the polymerization can be carried out in a Mbraun glove box or under the protection of nitrogen using standard Schlenk techniques. In the present invention, the polymerization reaction is preferably carried out under stirring, and the stirring method of the polymerization reaction is not particularly limited, and a stirring technique known to those skilled in the art can be employed.

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

In the present invention, the polymerization reaction time is preferably from 5 min to 180 min, more preferably from 10 min to 150 min, and most preferably from 15 min to 150 min. In the present invention, when the first compound has a structure represented by Formula 1, and the second compound has a structure represented by Formula 2, a cyclic olefin copolymer having a structure represented by Formula I is prepared. In the present invention, the time for the polymerization in the process of preparing the cyclic olefin copolymer having the structure of the formula I is preferably from 5 min to 60 min, more preferably from 10 min to 50 min, and most preferably from 10 min to 30 min.

In the present invention, when both the first compound and the second compound have the structure of the formula 1, when a compound having the structure of the formula 1 is subjected to polymerization, a cycloolefin having a structure represented by the formula II is prepared. Copolymer. In the present invention, the time for the polymerization in the process of preparing the cyclic olefin copolymer having the structure represented by the formula II is preferably from 60 min to 120 min, more preferably from 80 min to 110 min, and most preferably from 90 min to 100 min.

In the present invention, when the first compound has a structure represented by Formula 1, and the second compound has a structure represented by Formula 3, a cyclic olefin copolymer having a structure represented by Formula III is prepared. In the present invention, the time for the polymerization in the process of preparing the cyclic olefin copolymer having the structure represented by Formula III is preferably from 60 min to 180 min, more preferably from 80 min to 150 min, and most preferably from 100 min to 120 min.

In the present invention, when the first compound has a structure represented by Formula 1, and the second compound has a structure represented by Formula 4, a cyclic olefin copolymer having a structure represented by Formula IV is prepared. In the present invention, the time for the polymerization in the process of preparing the cyclic olefin copolymer having the structure of the formula IV is preferably from 60 min to 180 min, more preferably from 90 min to 120 min, most preferably 100min ~ 110min.

In the present invention, the catalyst is preferably a carbene type catalyst, more preferably a quinone carbene compound, and most preferably a compound having a structure represented by V:

In the formula V, 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 V is more preferably Cl; R _{1 is} more preferably Ph; and R is more preferably Cy. In the present invention, the catalyst is most preferably a compound having the structure of formula VI:

The present invention preferably catalyzes the polymerization reaction using a carbene type catalyst which has high activity and good polymerization tolerance, so that the present invention does not require the addition of a cocatalyst in the process of preparing the cyclic olefin copolymer; and the carbene type catalyst induces The polymerization rate of the first compound and the second compound is fast, so that the above polymerization reaction has a high polymerization conversion ratio.

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 hydrocarbon compound; more preferably cyclopentane, hexane, cyclohexane, decane, Isododecane, benzene, toluene, xylene, ethylbenzene, dichloromethane, chloroform or tetrahydrofuran; most preferably benzene, toluene, dichloromethane, cyclohexane or tetrahydrofuran. The source of the solvent in the catalyst solution of the present invention is not particularly limited, and a solvent of the above kind well known to those skilled in the art may be used, which is commercially available.

In the present invention, the molar concentration of the catalyst solution is preferably from 2.5 μmol/mL to 6 μmol/mL, more preferably from 3 μmol/mL to 5 μmol/mL, and most preferably from 3.5 μmol/mL to 4.5 μmol/mL. In the process of the present invention, in the preparation of a cyclic olefin copolymer having the structure of the formula I, The molar concentration of the catalyst solution is preferably from 2.5 μmol/mL to 4.5 μmol/mL, more preferably from 3 μmol/mL to 4 μmol/mL, and most preferably from 3.3 μmol/mL to 3.7 μmol/mL.

In the present invention, in the process of preparing a cyclic olefin copolymer having a structure represented by Formula II, the molar concentration of the catalyst solution is preferably from 3 μmol/mL to 6 μmol/mL, more preferably from 4 μmol/mL to 5.5 μmol/mL. Most preferably, it is 4.5 μmol/mL to 5 μmol/mL.

In the present invention, in the process of preparing a cyclic olefin copolymer having a structure represented by Formula III, the molar concentration of the catalyst solution is preferably from 2.5 μmol/mL to 4.5 μmol/mL, more preferably from 3 μmol/mL to 4 μmol/mL. Most preferably, it is 3.3 μmol/mL to 3.9 μmol/mL.

In the present invention, in the process of preparing a cyclic olefin copolymer having a structure represented by Formula IV, the molar concentration of the catalyst solution is preferably from 2.5 μmol/mL to 4.5 μmol/mL, more preferably from 3 μmol/mL to 4 μmol/mL. Most preferably, it is 3.4 μmol/mL to 3.8 μmol/mL.

In order to sufficiently 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 method of the present invention is not particularly limited, and an ultrasonic technique known to those skilled in the art may be employed. In the present invention, the time of the ultrasonication is preferably from 2 minutes to 5 minutes, more preferably from 3 minutes to 4 minutes.

The source of the catalyst of the present invention is not particularly limited, and it can be prepared by a method for preparing a catalyst of the above kind well known to those skilled in the art. In the present invention, the preparation method of the structural compound having the formula VI is preferably:

The phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine are reacted in an organic solvent to obtain a compound having the structure represented by the formula VI.

More preferably, the phenyldiazomethane, the organic solvent and the ruthenium tris(triphenylphosphine) are mixed, and tricyclohexylphosphine is added to the obtained mixture to carry out a reaction to obtain a compound having the structure represented by the formula VI. In the present invention, the temperature at which the phenyldiazomethane, the organic solvent and the dichlorotris(triphenylphosphine) ruthenium are mixed is preferably -80 ° C to -50 ° C, more preferably -78 ° C to -55 ° C. Most preferably, it is -75 ° C to -65 ° C. In the present invention, the temperature at which the tricyclohexylphosphine is added is preferably -70 ° C to -50 ° C, more preferably -60 ° C to -55 ° C. In the present invention, the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine are preferably reacted under the protection of nitrogen. Preferred in the present invention The phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine are reacted under stirring. The method for the reaction stirring of the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is not particularly limited, and a stirring technique known to those skilled in the art may be employed.

In the present invention, the temperature at which the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine are reacted 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 from 30 minutes to 50 minutes, more preferably from 35 minutes to 45 minutes, most It is preferably 40 minutes.

The source of the phenyldiazomethane of the present invention is not particularly limited and can be obtained commercially, or can be prepared by a method for preparing phenyldiazomethane well known to those skilled in the art. In the present invention, the preparation method of the phenyldiazomethane is preferably:

The benzaldehyde-p-methylbenzenesulfonyl hydrazide, sodium methoxide and triethylene glycol are subjected to a synthesis reaction to obtain phenyldiazomethane.

The present invention preferably performs the synthesis reaction under the conditions of a water bath. In the present invention, the temperature of the synthesis reaction is preferably from 50 ° C to 70 ° C, more preferably from 55 ° C to 65 ° C, and most preferably 60 ° C. In the present invention, the time of the synthesis reaction is preferably from 0.5 to 1.5 hours, more preferably from 1 hour. In the present invention, the mass ratio of the benzaldehyde-p-methylbenzenesulfonyl hydrazide, sodium methoxide and triethylene glycol is preferably 1: (2 to 3): (25 to 35), more preferably 1 : (2.4 to 2.9): (27 to 32), most preferably 1:2.8:25. The present invention has no particular limitation on the source of the benzaldehyde-p-methylbenzenesulfonyl hydrazide, sodium methoxide and triethylene glycol, and is commercially available.

After the completion of the synthesis reaction, the present invention preferably removes the methanol in the obtained synthesis reaction solution to obtain a synthesis reaction product; the synthesis reaction product is subjected to extraction and drying to obtain phenyldiazomethane. The method for removing methanol in the present invention is not particularly limited. In the embodiment of the present invention, a methanol pump may be used to extract methanol from the synthesis reaction solution. In the present invention, the synthesis reaction product is first subjected to a first extraction with n-pentane, and the obtained first extraction product is subjected to a second extraction with an aqueous solution of sodium chloride. In the present invention, the aqueous sodium chloride solution is preferably a saturated aqueous solution of sodium chloride. In the present invention, the method for drying the synthesis reaction product is preferably Spin dry. In the present invention, the temperature at which the synthesis reaction product is dried 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 phenyldiazomethane pentane solution is preferably from 90 mg/mL to 100 mg/mL, more preferably from 94 mg/mL to 98 mg/mL.

The source of the dichlorotris(triphenylphosphine) ruthenium is not particularly limited and can be obtained commercially.

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 the tricyclohexylphosphine is preferably 0.06 g/mL to 0.07 g/mL, and more preferably 0.064 g/mL to 0.068 g/mL. The source of the tricyclohexylphosphine is not particularly limited in the present invention and is commercially available.

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

In the present invention, the organic solvent is preferably dichloromethane. The amount of the organic solvent to be used in the present invention is not particularly limited, and the organic solvent can provide a liquid environment for the reaction of the above phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine. In order to exclude air in the organic solvent, the present invention preferably performs a liquid nitrogen freeze-thaw treatment on the organic solvent. In the present invention, the number of times of the liquid nitrogen freeze-thaw treatment is preferably three. The method for the liquid nitrogen freezing-thawing treatment of the present invention is not particularly limited, and a technical scheme of liquid nitrogen freezing-thawing treatment well known to those skilled in the art may be employed. In the present invention, the organic solvent can be subjected to liquid nitrogen freezing-thawing treatment according to the following method:

The organic solvent is charged into a Schlenk bottle, and the Schlenk bottle is frozen in liquid nitrogen;

The frozen Schlenk bottle was subjected to vacuum treatment, and then the organic solvent in the Schlenk bottle was thawed.

The present invention escapes bubbles during the thawing of the organic solvent, thereby removing air in the organic solvent.

After the phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine are completed, the present invention preferably obtains phenyldiazomethane and dichlorotris(triphenylphosphine). The hydrazine and tricyclohexylphosphine reaction solution are filtered, dissolved, concentrated, precipitated, washed, and dried to obtain a compound having the structure shown in Formula VI. The method of the filtration, dissolution, concentration, precipitation, washing and drying of the present invention is not particularly limited, and a technical solution of filtration, dissolution, concentration, precipitation, washing and drying which is well known to those skilled in the art can be employed. In the present invention, the precipitated reagent is preferably methanol. In the present invention, the reagent which is washed after precipitation of the reaction solution of phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably methanol and acetone. In the present invention, the method of drying the reaction solution of phenyldiazomethane, dichlorotris(triphenylphosphine) ruthenium and tricyclohexylphosphine is preferably vacuum drying. In the present invention, the reaction time of the reaction solution of the phenyldiazomethane, dichlorotris(triphenylphosphine)ruthenium and tricyclohexylphosphine is preferably from 2 hours to 4 hours, more preferably 3 hours.

In the present invention, the first compound has a structure represented by Formula 1, and the present invention has no particular limitation on the source of the first compound having the structure represented by Formula 1, and has a preparation formula well known to those skilled in the art. The method of the structural compound shown in 1 can be prepared. In the present invention, the preparation method of the first compound having the structure represented by Formula 1 is preferably:

The norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol are reacted to obtain a first compound having the structure shown in Formula 1.

The present invention preferably reacts the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol under vacuum. The present invention preferably reacts the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol under the conditions of a protective gas. In the present invention, the protective gas in the reaction of norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol is preferably nitrogen. In the present invention, the temperature at which the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol are reacted is preferably from 160 ° C to 200 ° C, more preferably from 170 ° C to 190 ° C, most preferably 180. °C. In the present invention, the reaction time of the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol is preferably from 25 hours to 35 hours, more preferably from 28 hours to 32 hours.

In the present invention, the molar ratio of the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol is preferably (1500 to 2000): (260 to 300): 1, more preferably (1600). ~1800): (270 ~ 295): 1, Most preferably (1700 to 1760): (284 to 290): 1. The present invention has no particular limitation on the source of the norbornadiene, anthracene and 2,6-di-tert-butyl-p-cresol, and is commercially available.

After the reaction of norbornadiene, hydrazine 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 first compound having the structure shown in Formula 1. The method of the present invention for cooling, standing, filtering and washing is not particularly limited, and a technical solution of cooling, standing, filtering and washing which is well known to those skilled in the art can be employed. In the present invention, the cooling temperature is preferably from 20 ° C to 30 ° C, more preferably from 24 ° C to 28 ° C. In the present invention, the standing time is preferably from 10 hours to 16 hours, more preferably from 12 hours to 14 hours. In the present invention, the reagent for washing the norbornadiene, hydrazine and 2,6-di-tert-butyl-p-cresol reaction product is preferably n-hexane.

In the present invention, the second compound has a structure represented by Formula 1, Formula 2, Formula 3 or Formula 4. The source of the second compound of the present invention is not particularly limited and may be commercially available or may be prepared according to a method well known to those skilled in the art. In the present invention, when the second compound has the structure represented by Formula 1, it can be produced by the method for producing the first compound having the structure represented by Formula 1 described in the above technical scheme. In the present invention, when the second compound has the structure represented by Formula 2, the second compound having the structure represented by Formula 2 is commercially available. In the present invention, when the second compound has a structure represented by Formula 3, the preparation method of the second compound having the structure represented by Formula 3 is preferably:

The dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol are reacted to obtain a second compound having the structure shown in Formula 3.

The present invention preferably reacts the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol under vacuum. The present invention preferably reacts the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol under conditions of a protective gas. In the present invention, the protective gas in the reaction of the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol is preferably nitrogen. In the present invention, the temperature at which the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol are reacted is preferably from 180 ° C to 220 ° C, more preferably from 190 ° C to 210 ° C, most preferably It is 200 °C. In the present invention, the reaction time of the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol is preferably from 12 hours to 20 hours, more preferably from 15 hours to 18 hours, most preferably It is 16 hours.

In the present invention, the molar ratio of the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol is preferably (1500 to 2000): (260 to 300): 1, more preferably (1600 to 1800): (270 to 295): 1, most preferably (1700 to 1760): (284 to 290): 1. The present invention has no particular limitation on the source of the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol, and is commercially available.

After the reaction of the dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl-p-cresol is completed, the present invention preferably obtains dicyclopentadiene, cyclopentene and 2,6-di-tert-butyl group. - The p-cresol reaction product is cooled, left standing, atmospheric distillation, and vacuum distillation to obtain a second compound having the structure shown in Formula 3. The method of the present invention for cooling, standing, atmospheric distillation and vacuum distillation is not particularly limited, and a technical solution of cooling, standing, atmospheric distillation and vacuum distillation which is well known to those skilled in the art can be employed. In the present invention, the cooling temperature is preferably from 20 ° C to 30 ° C, more preferably from 25 ° C to 28 ° C. In the present invention, the standing time is preferably from 10 hours to 16 hours, more preferably from 12 hours to 14 hours. In the present invention, the temperature of the atmospheric distillation is preferably from 40 ° C to 60 ° C, more preferably from 45 ° C to 50 ° C. In the present invention, the temperature of the vacuum distillation is preferably from 40 ° C to 80 ° C, more preferably from 50 ° C to 60 ° C. In the present invention, it is preferred to collect a fraction of 25 ° C to 30 ° C at the time of vacuum distillation, which is a second compound having a structure represented by Formula 3.

In the present invention, when the second compound has a structure represented by Formula 4, the preparation method of the second compound having the structure represented by Formula 4 is preferably:

The dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol are reacted to obtain a second compound having the structure shown in Formula 4.

The present invention preferably reacts the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol under vacuum. The present invention preferably reacts the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol under conditions of a protective gas. In the present invention, the protective gas in the reaction of the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol is preferably nitrogen. In the present invention, the temperature at which dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol are reacted is preferably from 220 ° C to 260 ° C, more preferably from 230 ° C to 250 ° C, most preferably 240. °C. In the present invention, the reaction time of the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol is preferably from 6 hours to 10 hours, more preferably from 7 hours to 9 hours, most preferably It is 8 hours.

In the present invention, the molar ratio of the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol is preferably (1500 to 2000): (500 to 1000): 1, more preferably (1600 to 1800): (550 to 750): 1, most preferably (1700 to 1750): (600 to 650): 1. The present invention has no particular limitation on the source of the dicyclopentadiene, n-octene, and 2,6-di-tert-butyl-p-cresol, and is commercially available.

After the reaction of the dicyclopentadiene, n-octene and 2,6-di-tert-butyl-p-cresol is completed, the present invention preferably obtains dicyclopentadiene, n-octene and 2,6-di-tert-butyl. - The p-cresol reaction product is cooled, left standing, atmospheric distillation, and vacuum distillation to obtain a second compound having the structure shown in Formula 4. The method of the present invention for cooling, standing, atmospheric distillation and vacuum distillation is not particularly limited, and a technical solution of cooling, standing atmospheric distillation and distillation well known to those skilled in the art may be employed. In the present invention, the cooling temperature is preferably from 20 ° C to 30 ° C, more preferably from 25 ° C to 28 ° C. In the present invention, the standing time is preferably from 10 hours to 16 hours, more preferably from 12 hours to 14 hours. In the present invention, the temperature of the atmospheric distillation is preferably from 120 ° C to 180 ° C, more preferably from 150 ° C to 160 ° C. In the present invention, the temperature of the vacuum distillation is preferably from 60 ° C to 150 ° C, more preferably from 70 ° C to 130 ° C. In the present invention, it is preferred to collect a fraction of 60 ° C to 80 ° C at the time of vacuum distillation, and the fraction is a second compound having a structure represented by Formula 4.

In the present invention, the kind and source of the polymerization solvent are the same as those of the solvent in the above catalyst solution, and will not be described herein. In the present invention, the solvent of the polymerization reaction may be the same as or different from the solvent in the catalyst solution described in the above technical scheme.

In the present invention, the ratio of the total number of moles of the first compound and the second compound to the number of moles of the catalyst is preferably (270 to 1000): 1, more preferably (300 to 700): 1, most preferably ( 350 ~ 600): 1. In the present invention, when preparing a cyclic olefin copolymer having a structure represented by Formula I, the total number of moles of the first compound having the structure represented by Formula 1 and the second compound having the structure of Formula 2 and the number of moles of the catalyst The ratio is preferably (300 to 500): 1, more preferably (350 to 450): 1, and most preferably (380 to 420): 1.

In the present invention, when a cyclic olefin copolymer having a structure represented by Formula II is prepared, the ratio of the number of moles of the first compound having the structure represented by Formula 1 to the number of moles of the catalyst is preferably (300 to 1000):1. More preferably (400-700): 1, and most preferably (500-600): 1.

In the present invention, when preparing a cyclic olefin copolymer having a structure represented by Formula III, the total number of moles of the first compound having the structure represented by Formula 1 and the second compound having the structure of Formula 3 and the number of moles of the catalyst The ratio is preferably (270 to 600): 1, more preferably (400 to 574): 1, and most preferably (420 to 468): 1.

In the present invention, when preparing a cyclic olefin copolymer having a structure represented by Formula IV, the total number of moles of the first compound having the structure represented by Formula 1 and the second compound having the structure represented by Formula 4 and the mole of the catalyst The ratio of the number is preferably (400 to 700): 1, more preferably (500 to 600): 1, and most preferably (520 to 580): 1.

In the present invention, the molar ratio of the first compound to the second compound is preferably (0.5 to 19): 1, more preferably (0.8 to 18): 1, and most preferably (1.5 to 9): 1. In the present invention, when a cyclic olefin copolymer having a structure represented by Formula I is prepared, a molar ratio of the first compound having a structure represented by Formula 1 to the second compound having a structure represented by Formula 2 is preferably (0.5 to 2). : 1, more preferably (0.5 to 1.5): 1.

In the present invention, when a cyclic olefin copolymer having a structure represented by Formula III is prepared, a molar ratio of the first compound having a structure represented by Formula 1 to the second compound having a structure represented by Formula 3 is preferably (0.8 to 9). :1 is more preferably (1.5 to 4): 1, and most preferably (2.3 to 3): 1.

In the present invention, when a cyclic olefin copolymer having a structure represented by Formula IV is prepared, a molar ratio of the first compound having a structure represented by Formula 1 to a second compound having a structure represented by Formula 4 is preferably (1 to 19). ): 1, more preferably (4 to 18): 1, most preferably (5 to 7): 1.

The amount of the polymerization solvent to be used in the present invention is not particularly limited, and the amount of the solvent in the polymerization reaction well known to those skilled in the art may be employed. In the present invention, the mass ratio of the first compound to the polymerization solvent is preferably 1: (10 to 30), more preferably 1: (15 to 28), and most preferably 1: (17 to 26). In the present invention, when the cyclic olefin copolymer having the structure of the formula I is prepared, the mass ratio of the first compound to the polymerization solvent is preferably 1: (20 to 30), more preferably 1: (24 to 28). . In the present invention, when a cyclic olefin copolymer having a structure represented by the formula II is prepared, the mass ratio of the first compound to the polymerization solvent is preferably 1: (10 to 25), more preferably 1: (15 to 20). . In the present invention, when a cycloolefin copolymer having a structure represented by Formula III is prepared, the mass ratio of the first compound to the polymerization solvent is preferably 1: (15 to 30), more preferably 1: (17~26). In the present invention, when a cyclic olefin copolymer having a structure represented by Formula IV is prepared, the mass ratio of the first compound to the polymerization solvent is preferably 1: (15 to 30), more preferably 1: (17 to 26). .

After the completion of the polymerization reaction, the present invention preferably terminates the polymerization reaction with a terminator to obtain a polymerization reaction solution; mixing the polymerization reaction solution and a precipitating agent to obtain a precipitated product; filtering, washing, and drying the precipitated product; A polymerization reaction product was obtained.

The type and source of the terminating agent are not particularly limited in the present invention, and a terminating agent used in the preparation of the cyclic olefin copolymer well known to those skilled in the art may be used, which is commercially available. 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 to 500): 1, more preferably (200 to 400): 1, and most preferably 300:1. In the present invention, the time for terminating the polymerization reaction is preferably from 20 minutes to 40 minutes, more preferably from 25 minutes to 35 minutes, and most preferably 30 minutes.

After the polymerization reaction solution is obtained, the polymerization reaction solution and the precipitant are preferably mixed in the present invention to obtain a precipitated product. The present invention is not particularly limited to the kind of the precipitating agent for precipitating the polymerization reaction solution, and a precipitating agent used in the preparation of the cyclic olefin copolymer well known to those skilled in the art may be employed. 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 temperature at which the polymerization reaction solution and the precipitant are mixed is preferably -10 ° C to 0 ° C, more preferably -8 ° C to 5 ° C.

After the precipitated product is obtained, the precipitated product is preferably filtered, washed, and dried to obtain a polymerization reaction product. The method for filtering, washing and drying the precipitated product of the present invention is not particularly limited, and a filtration, washing and drying technique well known to those skilled in the art may be employed. In the present invention, the reagent for washing the precipitated product is preferably acetone. In the present invention, the number of times the precipitated product is washed is preferably 2 to 4 times, more preferably 3 times. In the present invention, the method of drying the precipitated product is preferably vacuum drying. In the present invention, the temperature at which the precipitated product is dried is preferably from 20 ° C to 40 ° C, more preferably from 25 ° C to 35 ° C, and most preferably 30 ° C. In the present invention, the time during which the precipitated product is dried is preferably from 12 hours to 24 hours, more preferably from 16 hours to 20 hours, and most preferably 18 hours.

After obtaining the polymerization reaction product, the present invention hydrogenates the polymerization reaction product and the hydrogen source. Should, a cyclic olefin copolymer is obtained. The hydrogenation reaction is preferably carried out under the conditions of a protective gas in the present invention. In the present invention, the protective gas for the hydrogenation reaction is preferably nitrogen. The method of the hydrogenation reaction of the present invention is not particularly limited, and a hydrogenation reaction scheme well known to those skilled in the art may be employed.

The type of the hydrogen source is not particularly limited in the present invention, and the hydrogen source is preferably hydrogen or an anthraquinone compound, more preferably an anthracene compound, and most preferably p-toluenesulfonylhydrazide.

In the present invention, when the hydrogen source is a quinone compound, the present invention preferably produces a cyclic olefin copolymer by hydrogenation according to the following method:

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

In the present invention, the ratio of the number of moles of the double bond to the number of moles of the quinone compound in the polymerization reaction product is preferably 1: (3 to 6), and more preferably 1: (4 to 5). In the present invention, the hydrogenation reaction solvent is preferably toluene. The amount of the hydrogenation reaction solvent to be used in the present invention is not particularly limited, and the solvent to be used can provide a liquid environment for the above hydrogenation reaction. In the present invention, the reaction temperature at the time of hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 110 ° C to 150 ° C, more preferably from 120 ° C to 140 ° C, and most preferably 130 ° C. In the present invention, when a cyclic olefin copolymer having a structure represented by Formula I is prepared, the reaction temperature at the time of hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 120 ° C to 140 ° C, more preferably from 125 ° C to ～ 135 ° C, most preferably 130 ° C. In the present invention, when a cyclic olefin copolymer having a structure represented by Formula II is prepared, the reaction temperature at the time of hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 120 ° C to 140 ° C, more preferably from 125 ° C to ～ 135 ° C, most preferably 130 ° C. In the present invention, when a cyclic olefin copolymer having a structure represented by Formula III is prepared, the reaction temperature at the time of hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 110 ° C to 150 ° C, more preferably from 120 ° C to ～ 140 ° C, most preferably 130 ° C. In the present invention, when a cyclic olefin copolymer having a structure represented by Formula IV is prepared, the reaction temperature at the time of hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 110 ° C to 150 ° C, more preferably from 120 ° C to ～ 140 ° C, most preferably 130 ° C.

In the present invention, the reaction time in the hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 12 hours to 24 hours, more preferably from 14 hours to 20 hours. In the present invention, When the cyclic olefin copolymer having the structure of the formula I is prepared, the reaction time in the hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 12 hours to 24 hours, more preferably from 14 hours to 20 hours. In the present invention, when a cycloolefin copolymer having a structure represented by the formula II is prepared, the reaction time in the hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 12 hours to 20 hours, more preferably from 16 hours. 18 hours. In the present invention, when a cyclic olefin copolymer having a structure represented by the formula III is prepared, the reaction time in the hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 12 hours to 20 hours, more preferably from 13 hours. 16 hours. In the present invention, when a cyclic olefin copolymer having a structure represented by the formula IV is prepared, the reaction time in the hydrogenation reaction of the polymerization reaction product and the hydrazine compound is preferably from 12 hours to 20 hours, more preferably from 14 hours. 19 hours, most preferably 16 hours to 18 hours.

In order to prevent the above-mentioned polymerization reaction product and the hydrazine compound from undergoing a crosslinking reaction during the hydrogenation reaction, the reaction raw material in the case where the polymerization reaction product and the hydrazine compound are subjected to a hydrogenation reaction preferably further includes a radical scavenger. The present invention is not particularly limited to the kind and source of the radical scavenger, and a radical scavenger known to those skilled in the art may be used, which is commercially available. In the present invention, the radical scavenger is preferably 2,6-di-tert-butyl-4-methylphenol. The amount of the radical scavenger to be used in the present invention is not particularly limited, and the amount of the radical scavenger well known to those skilled in the art may be employed. In the present invention, the amount of the radical scavenger used is preferably from 0.05 eq to 3 eqv based on the number of moles of the catalyst described in the above technical scheme.

After completion of the hydrogenation reaction, the present invention preferably mixes the obtained hydrogenation reaction product with ethanol, and the resulting mixed product is filtered, washed, and dried to obtain a cyclic olefin copolymer. In the present invention, the purity of the ethanol is preferably from 97% to 99%. The method for filtering, washing and drying the mixed product of the present invention is not particularly limited, and a filtration, washing and drying technique well known to those skilled in the art may be employed. 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 from 12 hours to 24 hours, more preferably from 16 hours to 20 hours. In the present invention, the drying temperature of the mixed product is preferably from 40 ° C to 70 ° C, more preferably from 50 ° C to 65 ° C, and most preferably 60 ° C.

After preparing the cyclic olefin copolymer, the present invention performs nuclear magnetic resonance carbon spectrum detection and nuclear magnetic resonance spectrum detection on the obtained cyclic olefin copolymer, and the nuclear magnetic resonance carbon spectrum detection and nuclear magnetic resonance spectrum The detection method was determined by using a Varian Unity-400 NMR spectrometer at 25 ° C, tetramethylsilane (TMS) as an internal standard, and deuterated chloroform as a solvent. As a result of the measurement, the cycloolefin copolymer provided in the present invention has a structure represented by Formulas I to IV.

The invention adopts the differential thermal analysis method and the thermal weight loss method to test the glass transition temperature of the obtained cyclic olefin copolymer, and the detection method is a differential thermal analysis using a Perkin-ElmerPyris 1DSC differential scanning calorimeter, and the rate of temperature rise and decrease is 10 A second scan was performed at °C/min. The thermogravimetric weight was determined using a Perkin-Elmer Pyris type 1 instrument. The detection result is that the cyclic olefin copolymer provided by the invention has a glass transition temperature of 125 ° C to 224 ° C and has good thermal stability.

The mechanical properties of the cyclic olefin copolymers tested by the invention on INSTRON 1121, Canton, MA instruments are tested according to the standard of GB/T1040-1992 "Test method for tensile properties of plastics", and the spline spacing is 20.0 mm. The rate was 5 mm/min and each sample was tested at least 8 times to ensure data reliability. As a result of the test, the cyclic olefin copolymer provided by the present invention has a tensile strength of 21 MPa to 55 MPa, a tensile modulus of 1000 MPa to 1950 MPa, and an elongation at break of 1.7% to 4.9%.

The invention adopts the Shimadzu UV-3600 ultraviolet-visible-near-infrared spectrophotometer to test the transparency of the obtained cyclic olefin copolymer, and the test wavelength is 400 nm to 800 nm. The test results show that the cycloolefin copolymer obtained by the present invention has a light transmittance of >85%.

The molecular weight distribution and the number average molecular weight of the cyclic olefin copolymer obtained by the gel permeation chromatography test are measured by a waters 152 gel permeation chromatograph; the RI-Laser detector is used; the detection solvent is tetrahydrofuran, and the detection is performed. The temperature was 35 ° C; the mobile phase flow rate was 1.0 mL / min, and PL EasiCal PS-1 was used as a standard. The test results provide a cycloolefin copolymer having a molecular weight distribution of 1.20 to 1.52 and a number average molecular weight of 6.5 × 10 ⁴ g / mol to 32 × 10 ⁴ g / mol.

In order to further understand the present invention, the cyclic olefin copolymers provided by the present invention and the preparation method thereof will be described in detail below with reference to the examples, but these descriptions are only to further illustrate the features and advantages of the present invention, and they are not to be construed as Limit of invention protection set.

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

Example 1

800 mL of norbornadiene, 230 g of hydrazine, and 1 gram of 2,6-di-tert-butyl-p-cresol were sequentially added to a 2-liter stainless steel autoclave, and the autoclave was repeatedly evacuated three times. Nitrogen-filled operation; the autoclave was heated to 180 ° C, and the contents of the autoclave were reacted under stirring for 30 hours.

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

The product obtained above is subjected to nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG. 1. FIG. 1 is a nuclear magnetic resonance spectrum of the product obtained in Example 1 of the present invention, and FIG. 1 shows the product obtained in the first embodiment of the present invention. It is a compound having a structure represented by Formula 1.

Example 2

4.96 g of benzaldehyde-p-methylbenzenesulfonyl hydrazide, 1.75 g of sodium methoxide and 40 mL of triethylene glycol were placed in a 100 mL single-mouth bottle, and the single-mouth bottle was placed in a water bath at 60 ° C for 1 Hour synthesis reaction.

After the completion of the synthesis reaction, 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 aqueous solution of NaCl, The obtained extract product was spin-dried to obtain phenyldiazomethane; the yield of the phenyldiazomethane was 50%.

4.0 g of dichlorotris(triphenylphosphine) ruthenium was added to a 250 mL vial, and the air in the vial was replaced with nitrogen, and 40 mL of the liquid was filled into the vial. - melted methylene chloride; the vial was placed in a -78 ° C cold bath, and a pentane solution of phenyldiazomethane at a concentration of 98.5 mg/mL at -50 ° C was added under stirring. 10 mL of the mixture, the phenyldiazomethane in the phenyldiazomethane pentane solution is the phenyldiazomethane prepared above; the obtained mixture is stirred at -70 ° C for 10 min, then added to 40 mL, -50 ° C a mass concentration of 0.064 g/mL of a solution of tricyclohexylphosphine in dichloromethane, The reaction was carried out at 25 ° C for 30 min.

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

The product obtained above Proton NMR spectroscopy detected and phosphorus nuclear magnetic resonance analysis, results shown in FIGS. 2 and 3, FIG. 2 of the present invention, 2 H NMR products obtained in Example ⁽¹ H) spectrum 3 is a nuclear magnetic resonance phosphorus ( ^31P ) spectrum of the product obtained in Example 2 of the present invention. As is apparent from FIG. 2 and FIG. 3, the product obtained in Example 2 of the present invention is a compound having a structure represented by Formula VI.

Example 3

1 g of the first compound having the structure of Formula 1 prepared in Example 1 and 0.41 g of the second compound having the structure of

Formula

2 and 15 mL of dichloromethane were added to the dried polymerization flask at 25 ° C. The mixture was stirred for 10 min to obtain a mixture; 15.2 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min sonication. The compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added to the above polymerization under stirring. The reaction bottle was subjected to a polymerization reaction for 15 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound represented by the formula VI to the above-mentioned polymerization reaction bottle under stirring; the polymerization obtained after 30 minutes was obtained. 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 polymerization 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 a dry polymerization bottle, 0.8 g of the above polymerization product, 6.6 g, was sequentially added. p-Toluenesulfonylhydrazide, 2,6-di-tert-butyl-4-methylphenol (BHT) in moles of 1 eqv of the compound having the structure shown in the above formula VI, and 40 mL of toluene, refluxed at 130 ° C The hydrogenation reaction was carried out by stirring for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol, and the obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C. After the minute, the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was dried in a vacuum oven at 60 ° C for 12 hours to obtain 0.72 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 3 of the present invention gave a yield of a cyclic olefin copolymer of 90.0%.

The cyclic olefin copolymer obtained in Example 3 of the present invention was subjected to nuclear magnetic resonance carbon spectrum detection and nuclear magnetic resonance spectrum detection according to the method described in the above technical scheme. The detection results are shown in FIG. 4, and FIG. 4 is obtained in Example 3 of the present invention. From the nuclear magnetic resonance carbon spectrum of the cyclic olefin copolymer, it can be seen from FIG. 4 that the cyclic olefin copolymer obtained in Example 3 of the present invention has a structure represented by Formula I, wherein x is 285 and y is 50 in the formula I. 3 The structure of the obtained cyclic olefin copolymer is clear.

5 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 3 of the present invention, and FIG. 5 is a nuclear magnetic resonance spectrum of the polymerization reaction product obtained in Example 3 of the present invention, and curve 2 is The nuclear magnetic resonance spectrum of the cyclic olefin copolymer obtained in Example 3 of the present invention can be seen from FIG. 5, after the hydrogenation reaction of the polymerization reaction product obtained in Example 3 of the present invention, the double bond peak completely disappears, and the hydrogenation effect is good. The molar content of the first compound having the structure of Formula 1 in the cyclic olefin copolymer obtained in Example 3 of the present invention was calculated according to the following formula:

Mol%=(I _3.9~4.3 /I _5.42 )×100%

I _3.9-4.3 is the peak area of the chemical shift in the nuclear magnetic resonance spectrum at 3.9-4.3, and I _5.42 is the peak area of the chemical shift at 5.42 in the nuclear magnetic resonance spectrum. As a result of calculation, the molar content of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 3 of the present invention was 86.96%.

The cyclic olefin copolymer obtained in Example 3 of the present invention was subjected to gel permeation chromatography test according to the method described in the above technical scheme, and the test results are shown in Fig. 6. Fig. 6 is a copolymerization reaction product obtained by Example 3 of the present invention and cycloolefin copolymerization. The gel permeation chromatogram of the material, the curve 1 in FIG. 6 is the gel permeation chromatography of the polymerization reaction product obtained in Example 3 of the present invention, and the curve 2 is the gel permeation chromatography of the cyclic olefin copolymer obtained in Example 3 of the present invention. It can be seen from Fig. 6 that the polymerization product obtained in Example 3 of the present invention has a peak shape unchanged after hydrogenation reaction, and the hydrodynamic volume does not change much; the cycloolefin obtained in Example 6 of the present invention can be known by gel permeation chromatography. The copolymer had a molecular weight distribution of 1.35 and a number average molecular weight of 8.42 x 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 3 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme, and the test results are shown in Fig. 7. Fig. 7 is a cyclic olefin obtained in Examples 3 to 6 of the present invention. The differential scanning calorimetry curve of the copolymer, in FIG. 7, the curve 2 is the differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 3 of the present invention, and the cyclic olefin copolymer obtained in Example 3 of the present invention is known from FIG. The glass transition temperature of the cyclic olefin copolymer obtained in Example 3 of the present invention was 171.9 ° C without the melting temperature and in an amorphous state. The cyclic olefin copolymer obtained in Example 3 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme, and the test results are shown in Fig. 8. Fig. 8 is a cyclic olefin copolymer obtained in Examples 3 to 6 of the present invention. The thermogravimetric curve, curve 1 in Fig. 8 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 3 of the present invention, and Fig. 8 shows the decomposition rate of the cyclic olefin copolymer obtained in Example 3 of the present invention at 350 °C. It is 10% and has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 3 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 3 of the present invention had an elongation at break of 2.9% and a tensile strength of 33.0 MPa, tensile modulus is 1450 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 3 of the present invention was tested according to the method described in the above technical scheme, and the test results are shown in FIG. 9. FIG. 9 is a cyclic olefin copolymer obtained in Examples 3 to 6 of the present invention. Light transmittance, curve 1 in Fig. 9 is the light transmittance of the cyclic olefin copolymer obtained in Example 3 of the present invention. As is apparent from Fig. 9, the light olefin copolymer obtained in Example 3 of the present invention has a light transmittance of >85%.

Example 4

To the dried polymerization flask, 1 g of the first compound having the structure shown in Example 1 and 0.82 g of the second compound having the structure of

Formula

2 and 15 mL of dichloromethane were added to the dried polymerization flask at 25 ° C. The mixture was stirred for 10 min to obtain a mixture; 22.9 mg of the compound having the structure of the formula VI prepared in Example 2 was added to the small ampoule, and then the small An 5 mL of dichloromethane was added to the bottle for sonication for 3 minutes, and the compound having the structure of the formula VI was sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; under stirring, The compound solution having the structure represented by Formula VI is added to the above polymerization reaction bottle for polymerization for 15 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 4 of the present invention was 61.6%.

In a dry polymerization reaction bottle, 0.8 g of the above polymerization reaction product, 7.8 g of p-toluenesulfonyl hydrazide, and 0.05 eqv of 2,6-di-tert-butyl group relative to the above-mentioned structural compound having the formula VI were sequentially added. Base 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then dissolved again with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven. Drying at 60 ° C for 12 hours gave 0.75 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 4 of the present invention gave a yield of a cyclic olefin copolymer of 91.5%.

The structure of the cyclic olefin copolymer obtained in Example 4 of the present invention was examined by the method described in Example 3. As a result, the cyclic olefin copolymer obtained in Example 4 of the present invention has the structure represented by Formula I, Calculated according to the formula described in Example 3, 260, y was 86, and the molar content of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 4 of the present invention was 75.19%.

The cyclic olefin copolymer obtained in Example 4 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 4 of the present invention was 1.26, and the number average molecular weight was 6.54. × 10 ⁴ g/mol.

Copolymerization of the cyclic olefin obtained in Example 4 of the present invention according to the method described in the above technical scheme The material was subjected to differential thermal analysis test, and the test result is shown in FIG. 7. Curve 1 in FIG. 7 is a differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 4 of the present invention. FIG. 7 shows that the fourth embodiment of the present invention The resulting cyclic olefin copolymer had a glass transition temperature of 160.8 °C. The cyclic olefin copolymer obtained in Example 4 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 8. The curve 2 in Fig. 8 is the cyclic olefin copolymer obtained in Example 4 of the present invention. The thermogravimetric curve, as seen from Fig. 8, shows that the cyclic olefin copolymer obtained in Example 4 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 4 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 4 of the present invention had an elongation at break of 2.9% and a tensile strength of 32.9 MPa, tensile modulus is 1670 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 4 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in Fig. 9, and the curve 3 in Fig. 9 is the permeation of the cyclic olefin copolymer obtained in Example 4 of the present invention. As shown in Fig. 9, the light transmittance of the cycloolefin copolymer obtained in Example 4 of the present invention was >85%.

Example 5

To the dried polymerization reaction bottle, 1 g of the first compound having the structure shown in Formula 1 prepared in Example 1 and 0.205 g of the second compound having the structure of

Formula

2 and 20 mL of dichloromethane were added to the dried polymerization flask at 25 °C. The mixture was stirred for 10 min to obtain a mixture; 11.4 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min sonication. The compound having the structure represented by the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added to the above under stirring. Polymerization reaction was carried out in a polymerization flask for 15 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 product. Polymerization method provided by Embodiment 5 of the present invention The yield of the obtained polymerization reaction product was 87.5%.

In a dry polymerization reaction bottle, 0.8 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 2 eqv of the compound of the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 0.73 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 5 of the present invention gave a yield of a cyclic olefin copolymer of 90.1%.

The structure of the cyclic olefin copolymer obtained in Example 5 of the present invention was examined by the method described in Example 3. As a result, the cyclic olefin copolymer obtained in Example 5 of the present invention has the structure represented by Formula I, The molar ratio of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 5 of the present invention was 90.09% as calculated by the formula described in Example 3.

The cyclic olefin copolymer obtained in Example 5 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin 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.

The cyclic olefin copolymer obtained in Example 5 of the present invention was subjected to a differential thermal analysis method according to the method described in the above technical scheme. The test results are shown in FIG. 7, and the curve 3 in FIG. 7 is the cycloolefin copolymer obtained in Example 5 of the present invention. The difference scanning calorimetry curve of the material is shown in Fig. 7. The glass transition temperature of the cyclic olefin copolymer obtained in Example 5 of the present invention was 195.2 °C. The cyclic olefin copolymer obtained in Example 5 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 8. The curve 3 in Fig. 8 is the cyclic olefin copolymer obtained in Example 5 of the present invention. The thermogravimetric curve, as seen from Fig. 8, shows that the cyclic olefin copolymer obtained in Example 5 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 5 of the present invention were tested according to the method described in the above technical scheme, and the test results were the elongation at break of the cyclic olefin copolymer obtained in Example 5 of the present invention. The length ratio was 2.1%, the tensile strength was 32.5 MPa, and the tensile modulus was 1520 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 5 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in Fig. 9. The curve 2 in Fig. 9 is the permeation of the cyclic olefin copolymer obtained in Example 5 of the present invention. As shown in Fig. 9, the light transmittance of the cycloolefin copolymer obtained in Example 5 of the present invention was >85%.

Example 6

To the dried polymerization reaction bottle, 1 g of the first compound having the structure shown in Formula 1 prepared in Example 1 and 0.205 g of the second compound having the structure shown in

Formula

2 and 25 mL of dichloromethane were added to the dried polymerization flask at 25 °C. The mixture was stirred for 10 min to obtain a mixture; 11.4 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min sonication. The compound having the structure represented by the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added to the above under stirring. Polymerization reaction was carried out in a polymerization flask for 20 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 100 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 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 a dry polymerization reaction bottle, 0.8 g of the above polymerization reaction product, 8.0 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a molar ratio of 3 eqv to the above-mentioned structural compound represented by Formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 14 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 0.74 g of a cyclic olefin copolymer. The side of the hydrogenation reaction provided in Example 6 of the present invention The yield of the cyclic olefin copolymer obtained was 90.1%.

The structure of the cyclic olefin copolymer obtained in Example 6 of the present invention was examined by the method described in Example 3. As a result, the cyclic olefin copolymer obtained in Example 6 of the present invention has the structure represented by Formula I, The molar ratio of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 6 of the present invention was 90.91%, calculated as the formula of Example 3.

The cyclic olefin copolymer obtained in Example 6 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin 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.

The cyclic olefin copolymer obtained in Example 6 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 7, and the curve 4 in Fig. 7 is the cycloolefin copolymer obtained in Example 6 of the present invention. The difference scanning calorimetry curve of the article is shown in Fig. 7. The glass transition temperature of the cyclic olefin copolymer obtained in Example 6 of the present invention was 201.3 °C. The cyclic olefin copolymer obtained in Example 6 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 8. The curve 4 in Fig. 8 is the cyclic olefin copolymer obtained in Example 6 of the present invention. The thermogravimetric curve, as seen from Fig. 8, shows that the cyclic olefin copolymer obtained in Example 6 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 6 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 6 of the present invention had an elongation at break of 2.3% and a tensile strength of 32MPa, tensile modulus is 1580MPa.

The transparency of the cyclic olefin copolymer obtained in Example 6 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in Fig. 9, and the curve 4 in Fig. 9 is the permeation of the cyclic olefin copolymer obtained in Example 6 of the present invention. The light ratio, as seen from Fig. 9, is that the light olefin copolymer obtained in Example 6 of the present invention has a light transmittance of >85%.

Example 7

1 g of the first compound having the structure shown in Formula 1 prepared in Example 1 and 0.82 g of the second compound having the structure shown in

Formula

2 and 25 mL of hexane were added to the dried polymerization flask at 0 ° C, and stirred. Mix for 10 min to obtain a mixture; add 36.4 mg to the small ampoules Example 2 The compound obtained by the structure of the formula VI was prepared, and 5 mL of toluene was added to the small ampoule for 3 min sonication, and the compound having the structure represented by the formula VI was sufficiently dissolved in toluene. Obtaining a solution of the compound having the structure shown in Formula VI; adding the compound solution having the structure represented by Formula VI to the polymerization reaction bottle for 5 minutes under stirring;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 product.

The autoclave was pre-dried under vacuum for 5 hours, and 1 g of the polymerization reaction product prepared above, 300 mL of cyclohexane, and 0.5 g of a Pd/Al ₂ O ₃ catalyst were added to the autoclave. The autoclave was subjected to a pumping operation three times, and then the autoclave was charged with 30 MPa of hydrogen gas, 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. The hydrogenation reaction product was obtained; the hydrogenation reaction product was poured into ethanol to precipitate, and the obtained precipitated product was filtered and dried in a vacuum oven at 60 ° C for 12 hours to obtain 0.92 g of a cycloolefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 7 of the present invention were tested according to the method described in Example 3. The test result is that the cyclic olefin copolymer obtained in Example 7 of the present invention has the structure represented by Formula I, in Formula I. x is 320 and y is 53. The molar ratio of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 7 of the present invention to the cyclic olefin copolymer was 88.45%, and the glass transition of the cyclic olefin copolymer obtained in Example 7 of the present invention was obtained. The temperature was 186.3 ° C, and the cyclic olefin copolymer obtained in Example 7 of the present invention had a molecular weight distribution of 1.46 and a number average molecular weight of 6.48 × 10 ⁴ g/mol. The cyclic olefin copolymer obtained in Example 7 of the present invention had an elongation at break of 2.8%, a tensile strength of 35 MPa, and a tensile modulus of 1,750 MPa. The cycloolefin copolymer obtained in Example 7 of the present invention had a light transmittance of >85%. The cyclic olefin copolymer obtained in Example 7 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 8

To the dried polymerization reaction bottle, 1 g of the first compound having the structure of the formula 1 prepared in Example 1 and 0.205 g of the second compound having the structure of the

formula

2 and 25 mL of benzene were added to the dried polymerization reaction bottle at 50 ° C, and stirred and mixed. 10 min, the mixture was obtained; 3.34 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of cyclohexane was added to the small ampoule for 3 min sonication. The compound having the structure of the formula VI is sufficiently dissolved in cyclohexane to obtain a solution of the compound having the structure represented by the formula VI; and the solution of the compound having the structure represented by the formula VI is added to the above polymerization under stirring. 60 minutes of polymerization in the bottle;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 product.

In a dry polymerization reaction bottle, 0.8 g of the above polymerization reaction product, 8.0 g of p-toluenesulfonylhydrazine and 40 mL of toluene were successively added, and the mixture was stirred under reflux at 150 ° C for 20 hours to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; The hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol, and the obtained mixed product was filtered and dried, and then re-dissolved in 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of purity. The obtained mixed product was dried in a vacuum oven at 98 ° C for 12 hours in 98% ethanol to obtain 1.05 g of a cyclic olefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 8 of the present invention were tested according to the method described in Example 3. The test result is that the cyclic olefin copolymer obtained in Example 8 of the present invention has the structure represented by Formula I, in Formula I. x is 256 and y is 40. The molar content of the first compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 8 of the present invention in the cyclic olefin copolymer was 86.51%, and the glass transition of the cyclic olefin copolymer obtained in Example 8 of the present invention was obtained. The temperature of the cyclic olefin copolymer obtained in Example 8 of the present invention was 135 ° C, and the molecular weight distribution was 1.38, and the number average molecular weight was 7.56 × 10 ⁴ g / mol. The cyclic olefin copolymer obtained in Example 8 of the present invention had an elongation at break of 2.6%, a tensile strength of 33.5 MPa, and a tensile modulus of 1,580 MPa. The cycloolefin copolymer obtained in Example 8 of the present invention had a light transmittance of >85%. The cyclic olefin copolymer obtained in Example 8 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 9

2 g of the compound of the structure shown in Example 1 and 25 mL of dichloromethane prepared in Example 1 were added to the dried polymerization reaction bottle at 25 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 20.3 mg was added to the small ampoule. The compound of the structure of the formula VI prepared in Example 2 was prepared by adding 5 mL of dichloromethane to the small ampoule for 3 min so that the compound having the structure of the formula VI was sufficiently dissolved in dichloromethane. a solution of the compound having the structure shown in Formula VI is obtained; and the solution of the compound having the structure represented by Formula VI is added to the above polymerization bottle under stirring to carry out a polymerization reaction for 60 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed with acetone three times, and dried in a vacuum oven at 40 ° C for 12 hours to obtain 1.99 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 9 of the present invention was 99%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.17 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl of 0.05 eqv of the compound having the structural formula represented by the above formula VI were sequentially added. Base 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 12 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then dissolved again with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven. Drying at 60 ° C for 12 hours gave 1.43 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 9 of the present invention gave a yield of a cyclic olefin copolymer of 94.0%.

The cyclic olefin copolymer obtained in Example 9 of the present invention was subjected to nuclear magnetic resonance carbon spectrum detection and nuclear magnetic resonance spectrum detection according to the method described in the above technical scheme. The detection result is shown in FIG. 10, and FIG. 10 is obtained in Example 9 of the present invention. Nuclear magnetic resonance carbon spectrum of cyclic olefin copolymer, Figure 10 It is understood that the cyclic olefin copolymer obtained in Example 9 of the present invention has a structure represented by Formula II, and z in Formula II is 300. The structure of the cyclic olefin copolymer obtained in Example 9 of the present invention is clear.

Figure 11 is a nuclear magnetic resonance spectrum of a polymerization reaction product and a cyclic olefin copolymer obtained in Example 9 of the present invention, and Figure 1 is a nuclear magnetic resonance spectrum of the polymerization reaction product obtained in Example 9 of the present invention, and curve 2 is The nuclear magnetic resonance spectrum of the cyclic olefin copolymer obtained in Example 9 of the present invention can be seen from Fig. 11. The polymerization reaction product obtained in Example 9 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is good.

The cyclic olefin copolymer obtained in Example 9 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 9 of the present invention was 1.29, and the number average molecular weight was 9.25. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 9 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 12, and Fig. 12 is a cyclic olefin obtained in Examples 9 to 11 of the present invention. The differential scanning calorimetry curve of the copolymer, FIG. 12, curve 1 is the differential scanning calorimetry curve of the cyclic olefin copolymer obtained in Example 9 of the present invention, and FIG. 12 shows the cyclic olefin copolymer obtained in Example 9 of the present invention. The glass transition temperature was 212.6 °C. The cyclic olefin copolymer obtained in Example 9 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in FIG. 13, and FIG. 13 is a thermogravimetric curve of the cyclic olefin copolymer obtained in Example 9 of the present invention. Fig. 13 is a graph showing the thermogravimetric curve of the cyclic olefin copolymer obtained in the air of Example 9 of the present invention, and the curve 2 of Fig. 13 is the heat of the cyclic olefin copolymer obtained by testing the nitrogen gas in Example 9 of the present invention. The heavy curve, as seen from Fig. 13, shows that the cyclic olefin copolymer obtained in Example 9 of the present invention has a decomposition rate of 10% at 350 ° C and has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 9 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 9 of the present invention had an elongation at break of 1.7% and a tensile strength of 21.2 MPa, tensile modulus is 1415 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 9 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in FIG. 14. FIG. 14 is the light transmittance of the cyclic olefin copolymer obtained in Example 9 of the present invention. As is apparent from Fig. 14, the light olefin copolymer obtained in Example 9 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of the polymerization reaction in Example 9 of the present invention was tested by the method of product weighing, and the test result was that the polymerization conversion ratio of the polymerization reaction in Example 9 of the present invention was 100%.

Example 10

2 g of the compound of the structure of the

formula

1 and 25 mL of dichloromethane prepared in Example 1 were added to the dried polymerization flask at 25 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 15.3 mg was added to the small ampule. The compound of the structure of the formula VI prepared in Example 2 was prepared by adding 5 mL of dichloromethane to the small ampoule for 3 min so that the compound having the structure of the formula VI was sufficiently dissolved in the dichloro group. In methane, a solution of a compound having the structure shown in Formula VI is obtained; and the solution of the compound having the structure represented by Formula VI is added to the polymerization bottle for 2 hours under stirring;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed with acetone three times, and dried in a vacuum oven at 40 ° C for 12 hours to obtain 1.99 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 4 of the present invention was 99%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.17 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl group having a mole number of 1 eqv of the structural compound represented by the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.46 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 10 of the present invention gave a yield of a cyclic olefin copolymer of 94.8%.

The structure of the cyclic olefin copolymer obtained in Example 10 of the present invention was examined by the method described in Example 9. As a result, the cyclic olefin copolymer obtained in Example 10 of the present invention had a structure represented by Formula II, and Is 400.

The cyclic olefin copolymer obtained in Example 10 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 10 of the present invention was 1.35, and the number average molecular weight was 11.7. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 10 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 12, and the curve 2 in Fig. 12 is the cycloolefin copolymer obtained in Example 10 of the present invention. From the difference scanning calorimetry curve of the article, as seen from Fig. 12, the glass transition temperature of the cyclic olefin copolymer obtained in Example 10 of the present invention was 214.2 °C.

The mechanical properties of the cyclic olefin copolymer obtained in Example 10 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 10 of the present invention had an elongation at break of 2.0% and a tensile strength of 35MPa, tensile modulus is 1520MPa.

The transparency of the cyclic olefin copolymer obtained in Example 10 of the present invention was tested according to the method described in the above technical scheme. The test result was that the cycloolefin copolymer obtained in Example 10 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of the polymerization reaction in Example 10 of the present invention was tested in accordance with the method described in Example 9, and the test result was that the polymerization conversion ratio of the polymerization reaction in Example 10 of the present invention was 100%.

Example 11

2 g of the compound of the structure shown in Example 1 and 25 mL of dichloromethane prepared in Example 1 were added to the dried polymerization flask at 25 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 12.2 mg was added to the small ampule. The compound of the structure of the formula VI prepared in Example 2 was prepared by adding 5 mL of dichloromethane to the small ampoule for 3 min so that the compound having the structure of the formula VI was sufficiently dissolved in the dichloro group. In methane, a solution of a compound having the structure shown in Formula VI is obtained; and the solution of the compound having the structure represented by Formula VI is added to the polymerization bottle for 2 hours under stirring;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed with acetone three times, and dried in a vacuum oven at 40 ° C for 12 hours to obtain 1.99 g of a polymerization product. Polymerization method provided by Embodiment 11 of the present invention The yield of the obtained polymerization reaction product was 99%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 4.14 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl group having a mole number of 2 eqv of the compound of the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.45 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 11 of the present invention gave a yield of a cyclic olefin copolymer of 94.5%.

The structure of the cyclic olefin copolymer obtained in Example 11 of the present invention was examined by the method described in Example 9. As a result, the cyclic olefin copolymer obtained in Example 11 of the present invention had a structure represented by Formula II, and Is 500.

The cyclic olefin copolymer obtained in Example 11 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 11 of the present invention had a molecular weight distribution of 1.25 and a number average molecular weight of 14 × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 11 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 12, and the curve 3 in Fig. 12 is the cycloolefin copolymer obtained in Example 11 of the present invention. From the difference scanning calorimetry curve of the article, as seen from Fig. 12, the glass transition temperature of the cyclic olefin copolymer obtained in Example 11 of the present invention was 223.6 °C.

The mechanical properties of the cyclic olefin copolymer obtained in Example 11 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 11 of the present invention had an elongation at break of 2.7% and a tensile strength of 53.2 MPa, tensile modulus is 1940 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 11 of the present invention was tested according to the method described in the above technical scheme. The test result was that the cycloolefin copolymer obtained in Example 11 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of the polymerization reaction in Example 11 of the present invention was tested in accordance with the method described in Example 9, and the test result was that the polymerization conversion ratio of the polymerization reaction in Example 11 of the present invention was 100%.

Example 12

2 g of the compound of the structure shown in Example 1 and 25 mL of tetrahydrofuran prepared in Example 1 were added to the dried polymerization reaction bottle at 0 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 10.2 mg of the Example was added to the small ampoule. 2 The compound having the structure of the formula VI is prepared, and 5 mL of tetrahydrofuran is added to the small ampoule for 5 min so as to dissolve the compound having the structure of the formula VI in tetrahydrofuran to obtain a formula. a compound solution of the structure shown in VI; the compound solution having the structure of the formula VI is added to the above polymerization bottle under stirring to carry out a polymerization reaction for 180 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 100 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed with acetone three times, and dried in a vacuum oven at 40 ° C for 12 hours to obtain 1.99 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 12 of the present invention was 99.2%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 3.10 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 1 eqv of the structural compound represented by the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 110 ° C for 20 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.46 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 12 of the present invention gave a yield of a cyclic olefin copolymer of 95.1%.

The structure and properties of the cyclic olefin copolymer obtained in Example 12 of the present invention were tested according to the method described in Example 9. The test result is that the cyclic olefin copolymer obtained in Example 12 of the present invention has the structure shown in Formula II, in Formula II. z is 600. The cyclic olefin copolymer obtained in Example 12 of the present invention had a glass transition temperature of 223.8 ° C, and the cyclic olefin copolymer obtained in Example 12 of the present invention had a molecular weight distribution of 1.35 and a number average molecular weight of 15.6 × 10 ⁴ g/mol. The cyclic olefin copolymer obtained in Example 12 of the present invention had an elongation at break of 2.6%, a tensile strength of 53.5 MPa, and a tensile modulus of 1,850 MPa. The cycloolefin copolymer obtained in Example 12 of the present invention had a light transmittance of >90%. The polymerization conversion ratio of the polymerization reaction in Example 12 of the present invention was 100%. The cyclic olefin copolymer obtained in Example 12 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 13

2 g of the compound of the structure shown in Example 1 and 35 mL of toluene prepared in Example 1 were added to the dried polymerization reaction bottle at 50 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 8.7 mg of the sample was added to the small ampoule. 2 The compound having the structure of the formula VI is prepared, and 5 mL of toluene is added to the small ampoule for 5 min sonication, and the compound having the structure of the formula VI is sufficiently dissolved in toluene to obtain a formula. a compound solution of the structure shown in VI; the compound solution having the structure of the formula VI is added to the above polymerization bottle under stirring to carry out a polymerization reaction for 60 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 1.98 g of a polymerization product.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 6.21 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 3 eqv of the structural compound represented by the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 150 ° C for 20 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of ethanol having a purity of 98%. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.47 of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 13 of the present invention gave a yield of a cyclic olefin copolymer of 96.2%.

The structure and properties of the cyclic olefin copolymer obtained in Example 13 of the present invention were tested according to the method described in Example 9. The test result is that the cyclic olefin copolymer obtained in Example 13 of the present invention has the structure shown in Formula II, in Formula II. z is 700. The glass transition temperature of the cyclic olefin copolymer obtained in Example 13 of the present invention was 221.5 ° C, and the molecular weight distribution of the cyclic olefin copolymer obtained in Example 13 of the present invention was 1.33, and the number average molecular weight was 18.6 × 10 ⁴ g / mol. The cyclic olefin copolymer obtained in Example 13 of the present invention had an elongation at break of 2.5%, a tensile strength of 55.0 MPa, and a tensile modulus of 1,880 MPa. The cycloolefin copolymer obtained in Example 13 of the present invention had a light transmittance of >90%. The polymerization conversion ratio of the polymerization reaction in Example 13 of the present invention was 100%. The cyclic olefin copolymer obtained in Example 13 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 14

2 g of the compound of the structure of the

formula

1 and 25 mL of tetrahydrofuran prepared in Example 1 were added to the dried polymerization flask at 25 ° C, and the mixture was stirred for 10 minutes to obtain a mixture; 6.1 mg of the sample was added to the small ampoule. 2 The compound having the structure of the formula VI is prepared, and 5 mL of tetrahydrofuran is added to the small ampoule for 5 min so as to dissolve the compound having the structure of the formula VI in tetrahydrofuran to obtain a formula. a compound solution of the structure shown in VI; the compound solution having the structure represented by the formula VI is added to the above polymerization bottle under stirring to carry out a polymerization reaction for 120 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 400 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 1.98 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 14 of the present invention was 99.0%.

The autoclave was pre-dried under vacuum for 5 hours, and 1 g of the polymerization reaction product prepared above, 300 mL of cyclohexane, and 0.5 g of a Pd/Al ₂ O ₃ catalyst were added to the autoclave. The autoclave was subjected to a pumping operation three times, and then the autoclave was charged with 30 MPa of hydrogen gas, hydrogenated at 150 ° C for 24 hours, and the obtained hydrogenation reaction solution was filtered to recover the Pd/Al ₂ O ₃ catalyst therein. The hydrogenation reaction product was obtained; the hydrogenation reaction product was poured into ethanol to precipitate, and the obtained precipitated product was filtered and dried in a vacuum oven at 60 ° C for 12 hours to obtain 0.90 g of a cycloolefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 14 of the present invention were tested according to the method described in Example 9. The test result is that the cyclic olefin copolymer obtained in Example 14 of the present invention has the structure represented by Formula II, in Formula II. z is 1000. The cyclic olefin copolymer obtained in Example 14 of the present invention had a glass transition temperature of 224.0 ° C, and the cyclic olefin copolymer obtained in Example 14 of the present invention had a molecular weight distribution of 1.34 and a number average molecular weight of 32.1 × 10 ⁴ g/mol. The cyclic olefin copolymer obtained in Example 14 of the present invention had an elongation at break of 2.7%, a tensile strength of 54.1 MPa, and a tensile modulus of 1820 MPa. The cycloolefin copolymer obtained in Example 14 of the present invention had a light transmittance of >90%. The polymerization conversion ratio of the polymerization reaction in Example 14 of the present invention was 100%. The cyclic olefin copolymer obtained in Example 14 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 15

550 mL of cyclopentene, 120 mL of dicyclopentadiene, and 1 g of 2,6-di-tert-butyl-p-cresol were sequentially added to a 2-liter stainless steel autoclave, and the autoclave was repeatedly evacuated three times. The operation was followed by nitrogen charging; the autoclave was heated to 200 ° C, and the contents of the autoclave were reacted under stirring for 16 hours.

After the completion of the reaction, the obtained reaction product was cooled to 25 ° C, allowed to stand for 12 hours, and then subjected to atmospheric distillation at 50 ° C to collect unreacted cyclopentene; the product obtained after atmospheric distillation was at 60 ° C Distillation under reduced pressure was carried out, and a fraction at 30 ° C during vacuum distillation was collected to obtain 114 g of a product. The yield of the product prepared by the method provided in Example 15 of the present invention was 46.7%.

The product obtained above was subjected to nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG. 15. FIG. 15 is a nuclear magnetic resonance spectrum of the product obtained in Example 15 of the present invention. FIG. 15 shows that the obtained example 15 of the present invention is obtained. The product is a compound having the structure shown in Formula 3.

Example 16

To the dried polymerization reaction bottle, 1.896 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.105 g of the compound having the structure of the

formula

3 and 25 mL of the compound prepared in Example 15 were added at 25 ° C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 16.1 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min. The compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a formula VI. a compound solution of the structure; adding the compound solution having the structure represented by the formula VI to the polymerization reaction bottle under stirring for 120 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 16 of the present invention was 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 4 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl group having a mole number of 1 eqv relative to the compound having the structure represented by the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.40 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 16 of the present invention gave a yield of a cyclic olefin copolymer of 93.5%.

The cyclic olefin copolymer obtained in Example 16 of the present invention was subjected to nuclear magnetic resonance spectrum detection according to the method described in the above technical scheme, and the detection result is shown in FIG. 16. FIG. 16 is a polymerization reaction product and a ring obtained in Example 16 of the present invention. The nuclear magnetic resonance spectrum of the olefin copolymer, the curve 1 in Fig. 16 is the nuclear magnetic resonance spectrum of the polymerization reaction product obtained in Example 16 of the present invention, and the curve 2 is the nuclear magnetic resonance hydrogen of the cyclic olefin copolymer obtained in Example 16 of the present invention. It can be seen from Fig. 16 that the polymerization reaction product obtained in Example 16 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is good. As is apparent from the curve 2 in Fig. 16, the cyclic olefin copolymer obtained in Example 16 of the present invention has a structure represented by Formula III, wherein m is 360 and n is 40.

According to the formula described in Example 3, the cyclic olefin copolymer obtained in Example 16 of the present invention had a molar content of the structural compound represented by Formula 1 of 88.5%.

The cyclic olefin copolymer obtained in Example 16 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 16 of the present invention was 1.32, and the number average molecular weight was 10.9. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 16 of the present invention was subjected to a differential thermal analysis method according to the method described in the above technical scheme, and the test results are shown in Fig. 18. Fig. 18 shows the variation of the cyclic olefin copolymer obtained in Example 16 of the present invention. From the scanning calorimetry curve, it can be seen from Fig. 18 that the cyclic olefin copolymer obtained in Example 16 of the present invention has no melting temperature and is amorphous, and the glass transition temperature of the cyclic olefin copolymer obtained in Example 16 of the present invention is 219.6 °C. The cyclic olefin copolymer obtained in Example 16 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Figs. 24 and 25, and Fig. 24 is a ring obtained in Examples 16 to 20 of the present invention. The thermogravimetric curve of the olefin copolymer in nitrogen, curve 1 in Fig. 24 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 16 of the present invention in nitrogen; and Fig. 25 is obtained in Examples 16 to 20 of the present invention. The thermogravimetric curve of the cyclic olefin copolymer in air, curve 1 in Fig. 25 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 16 of the present invention in air. 24 and 25, the cyclic olefin copolymer obtained in Example 16 of the present invention has a decomposition rate of 10% at 350 ° C and has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 16 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 16 of the present invention had an elongation at break of 3.8% and a tensile strength of 49 MPa, tensile modulus is 1390 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 16 of the present invention was tested according to the method described in the above technical scheme, and the test results are shown in Fig. 26. Fig. 26 is a ring obtained in Example 16, Example 18 and Example 20 of the present invention. The light transmittance of the olefin copolymer, the curve 1 in Fig. 26 is the light transmittance of the cycloolefin copolymer obtained in Example 16 of the present invention, and the light transmittance of the cycloolefin copolymer obtained in Example 16 of the present invention is known from Fig. 26. >90%.

The polymerization conversion ratio of Example 16 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was 100% of the polymerization conversion rate in the above-mentioned polymerization reaction of Example 16 of the present invention.

Example 17

1.78 g of the material prepared in Example 1 was added to the dried polymerization bottle at 25 °C. A compound having the structure shown in Formula 1 and 0.22 g of the compound having the structure shown in Formula 3 prepared in Example 15 and 25 mL of dichloromethane were stirred and mixed for 10 min to obtain a mixture; and 16.9 mg of Example 2 was added to a small ampoule. Preparing the obtained compound having the structure of the formula VI, adding 5 mL of dichloromethane to the small ampoule for 3 min sonication, and fully dissolving the compound having the structure of the formula VI in dichloromethane. Obtaining a compound solution having the structure represented by Formula VI; adding the compound solution having the structure represented by Formula VI to the above polymerization bottle under stirring to carry out a polymerization reaction for 100 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The polymerization product obtained by the polymerization method provided in Example 17 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5 g of p-toluenesulfonyl hydrazide, and 0.05 eqv of 2,6-di-tert-butyl group relative to the above-mentioned structural compound having the formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.38 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 17 of the present invention gave a yield of a cyclic olefin copolymer of 92.9%.

The structure of the cyclic olefin copolymer obtained in Example 17 of the present invention was examined by the method described in Example 16. As a result, the cyclic olefin copolymer obtained in Example 17 of the present invention has a structure represented by Formula III, m in Formula III. The molar content of the structural compound represented by Formula 1 in the cyclic olefin copolymer obtained in Example 17 of the present invention was calculated by the method described in Example 3 to be 78.1%.

The cyclic olefin copolymer obtained in Example 17 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 17 of the present invention was 1.31, and the number average molecular weight was 10.4. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 17 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 19, and Fig. 19 is a variation of the cyclic olefin copolymer obtained in Example 17 of the present invention. From the scanning calorimetry curve, it is understood from Fig. 19 that the cyclic olefin copolymer obtained in Example 17 of the present invention had a glass transition temperature of 193 °C. The cyclic olefin copolymer obtained in Example 17 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 24 and Fig. 25, and the curve 2 in Fig. 24 is the cyclic olefin obtained in Example 17 of the present invention. The thermogravimetric curve of the copolymer in nitrogen; curve 2 in Fig. 25 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 17 of the present invention in air. As is apparent from Fig. 24 and Fig. 25, the cyclic olefin copolymer obtained in Example 17 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 17 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 17 of the present invention had an elongation at break of 4.1% and a tensile strength of 48.9 MPa, tensile modulus is 1600 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 17 of the present invention was tested according to the method described in the above technical scheme. The test result was that the cycloolefin copolymer obtained in Example 17 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of Example 17 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9. The test result was 100% of the polymerization conversion rate in the above-mentioned polymerization reaction of Example 17 of the present invention.

Example 18

To the dried polymerization reaction bottle, 1.65 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.35 g of the compound having the structure of the formula 3 prepared in Example 15 and 25 mL were added to the dried polymerization flask at 25 °C. Dichloromethane, stirred and mixed for 10 min to obtain a mixture; 18.0 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min. Soothing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound having the structure represented by the formula VI is stirred under stirring. The solution is added to the above polymerization bottle for polymerization for 120 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 18 of the present invention was 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 2 eqv of the compound of the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.45 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 18 of the present invention gave a yield of a cyclic olefin copolymer of 93.8%.

The structure of the cyclic olefin copolymer obtained in Example 18 of the present invention was examined by the method described in Example 16. As a result, the cyclic olefin copolymer obtained in Example 18 of the present invention had a structure represented by Formula III, m in Formula III. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 18 of the present invention was calculated to have a molar content of 71.1% as 280, n was 120.

The cyclic olefin copolymer obtained in Example 18 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 18 of the present invention had a molecular weight distribution of 1.25 and a number average molecular weight of 11.1. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 18 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 20, and Fig. 20 is a variation of the cyclic olefin copolymer obtained in Example 18 of the present invention. Scanning calorimetry curve, as seen from Fig. 20, the glass transition temperature of the cyclic olefin copolymer obtained in Example 18 of the present invention was 183.5 °C. According to the above technical side The cyclic olefin copolymer obtained in Example 18 of the present invention was subjected to a thermogravimetric test, and the test results are shown in Fig. 24 and Fig. 25. The curve 3 in Fig. 24 is the cyclic olefin copolymer obtained in Example 18 of the present invention. The thermogravimetric curve in nitrogen; curve 3 in Fig. 25 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 18 of the present invention in air. As is apparent from Fig. 24 and Fig. 25, the cyclic olefin copolymer obtained in Example 18 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 18 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 18 of the present invention had an elongation at break of 4.1% and a tensile strength of 41.4 MPa, tensile modulus is 1250 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 18 of the present invention was tested in accordance with the method described in the above technical scheme. The test results are shown in Fig. 26. The curve 2 in Fig. 26 is the permeation of the cyclic olefin copolymer obtained in Example 18 of the present invention. As a light ratio, as seen from Fig. 26, the light olefin copolymer obtained in Example 18 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio in the above-mentioned polymerization reaction of Example 18 of the present invention was tested in accordance with the method described in Example 9, and the test result was 100% in the polymerization reaction in the above-mentioned polymerization reaction of Example 18 of the present invention.

Example 19

1.5 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.5 g of the compound having the structure shown in

Formula

3 and 25 mL of the compound prepared in Example 15 were added to the dried polymerization bottle at 25 °C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 19.1 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for 120 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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. After 12 hours, 2 g of a polymerization product was obtained. The polymerization product obtained by the polymerization method provided in Example 19 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonylhydrazine, and 2,6-di-tert-butyl group having a molar ratio of 3 eqv to the above-mentioned structural compound represented by Formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.48 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 19 of the present invention gave a yield of a cyclic olefin copolymer of 94.2%.

The structure of the cyclic olefin copolymer obtained in Example 19 of the present invention was examined by the method described in Example 16. As a result, the cyclic olefin copolymer obtained in Example 19 of the present invention had a structure represented by Formula III, m in Formula III. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 19 of the present invention was calculated to have a molar content of 59.5% as obtained by the method described in Example 3.

The cyclic olefin copolymer obtained in Example 19 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 19 of the present invention was 1.32, and the number average molecular weight was 11. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 19 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 21, and Fig. 21 is a variation of the cyclic olefin copolymer obtained in Example 19 of the present invention. The calorimetry curve was traced. As is apparent from Fig. 21, the glass transition temperature of the cyclic olefin copolymer obtained in Example 19 of the present invention was 178.7 °C. The cyclic olefin copolymer obtained in Example 19 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme, and the test results are shown in Fig. 24 and Fig. 25. The curve 4 in Fig. 24 is the cyclic olefin obtained in Example 19 of the present invention. The thermogravimetric curve of the copolymer in nitrogen; curve 4 in Fig. 25 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 19 of the present invention in air. As is apparent from Fig. 24 and Fig. 25, the cyclic olefin copolymer obtained in Example 19 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 19 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 19 of the present invention had an elongation at break of 4.6% and a tensile strength of 39MPa, tensile modulus is 1200MPa.

The transparency of the cyclic olefin copolymer obtained in Example 19 of the present invention was tested according to the method described in the above technical scheme. The test result was that the cycloolefin copolymer obtained in Example 19 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of Example 19 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was 100% in the polymerization reaction in the above-mentioned polymerization reaction of Example 19 of the present invention.

Example 20

To the dried polymerization reaction bottle, 1.245 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.755 g of the compound having the structure shown in the

formula

3 and 25 mL of the compound prepared in Example 15 were added at 25 ° C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 31.3 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for 120 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 20 of the present invention was 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.05 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl group having a molar ratio of 3 eqv to the above-mentioned structural compound represented by Formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred at 130 ° C for 16 hours under reflux to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise The obtained mixed product was filtered and drained into 300 mL of 98% pure ethanol, and then re-dissolved in 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% pure ethanol. The obtained mixed product was dried in a vacuum oven at 60 ° C for 12 hours to obtain 1.35 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 20 of the present invention gave a yield of the cyclic olefin copolymer of 92%.

The structure of the cyclic olefin copolymer obtained in Example 20 of the present invention was examined by the method described in Example 16. As a result, the cyclic olefin copolymer obtained in Example 20 of the present invention has a structure represented by Formula III, m in Formula III. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 20 of the present invention was calculated to have a molar content of 44.6% as determined by the method described in Example 3.

The cyclic olefin copolymer obtained in Example 20 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 20 of the present invention was 1.31, and the number average molecular weight was 10.6. × 10 ⁴ g/mol.

The reactivity ratio curves of the compounds having the structure shown in Formula 1 and the compounds having the structure shown in Formula 3 in the preparation of the cyclic olefin copolymers of Examples 16 to 20 of the present invention were tested by the Fineman-Ross method. The test results are shown in the figure. 17 is a graph showing the reactivity ratio curves of the compound having the structure shown in Formula 1 and the compound having the structure shown in Formula 3 in the preparation of the cyclic olefin copolymer in Examples 16 to 20 of the present invention. In Fig. 17, the abscissa is f/F ² and the ordinate is (f-1)/F, wherein f is a quantity group of a substance having a structure represented by Formula 1 in the polymer and a compound having a structure represented by Formula 3 In the fractional ratio, F is an amount ratio of a substance having a structure represented by Formula 1 and a compound having a structure represented by Formula 3 when the polymerization is not started, and the conversion ratio of the two monomers is controlled to be less than 10%. From the relationship of (f-1)F=-1.30×f/F ² +0.55, it is understood that the compound having the structure of the formula 1 has a reactivity ratio of 0.55, and the compound having the structure represented by Formula 3 is obtained. The reactivity ratio was 1.30, indicating that the polymerization rate of the compound having the structure of Formula 1 was significantly lower than that of the compound having the structure of Formula 3 due to steric hindrance, and the reactivity ratio and formula of the compound having the structure shown in Formula 1 were obtained. The product of the reactivity ratio of the compound of the structure shown in 3 is 0.71, and the value is less than 1, indicating that the polymer obtained by random copolymerization of the compound having the structure represented by Formula 1 and the compound having the structure of Formula 3 is a typical random. Copolymer.

The cyclic olefin copolymer obtained in Example 20 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 22, and Fig. 22 is a variation of the cyclic olefin copolymer obtained in Example 20 of the present invention. Scanning the calorimetry curve, as seen from Fig. 22, the glass transition temperature of the cyclic olefin copolymer obtained in Example 20 of the present invention was 166.2 °C. Figure 23 is a graph showing the relationship between the glass transition temperature of the cyclic olefin copolymer obtained in Examples 16 to 20 and Example 14 of the present invention and the content of the compound having the formula 1 in the cyclic olefin copolymer, as Fig. 23 The more the compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained by the present invention, the higher the glass transition temperature of the cyclic olefin copolymer.

The cyclic olefin copolymer obtained in Example 20 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 24 and Fig. 25, and the curve 5 in Fig. 24 is the cyclic olefin obtained in Example 20 of the present invention. The thermogravimetric curve of the copolymer in nitrogen; curve 5 in Fig. 25 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 20 of the present invention in air. As is apparent from Fig. 24 and Fig. 25, the cyclic olefin copolymer obtained in Example 20 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 20 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 20 of the present invention had an elongation at break of 4.9% and a tensile strength of 48MPa, tensile modulus is 1310MPa.

The transparency of the cyclic olefin copolymer obtained in Example 20 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in Fig. 26. The curve 3 in Fig. 26 is the permeation of the cyclic olefin copolymer obtained in Example 20 of the present invention. The light ratio, as seen from Fig. 26, shows that the cycloolefin copolymer obtained in Example 20 of the present invention has a light transmittance of >90%.

The polymerization conversion ratio of Example 20 of the present invention in carrying out the above polymerization reaction was tested in the same manner as in Example 9, and the test result was 100% in the polymerization reaction in the above-mentioned polymerization reaction of Example 20 of the present invention.

Example 21

To the dried polymerization reaction bottle, 1.896 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.31 g of the compound having the structure shown in

Formula

3 and 25 mL of the compound prepared in Example 15 were added at 0 °C. The alkane was stirred and mixed for 10 min to obtain a mixture; 13.4 mg of the compound having the structure of the formula VI prepared in Example 2 was added to the small ampoule, and then 5 mL of toluene was added to the small ampule for 3 min sonication, and the compound having the structure of the formula VI was sufficiently dissolved in toluene to obtain a compound solution having the structure represented by the formula VI; under stirring, The compound solution having the structure represented by Formula VI is added to the above polymerization reaction bottle for polymerization for 180 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 1.95 g of a polymerization product.

The autoclave was pre-dried under vacuum for 5 hours, and 1 g of the polymerization reaction product prepared above, 300 mL of cyclohexane, and 0.5 g of a Pd/Al ₂ O ₃ catalyst were added to the autoclave. The autoclave was subjected to a pumping operation three times, and then the autoclave was charged with 30 MPa of hydrogen gas, 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. The hydrogenation reaction product was obtained; the hydrogenation reaction product was poured into ethanol to precipitate, and the obtained precipitated product was filtered and dried in a vacuum oven at 60 ° C for 12 hours to obtain 0.94 g of a cyclic olefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 21 of the present invention were tested according to the method described in Example 16. The test result is that the cyclic olefin copolymer obtained in Example 21 of the present invention has a structure represented by Formula III, and Formula III m is 430 and n is 170. The cyclic olefin copolymer obtained in Example 21 of the present invention has a compound having a structure represented by Formula 1 in a molar ratio of 72.5% in the cyclic olefin copolymer, and the glass transition temperature of the cyclic olefin copolymer obtained in Inventive Example 21 is The cyclic olefin copolymer obtained in Example 21 of the present invention had a molecular weight distribution of 1.29 and a number average molecular weight of 17.3 × 10 ⁴ g/mol at 185.3 °C. The cyclic olefin copolymer obtained in Example 21 of the present invention had an elongation at break of 4.0%, a tensile strength of 40 MPa, and a tensile modulus of 1,300 MPa. The cycloolefin copolymer obtained in Example 21 of the present invention had a light transmittance of >90%. In the inventive example 21, the polymerization conversion ratio at the time of the above polymerization reaction was 100%. The cyclic olefin copolymer obtained in Example 21 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 22

To the dried polymerization flask, 1.896 g of the compound having the structure shown in Example 1 and 0.18 g of the compound having the structure shown in

Formula

3 and 25 mL of benzene prepared in Example 15 were placed at 50 ° C. The mixture was stirred for 10 min to obtain a mixture; 14.1 mg of the compound having the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of cyclohexane was added to the small ampoule for 3 min of sonication. The compound having the structure of the formula VI is sufficiently dissolved in cyclohexane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added to the mixture under stirring. The polymerization reaction bottle was subjected to a polymerization reaction for 60 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. The solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered, washed with acetone three times, and dried in a vacuum oven at 40 ° C for 12 hours to obtain 1.99 g of a polymerization product.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.8 g of p-toluenesulfonylhydrazine and 40 mL of toluene were successively added, and the mixture was stirred under reflux at 150 ° C for 20 hours to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; The hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol, and the obtained mixed product was filtered and dried, and then re-dissolved in 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of purity. The obtained mixed product was dried in a vacuum oven at 98 ° C for 12 hours in 98% ethanol to obtain 1.35 g of a cyclic olefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 22 of the present invention were tested according to the method described in Example 16. The test result is that the cyclic olefin copolymer obtained in Example 22 of the present invention has the structure shown in Formula III, in Formula III. m is 410 and n is 90. The cyclic olefin copolymer obtained in Example 22 of the present invention has a compound having a structure represented by Formula 1 in a molar ratio of 82.1% in the cyclic olefin copolymer, and the glass transition temperature of the cyclic olefin copolymer obtained in Inventive Example 22 is The cyclic olefin copolymer obtained in Example 22 of the present invention had a molecular weight distribution of 1.32 and a number average molecular weight of 15.6 × 10 ⁴ g/mol at 198.0 °C. The cyclic olefin copolymer obtained in Example 22 of the present invention had an elongation at break of 3.9%, a tensile strength of 41.5 MPa, and a tensile modulus of 1,500 MPa. The cycloolefin copolymer obtained in Inventive Example 22 had a light transmittance of >90%. In the example 22 of the present invention, the polymerization conversion ratio at the time of the above polymerization reaction was 100%. The cyclic olefin copolymer obtained in Example 22 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 23

300 mL of n-octene, 108 mL of dicyclopentadiene and 1 g of 2,6-di-tert-butyl-p-cresol were sequentially added to a 2-liter stainless steel autoclave, and the autoclave was repeatedly evacuated three times. The operation was followed by nitrogen charging; the autoclave was heated to 240 ° C, and the contents of the autoclave were reacted under stirring for 8 hours.

After the completion of the reaction, the obtained reaction product was cooled to 25 ° C, allowed to stand for 12 hours, and then distilled at 120 ° C under normal pressure to collect unreacted n-octene, and then the obtained atmospheric distillation product was decompressed at 80 ° C. Distillation was carried out to collect a fraction at 68 ° C to 80 ° C to obtain 108 g of a product. The yield of the product prepared by the method provided in Example 23 of the present invention was 38.9%.

The product obtained above was subjected to nuclear magnetic resonance spectrum detection, and the detection result is shown in FIG. 27. FIG. 27 is a nuclear magnetic resonance spectrum of the product obtained in Example 23 of the present invention. FIG. 27 shows that the obtained example 23 of the present invention is obtained. The product is a compound having the structure shown in Formula 4.

Example 24

To the dried polymerization reaction bottle, 1.933 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.067 g of the compound having the structure shown in the

formula

4 and 25 mL of the compound prepared in Example 23 were added at 25 ° C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 15.5 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of sonication. The compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added under stirring. The polymerization reaction was carried out in the above polymerization bottle for 120 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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. After 12 hours, 2 g of a polymerization product was obtained. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 24 of the present invention was 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl having a mole number of 0.1 eqv relative to the compound having the structure represented by the above formula VI were sequentially added. Base 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 12 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then dissolved again with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven. Drying at 60 ° C for 12 hours gave 1.41 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 24 of the present invention gave a yield of a cyclic olefin copolymer of 93.6%.

The polymerization reaction product obtained in Example 24 of the present invention and the cyclic olefin copolymer were subjected to nuclear magnetic resonance spectrum detection according to the method described in the above technical scheme, and the detection results are shown in Fig. 28. Fig. 28 is a polymerization reaction obtained in Example 24 of the present invention. The nuclear magnetic resonance spectrum of the product and the cyclic olefin copolymer, the curve 1 in Fig. 28 is the nuclear magnetic resonance spectrum of the polymerization reaction product obtained in Example 24 of the present invention, and the curve 2 is the cyclic olefin copolymer obtained in Example 24 of the present invention. The nuclear magnetic resonance spectrum, as can be seen from Fig. 28, the polymerization reaction product obtained in Example 24 of the present invention completely disappeared after the hydrogenation reaction, and the hydrogenation effect was good. As is apparent from the curve 2 in Fig. 28, the cyclic olefin copolymer obtained in Example 24 of the present invention has a structure represented by Formula IV, wherein i is 380 and j is 20.

The molar content of the compound having the formula 1 in the cyclic olefin copolymer obtained in Example 24 of the present invention was calculated by the method described in Example 3 to be 95.23%.

The cyclic olefin copolymer obtained in Example 24 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 24 of the present invention was 1.27, and the number average molecular weight was 10.6. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 24 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 30, and Fig. 30 is a variation of the cyclic olefin copolymer obtained in Example 24 of the present invention. Scanning calorimetry curve, as can be seen from FIG. 30, the cyclic olefin copolymer obtained in Example 24 of the present invention has no melting temperature and is amorphous, and inventive Example 24 The resulting cyclic olefin copolymer had a glass transition temperature of 214.7 °C. The cyclic olefin copolymer obtained in Example 24 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test result is that the cyclic olefin copolymer obtained in Example 24 of the present invention has a decomposition rate of 10% at 360 ° C, Better thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 24 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 24 of the present invention had an elongation at break of 3.8% and a tensile strength of 31.8 MPa, tensile modulus is 1650 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 24 of the present invention was tested according to the method described in the above technical scheme, and the test results are shown in Fig. 38, and Fig. 38 is a cyclic olefin copolymer obtained in Examples 24 to 28 of the present invention. Light transmittance, curve 1 in Fig. 38 is the light transmittance of the cyclic olefin copolymer obtained in Example 24 of the present invention. As is apparent from Fig. 38, the light olefin copolymer obtained in Example 24 of the present invention has a light transmittance of >90%.

The polymerization conversion ratio of Example 24 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was 100% of the polymerization conversion rate in the above-mentioned polymerization reaction of Example 24 of the present invention.

Example 25

To the dried polymerization flask, 1.892 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.108 g of the compound having the structure shown in

Formula

4 and 25 mL of the second compound prepared in Example 23 were added at 25 °C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 15.6 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for 120 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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. After 12 hours, 2 g of a polymerization product was obtained. The polymerization product obtained by the polymerization method provided in Example 25 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5 g of p-toluenesulfonyl hydrazide, and 0.05 eqv of 2,6-di-tert-butyl group relative to the above-mentioned structural compound having the formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.35 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 25 of the present invention gave a yield of a cyclic olefin copolymer of 92.4%.

The structure of the cyclic olefin copolymer obtained in Example 25 of the present invention was examined by the method described in Example 24, and as a result, the cyclic olefin copolymer obtained in Example 25 of the present invention has a structure represented by Formula IV, i in Formula IV. The compound having the structural formula represented by the formula 1 obtained in the cyclic olefin copolymer obtained in Example 25 of the present invention was calculated to have a molar content of 92.59% as 370, j was 30.

The cyclic olefin copolymer obtained in Example 25 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 25 of the present invention had a molecular weight distribution of 1.22 and a number average molecular weight of 9.8. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 25 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 31, and Fig. 31 is a variation of the cyclic olefin copolymer obtained in Example 25 of the present invention. From the scanning calorimetry curve, it can be seen from Fig. 31 that the cyclic olefin copolymer obtained in Example 25 of the present invention had a glass transition temperature of 195.6 °C. The cyclic olefin copolymer obtained in Example 25 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 25 of the present invention had good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 25 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 25 of the present invention had an elongation at break of 3.7% and a tensile strength of 31 MPa, tensile modulus is 1590 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 25 of the present invention was tested according to the method described in the above technical scheme. The test results are shown in Fig. 38, and the curve 2 in Fig. 38 is the permeation of the cyclic olefin copolymer obtained in Example 25 of the present invention. The light ratio, as seen from Fig. 38, shows that the cycloolefin copolymer obtained in Example 25 of the present invention has a light transmittance of > 90%.

The polymerization conversion ratio of Example 25 of the present invention in carrying out the above polymerization reaction was tested in the same manner as in Example 9, and the test result was 100% in the polymerization reaction in the above-mentioned polymerization reaction of Example 25 of the present invention.

Example 26

To the dried polymerization reaction bottle, 1.835 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.165 g of the compound having the structure shown in the

formula

4 and 25 mL of the compound prepared in Example 23 were added at 25 ° C. Dichloromethane, stirred and mixed for 10 min to obtain a mixture; 15.9 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min. Soothing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound having the structure represented by the formula VI is stirred under stirring The solution is added to the above polymerization bottle for polymerization for 120 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The polymerization product obtained by the polymerization method provided in Example 26 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.8 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 2 eqv of the compound of the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred at 130 ° C for 20 hours under reflux to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved in 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL. The obtained mixed product was dried in a vacuum oven at 60 ° C for 12 hours in a purity of 98% ethanol to obtain 1.44 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 26 of the present invention gave a yield of a cyclic olefin copolymer of 93.8%.

The structure of the cyclic olefin copolymer obtained in Example 26 of the present invention was examined by the method described in Example 24, and as a result, the cyclic olefin copolymer obtained in Example 26 of the present invention had a structure represented by Formula IV, i in Formula IV. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 26 of the present invention was calculated to have a molar content of 87.7% as determined by the method described in Example 3.

The cyclic olefin copolymer obtained in Example 26 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 26 of the present invention was 1.21, and the number average molecular weight was 11.9. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 26 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 32, and Fig. 32 is a variation of the cyclic olefin copolymer obtained in Example 26 of the present invention. Scanning calorimetry curve, as seen from Fig. 32, the glass transition temperature of the cyclic olefin copolymer obtained in Example 26 of the present invention was 190.9 °C. The cyclic olefin copolymer obtained in Example 26 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 26 of the present invention had good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 26 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 26 of the present invention had an elongation at break of 4.1% and a tensile strength of 30.7 MPa, tensile modulus is 1240 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 26 of the present invention was tested in accordance with the method described in the above technical scheme. The test results are shown in Fig. 38, and the curve 3 in Fig. 38 is the permeation of the cyclic olefin copolymer obtained in Example 26 of the present invention. As a light ratio, as seen from Fig. 38, the light olefin copolymer obtained in Example 26 of the present invention had a light transmittance of >90%.

The polymerization conversion ratio of Example 26 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was 100% of the polymerization conversion rate in the above-mentioned polymerization reaction of Example 26 of the present invention.

Example 27

To the dried polymerization reaction bottle, 1.78 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.22 g of the compound having the structure shown in

Formula

4 and 25 mL of the compound prepared in Example 23 were added at 25 ° C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 16.1 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for 180 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The polymerization product obtained by the polymerization method provided in Example 27 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonylhydrazine, and 2,6-di-tert-butyl group having a molar ratio of 3 eqv to the above-mentioned structural compound represented by Formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 18 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.46 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 27 of the present invention gave a yield of a cyclic olefin copolymer of 94.1%.

The structure of the cyclic olefin copolymer obtained in Example 27 of the present invention was examined by the method described in Example 24, and as a result, the cyclic olefin copolymer obtained in Example 27 of the present invention had a structure represented by Formula IV, i in Formula IV. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 27 of the present invention was calculated to have a molar content of 84.03% according to the method described in Example 3.

The cyclic olefin copolymer obtained in Example 27 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 27 of the present invention was 1.32, and the number average molecular weight was 11. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 27 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 33, and Fig. 33 is a variation of the cyclic olefin copolymer obtained in Example 27 of the present invention. From the scanning calorimetry curve, it is understood from Fig. 33 that the cyclic olefin copolymer obtained in Example 27 of the present invention had a glass transition temperature of 179.6 °C. The cyclic olefin copolymer obtained in Example 27 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 27 of the present invention had good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 27 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 27 of the present invention had an elongation at break of 4.5% and a tensile strength of 32.8 MPa, tensile modulus is 1350 MPa.

The transparency of the cyclic olefin copolymer obtained in Example 27 of the present invention was tested in accordance with the method described in the above technical scheme. The test results are shown in Fig. 38, and the curve 4 in Fig. 38 is the permeation of the cyclic olefin copolymer obtained in Example 27 of the present invention. Light rate >90%.

The polymerization conversion ratio of Example 27 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was 100% in the polymerization conversion rate in the above-mentioned polymerization reaction of Example 27 of the present invention.

Example 28

To the dried polymerization reaction flask, 1.73 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.268 g of the compound having the structure shown in

Formula

4 and 25 mL of the second compound prepared in Example 23 were added at 50 °C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 16.3 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for polymerization for 60 minutes;

After the polymerization reaction is completed, the relative polymerization bottle is added to the above polymerization bottle under stirring. The polymerization reaction was terminated by the above-mentioned vinyl ether having a molecular weight of 300 eqv of the structural compound represented by the formula VI; after 30 minutes, the obtained polymerization reaction solution was poured into anhydrous methanol to obtain a precipitated product; the precipitated product was filtered and used. The acetone was washed 3 times and dried in a vacuum oven at 40 ° C for 12 hours to obtain 2 g of a polymerization reaction product. The yield of the polymerization reaction product obtained by the polymerization method provided in Example 28 of the present invention was 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonylhydrazide, and 2,6-di-tert-butyl group having a mole number of 2 eqv of the compound of the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 16 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.35 g of a cyclic olefin copolymer. The process of the hydrogenation reaction provided in Example 28 of the present invention gave a yield of the cyclic olefin copolymer of 92%.

The structure of the cyclic olefin copolymer obtained in Example 28 of the present invention was examined by the method described in Example 24, and as a result, the cyclic olefin copolymer obtained in Example 28 of the present invention had a structure represented by Formula IV, i in Formula IV. The compound having the structure of the formula 1 in the cyclic olefin copolymer obtained in Example 28 of the present invention was calculated to have a molar content of 81.3% as 325, j was 75.

The cyclic olefin copolymer obtained in Example 28 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the molecular weight distribution of the cyclic olefin copolymer obtained in Example 28 of the present invention was 1.22, and the number average molecular weight was 10.7. × 10 ⁴ g/mol.

The reactivity ratio curve of the compound having the structure of the formula 1 and the compound having the structure of the formula 4 in the process for producing the cycloolefin copolymer of the present invention was tested by the Fineman-Ross method, and the test results are shown in Fig. 29, and Fig. 29 is The reactivity ratio curves of the compound having the structure of the formula 1 and the compound having the structure of the formula 4 in the preparation of the cyclic olefin copolymer in the preparation of the cyclic olefin copolymer of the present invention, and the abscissa of FIG. 29 is f/F ² , The ordinate is (f-1)/F, where f is the amount-to-component ratio of the substance having the structure represented by Formula 1 in the polymer and the compound having the structure of Formula 4, and F is a formula when the polymerization is not started The amount ratio of the compound of the structure shown in Fig. 1 and the substance of the compound having the structure of the formula 4, controlling the conversion of the two monomers to less than 10%. From Fig. 29, the relationship can be obtained: (f-1) F = -1.61 × f / F ² + 0.54, and it is understood that the compound having the structure of the formula 1 has a reactivity ratio of 0.54, and the compound having the structure of the formula 4 is The reactivity ratio was 1.61, indicating that the polymerization rate of the compound having the structure of Formula 1 was significantly lower than that of the compound having the structure of Formula 4 due to steric hindrance, and the reactivity ratio and formula of the compound having the structure of Formula 1 were obtained. The product of the reactivity ratio of the compound of the structure shown in 4 is 0.87, and the value is less than 1, indicating that the polymer obtained by random copolymerization of the compound having the structure represented by Formula 1 and the compound having the structure of Formula 3 is a typical random. Copolymer.

The cyclic olefin copolymer obtained in Example 28 of the present invention was subjected to differential thermal analysis according to the method described in the above technical scheme. The test results are shown in Fig. 34, and Fig. 34 is a variation of the cyclic olefin copolymer obtained in Example 28 of the present invention. Scanning the calorimetry curve, as seen from Fig. 34, the glass transition temperature of the cyclic olefin copolymer obtained in Example 28 of the present invention was 166.8 °C.

The cyclic olefin copolymer obtained in Example 28 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test results are shown in Fig. 36, and the curve 1 in Fig. 36 is the cyclic olefin copolymer obtained in Example 28 of the present invention. The thermogravimetric curve in nitrogen; curve 2 in Fig. 36 is the thermogravimetric curve of the cyclic olefin copolymer obtained in Example 28 of the present invention in air. As is apparent from Fig. 36, the cyclic olefin copolymer obtained in Example 28 of the present invention has good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 28 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 28 of the present invention had an elongation at break of 4.6% and a tensile strength of 26MPa, tensile modulus is 1200MPa.

The transparency of the cyclic olefin copolymer obtained in Example 28 of the present invention was tested in accordance with the method described in the above technical scheme. The test results are shown in Fig. 38, and the curve 5 in Fig. 38 is the permeation of the cyclic olefin copolymer obtained in Example 28 of the present invention. The light ratio, as seen from Fig. 38, shows that the cycloolefin copolymer obtained in Example 28 of the present invention has a light transmittance of >90%.

The polymerization conversion ratio of Example 28 of the present invention in carrying out the above polymerization reaction was tested in accordance with the method described in Example 9, and the test result was that the polymerization conversion ratio in the above-mentioned polymerization reaction of Example 28 of the present invention was 100%.

Example 29

To the dried polymerization reaction bottle, 1.48 g of the compound having the structure shown in Example 1 prepared in Example 1 and 0.52 g of the compound having the structure shown in

Formula

4 and 25 mL of the compound prepared in Example 23 were added at 25 ° C. Methyl chloride, stirred and mixed for 10 min to obtain a mixture; 17.4 mg of the compound of the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of dichloromethane was added to the small ampoule for 3 min of ultrasound. Processing, the compound having the structure of the formula VI is sufficiently dissolved in dichloromethane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is stirred under stirring Adding to the above polymerization bottle for 120 minutes of polymerization;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 500 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure represented by the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2 g of a polymerization product. The polymerization product obtained by the polymerization method provided in Example 29 of the present invention had a yield of 100%.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.0 g of p-toluenesulfonyl hydrazide, and 2,6-di-tert-butyl group having a mole number of 1 eqv of the structural compound represented by the above formula VI were sequentially added. 4-methylphenol (BHT) and 40 mL of toluene were stirred under reflux at 130 ° C for 12 hours to obtain a hydrogenation reaction product; the hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol. The obtained mixed product was filtered and dried, and then re-dissolved with 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of 98% purity ethanol, and the obtained mixed product was placed in a vacuum oven at 60 Drying at ° C for 12 hours gave 1.34 g of a cyclic olefin copolymer. The method of the hydrogenation reaction provided in Example 29 of the present invention gave a yield of a cyclic olefin copolymer of 92.1%.

The structure of the cyclic olefin copolymer obtained in Example 29 of the present invention was examined by the method described in Example 24, and as a result, the cyclic olefin copolymer obtained in Example 29 of the present invention had a structure represented by Formula IV, i in Formula IV. Calculating the compound having the structure of Formula 1 in the cyclic olefin copolymer obtained in Example 29 of the present invention by the method described in Example 3, 256, j was 144. The molar content was 64.1%.

The cyclic olefin copolymer obtained in Example 29 of the present invention was subjected to a gel permeation chromatography test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 29 of the present invention had a molecular weight distribution of 1.23 and a number average molecular weight of 9.5. × 10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 29 of the present invention was subjected to a differential thermal analysis method according to the method described in the above technical scheme. The test results are shown in Fig. 35, and Fig. 35 is a variation of the cyclic olefin copolymer obtained in Example 29 of the present invention. Scanning the calorimetry curve, as seen from Fig. 35, the glass transition temperature of the cyclic olefin copolymer obtained in Example 29 of the present invention was 125.8 °C. Figure 37 is a graph showing the relationship between the glass transition temperature of the cyclic olefin copolymer obtained in Examples 24 to 29 and Example 14 of the present invention and the content of the compound having the formula 1 in the cyclic olefin copolymer, as Fig. 37 The more the compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained by the present invention, the higher the glass transition temperature of the cyclic olefin copolymer.

The cyclic olefin copolymer obtained in Example 29 of the present invention was subjected to a thermogravimetric test according to the method described in the above technical scheme. The test result was that the cyclic olefin copolymer obtained in Example 29 of the present invention had good thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 29 of the present invention were tested according to the method described in the above technical scheme. The test results showed that the cyclic olefin copolymer obtained in Example 29 of the present invention had an elongation at break of 4.9% and a tensile strength of 23.4 MPa, tensile modulus is 1030 MPa. The cycloolefin copolymer obtained in Example 29 of the present invention had a light transmittance of >90%. The cyclic olefin copolymer obtained in Example 29 of the present invention has a high glass transition temperature, mechanical properties and transparency.

The polymerization conversion ratio of Example 29 of the present invention in carrying out the above polymerization reaction was tested in the same manner as in Example 9, and the test result was 100% in the polymerization reaction in the above-mentioned polymerization reaction of Example 29 of the present invention.

Example 30

Formula

4 and 25 mL of the compound prepared in Example 23 were added at 0 °C. The alkane was stirred and mixed for 10 min to obtain a mixture; 10.7 mg of the compound having the structure of the formula VI prepared in Example 2 was added to the small ampoule, and then 5 mL of toluene was added to the small ampule for 3 min sonication, and the compound having the structure of the formula VI was sufficiently dissolved in toluene to obtain a compound solution having the structure represented by the formula VI; under stirring, The compound solution having the structure represented by Formula VI is added to the above polymerization reaction bottle for polymerization for 180 minutes;

The autoclave was pre-dried under vacuum for 5 hours, and 1 g of the polymerization reaction product prepared above, 300 mL of cyclohexane, and 0.5 g of a Pd/Al ₂ O ₃ catalyst were added to the autoclave. The autoclave was subjected to a pumping operation three times, and then the autoclave was charged with 30 MPa of hydrogen gas, 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. The hydrogenation reaction product was obtained; the hydrogenation reaction product was poured into ethanol to precipitate, and the obtained precipitated product was filtered and dried in a vacuum oven at 60 ° C for 12 hours to obtain 0.85 g of a cyclic olefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 30 of the present invention were tested according to the method described in Example 24. The test result is that the cyclic olefin copolymer obtained in Example 30 of the present invention has the structure shown in Formula IV, in Formula IV. i is 500 and j is 100. The compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 30 of the present invention has a molar content of 84.6% in the cyclic olefin copolymer, and the glass transition temperature of the cyclic olefin copolymer obtained in Example 30 of the present invention is The cyclic olefin copolymer obtained in Example 30 of the present invention had a molecular weight distribution of 1.30 and a number average molecular weight of 14.9 × 10 ⁴ g/mol at 180.3 °C. The cyclic olefin copolymer obtained in Example 30 of the present invention had an elongation at break of 4.1%, a tensile strength of 35.8 MPa, and a tensile modulus of 1,360 MPa. The cycloolefin copolymer obtained in Example 30 of the present invention had a light transmittance of >90%. In the embodiment 30 of the present invention, the polymerization conversion ratio at the time of the above polymerization reaction was 100%. The cyclic olefin copolymer obtained in Example 30 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Example 31

To the dried polymerization reaction bottle, 1.78 g of the compound having the structure of the formula 1 prepared in Example 1 and 0.22 g of the compound having the structure of the

formula

4 and 25 mL of benzene prepared in Example 23 were added at 50 °C. The mixture was stirred for 10 min to obtain a mixture; 12.8 mg of the compound having the structure of the formula VI prepared in Example 2 was added to the small ampoule, and 5 mL of cyclohexane was added to the small ampoule for 3 min sonication. The compound having the structure of the formula VI is sufficiently dissolved in cyclohexane to obtain a compound solution having the structure represented by the formula VI; and the compound solution having the structure represented by the formula VI is added to the mixture under stirring. The polymerization reaction bottle was subjected to a polymerization reaction for 60 minutes;

After the completion of the polymerization reaction, the polymerization reaction was terminated by adding 300 eqv of vinyl ethyl ether with respect to the above-mentioned structural compound having the structure of the formula VI under stirring, and the polymerization reaction was obtained after 30 minutes. 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 2.0 g of a polymerization product.

In a dry polymerization reaction bottle, 1.5 g of the above polymerization reaction product, 5.2 g of p-toluenesulfonylhydrazine and 40 mL of toluene were successively added, and the mixture was stirred under reflux at 150 ° C for 20 hours to carry out a hydrogenation reaction to obtain a hydrogenation reaction product; The hydrogenation reaction product was added dropwise to 300 mL of 98% purity ethanol, and the obtained mixed product was filtered and dried, and then re-dissolved in 40 mL of toluene at 130 ° C for 30 minutes, and the dissolved solution was again added to 300 mL of purity. The obtained mixed product was dried in a vacuum oven at 98 ° C for 12 hours in 98% ethanol to obtain 1.40 g of a cyclic olefin copolymer.

The structure and properties of the cyclic olefin copolymer obtained in Example 31 of the present invention were tested according to the method described in Example 24. The test result is that the cyclic olefin copolymer obtained in Example 31 of the present invention has the structure shown in Formula IV, in Formula IV. i is 420 and j is 80. The molar content of the compound having the structure represented by Formula 1 in the cyclic olefin copolymer obtained in Example 31 of the present invention in the cyclic olefin copolymer was 84.1%, and the glass transition temperature of the cyclic olefin copolymer obtained in Example 31 of the present invention was The cyclic olefin copolymer obtained in Example 31 of the present invention had a molecular weight distribution of 1.23 and a number average molecular weight of 13.5 × 10 ⁴ g/mol at 181.3 °C. The cyclic olefin copolymer obtained in Example 31 of the present invention had an elongation at break of 4.2%, a tensile strength of 33.5 MPa, and a tensile modulus of 1,420 MPa. The cycloolefin copolymer obtained in Example 31 of the present invention had a light transmittance of >90%. In the embodiment 31 of the present invention, the polymerization conversion ratio at the time of the above polymerization reaction was 100%. The cyclic olefin copolymer obtained in Example 31 of the present invention has a high glass transition temperature, mechanical properties and transparency.

Claims

A cyclic olefin copolymer having the structure of Formula I, Formula II, Formula III or Formula IV:

In formula I, 100≤x≤350, 25≤y≤150;

In Formula II, 300 ≤ z ≤ 1000;

In Formula III, 180 ≤ m ≤ 430, 40 ≤ n ≤ 220;

In Formula IV, 250 ≤ i ≤ 500, and 20 ≤ j ≤ 144.
The cyclic olefin copolymer according to claim 1, wherein in the formula I, 230 ≤ x ≤ 320, 40 ≤ y ≤ 86;

In the formula II, 400≤z≤700;

In the formula III, 240≤m≤410, 80≤n≤170;

In the formula IV, 325 ≤ i ≤ 475, and 30 ≤ j ≤ 125.
A method for preparing a cyclic olefin copolymer, comprising the steps of:

1), under the action of a catalyst, the first compound and the second compound are polymerized in a solvent to obtain a polymerization reaction product;

2) hydrogenating the polymerization reaction product and the hydrogen source to obtain a cyclic olefin copolymer;

The first compound has the structure shown in Formula 1:

The second compound has the structure shown in Formula 1, Formula 2, Formula 3 or Formula 4:
The method of claim 3 wherein said catalyst is a carbene type catalyst.
The method of claim 4 wherein said catalyst is a ruthenium carbene compound.
The method according to claim 3, wherein the ratio of the total number of moles of the first compound and the second compound to the number of moles of the catalyst is (270 to 1000): 1;

The molar ratio of the first compound to the second compound is (0.5 to 19):1.
The method according to claim 3, wherein the temperature of the polymerization in the step 1) is from 0 ° C to 50 ° C;

The polymerization reaction time in the step 1) is from 5 minutes to 180 minutes.
The method of claim 3 wherein the source of hydrogen in step 2) is a terpenoid.
The method according to claim 8, wherein the ratio of the number of moles of the double bond of the polymerization reaction product to the number of moles of the hydrogen source in the step 2) is 1: (3 to 6).
The method according to claim 8, wherein the temperature of the hydrogenation reaction in the step 2) is from 110 ° C to 150 ° C;

The hydrogenation reaction in the step 2) is carried out for a period of from 12 hours to 24 hours.