CN107216444A - A kind of transparent, high heat-resisting cyclic olefine copolymer and preparation method thereof - Google Patents

Abstract

The present invention provides a transparent, high heat-resistant cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer provided by the present invention has a specific structure, so that the glass transition temperature of the cyclic olefin copolymer provided by the present invention can be precisely adjusted. , the range is 105-169°C, the solution coating film, the light transmittance of the material can reach 91%, the tensile test shows that the material has excellent mechanical properties, the tensile strength is between 25-50MPa, and the tensile modulus is 1600- 2800MPa, the elongation at break is between 2.5-5.4%, and the 10% thermal decomposition temperature is greater than 410 ° C, with good thermal stability. In the preparation method provided by the invention, by selecting a specific catalyst, the catalytic conversion rate can reach 100%, and side reactions such as crosslinking do not occur; and no co-catalyst is required, the polymerization tolerance is very good, the molecular weight distribution is adjustable, and the Good application prospects.

Description

A kind of transparent, high heat resistance cyclic olefin copolymer and preparation method thereof

technical field

The invention relates to the field of polymer materials, in particular to a transparent, high heat-resistant cyclic olefin copolymer and a preparation method thereof.

Background technique

Cyclic olefin copolymer (COC) is an amorphous transparent copolymer polymer with a cycloolefin structure. It has optical properties comparable to PMMA, is more stable in size than PMMA and PC, and has higher heat resistance than PC. COC has low dielectric constant (insulation), adjustable glass transition temperature, light transmittance greater than 91%, heat resistance has better heat resistance temperature and oxidation resistance, thermal decomposition temperature is higher than 400 degrees, and has Good biocompatibility and high fluidity. COC materials use non-toxic monomers as raw materials, high-purity polymers, very low water permeability, no cytotoxicity, no induced mutations in organisms, no irritation, and meet FDA standards. Therefore, cycloolefin copolymers are widely used in the manufacture of various optics, information, electrical appliances, and medical materials.

The heat resistance and thermal stability of cycloolefin copolymers are important properties of this material. In some high-temperature environments, if the heat resistance of the cycloolefin copolymer is poor, the cycloolefin copolymer will undergo dimensional changes such as distortion and deformation, which will directly affect the optical properties and properties of the cycloolefin copolymer. mechanical properties. Therefore, improving the heat resistance and thermal stability of cyclic olefin copolymers can greatly expand the scope of use of cyclic olefin copolymers, and providing cyclic olefin copolymers with good heat resistance and thermal stability is an important subject of current research.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a transparent, highly heat-resistant cyclic olefin copolymer and a preparation method thereof. The cyclic olefin copolymer provided by the invention not only has good heat resistance, but also has good heat resistance. stability.

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

Among them, 140≤m≤220, 170≤n≤280, 1≤x≤4.

Preferably, the m is 170≤m≤190.

Preferably, the n is 170≤n≤190.

Preferably, the x is 2≤x≤3.

The present invention also provides a kind of preparation method of cycloolefin copolymer, comprising:

1) Polymerize the compound having the structure of formula (II) and the compound of formula (III) under the action of a catalyst of the structure of formula (IV) to obtain a polymer;

Among them, x is 1≤x≤4;

2) The obtained polymer is subjected to a hydrogenation reduction reaction with a heterogeneous metal catalyst to obtain a cycloolefin copolymer.

Preferably, the molar ratio of the compound of the formula (II) to the compound of the formula (III) is (9˜1):1.

Preferably, the solvent for the polymerization reaction is C1-C15 alkanes, C1-C15 halogenated hydrocarbons, C3-C15 cycloalkanes or C5-C20 aromatic hydrocarbons.

Preferably, the temperature of the polymerization reaction is 10-50° C., and the time of the polymerization reaction is 4-12 hours.

Preferably, the molar ratio of the total moles of the compound of the formula (II) and the compound of the formula (III) to the catalyst of the formula (IV) is (25-1000):1.

Preferably, the heterogeneous metal catalyst is 5-10% wet palladium carbon, 10% Pd/C, Pd/C/BaSO ₄ or Pt/SiO ₂ .

Compared with the prior art, the present invention provides a kind of transparent, highly heat-resistant cyclic olefin copolymer and preparation method thereof, the cyclic olefin copolymer provided by the invention is by selecting specific structure, makes the cyclic olefin copolymer provided by the present invention The glass transition temperature is precisely adjustable, ranging from 105-169°C, and the light transmittance of the material can reach 91%. The tensile test shows that the material has excellent mechanical properties, and the tensile strength is between 25-50MPa. The tensile modulus is 1600-2800MPa, the elongation at break is between 2.5-5.4%, and the 10% thermal decomposition temperature is greater than 410°C, which has good thermal stability.

In addition, the present invention also provides a preparation method of the transparent, high heat-resistant cycloolefin copolymer cycloolefin copolymer, the preparation method provided by the present invention adopts the benzylidene dichloride having the structure of formula (IV) The bis(tricyclohexylphosphine) ruthenium complex catalyzes the reaction of the polycyclic cycloalkene monomer (TCPD) with the structure of formula (II) and the norbornene monomer with short-chain ester bonds of the structure of formula (III) Random copolymerization not only has a fast initiation rate, but the catalytic conversion rate reaches 100%, and side reactions such as crosslinking do not occur; compared with the W-series and Mo-series catalysts with unclear structures, the polymerization method of the present invention does not require a co-catalyst. Polymerization is very well tolerated and the molecular weight distribution is adjustable. The obtained ring-opening metathesis polymer is subjected to hydrogenation reduction to obtain a polymer with a fully saturated main chain.

Description of drawings

Fig. 1 is the proton nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 1 obtains;

Fig. 2 is the proton nuclear magnetic resonance spectrogram of the product that the embodiment of the present invention 2 obtains;

Fig. 3 is the proton nuclear magnetic resonance spectrogram before and after hydrogenation of the polymerization reaction product that the embodiment of the present invention 3 obtains;

Fig. 4 is the differential scanning calorimetry curve of the cyclic olefin copolymer that embodiment 3 of the present invention, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 obtain;

Fig. 5 is embodiment 3 of the present invention, embodiment 4, embodiment 5, embodiment 6 and embodiment 7 obtain the thermogravity curve of cycloolefin copolymer in nitrogen;

Fig. 6 is the light transmittance of the cycloolefin copolymer obtained in Example 3, Example 5 and Example 7 of the present invention;

Fig. 7 is the proton nuclear magnetic resonance spectrogram before and after the hydrogenation of the polymerization reaction product obtained in embodiment 4 of the present invention;

Fig. 8 is the proton nuclear magnetic resonance spectrogram before and after the hydrogenation of the polymerization reaction product that the embodiment 5 of the present invention obtains;

Fig. 9 is the proton nuclear magnetic resonance spectra before and after hydrogenation of the polymerization product obtained in Example 6 of the present invention;

Fig. 10 is the H NMR spectra of the polymerization reaction product obtained in Example 7 of the present invention before and after hydrogenation.

detailed description

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

Wherein, said 140≤m≤220, 170≤n≤280, 1≤x≤4.

According to the present invention, said m is preferably 170≤m≤190. The n is preferably 170≤n≤190. The x is preferably 1≤x≤2, more preferably 1; the cycloolefin copolymer is a random copolymer; the weight average molecular weight of the copolymer is 7.0-15.0×10 ⁴ g/mol, and the molecular weight distribution index is 1.4～2.0, glass transition temperature is 105～169℃.

The cyclic olefin copolymer provided by the present invention can precisely adjust the glass transition temperature of the cyclic olefin copolymer provided by the present invention by selecting a specific structure, ranging from 105 to 169°C, and the thickness of the cyclic olefin polymer film is 50 to 120 μm The light transmittance is greater than 91%, the mechanical properties are excellent, the tensile strength is between 25-50MPa, the tensile modulus is 1600-2800MPa, the elongation at break is between 2.5-5.4%, and the 10% thermal decomposition temperature is uniform. Greater than 410°C, it has good thermal stability.

The present invention also provides a kind of preparation method of cycloolefin copolymer, comprising:

1) Polymerize the compound having the structure of formula (II) and the compound of formula (III) under the action of a catalyst of the structure of formula (IV) to obtain a polymer;

Among them, x is 1≤x≤4;

2) The obtained polymer is subjected to hydrogenation reduction with a heterogeneous metal catalyst to obtain a cycloolefin copolymer.

According to the present invention, the present invention will have the compound of formula (II) structure and the compound of formula (III) structure to carry out polymerization reaction under the catalyst effect of formula (IV) structure, obtain polymer; Said compound of formula (II) structure The molar ratio with the compound of the formula (III) structure is preferably (9-1): 1, more preferably (7-2): 1, most preferably (6-3): 1; The molar ratio of the total molar number of the compound of the formula (II) structure and the compound of the formula (III) structure to the catalyst of the formula (IV) structure is preferably (25～1000): 1, more preferably (50～100) : 1; the temperature of the polymerization reaction is preferably 10～50°C, more preferably 25～30°C; the time of the polymerization reaction is preferably 4～12h, more preferably 7～9 hours; the polymerization reaction also adds A chain terminator terminates the reaction. The terminator is preferably vinyl ether, and the molar amount of the terminator is preferably 100 to 500 times, more preferably 300 to 400 times, the molar number of the catalyst with the structure of formula (IV).

Specifically, the present invention preferably firstly mixes a compound having a structure of formula (II) and a compound of formula (III) with a solvent; wherein, the concentration of the concentrated polymer solution is preferably 5 to 15 wt %, more preferably 8 to 10 wt % %. The present invention has no special requirements on the mixing method, and any mixing method known in the art can be used, wherein the stirring time during the mixing is preferably 5 minutes to 15 minutes, more preferably 8 minutes to 12 minutes, most preferably 10 minutes . The solvent is preferably the solvent of the polymerization reaction, preferably C1-C15 alkanes, C1-C15 halogenated hydrocarbons, C3-C15 cycloalkanes or C5-C20 aromatic hydrocarbons, more preferably C5-C8 alkanes, C1 ～C5 halogenated hydrocarbons, C5～C8 cycloalkanes or C6～C15 aromatics, most preferably dichloromethane; the present invention has no special requirements on the source of the solvent, and only needs an anhydrous and air-free solvent. The treatment method of anhydrous and air-free solvent is preferably treated by liquid nitrogen freezing to thawing treatment.

Polymerization reaction of the present invention is preferably carried out under dry, anaerobic conditions, and the present invention has no special requirement to the apparatus of polymerization reaction, can carry out in Braun (Mbraun) glove box, also can adopt standard Schlenk (Schlenk) The technique was performed under the protection of nitrogen.

According to the present invention, after the polymerization reaction is completed, the present invention preferably stops stirring to terminate the polymerization reaction to obtain a polymerization reaction solution; mix the polymerization reaction solution with a precipitating agent to obtain a precipitated product; filter the precipitated product, Washing and drying to obtain a polymerization reaction product. Wherein, the precipitating agent is preferably anhydrous methanol; the present invention has no special limitation on the method of filtering, washing and drying the precipitated product, and the technical solution of filtering, washing and drying well known to those skilled in the art can be adopted. In the present invention, the reagent for washing the precipitated product is preferably ethanol. In the present invention, the number of washings of the precipitated product is preferably 2 to 4 times, more preferably 3 times. In the present invention, the method for drying the precipitated product is preferably vacuum drying. In the present invention, the drying temperature of the precipitation product is preferably 20°C-40°C, more preferably 25°C-35°C, most preferably 30°C. In the present invention, the drying time of the precipitated product is preferably 12 hours to 24 hours, more preferably 16 hours to 20 hours, most preferably 18 hours.

In the present invention, there is no special limitation on the source of the compounds having the structures of formulas II and III, which can be prepared by methods well known to those skilled in the art. In the present invention, the preparation method of the compound having the structure of formula II is preferably:

Dicyclopentadiene and 2,6-di-tert-butyl-p-methylphenol are reacted to obtain a compound having the structure of formula II. Wherein, the molar ratio of said dicyclopentadiene and 2,6-di-tert-butyl-p-cresol is preferably (800～1200): 1, more preferably (900～1100): 1, most preferably (1000 ~1100):1. The atmosphere of the reaction is preferably vacuum or nitrogen atmosphere; the temperature of the reaction is preferably 180°C-220°C, more preferably 190°C-210°C, most preferably 200°C. The reaction time is preferably 14 hours to 18 hours, more preferably 15 hours to 17 hours.

After described dicyclopentadiene and 2,6-di-tert-butyl-p-cresol have reacted, the present invention preferably obtains dicyclopentadiene and 2,6-di-tert-butyl-p-cresol reactant cooling, Distill under reduced pressure, add alcohol to the residue, filter out insoluble matter, and recrystallize at low temperature. After the solid is precipitated, recrystallize with alcohol at low temperature again to obtain the compound with the structure of formula II. The present invention has no special restrictions on the cooling, vacuum distillation, filtration and low-temperature recrystallization methods, and the cooling, vacuum distillation, filtration and low-temperature recrystallization technical solutions well known to those skilled in the art can be used. In the present invention, the cooling temperature is preferably 20°C to 30°C, more preferably 24°C to 28°C. In the present invention, the temperature of the vacuum distillation is preferably 40°C to 80°C, more preferably 50°C to 60°C. In the present invention, the temperature of the low-temperature recrystallization is preferably ~20°C to 0°C, more preferably ~10°C to ~5°C.

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

Dicyclopentadiene, methyl acrylate and 2,6-di-tert-butyl-p-methylphenol are reacted to obtain a compound with the structure of formula III; the reaction is preferably carried out under vacuum or nitrogen protection atmosphere; the reaction The temperature is preferably 180°C to 220°C, more preferably 190°C to 210°C, most preferably 200°C. In the present invention, the reaction time is preferably 4 hours to 8 hours, more preferably 5 hours to 7 hours, most preferably 6 hours.

After described dicyclopentadiene, methyl acrylate and 2,6-di-tert-butyl p-methylphenol have reacted, the present invention preferably obtains dicyclopentadiene, methyl acrylate and 2,6-di-tert-butyl The p-cresol reaction product was cooled, left to stand, and distilled under reduced pressure to obtain a compound with the structure of formula III. The present invention has no special restrictions on the cooling, standing and vacuum distillation methods, and the technical solutions of cooling, standing and vacuum distillation well known to those skilled in the art can be adopted. In the present invention, the cooling temperature is preferably 20°C to 30°C, more preferably 25°C to 28°C. In the present invention, the standing time is preferably 10 hours to 16 hours, more preferably 12 hours to 14 hours. In the present invention, the temperature of the vacuum distillation is preferably 110°C to 160°C, more preferably 120°C to 150°C. In the present invention, the fraction at 130° C. to 140° C. during the vacuum distillation is preferably collected, and the fraction is the compound having the structure of formula III.

According to the present invention, the obtained polymer is hydrogenated and reduced with a heterogeneous metal catalyst to obtain a cycloolefin copolymer. Wherein, the heterogeneous metal catalyst is preferably 5% to 10% wet palladium carbon; the mass ratio of the heterogeneous metal catalyst described in this paper to the polymerized polymer is preferably (3 to 6): 1, more preferably It is (5～6): 1; The solvent of described reaction is preferably cyclohexane; Described reaction preferably also adds a small amount of promoter BHT; The pressure of hydrogen in described reaction is preferably 5.5～6.0MPa, more preferably 5.8～ 5.9MPa; the reaction temperature is preferably 120-130°C; the reaction time is preferably 22-24 hours. After the reaction is completed, the present invention preferably slowly pours the reaction solution into industrial ethanol, and precipitates a large amount of white solid, filters, washes repeatedly three times, and then puts it into a vacuum oven at 60° C. for 12 to 24 hours to obtain a cycloolefin copolymer.

More specifically, the preparation of the cyclic olefin copolymer (COC) of the present invention can be carried out according to the following reaction formula:

The preparation method of the cycloolefin copolymer provided by the invention, by adopting the benzylidene dichloro bis(tricyclohexylphosphine) ruthenium complex with the structure of the formula (IV) to catalyze the compound of the structure of the formula (II) Random copolymerization of polycyclic cycloalkene monomer (TCPD) and norbornene monomer (NBMA) with short-chain ester bond of formula (III) structure, not only the initiation rate is fast, but the catalytic conversion rate reaches 100%, And side reactions such as crosslinking do not occur; compared with the W-series and Mo-series catalysts with unclear structures, the polymerization method of the present invention does not require a co-catalyst, the polymerization tolerance is very good, and the molecular weight distribution is adjustable. The obtained ring-opening metathesis polymer is subjected to hydrogenation reduction to obtain a polymer with a fully saturated main chain. And the present invention can control the glass transition temperature of the cycloolefin copolymer prepared by controlling the amount of the polymerization reaction raw material. The more compounds having the structure of formula II in the cycloolefin copolymer prepared by the present invention, the higher the glass transition temperature of the cycloolefin copolymer.

A clear and complete description will be made below in conjunction with the technical solutions of the embodiments of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

Anhydrous and oxygen-free solvents such as dichloromethane and toluene in the following examples are produced by the MBraun SPS solvent purification treatment system; the Grubbs first-generation catalyst used is prepared according to the method described in the literature (JACS, 1996, 118, 100-110) , the polymorphic polyolefin monomer (TCPD) was prepared according to the method described in the literature (2010 Wiley Periodicals, Inc. J Polym Sci PartA: Polym Chem 49: 938-944, 2011). All other raw materials are commercially available products.

In the process of detecting the prepared high-performance cycloolefin copolymer, the application uses nuclear magnetic resonance spectroscopy to measure the molecular structure of the copolymer; uses differential thermal analysis to measure the melting temperature of the polymer; uses gel permeation chromatography to measure the polymer Molecular weight and molecular weight distribution index. Wherein, nuclear magnetic resonance spectrum refers to the ¹ H and ¹³ C NMR spectra of polymers measured by a Varian Unity-400 nuclear magnetic resonance spectrometer at 25°C, with TMS as the internal standard and deuterated chloroform as the solvent. Differential thermal analysis (DSC) means that the glass transition temperature of the polymer is measured by a Perkin-ElmerPyrisl DSC differential scanning calorimeter, with a heating and cooling rate of 20°C/min, and two scans. Thermogravimetric loss (TGA) was measured with a Perkin-Elmer Pyris type 1 instrument. The light transmittance is measured with a Shimadzu UV-3600 ultraviolet-visible light-near-infrared spectrophotometer, and the measurement wavelength is 400-800 nm. Tensile test: The characterization of the mechanical properties of the polymer is carried out on the INSTRON 1121, Canton, MA instrument, with GB/T1040~1992 as the standard, the distance between the sample bars is 20.0mm, and the test speed is 5mm/min. Each sample Test at least 8 times to ensure the reliability of the data. Gel permeation chromatography (GPC) means that the molecular weight and molecular weight distribution index of the polymer are measured by waters1525 type gel permeation chromatography; using RI～Laser detector, the solvent is tetrahydrofuran (THF), the test temperature is 35 ° C, and the flow rate is 1.0mL/min, using PL EasiCal PS~1 as the standard sample.

Example 1

Add 1.5 liters of dicyclopentadiene and 1 gram of 2,6-di-tert-butyl-p-cresol successively to a 2-liter single-mouth bottle, and repeat the operation of vacuumizing the single-mouth bottle 3 times and filling with nitrogen; The one-necked bottle was heated to 200° C., and the contents in the one-necked bottle were reacted for 16 hours under stirring conditions.

After the reaction was finished, the obtained reaction product was cooled to 25° C., and 1100 g of unreacted matter with a low boiling point was obtained by distillation under reduced pressure. 1 liter of ethanol was added to the residue, and the filtrate was frozen for 3 hours after removing insoluble matter by filtration. After recrystallization, 389 grams of solid were obtained by filtration, and 315 grams of solid were obtained by recrystallization with 800 ml of ethanol again. The yield of the product prepared by the method provided in Example 1 of the present invention was 78%.

The product obtained above is carried out proton nuclear magnetic resonance spectrum detection, detection result is as Fig. 1, and Fig. 1 is the proton nuclear magnetic resonance spectrum figure of the product that the embodiment of the present invention 1 obtains, as can be seen from Fig. 1, the product that the embodiment of the present invention 1 obtains is A compound having the structure of formula II.

Example 2

Add 115 grams of dicyclopentadiene, 310 grams of methyl acrylate, and 1 gram of 2,6-di-tert-butyl-p-methylphenol successively in a 1-liter stainless steel autoclave, and repeatedly vacuumize the autoclave 3 times The operation of post-filling with nitrogen: the autoclave was heated to 200°C, and the contents in the autoclave were reacted for 16 hours under the condition of stirring.

After the reaction, the obtained reaction product was cooled to 25°C, and after standing for 12 hours, it was subjected to vacuum distillation at 65°C to collect unreacted dicyclopentadiene and cyclopentadiene; the product obtained after vacuum distillation Carry out vacuum distillation again at 100 DEG C, collect the cut during vacuum distillation, obtain 114 grams of products. The yield of the product prepared by the method provided in Example 2 of the present invention was 70%.

The above-mentioned obtained product is carried out proton nuclear magnetic resonance spectrum detection, detection result is as Fig. 2, and Fig. 2 is the proton nuclear magnetic resonance spectrum figure of the product that the embodiment of the present invention 2 obtains, as can be seen from Fig. 2, the product that the embodiment of the present invention 2 obtains is A compound having the structure of formula III.

Example 3

At room temperature, add 0.12g TCPD monomer and 0.01g NBMA monomer to a dry polymerization reaction bottle, add 50ml dichloromethane, stir thoroughly for 10min, weigh 2.5mg (G1 in a small ampoule, add 5ml dichloromethane, ultrasonic 3min , make fully dissolving, import in the polymerization bottle, polymerization begins, within five minutes, solution gradually becomes orange-yellow by purple, continues to stir for 7 hours, adds vinyl ethyl ether EVE (500 equivalents) to terminate polymerization, stirs for half an hour. The reaction solution was poured into anhydrous methanol, and a large amount of white polymer was separated out. The product obtained by filtration was washed 3 times with acetone and then put into a vacuum oven for 12 hours at 40°C. Weighed 0.13g polymer, and the yield was 100% .

In a dry autoclave, sequentially add 0.13g of the above polymer, 0.52g (4eqv) of 5% wet palladium carbon, a little BHT, 40ml of cyclohexane solvent, increase the pressure to 5.8Mp, raise the temperature to 130°C, stir for 24 hours, and filter Finally, the reaction solution was slowly added dropwise to 100ml industrial ethanol, a large amount of white solid was precipitated, filtered and drained, and the resulting white solid was re-dissolved with 40ml toluene for half an hour, then slowly added dropwise to 300ml industrial ethanol, filtered and drained , the process was repeated twice, then placed in a vacuum oven, and dried at 60° C. for 12 hours to obtain 0.12 g of the product with a yield of 92.3% and a purity greater than 99.9%.

The cyclic olefin copolymer obtained in Example 3 of the present invention is carried out to hydrogen nuclear magnetic resonance spectrum detection, and the detection result is shown in Figure 3, and Figure 3 is the hydrogen nuclear magnetic resonance spectrum figure of the polymerization reaction product and cycloolefin copolymer obtained in Example 3 of the present invention, Fig. In 3, curve 1 is the proton nuclear magnetic resonance spectrum of the polymerization reaction product obtained before the hydrogenation of embodiment 3 of the present invention, and curve 2 is the hydrogen nuclear magnetic resonance spectrum of the cycloolefin copolymer obtained after the hydrogenation of embodiment 3 of the present invention, as can be seen from Fig. 3 It can be seen that the double bond peak of the polymerization reaction product obtained in Example 3 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better.

The cycloolefin copolymer obtained in Example 3 of the present invention was tested by gel permeation chromatography. The test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 3 of the present invention was 1.4, and the weight average molecular weight was 7.0×10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 3 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4, and Figure 4 is the cyclic olefin copolymer obtained in Example 3 of the present invention, Example 4, Example 5, Example 6, and Example 7 The differential scanning calorimetry curve, as can be seen from curve 1 in Fig. 4, the cyclic olefin copolymer that the embodiment of the present invention 3 obtains does not have melting temperature, is amorphous state, the glass transition of the cyclic olefin copolymer that the embodiment of the present invention 3 obtains The temperature was 169°C. The cyclic olefin copolymer that the embodiment of the present invention 3 obtains is carried out thermogravimetric test, and test result is as Fig. 5, and Fig. 5 is embodiment 3 of the present invention, example 4, example 5, example 6, the cyclic olefin copolymer that example 7 obtains in Thermogravimetric curve in nitrogen, curve 1 in Fig. 5 is the thermogravimetric curve of the cyclic olefin copolymer that the embodiment of the present invention 3 obtains in nitrogen; As can be seen from Fig. 5, the cyclic olefin copolymer that the embodiment of the present invention 3 obtains is in 410 The decomposition rate at ℃ is 10%, and it has high thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in the embodiment of the present invention 3 are tested, and the test result is that the elongation at break of the cyclic olefin copolymer obtained in the embodiment 3 of the present invention is 2.5%, the tensile strength is 25MPa, and the tensile modulus It is 1600MPa.

The transparency of the cycloolefin copolymer obtained in Example 3 of the present invention is tested, and the test results are shown in Figure 6, and Figure 6 shows the light transmittance of the cycloolefin copolymer obtained in Example 3, Example 5 and Example 7 of the present invention, Curve 1 in FIG. 6 is the light transmittance of the cycloolefin copolymer obtained in Example 3 of the present invention. It can be seen from FIG. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 3 of the present invention is >91%.

Example 4

At room temperature, add 0.21g of TCPD monomer and 0.04g of NBMA monomer into a dry polymerization reaction bottle, add 50ml of dichloromethane, stir thoroughly for 10min, weigh 10mg (G1 in a small ampoule, add 5ml of dichloromethane, ultrasonic for 3min, Make fully dissolved, import in the polymerization bottle, polymerization starts, within five minutes, the solution gradually changes from purple to orange yellow, continue to stir for 7 hours, add vinyl ethyl ether EVE (500 equivalents) to terminate polymerization, stir for half an hour.Reaction The liquid was poured into anhydrous methanol, and a large amount of white polymers were separated out. The product obtained by filtration was washed 3 times with acetone and then dried in a vacuum oven at 40°C for 12 hours. Weighed 0.25g polymer, and the yield was 100%.

In a dry autoclave, sequentially add 0.25g of the above polymer, 1g (4eqv) of 5% wet palladium carbon, a little BHT, 40ml of cyclohexane solvent, increase the pressure to 5.8Mp, raise the temperature to 130°C, stir for 24 hours, and filter Slowly add the reaction solution dropwise into 100ml of industrial ethanol, a large amount of white solid is precipitated, filter and drain, heat and dissolve the resulting white solid with 40ml of toluene for half an hour, then slowly add dropwise to 300ml of industrial ethanol, filter and drain, This process was repeated twice and then placed in a vacuum oven, dried at 60°C for 12 hours to obtain 0.24g of product with a yield of 96% and a purity greater than 99.9%.

The cyclic olefin copolymer obtained in Example 4 of the present invention is subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection results are shown in Figure 7, and Figure 7 is the hydrogen nuclear magnetic resonance spectrum of the polymerization reaction product and cycloolefin copolymer obtained in Example 4 of the present invention, Figure 7 Curve 1 in 4 is the H NMR spectrum of the polymerization reaction product obtained before the hydrogenation of Example 4 of the present invention, and Curve 2 is the H NMR spectrum of the cycloolefin copolymer obtained after the hydrogenation of Example 4 of the present invention, as can be seen from Figure 7 It can be seen that the double bond peak of the polymerization reaction product obtained in Example 4 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better.

The cycloolefin copolymer obtained in Example 4 of the present invention was tested by gel permeation chromatography. The test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 4 of the present invention was 1.4, and the weight average molecular weight was 9.4×10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 4 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4, and Figure 4 shows the cyclic olefin copolymer obtained in Example 3, Example 4, Example 5, Example 6, and Example 7 of the present invention The differential scanning calorimetry curve, as can be seen from curve 2 in Fig. 4, the cyclic olefin copolymer that the embodiment of the present invention 4 obtains does not have melting temperature, is amorphous state, the glass transition of the cyclic olefin copolymer that the embodiment of the present invention 4 obtains The temperature was 154°C. The cyclic olefin copolymer that the embodiment of the present invention 4 obtains carries out thermogravimetric test, test result is as Fig. 5, and Fig. 5 is the embodiment of the present invention 3, example 4, example 5, example 6, the cyclic olefin copolymer that example 7 obtains in The thermogravimetric curve in nitrogen, curve 2 in Fig. 5 is the thermogravimetric curve of the cyclic olefin copolymer that the embodiment of the present invention 4 obtains in nitrogen; As can be seen from Fig. 5, the cyclic olefin copolymer that the embodiment of the present invention 4 obtains is in 413 The decomposition rate at ℃ is 10%, and it has high thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 4 of the present invention are tested, and the test result is that the elongation at break of the cyclic olefin copolymer obtained in Example 4 of the present invention is 2.8%, the tensile strength is 32MPa, and the tensile modulus It is 2200MPa.

Example 5

At room temperature, add 0.76g of TCPD monomer and 0.25g of NBMA monomer into a dry polymerization reaction bottle, add 50ml of dichloromethane, stir thoroughly for 10min, weigh 20mg (G1 in a small ampoule, add 5ml of dichloromethane, ultrasonic for 3min, Make fully dissolved, import in the polymerization bottle, polymerization starts, within five minutes, the solution gradually changes from purple to orange yellow, continue to stir for 7 hours, add vinyl ethyl ether EVE (500 equivalents) to terminate polymerization, stir for half an hour.Reaction The liquid was poured into anhydrous methanol, and a large amount of white polymers were separated out. The product obtained by filtration was washed 3 times with acetone and then dried in a vacuum oven at 40° C. for 12 hours. Weighed 1.01 g of polymers, and the yield was 100%.

In a dry autoclave, sequentially add 1.01g of the above polymer, 4g (4eqv) of 5% wet palladium carbon, a little BHT, 40ml of cyclohexane solvent, increase the pressure to 5.8Mp, raise the temperature to 130°C, stir for 24 hours, and filter Slowly add the reaction solution dropwise into 100ml of industrial ethanol, a large amount of white solid is precipitated, filter and drain, heat and dissolve the resulting white solid with 40ml of toluene for half an hour, then slowly add dropwise to 300ml of industrial ethanol, filter and drain, This process was repeated twice and then placed in a vacuum oven, dried at 60°C for 12 hours to obtain 9.9 g of product with a yield of 98.1% and a purity greater than 99.9%.

The cyclic olefin copolymer obtained in Example 5 of the present invention is subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection results are shown in Figure 8, and Figure 8 is the hydrogen nuclear magnetic resonance spectrum of the polymerization reaction product and cycloolefin copolymer obtained in Example 5 of the present invention, Figure 8 Curve 1 in 8 is the H NMR spectrum of the polymerization reaction product obtained before the hydrogenation of Example 5 of the present invention, and Curve 2 is the H NMR spectrum of the cycloolefin copolymer obtained after the hydrogenation of Example 5 of the present invention, as can be seen from Figure 8 It can be seen that the double bond peak of the polymerization reaction product obtained in Example 5 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better.

The cycloolefin copolymer obtained in Example 5 of the present invention was tested by gel permeation chromatography. The test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 5 of the present invention was 1.4, and the weight average molecular weight was 11.8×10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 5 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4, and Figure 4 is the cyclic olefin copolymer obtained in Example 3, Example 4, Example 5, Example 6, and Example 7 of the present invention The differential scanning calorimetry curve, as can be seen from curve 1 in Fig. 4, the cyclic olefin copolymer that the embodiment of the present invention 3 obtains does not have melting temperature, is amorphous state, the glass transition of the cyclic olefin copolymer that the embodiment of the present invention 5 obtains The temperature was 147°C. The cyclic olefin copolymer that the embodiment of the present invention 5 obtains is carried out thermogravimetric test, and test result is as Fig. 5, and Fig. 5 is the embodiment of the present invention 3, example 4, example 5, example 6, the cyclic olefin copolymer that example 7 obtains in The thermogravimetric curve in nitrogen, curve 3 in Fig. 5 is the thermogravimetric curve of the cyclic olefin copolymer that the embodiment of the present invention 5 obtains in nitrogen; As can be seen from Fig. 5, the cyclic olefin copolymer that the embodiment of the present invention 5 obtains is in 415 The decomposition rate at ℃ is 10%, and it has high thermal stability.

The mechanical properties of the cycloolefin copolymer obtained in Example 5 of the present invention are tested, and the test result is that the elongation at break of the cycloolefin copolymer obtained in Example 5 of the present invention is 3.1%, the tensile strength is 36MPa, and the tensile modulus It is 2400MPa.

The transparency of the cycloolefin copolymer obtained in Example 5 of the present invention is tested, and the test results are shown in Figure 6, and Figure 6 shows the light transmittance of the cycloolefin copolymer obtained in Example 3, Example 5 and Example 7 of the present invention, Curve 2 in Fig. 6 is the light transmittance of the cycloolefin copolymer obtained in Example 5 of the present invention. It can be seen from Fig. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 5 of the present invention is >91%.

Example 6

At room temperature, add 0.7g of TCPD monomer and 0.3g of NBMA monomer into a dry polymerization reaction bottle, add 50ml of dichloromethane, stir thoroughly for 10min, weigh 20mg (G1 in a small ampoule, add 5ml of dichloromethane, ultrasonic for 3min, Make fully dissolved, import in the polymerization bottle, polymerization starts, within five minutes, the solution gradually changes from purple to orange yellow, continue to stir for 7 hours, add vinyl ethyl ether EVE (500 equivalents) to terminate polymerization, stir for half an hour.Reaction The solution was poured into anhydrous methanol, and a large amount of white polymer was separated out. The product obtained by filtration was washed 3 times with acetone and then put into a vacuum oven at 40° C. for 12 hours. Weighed 1 g polymer, and the yield was 100%.

In a dry autoclave, sequentially add 1 g of the above-mentioned polymer, 4 g (4 eqv) of 5% wet palladium carbon, a little BHT, 40 ml of cyclohexane solvent, increase the pressure to 5.8 Mp, raise the temperature to 130 ° C, stir for 24 hours, and filter the The reaction solution was slowly added dropwise to 100ml of industrial ethanol, a large amount of white solid was precipitated, filtered and drained, and the resulting white solid was re-dissolved with 40ml of toluene for half an hour, then slowly added dropwise to 300ml of industrial ethanol, filtered and drained, the After the process was repeated twice, it was placed in a vacuum oven and dried at 60° C. for 12 hours to obtain 0.96 g of the product with a yield of 96% and a purity of greater than 99.9%.

The cyclic olefin copolymer obtained in Example 6 of the present invention is subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection result is shown in Figure 9, and Figure 9 is the hydrogen nuclear magnetic resonance spectrum of the polymerization reaction product and cycloolefin copolymer obtained in Example 6 of the present invention, Figure 9 Curve 1 in 9 is the H NMR spectrum of the polymerization reaction product obtained before the hydrogenation of Example 6 of the present invention, and Curve 2 is the H NMR spectrum of the cycloolefin copolymer obtained after the hydrogenation of Example 6 of the present invention, as can be seen from Figure 9 It can be seen that the double bond peak of the polymerization reaction product obtained in Example 6 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better.

The cycloolefin copolymer obtained in Example 6 of the present invention was tested by gel permeation chromatography. The test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 6 of the present invention was 1.4, and the weight average molecular weight was 13.9×10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 6 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4, and Figure 4 shows the cyclic olefin copolymer obtained in Example 3, Example 4, Example 5, Example 6, and Example 7 of the present invention The differential scanning calorimetry curve, as can be seen from curve 4 in Fig. 4, the cyclic olefin copolymer that the embodiment of the present invention 6 obtains does not have melting temperature, is amorphous state, the glass transition of the cyclic olefin copolymer that the embodiment of the present invention 6 obtains The temperature was 131°C. The cyclic olefin copolymer that the embodiment of the present invention 6 obtains carries out thermogravimetric test, test result is as Fig. 5, and Fig. 5 is the embodiment of the present invention 3, example 4, example 5, example 6, the cyclic olefin copolymer that example 7 obtains in The thermogravimetric curve in nitrogen, curve 4 in Fig. 5 is the thermogravimetric curve of the cyclic olefin copolymer that the embodiment of the present invention 6 obtains in nitrogen; As can be seen from Fig. 5, the cyclic olefin copolymer that the embodiment of the present invention 6 obtains is in 415 The decomposition rate at ℃ is 10%, and it has high thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 6 of the present invention are tested, and the test result is that the elongation at break of the cyclic olefin copolymer obtained in Example 6 of the present invention is 3.7%, the tensile strength is 402MPa, and the tensile modulus It is 2400MPa.

Example 7

At room temperature, add 0.6g of TCPD monomer and 0.44g of NBMA monomer into a dry polymerization reaction bottle, add 50ml of dichloromethane, stir thoroughly for 10min, weigh 20mg (G1 in a small ampoule, add 5ml of dichloromethane, ultrasonic for 3min, Make fully dissolved, import in the polymerization bottle, polymerization starts, within five minutes, the solution gradually changes from purple to orange yellow, continue to stir for 7 hours, add vinyl ethyl ether EVE (500 equivalents) to terminate polymerization, stir for half an hour.Reaction The solution was poured into anhydrous methanol, and a large amount of white polymer was separated out. The product obtained by filtration was washed 3 times with acetone and then dried in a vacuum oven at 40° C. for 12 hours. Weighed 1.04 g polymer, and the yield was 100%.

In a dry autoclave, add 1.04g of the above-mentioned polymer, 4g (4eqv) of 5% wet palladium carbon, a little BHT, 40ml of cyclohexane solvent in sequence, increase the pressure to 5.8Mp, raise the temperature to 130°C, stir for 24 hours, and filter Slowly add the reaction solution dropwise into 100ml of industrial ethanol, a large amount of white solid is precipitated, filter and drain, heat and dissolve the resulting white solid with 40ml of toluene for half an hour, then slowly add dropwise to 300ml of industrial ethanol, filter and drain, After repeating this process twice, put it into a vacuum oven and dry it at 60° C. for 12 hours to obtain 1 g of product with a yield of 96.1% and a purity of more than 99.9%.

The cycloolefin copolymer obtained in Example 7 of the present invention is subjected to hydrogen nuclear magnetic resonance spectrum detection, and the detection results are shown in Figure 10, and Figure 10 is a hydrogen nuclear magnetic resonance spectrum diagram of the polymerization reaction product and cycloolefin copolymer obtained in Example 7 of the present invention, Figure 10 Curve 1 in 10 is the H NMR spectrum of the polymerization reaction product obtained before the hydrogenation of Example 7 of the present invention, and curve 2 is the H NMR spectrum of the cycloolefin copolymer obtained after the hydrogenation of Example 7 of the present invention, as can be seen from Figure 10 It can be seen that the double bond peak of the polymerization reaction product obtained in Example 7 of the present invention completely disappears after the hydrogenation reaction, and the hydrogenation effect is better.

The cycloolefin copolymer obtained in Example 7 of the present invention was tested by gel permeation chromatography. The test results showed that the molecular weight distribution of the cycloolefin copolymer obtained in Example 7 of the present invention was 2.0, and the weight average molecular weight was 15.5×10 ⁴ g/mol.

The cyclic olefin copolymer obtained in Example 7 of the present invention is tested by differential thermal analysis, and the test results are shown in Figure 4, and Figure 4 shows the cyclic olefin copolymer obtained in Example 3, Example 4, Example 5, Example 6, and Example 7 of the present invention The differential scanning calorimetry curve, as can be seen from curve 5 in Fig. 4, the cyclic olefin copolymer that the embodiment of the present invention 7 obtains does not have melting temperature, is amorphous state, the glass transition of the cyclic olefin copolymer that the embodiment of the present invention 7 obtains The temperature was 105°C. The cyclic olefin copolymer that the embodiment of the present invention 5 obtains is carried out thermogravimetric test, and test result is as Fig. 5, and Fig. 5 is the embodiment of the present invention 3, example 4, example 5, example 6, the cyclic olefin copolymer that example 7 obtains in The thermogravimetric curve in nitrogen, curve 5 in Fig. 5 is the thermogravimetric curve of the cyclic olefin copolymer that the embodiment of the present invention 7 obtains in nitrogen; As can be seen from Fig. 5, the cyclic olefin copolymer that the embodiment of the present invention 7 obtains is in 418 The decomposition rate at ℃ is 10%, and it has high thermal stability.

The mechanical properties of the cyclic olefin copolymer obtained in Example 7 of the present invention are tested, and the test result is that the elongation at break of the cyclic olefin copolymer obtained in Example 7 of the present invention is 5.4%, the tensile strength is 50MPa, and the tensile modulus It is 2800MPa.

The transparency of the cycloolefin copolymer obtained in Example 7 of the present invention is tested, and the test results are shown in Figure 6, and Figure 6 shows the light transmittance of the cycloolefin copolymer obtained in Example 3, Example 5 and Example 7 of the present invention, Curve 3 in FIG. 6 is the light transmittance of the cycloolefin copolymer obtained in Example 7 of the present invention. It can be seen from FIG. 6 that the light transmittance of the cycloolefin copolymer obtained in Example 7 of the present invention is >91%.

Specifically, the feeding reaction conditions in Embodiment 3 to Embodiment 7 of the present invention are shown in Table 1;

Table 1

The descriptions of the above embodiments are only used to help understand the method and core idea of the present invention. It should be pointed out that for those skilled in the art, without departing from the principle of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

1. a cycloolefin copolymer has a structure shown in formula (I), Among them, 140≤m≤220, 170≤n≤280, 1≤x≤4. 2. The cycloolefin copolymer according to claim 1, characterized in that, the m is 170≤m≤190. 3. The cycloolefin copolymer according to claim 1, characterized in that, said n is 170≤n≤190. 4. The cycloolefin copolymer according to claim 1, characterized in that, said x is 1≤x≤2. 5. A preparation method of cycloolefin copolymer, comprising: 1) Polymerize the compound having the structure of formula (II) and the compound of formula (III) under the action of a catalyst of the structure of formula (IV) to obtain a polymer; Among them, x is 1≤x≤4; 2) The obtained polymer is subjected to a hydrogenation reduction reaction with a heterogeneous metal catalyst to obtain a cycloolefin copolymer. 6. The preparation method according to claim 5, characterized in that the molar ratio of the compound of the formula (II) to the compound of the formula (III) is (9-1):1. 7. The preparation method according to claim 5, characterized in that, the solvent for the polymerization reaction is C1-C15 alkanes, C1-C15 halogenated hydrocarbons, C3-C15 cycloalkanes or C5-C20 aromatic hydrocarbons. 8 . The preparation method according to claim 5 , characterized in that, the temperature of the polymerization reaction is 10-50° C., and the time of the polymerization reaction is 4-12 hours. 9. preparation method according to claim 5, is characterized in that, the compound of described formula (II) structure and the molar ratio of the compound of formula (III) structure and the catalyzer of described formula (IV) structure It is (25～1000):1. 10 . The preparation method according to claim 5 , wherein the heterogeneous metal catalyst is 5-10% wet palladium carbon, 10% Pd/C, Pd/C/BaSO ₄ or Pt/SiO ₂ .