CN118027264A - Cycloolefin copolymer and preparation method thereof - Google Patents

Abstract

The present invention belongs to the technical field of novel high-end polyolefins, and discloses a cycloolefin copolymer and a preparation method thereof. The structural formula of the cycloolefin copolymer is In the formula, 1≤X/Y≤9, 2≤X/Z≤90, 25≤n≤5000, 1≤m≤10; the preparation method is: ternary copolymerization of olefin monomer, cycloolefin monomer and comonomer containing high refractive index group to obtain cycloolefin copolymer; wherein the structural formula of olefin monomer is The structural formula of cycloolefin monomer is The structural formula of the comonomer containing a high refractive index group is The invention solves the technical problem that the third monomer with high refractive index introduced in the prior art generates side reactions, thereby reducing the catalytic activity of the catalyst and widening the molecular weight distribution, and has good heat resistance and high refractive index.

Description

A cyclic olefin copolymer and preparation method thereof

Technical Field

The invention belongs to the technical field of novel high-end polyolefins, and in particular relates to a cycloolefin copolymer and a preparation method thereof.

Background Art

As a low-cost, easy-to-prepare, easy-to-process and recyclable material, polyolefins are widely used in daily life, with an annual market size of hundreds of billions of dollars. In addition to ordinary polyolefin materials, new high-end polyolefin materials are also developing rapidly. Polyolefin materials containing cyclic olefins in the main chain are usually prepared by ring-opening metathesis polymerization or addition coordination polymerization. Among them, the preparation of cyclic olefin copolymers is mainly prepared by addition coordination polymerization. Cyclic olefin copolymers are also commercially known as COC.

Cyclic olefin copolymers (COC) prepared by prior art are generally amorphous polymer materials obtained by direct addition copolymerization of ethylene or α-olefins and cycloolefin monomers under metallocene catalysis, and have excellent optical properties such as high transparency, low birefringence, and high transmittance, as well as electrical properties, adhesion properties, and thermal properties such as low dielectric loss, low water absorption, low adhesion, and high heat resistance, among which the optical properties are the most outstanding. Cyclic olefin copolymers do not require hydrogenation treatment, and the important indicators of optical properties such as refractive index, dispersion, and transmittance can be improved by regulating the chain segment ratio and sequence distribution of cycloolefin monomers and comonomers. Currently commercialized cycloolefin copolymers include the Topas series of Japan Polyplastics using norbornene (NB) as the cycloolefin monomer, and the APEL series of Japan Mitsui Chemicals using tetracyclododecene (TCD) as the cycloolefin monomer. The refractive index of the cycloolefin copolymer of the Topas series is up to 1.53, and TCD has an additional NB alicyclic ring compared to NB, which has a higher molar refractive index. Therefore, the refractive index of the cycloolefin copolymer obtained from the APEL series will also be higher than that of the cycloolefin copolymer of the Topas series. The refractive index of the cycloolefin copolymer obtained from the APEL series can reach 1.544. For lens materials, cycloolefin copolymers with high refractive index are high-quality substitutes for traditional optical materials PMMA and PC in many aspects.

The prior art mainly focuses on introducing a third comonomer containing a high refractive index group into the ethylene/cycloolefin copolymer chain, thereby increasing the refractive index of the cycloolefin copolymer. However, the introduced third comonomer will cause side reactions during the polymerization process. For example, patent CN115028763B discloses a cycloolefin copolymer and a preparation method thereof. The patent uses a variety of polar comonomers with heteroatoms, and ternary copolymerizes with ethylene and cycloolefin monomers under metallocene catalysis to obtain a cycloolefin terpolymer with a refractive index of 1.55-1.6. However, the third comonomer provided by the method contains heteroatoms such as N, O, and S, which will coordinate to the metal active center of the metallocene catalyst, resulting in a decrease in catalytic activity, which ranges from 1.5×10 ⁵ g·mol ^-1 ·h ^{-1 to} 9.3×10 ⁵ g·mol ^-1 ·h ^-1 .

Patent JP201838858 adds aromatic monomers without heteroatoms to ethylene or α-olefin/cycloolefin copolymerization, which can also significantly increase the refractive index of the terpolymer, up to 1.581. However, the document "Macromolecules, 2022, 55: 125-132." shows that when an olefin monomer containing an aromatic ring or spirocyclic structure is used as a comonomer of a cycloolefin copolymer, the tertiary carbon atom at the terminal node of the olefin monomer long chain also has an unsubstituted active hydrogen atom, which can easily generate a carbon cation and easily couple with another polymer chain, resulting in a high molecular weight copolymer, which widens its molecular weight distribution, which will seriously affect the subsequent processing performance of the copolymer.

Summary of the invention

The purpose of the present invention is to solve the problems existing in the prior art and provide a method for preparing a cycloolefin copolymer. The third monomer involved in the copolymerization of the present invention is an aromatic monomer containing only one olefin chain substituted with a tertiary carbon atom at the end, and the hydrogen atom connected to the tertiary carbon atom is replaced by a group with a high molar refractive index. The monomer does not contain active hydrogen atoms, thereby avoiding cross-linking during the polymerization process and further improving the refractive index. The overall structure also does not contain heteroatoms that poison the transition metal center, and the catalytic activity during the polymerization process can be maintained.

To achieve the above object, the technical solution adopted by the present invention is as follows:

A method for preparing a cycloolefin copolymer comprises subjecting an olefin monomer, a cycloolefin monomer and a comonomer containing a high refractive index group to a ternary copolymerization reaction to prepare the cycloolefin copolymer. The structural formula of the olefin monomer is as follows:

R ₁ is a hydrogen atom, -CH ₃ or -(CH ₂ ) _a CH ₃ , 1≤a≤17;

The structural formula of cycloolefin monomer is as follows:

In the formula, i is 0, 1 or 2, and R ₂ -R ₅ are each independently selected from a hydrogen atom, an alkyl group and a cycloalkyl group;

The structural formula of the comonomer containing a high refractive index group is as follows:

In the formula, 1≤m≤10, R ₆ -R ₁₃ are independently selected from hydrogen atom, alkyl, aryl, silane, wherein R _b and R _b+1 are bonded or not bonded, 6≤b≤12, R ₁₄ is selected from alkyl, aryl and silane, the number of carbon atoms is 1-14, and the dotted line indicates whether the position is bonded or not bonded.

The present invention can avoid side reactions during the ternary copolymerization process, because _R14 replaces the active hydrogen atom originally present at the position, thereby avoiding the separation of the hydrogen atom to generate a carbon cation, thereby causing coupling.

As the preferred technical solution:

In the method for preparing a cyclic olefin copolymer as described above, the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene.

In the method for preparing a cycloolefin copolymer as described above, the cycloolefin monomer is one or more of norbornene, tetracyclododecene and 1,4,5,8,9,10-trimethylene dodecahydroanthracene.

In the method for preparing a cycloolefin copolymer as described above, the structural formula of the comonomer containing a high refractive index group is one of Formulas 1-28, and Formulas 1-28 are as follows:

In the method for preparing a cycloolefin copolymer as described above, the molar ratio of the cycloolefin monomer, the olefin monomer and the comonomer containing a high refractive index group is 1.5-7.5:1:0.5-4.5; the temperature of the ternary copolymerization reaction is 20-130°C and the time is 0.5-180min.

In the method for preparing a cycloolefin copolymer as described above, the terpolymerization reaction is carried out in an inert organic solvent and under the action of a catalytic system consisting of a main catalyst and a co-catalyst.

In the method for preparing a cycloolefin copolymer as described above, the main catalyst is a metallocene catalyst, and the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000-200000; the co-catalyst is an alkyl aluminum co-catalyst or an organic boron co-catalyst, and the molar ratio of the alkyl aluminum co-catalyst to the main catalyst is 10-1000:1, and the molar ratio of the organic boron co-catalyst to the main catalyst is 1.0-1.5:1.

In the above-mentioned method for preparing a cycloolefin copolymer, the structural formula of the metallocene catalyst is one of Formulas A1-A6, and Formulas A1-A6 are as follows:

In the method for preparing a cycloolefin copolymer as described above, during the ternary copolymerization reaction, the catalytic activity of the catalytic system reaches 9.0×10 ⁸ to 34×10 ⁸ g·mol ^-1 ·h ^-1 , which is a high-activity catalytic system that meets industrial requirements, and there is no heteroatom poisoning effect in the system.

The present invention also provides a cycloolefin copolymer prepared by the method for preparing a cycloolefin copolymer as described in any of the preceding items, and the structural formula is as follows:

In the formula, 1≤X/Y≤9, 2≤X/Z≤90, 25≤n≤5000, 1≤m≤10.

As the preferred technical solution:

The cycloolefin copolymer as described above has an insertion rate of a comonomer containing a high refractive index group in the cycloolefin copolymer of more than 1 mol%, thereby ensuring that the cycloolefin copolymer has a high refractive index, and an insertion rate of a cycloolefin monomer of more than 10 mol%, thereby ensuring that the cycloolefin copolymer has optical indicators such as rigidity and high transparency; the _Mn value of the cycloolefin copolymer is 1.0×10 ⁴ -35.0×10 ⁴ g/mol, the molecular weight distribution curve is a narrow single peak, the PDI is 1.57-2.64, showing good film-forming properties, and the _Tg is 60-200°C. The presence of the comonomer containing a high refractive index group can significantly reduce the _Tg of the cycloolefin copolymer linearly, the thermal weight loss temperature of 5wt% is 390-401°C, the visible light transmittance is 86-91%, and the refractive index is 1.550-1.610, which exceeds the refractive index of COC produced by Topas and APEL on the market, which is caused by the introduction of the high refractive index group.

Beneficial effects:

(1) The method for preparing the cycloolefin copolymer provided by the present invention selects a third monomer whose high refractive index group is far away from the carbon-carbon double bond, and the catalyst system used can take into account both high copolymerization activity and copolymerization ability.

(2) The present invention solves the technical problem that the third monomer with a high refractive index introduced in the prior art undergoes a side reaction, thereby reducing the catalytic activity of the catalyst and widening the molecular weight distribution, and has good heat resistance and a high refractive index.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a ¹ H NMR spectrum (CDCl ₃ , 298K) of the comonomer containing a high refractive index group in Example 2 of the present invention;

FIG2 is a ¹³ C NMR spectrum (CDCl ₃ , 298K) of the comonomer containing a high refractive index group in Example 2 of the present invention;

FIG3 is a ¹³ C NMR spectrum (C ₂ D ₂ Cl ₄ , 368K) of the cycloolefin copolymer prepared in Example 2 of the present invention;

FIG4 is a GPC curve diagram of the cycloolefin copolymer prepared in Example 2 of the present invention;

FIG5 is a DSC curve diagram of the cycloolefin copolymer prepared in Example 2 of the present invention.

DETAILED DESCRIPTION

The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

The structural formulas of the metallocene catalysts corresponding to A1-A6 in the examples are shown in the following table:

Table 1

The reaction equation of the comonomer containing a high refractive index group is as follows:

The specific preparation process of the comonomer containing a high refractive index group is as follows:

(1) Weigh 30 mmol of the raw material and place it in a standard Schlenk double-necked reaction flask. Replace the atmosphere in the reaction flask with nitrogen (CAS: 7727-37-9) while stirring. Add 150 mL of purified anhydrous ether (CAS: 109-72-8) solvent into the reaction flask. After the raw material is completely dissolved, place the reaction flask in an ice-water bath and slowly drop 33 mmol of n-butyl lithium solution (solute: n-butyl lithium (CAS: 109-72-8), solvent: n-hexane, concentration: 2.5 M) at 0°C. Then, return the reaction system to room temperature, stir the reaction for 4 hours, and then cool the reaction system to -78°C. Add 30 mmol of CH ₂ =CH(CH ₂ ) _m Br was slowly added dropwise to the reaction flask, the reaction system was restored to room temperature, and the reaction was fully reacted for 12 hours; 50 mL of deionized water was added dropwise to the reaction flask in an ice-water bath at 0°C to quench the reaction; the organic phase was then separated by extraction with anhydrous ether solvent, dried with anhydrous sodium sulfate (CAS 15124-09-1), dried under reduced pressure and filtered to obtain product L1;

(2) Under nitrogen atmosphere, 20 mmol of L1 obtained above and 80 mL of purified anhydrous ether solvent were added to a standard Schlenk double-necked reaction bottle, and then the reaction bottle was placed in an ice-water bath, and 22 mmol of n-butyl lithium solution (solute is n-butyl lithium (CAS 109-72-8), solvent is n-hexane, concentration is 2.5 M) was slowly added dropwise at 0°C, and then the reaction system was restored to room temperature, stirred and reacted for 4 hours, and then the reaction system was cooled to -78°C, and 20 mmol of R ₁₄ Br was slowly added dropwise to the reaction bottle, and the reaction system was restored to room temperature and reacted for 12 hours; in an ice-water bath at 0°C, 50 mL of deionized water was added dropwise to the reaction bottle to quench the reaction, and the organic phase was separated by extraction with anhydrous ether solvent, and then dried with anhydrous sodium sulfate (CAS 15124-09-1), dried under reduced pressure and filtered to obtain product L2, which is a copolymer monomer containing a high refractive index group.

The structural formulas of the comonomers containing high refractive index groups corresponding to B1-B28 in the examples and the reaction raw materials are shown in the following table:

Table 2

The following are the test methods for each performance in the embodiments:

Catalytic activity: calculated by the formula: Wherein, Activity is the copolymerization catalytic activity, in kg·mol ^-1 ·h ^-1 ; W _polymer is the mass of the obtained copolymer, in kg; [M] is the amount of the main catalyst used, in mol; t is the polymerization time, in h.

Number average molecular weight ( _Mn ) and molecular weight distribution (PDI): The number average molecular weight ( _Mn ) and molecular weight distribution (PDI) of the prepared cycloolefin copolymer were determined using a high temperature gel permeation chromatograph (PLGPC-220); the high temperature gel permeation chromatograph was calibrated using a single distribution polystyrene standard, K = 1.78 × ^10-4 , α = 0.70, and the specific operation was as follows: 10 mg of the cycloolefin copolymer was placed in 10 mL of 1,2,4-trichlorobenzene, heated to 150°C on a constant temperature oscillator and fully dissolved for 12 hours, then the cycloolefin copolymer solution was filtered into a special sample bottle using a special filter gun, and discharged to an automatic sampler, and the test program was set to test at a flow rate of 1.0 mL/min, and the test results were analyzed using Cirrus software.

Nuclear magnetic resonance spectra: ¹ H NMR and ¹³ C NMR tests were performed using a fully digital nuclear magnetic resonance spectrometer (Bruker advance III 600 MHz), using deuterated chloroform or 1,1,2,2-deuterated tetrachloroethane as solvent (CDCl ₃ , δ: H, 7.26 ppm; C, 77.16 ppm; 1,1,2,2-C ₂ D ₂ Cl ₄ , δ: H, 6.00 ppm; C, 74.47 ppm), and the test results were analyzed in MestReNova software; ¹ H NMR determination: 10 mg of sample was dissolved in 0.5 mL of deuterated reagent and tested after full dissolution; ¹³ C NMR determination: 100 mg of sample was dissolved in 0.5 mL of deuterated reagent to make it fully dissolved, and ^{the 13} C NMR of small molecules was tested at 298 K; the ¹³ C NMR of polymers was quantitatively tested at 368 K under liquid nitrogen protection.

Glass transition temperature (T _g ): The glass transition temperature (T _g ) of the copolymer was determined using a differential scanning calorimeter TA DSC Q2000. 5 mg of the cycloolefin copolymer was weighed and placed in an aluminum crucible. The test was performed under a nitrogen atmosphere. The heating rate was set to 10°C/min, the heating and cooling range was 40°C to 250°C, and the program set the heating and cooling sequence to heating-cooling-heating. First, the sample was kept at a constant temperature at 40°C for 2 min, then the temperature was increased from 40°C to 250°C at a heating rate of 10°C/min to eliminate the thermal history, then the temperature was decreased from 250°C to 40°C at a cooling rate of 10°C/min and kept at a constant temperature for 2 min again, and finally the temperature was increased from 40°C to 250°C again, the heat flow curve of the second heating was retained, and then the data of the two heating processes were taken for analysis in the Universal Analysis software, and the glass transition temperature was obtained by calculating the midline of the calibration slope.

Thermal weight loss 5wt% temperature: Use a thermogravimetric analyzer (NETZSCH TG 209F1 Libra) to measure the thermal weight loss 5wt% temperature of the obtained polymer; weigh 1-5 mg of cycloolefin copolymer and place it in an alumina crucible, set the test parameters, test in a nitrogen atmosphere, set the heating rate to 10℃/min, and the test temperature range is 35℃ to 800℃.

Refractive index: The polymer film was prepared by solvent coating method; 0.5 g of cycloolefin copolymer was taken into a single-mouth bottle. To ensure that it was fully dissolved, 20 ml of toluene was added and placed in a 60°C oil bath for 3 h. After it was fully dissolved, it was ultrasonicated for 3 h. Then it was poured into a surface dish with a diameter of 60/70 mm and covered with a layer of perforated tin foil. To ensure that the toluene solvent evaporated evenly and the product did not precipitate, the surface dish was placed in a blast oven at 40°C for 12 h. After the product was formed into a film, a polymer film with a thickness of 150 μm was obtained. It was carefully taken out with tweezers. Before testing; use Abbe refractometer (WAY-2WAJ) to measure the refractive index of the obtained polymer film. The instrument should be calibrated before use, then put the instrument in a bright place, wipe the crystal surface with acetone, add 1-2 drops of naphthalene bromide on the stage, put the calibration glass block, adjust the reading knob and the dispersion compensator until the light and dark boundary coincides with the intersection of the crosshairs. If the reading is inconsistent with the indication on the calibration glass block, use a hexagonal wrench to adjust the instrument calibration. After calibration, cut the film into a size of 1cm×2cm and perform test readings. Read each sample three times and take the average value.

Visible light transmittance: The polymer film was prepared by solvent coating method; 0.5 g of cycloolefin copolymer was taken into a single-mouth bottle. To ensure that it was fully dissolved, 20 ml of toluene was added and placed in a 60°C oil bath for 3 hours. After it was fully dissolved, it was ultrasonicated for 3 hours. Then it was poured into a watch glass with a diameter of 60/70 mm and covered with a layer of perforated tin foil. To ensure that the toluene solvent evaporated evenly and the product did not precipitate, the watch glass was placed in a blast oven at 40°C for 12 hours. After the product formed a film, A polymer film with a thickness of 150 μm is obtained, which is carefully taken out with tweezers for testing. The visible light transmittance of the obtained polymer film is measured using an ultraviolet-visible-near-infrared spectrophotometer (Lambda950). The obtained polymer film is placed in a vacuum oven at 40°C for 3 hours. After sufficient drying, the film is cut into 15 mm × 30 mm slices for testing. The ultraviolet-visible-near-infrared spectrophotometer is preheated and calibrated, and the test wavelength is set to 400 to 800 nm for testing.

Example 1

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B4 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A1 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 20° C. for 0.5 min to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 14, and n is 273); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000, the molar ratio of the co-catalyst to the main catalyst is 10:1, and the catalytic activity of the catalytic system reaches 11.74×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 2.9 mol%, and the insertion rate of the cycloolefin monomer is 54.8 mol%. The _Mn value of the cycloolefin copolymer is 15.94× ¹⁰⁴ g/mol, the PDI is 2.64, the _Tg is 200℃, the thermal weight loss temperature of 5wt% is 390℃, the visible light transmittance is 90%, and the refractive index is 1.550.

Example 2

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B6 in Table 2 (as shown in Figures 1 and 2);

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A1 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 40° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 20, and n is 286); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.5:1, and the catalytic activity of the catalytic system reaches 9.58×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer (as shown in Figures 3 to 5) is 2.4 mol%, and the insertion rate of the cycloolefin monomer is 53.1 mol%; the _Mn value of the cycloolefin copolymer is 14.69× ¹⁰⁴ g/mol, the PDI is 1.57, the _Tg is 162°C, the thermal weight loss temperature of 5wt% is 395°C, the visible light transmittance is 91%, and the refractive index is 1.551.

Example 3

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B5 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A2 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 4:1:1 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 60° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 484); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.2:1, and the catalytic activity of the catalytic system reaches 12.32×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 6.8 mol%, and the insertion rate of the cycloolefin monomer is 53.0 mol%. The _Mn value of the cycloolefin copolymer is 24.83× ¹⁰⁴ g/mol, the PDI is 1.68, the _Tg is 166°C, the thermal weight loss 5wt% temperature is 392°C, the visible light transmittance is 91%, and the refractive index is 1.578.

Example 4

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B11 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A2 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 3:1:2.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 80° C. for 80 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 357); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.5:1, and the catalytic activity of the catalytic system reaches 10.03×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 8.1 mol%, and the insertion rate of the cycloolefin monomer is 40.6 mol%. The _Mn value of the cycloolefin copolymer is 18.30× ¹⁰⁴ g/mol, the PDI is 1.91, the _Tg is 133°C, the thermal weight loss temperature of 5wt% is 395°C, the visible light transmittance is 90%, and the refractive index is 1.580.

Example 5

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B7 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A3 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 2:1:3 into an inert organic solvent, and adding a catalytic system consisting of a main catalyst and a co-catalyst, and reacting at 100° C. for 120 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 2, X/Z is 2, and n is 251); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 800:1, and the catalytic activity of the catalytic system reaches 9.00×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 20.7 mol%, and the insertion rate of the cycloolefin monomer is 26.8 mol%. The _Mn value of the cycloolefin copolymer is 14.70× ¹⁰⁴ g/mol, the PDI is 2.27, the _Tg is 109°C, the thermal weight loss 5wt% temperature is 392°C, the visible light transmittance is 90%, and the refractive index is 1.560.

Example 6

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: ethylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B12 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A3 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 1.5:1:4.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 180 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 3, X/Z is 4, and n is 104); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 1000:1, and the catalytic activity of the catalytic system reaches 14.78×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 18.5 mol%, and the insertion rate of the cycloolefin monomer is 20.3 mol%. The _Mn value of the cycloolefin copolymer is 6.13× ¹⁰⁴ g/mol, the PDI is 1.88, the _Tg is 110°C, the thermal weight loss 5wt% temperature is 394°C, the visible light transmittance is 86%, and the refractive index is 1.573.

Example 7

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-butene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B3 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A4 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 20° C. for 0.5 min to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 9, and n is 5000); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000, the molar ratio of the co-catalyst to the main catalyst is 10:1, and the catalytic activity of the catalytic system reaches 14.39×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 5.6 mol%, and the insertion rate of the cycloolefin monomer is 42.4 mol%. The _Mn value of the cycloolefin copolymer is 25.64× ¹⁰⁴ g/mol, the PDI is 2.02, the _Tg is 183°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 90%, and the refractive index is 1.610.

Example 8

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-pentene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B9 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A4 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 40° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 4, and n is 138); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1:1, and the catalytic activity of the catalytic system reaches 10.99×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 6.9 mol%, and the insertion rate of the cycloolefin monomer is 64 mol%. The _Mn value of the cycloolefin copolymer is 7.98× ¹⁰⁴ g/mol, the PDI is 1.83, the _Tg is 153°C, the thermal weight loss 5wt% temperature is 393°C, the visible light transmittance is 90%, and the refractive index is 1.558.

Embodiment 9

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-hexene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B8 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A5 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 4:1:1.5 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 80° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 2, X/Z is 9, and n is 582); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.2:1, and the catalytic activity of the catalytic system reaches 9.56×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 6.9 mol%, and the insertion rate of the cycloolefin monomer is 38.2 mol%. The _Mn value of the cycloolefin copolymer is 33.72× ¹⁰⁴ g/mol, the PDI is 1.75, the _Tg is 141°C, the thermal weight loss temperature of 5wt% is 395°C, the visible light transmittance is 89%, and the refractive index is 1.581.

Example 10

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-heptene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B10 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A5 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 1.5:1:4.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 180 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 2, X/Z is 3, and n is 30); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 800:1, and the catalytic activity of the catalytic system reaches 13.56×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 19.7 mol%, and the insertion rate of the cycloolefin monomer is 21.8 mol%. The _Mn value of the cycloolefin copolymer is 1.93× ¹⁰⁴ g/mol, the PDI is 2.26, the _Tg is 112°C, the thermal weight loss 5wt% temperature is 392°C, the visible light transmittance is 86%, and the refractive index is 1.572.

Embodiment 11

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-octene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B1 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A6 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:1.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 60° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 4, and n is 334); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1:1, and the catalytic activity of the catalytic system reaches 9.88×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 10.3 mol%, and the insertion rate of the cycloolefin monomer is 47.8 mol%. The _Mn value of the cycloolefin copolymer is 9.98× ¹⁰⁴ g/mol, the PDI is 1.86, the _Tg is 135°C, the thermal weight loss 5wt% temperature is 391°C, the visible light transmittance is 91%, and the refractive index is 1.562.

Example 12

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-nonene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B2 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A6 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7:1:1 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 5, and n is 687); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 1000:1, and the catalytic activity of the catalytic system reaches 11.39×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 7.4 mol%, and the insertion rate of the cycloolefin monomer is 56.7 mol%. The _Mn value of the cycloolefin copolymer is 10.52× ¹⁰⁴ g/mol, the PDI is 2.26, the _Tg is 107°C, the thermal weight loss temperature of 5wt% is 393°C, the visible light transmittance is 90%, and the refractive index is 1.551.

Example 13

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-decene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B16 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A1 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 20° C. for 0.5 min to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 9, X/Z is 90, and n is 359); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000, the molar ratio of the co-catalyst to the main catalyst is 10:1, and the catalytic activity of the catalytic system reaches 23.16×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 1.0 mol%, and the insertion rate of the cycloolefin monomer is 10.0 mol%. The _Mn value of the cycloolefin copolymer is 19.80× ¹⁰⁴ g/mol, the PDI is 1.81, the _Tg is 153°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 88%, and the refractive index is 1.589.

Embodiment 14

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-undecene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B18 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A1 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 40° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 12, and n is 422); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.5:1, and the catalytic activity of the catalytic system reaches 34.0×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 2.7 mol%, and the insertion rate of the cycloolefin monomer is 65.2 mol%. The _Mn value of the cycloolefin copolymer is 22.21× ¹⁰⁴ g/mol, the PDI is 1.79, the _Tg is 148°C, the thermal weight loss temperature of 5wt% is 393°C, the visible light transmittance is 89%, and the refractive index is 1.550.

Embodiment 15

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-dodecene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B17 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A2 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 4:1:1 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 60° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 9, and n is 319); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.2:1, and the catalytic activity of the catalytic system reaches 28.92×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 5.2 mol%, and the insertion rate of the cycloolefin monomer is 50.6 mol%. The _Mn value of the cycloolefin copolymer is 16.7× ¹⁰⁴ g/mol, the PDI is 2.51, the _Tg is 139°C, the thermal weight loss temperature of 5wt% is 400°C, the visible light transmittance is 90%, and the refractive index is 1.563.

Example 16

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: propylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B23 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A2 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 3:1:2.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 80° C. for 80 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 305); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.5:1, and the catalytic activity of the catalytic system reaches 27.96×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 8.4 mol%, and the insertion rate of the cycloolefin monomer is 47.1 mol%. The _Mn value of the cycloolefin copolymer is 15.93× ¹⁰⁴ g/mol, the PDI is 1.64, the _Tg is 127°C, the thermal weight loss 5wt% temperature is 392°C, the visible light transmittance is 91%, and the refractive index is 1.588.

Embodiment 17

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: propylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B19 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A3 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 2:1:3 into an inert organic solvent, and adding a catalytic system consisting of a main catalyst and a co-catalyst, and reacting at 100° C. for 120 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 5, and n is 249); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 800:1, and the catalytic activity of the catalytic system reaches 12.36×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 11.6 mol%, and the insertion rate of the cycloolefin monomer is 30.8 mol%. The _Mn value of the cycloolefin copolymer is 14.54× ¹⁰⁴ g/mol, the PDI is 2.19, the _Tg is 115°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 90%, and the refractive index is 1.600.

Embodiment 18

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: propylene;

Cyclic olefin monomer: norbornene;

Comonomer containing a high refractive index group: the structural formula is B24 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A3 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 180 minutes to obtain a cycloolefin copolymer (structural formula: In the formula, X/Y is 8, X/Z is 46, and n is 182); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 1000:1, and the catalytic activity of the catalytic system reaches 9.6×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 1.9 mol%, and the insertion rate of the cycloolefin monomer is 87.2 mol%. The _Mn value of the cycloolefin copolymer is 10.63× ¹⁰⁴ g/mol, the PDI is 2.17, the _Tg is 101°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 87%, and the refractive index is 1.591.

Embodiment 19

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: propylene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B15 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A4 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 20° C. for 0.5 min to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 7, and n is 169); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000, the molar ratio of the co-catalyst to the main catalyst is 10:1, and the catalytic activity of the catalytic system reaches 25.2×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 5.9 mol%, and the insertion rate of the cycloolefin monomer is 56.4 mol%. The _Mn value of the cycloolefin copolymer is 10.4× ¹⁰⁴ g/mol, the PDI is 1.77, the _Tg is 120℃, the thermal weight loss temperature of 5wt% is 401℃, the visible light transmittance is 90%, and the refractive index is 1.574.

Embodiment 20

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: propylene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B21 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A4 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 40° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 10, and n is 25); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1:1, and the catalytic activity of the catalytic system reaches 11.56×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 4.4 mol%, and the insertion rate of the cycloolefin monomer is 53.3 mol%. The _Mn value of the cycloolefin copolymer is 1× ¹⁰⁴ g/mol, the PDI is 1.83, the _Tg is 134°C, the thermal weight loss temperature of 5wt% is 398°C, the visible light transmittance is 90%, and the refractive index is 1.566.

Embodiment 21

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-tridecene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B20 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A5 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 4:1:1.5 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 80° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 590); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1:1, and the catalytic activity of the catalytic system reaches 9.86×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 8.5 mol%, and the insertion rate of the cycloolefin monomer is 45.6 mol%. The _Mn value of the cycloolefin copolymer is 35× ¹⁰⁴ g/mol, the PDI is 1.68, the _Tg is 102°C, the thermal weight loss 5wt% temperature is 395°C, the visible light transmittance is 89%, and the refractive index is 1.553.

Embodiment 22

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-tetradecene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B22 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A5 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 1.5:1:4.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 180 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 2, X/Z is 6, and n is 300); wherein, the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 800:1, and the catalytic activity of the catalytic system reaches 13.22×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 11.4 mol%, and the insertion rate of the cycloolefin monomer is 25.4 mol%. The _Mn value of the cycloolefin copolymer is 19.53× ¹⁰⁴ g/mol, the PDI is 1.84, the _Tg is 60℃, the thermal weight loss 5wt% temperature is 392℃, the visible light transmittance is 86%, and the refractive index is 1.580.

Embodiment 23

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-pentadecene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B13 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A6 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:1.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 60° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 4, and n is 892); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.2:1, and the catalytic activity of the catalytic system reaches 9.86×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 9.5 mol%, and the insertion rate of the cycloolefin monomer is 50.2 mol%. The _Mn value of the cycloolefin copolymer is 11.26× ¹⁰⁴ g/mol, the PDI is 1.71, the _Tg is 151°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 87%, and the refractive index is 1.571.

Embodiment 24

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-hexadecene;

Cycloolefin monomer: tetracyclododecene;

Comonomer containing a high refractive index group: the structural formula is B14 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A6 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7:1:1 into an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 60 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 722); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 1000:1, and the catalytic activity of the catalytic system reaches 14.13×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 6.6 mol%, and the insertion rate of the cycloolefin monomer is 54.8 mol%. The _Mn value of the cycloolefin copolymer is 13.87× ¹⁰⁴ g/mol, the PDI is 1.83, the _Tg is 98°C, the thermal weight loss temperature of 5wt% is 396°C, the visible light transmittance is 88%, and the refractive index is 1.582.

Embodiment 25

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-heptadecene;

Cycloolefin monomer: 1,4,5,8,9,10-trimethylene dodecahydroanthracene;

Comonomer containing a high refractive index group: the structural formula is B25 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A1 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 7.5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 20° C. for 0.5 min to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 26, and n is 866); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1:1, and the catalytic activity of the catalytic system reaches 15.36×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 1.9 mol%, and the insertion rate of the cycloolefin monomer is 49.3 mol%. The _Mn value of the cycloolefin copolymer is 19.88× ¹⁰⁴ g/mol, the PDI is 2.25, the _Tg is 168°C, the thermal weight loss 5wt% temperature is 391°C, the visible light transmittance is 90%, and the refractive index is 1.563.

Embodiment 26

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-octadecene;

Cycloolefin monomer: 1,4,5,8,9,10-trimethylene dodecahydroanthracene;

Comonomer containing a high refractive index group: the structural formula is B26 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A2 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 5:1:0.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 40° C. for 10 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 15, and n is 481); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 800:1, and the catalytic activity of the catalytic system reaches 19.82×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 2.8 mol%, and the insertion rate of the cycloolefin monomer is 56.3 mol%. The _Mn value of the cycloolefin copolymer is 16.34× ¹⁰⁴ g/mol, the PDI is 1.94, the _Tg is 152°C, the thermal weight loss temperature of 5wt% is 393°C, the visible light transmittance is 91%, and the refractive index is 1.556.

Embodiment 27

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-nonadecene;

Cycloolefin monomer: 1,4,5,8,9,10-trimethylene dodecahydroanthracene;

Comonomer containing a high refractive index group: the structural formula is B27 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A3 in Table 1;

Co-catalyst: Ph ₃ CB(C ₆ F ₅ ) ₄ , manufacturer is Changcheng Reagent, brand name is PS-0053;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 2:1:3 into an inert organic solvent, and adding a catalytic system consisting of a main catalyst and a co-catalyst, and reacting at 100° C. for 120 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 6, and n is 935); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:28000, the molar ratio of the co-catalyst to the main catalyst is 1.5:1, and the catalytic activity of the catalytic system reaches 14.77×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 7.4 mol%, and the insertion rate of the cycloolefin monomer is 45.6 mol%. The _Mn value of the cycloolefin copolymer is 18.54× ¹⁰⁴ g/mol, the PDI is 2.16, the _Tg is 166°C, the thermal weight loss temperature of 5wt% is 392°C, the visible light transmittance is 88%, and the refractive index is 1.587.

Embodiment 28

A method for preparing a cycloolefin copolymer, comprising the following steps:

(1) Preparation of raw materials;

Olefin monomer: 1-eicosene;

Cycloolefin monomer: 1,4,5,8,9,10-trimethylene dodecahydroanthracene;

Comonomer containing a high refractive index group: the structural formula is B28 in Table 2;

Inert organic solvent: toluene;

Main catalyst: metallocene catalyst, the structural formula of which is A4 in Table 1;

Co-catalyst: MMAO, manufactured by Tosoh Corporation of Japan, brand name MMAO-3A;

(2) adding a cycloolefin monomer, an olefin monomer and a comonomer containing a high refractive index group in a molar ratio of 1.5:1:4.5 to an inert organic solvent, and adding a catalyst system consisting of a main catalyst and a co-catalyst, and reacting at 130° C. for 180 minutes to obtain a cycloolefin copolymer (structural formula: Wherein, X/Y is 1, X/Z is 4, and n is 964); wherein the molar ratio of the main catalyst to the cycloolefin monomer is 1:200000, the molar ratio of the co-catalyst to the main catalyst is 1000:1, and the catalytic activity of the catalytic system reaches 13.02×10 ⁸ g·mol ^-1 ·h ^-1 .

The insertion rate of the comonomer containing the high refractive index group in the finally prepared cycloolefin copolymer is 10.2 mol%, and the insertion rate of the cycloolefin monomer is 47.1 mol%. The _Mn value of the cycloolefin copolymer is 10.23× ¹⁰⁴ g/mol, the PDI is 1.69, the _Tg is 124°C, the thermal weight loss temperature of 5wt% is 390°C, the visible light transmittance is 88%, and the refractive index is 1.551.

Claims (10)

1. A preparation method of cycloolefin copolymer is characterized in that olefin monomer, cycloolefin monomer and comonomer containing high refractive index group are subjected to ternary polymerization reaction to prepare cycloolefin copolymer, and the cycloolefin copolymer is characterized in that the structural formula of the olefin monomer is as follows:

R ₁ is a hydrogen atom, -CH ₃ or- (CH ₂)_aCH₃), a is more than or equal to 1 and less than or equal to 17;

The structural formula of the cycloolefin monomer is as follows:

Wherein i is 0, 1 or 2, and R ₂-R₅ is each independently selected from the group consisting of a hydrogen atom, an alkyl group and a cycloalkyl group;

the structural formula of the comonomer containing the high refractive index group is as follows:

Wherein 1.ltoreq.m.ltoreq.10, R ₆-R₁₃ is each independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a silyl group, wherein R _b、R_b+1 is bonded or not bonded, 6.ltoreq.b.ltoreq.12, R ₁₄ is selected from the group consisting of an alkyl group, an aryl group, and a silyl group, the number of carbon atoms is 1 to 14, and the dotted line indicates that the position is bonded or not bonded.

2. The method for producing a cycloolefin copolymer according to claim 1, wherein the olefin monomer is one or more of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene.

3. The method for producing a cycloolefin copolymer according to claim 1, characterized in that the cycloolefin monomer is one or more of norbornene, tetracyclododecene and 1,4,5,8,9,10-trimethylenedodecanthracene.

4. The method for preparing a cycloolefin copolymer according to claim 1, characterized in that the comonomer containing the group having a high refractive index has a structural formula of one of the formulae 1 to 28, and the formulae 1 to 28 are as follows:

5. The method for preparing a cycloolefin copolymer according to claim 1, characterized in that the molar ratio of cycloolefin monomer, olefin monomer to comonomer containing a group having a high refractive index is 1.5 to 7.5:1:0.5 to 4.5; the temperature of the ternary polymerization reaction is 20-130 ℃ and the time is 0.5-180min.

6. The process for preparing cycloolefin copolymers according to claim 1, characterized in that the ternary polymerization is carried out in an inert organic solvent while under the action of a catalytic system consisting of a procatalyst and a cocatalyst.

7. The process for preparing a cycloolefin copolymer according to claim 6, characterized in that the main catalyst is a metallocene catalyst, and the molar ratio of the main catalyst to the cycloolefin monomer is 1:20000-200000; the cocatalyst is alkyl aluminum cocatalyst or organic boron cocatalyst, the mol ratio of the alkyl aluminum cocatalyst to the main catalyst is 10-1000:1, and the mol ratio of the organic boron cocatalyst to the main catalyst is 1.0-1.5:1.

8. The method for preparing a cycloolefin copolymer according to claim 7, characterized in that the structural formula of the metallocene catalyst is one of the formulae A1 to A6, and the formulae A1 to A6 are as follows:

9. The process for preparing cycloolefin copolymers according to claim 8, characterized in that the catalytic activity of the catalytic system reaches 9.0X10 ⁸～34×10⁸g·mol^-1·h^-1 during the course of the terpolymerization.

10. Cycloolefin copolymer obtainable by the process according to any of claims 1 to 9, characterized in that the structural formula is as follows:

wherein, X/Y is more than or equal to 1 and less than or equal to 9, X/Z is more than or equal to 2 and less than or equal to 90, n is more than or equal to 25 and less than or equal to 5000, and m is more than or equal to 1 and less than or equal to 10.