Cycloolefin terpolymer, preparation method thereof and optical element

Abstract

The invention relates to a cycloolefin terpolymer, a preparation method thereof and an optical element. The preparation method of the cycloolefin terpolymer comprises the following steps: mixing an ethylene monomer, a cycloolefin monomer and a conjugated aryl-substituted olefin monomer, and carrying out polymerization reaction in the presence of a catalyst and a cocatalyst to prepare the cycloolefin terpolymer, the conjugated aryl substituted olefin monomer has the following structural characteristics: m is an integer from 1 to 10, and R1 is naphthyl, anthryl, phenanthryl, pyrenyl, acenaphthenyl or chrysenyl; the catalyst comprises a metallocene catalyst; the cocatalyst comprises one or more of an aluminum compound and a boron compound; the conditions of the polymerization reaction are as follows: the pressure is 2.2 MPa to 10 MPa. The polymerization activity of the preparation method is obviously improved, and the prepared cycloolefin terpolymer has relatively high refractive index and mechanical property and relatively low water absorption.

Description

Technical Field

[0001] This application relates to olefin polymers, and more particularly to a cyclic olefin terpolymer, a method for preparing the same, and optical elements thereof. Background Technology

[0002] Unlike polymers containing halogens, metals, or other heteroatoms, pure hydrocarbon polymers offer multiple advantages in optical applications. Represented by cyclic olefin copolymers, they typically possess excellent chemical resistance, high thermal stability, good biocompatibility, and superior optical transparency. Furthermore, the pure hydrocarbon structure endows these polymers with low water absorption and weak interaction with water, enabling them to remain stable in humid environments and avoid dimensional changes or optical performance degradation due to water absorption. Currently, commercially available optical-grade cyclic olefin copolymers are typically produced by the addition polymerization of ethylene and cyclic olefin monomers, with a refractive index of 1.52–1.54 and extremely low water absorption (≤0.01%), thus exhibiting long service life and stable performance in optical devices. However, the refractive index and mechanical properties of commercially available pure hydrocarbon cyclic olefin copolymers still limit their development in high-end optical applications.

[0003] There are methods to prepare cyclic olefin terpolymers by further introducing monomers containing highly polar groups (such as biphenyl, naphthyl, anthracene, etc.) on the basis of ethylene and cyclic olefin monomers, which can effectively improve the refractive index. However, the polymerization activity of such cyclic olefin terpolymers is low, which makes it difficult to meet the needs of industrial applications. Summary of the Invention

[0004] Based on this, this application provides a cyclic olefin terpolymer and its preparation method. The polymerization activity of this preparation method is significantly improved, and the resulting cyclic olefin terpolymer exhibits high refractive index and mechanical properties, as well as low water absorption.

[0005] A first aspect of this application provides a method for preparing a cyclic olefin terpolymer, comprising the following steps:

[0006] The cyclic olefin terpolymer is prepared by mixing ethylene monomer, cyclic olefin monomer and conjugated aryl-substituted olefin monomer and carrying out polymerization reaction in the presence of catalyst and co-catalyst.

[0007] The conjugated aryl-substituted olefin monomers have the following structural features:

[0008] Where m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin;

[0009] The catalyst includes a metallocene catalyst;

[0010] The cocatalyst includes one or more of aluminum compounds and boron compounds;

[0011] The conditions for the polymerization reaction include a pressure of 2.2 MPa to 10 MPa.

[0012] In one embodiment, the polymerization reaction conditions include a pressure of 2.2 MPa to 5 MPa.

[0013] In one embodiment, the metallocene catalyst comprises one or more of Cat1 (ethyl-bridged bis(indene)zirconia catalyst), Cat2 (dimethylsilyl-bridged bis(indene)zirconia catalyst), Cat3 (isopropylidene-bridged fluorene-zirconia catalyst), Cat4 (dimethylsilyl-bridged restricted geometry titanium catalyst), Cat5 (di-tert-butylimine-based monotitanium cadmium catalyst), and Cat6 (trimethylsilyl-substituted cyclopentadienyl monotitanium cadmium catalyst); and / or,

[0014] The aluminum compound includes one or more of methylaluminoxane, modified methylaluminoxane, trialkylaluminum, dialkylaluminum chloride, monoalkylaluminum dichloride, and trialkylaluminum trichloride; and / or,

[0015] The boron compound includes one or more of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate, N,N-diethylphenylamine tetra(pentafluorophenyl)borate, N,N-di(hexadecyl)phenylamine tetra(pentafluorophenyl)borate, tri(pentafluorophenyl)borate, triphenylcarbazide tetra(pentafluorophenyl)borate, and triphenylmethyltetra(pentafluorophenyl)borate; and / or,

[0016] The cyclic olefin monomers include one or more of norbornene and tetracyclododecene.

[0017] In one embodiment, the molar ratio of the catalyst to the cyclic olefin monomer is 1:(500~40000), optionally 1:(800~30000); and / or,

[0018] The molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer is 1:(50~40000), optionally 1:(200~30000); and / or,

[0019] The molar ratio of the catalyst to the co-catalyst is 1:(1~5000), and can be optionally 1:(1~3000).

[0020] In one embodiment, the polymerization reaction conditions further include a temperature of 0°C to 200°C, optionally 50°C to 90°C.

[0021] In one embodiment, the conjugated aryl-substituted olefin monomer comprises one or more of compounds 1 to 10:

[0022] .

[0023] In one embodiment, based on the total molar number of the ethylene monomer, the cyclic olefin monomer, and the conjugated aryl-substituted olefin monomer, the molar percentage of the ethylene monomer is 40% to 80%, the molar percentage of the cyclic olefin monomer is 19.9% ​​to 40%, and the molar percentage of the conjugated aryl-substituted olefin monomer is 0.1% to 20%.

[0024] A second aspect of this application provides a cyclic olefin terpolymer having the following structural features:

[0025] ,

[0026] in,

[0027] m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin;

[0028] p is 0 or 1;

[0029] 50≤n≤5000;

[0030] X: Y: Z=40%~80%: 19.9%~40%: 0.1%~20%.

[0031] In one embodiment, it is prepared by the preparation method described above.

[0032] A third aspect of this application provides an optical element comprising a cyclic olefin terpolymer prepared by the preparation method described in the first aspect or a cyclic olefin terpolymer described in the second aspect.

[0033] Research has shown that by using suitable monomers to prepare cyclic olefin terpolymers, where the conjugated aryl-substituted olefin monomers have substituents that create a π-π stacking effect on the benzene ring, and by employing metallocene catalysts and one or more aluminum and boron compounds as co-catalysts for terpolymerization under high pressure conditions, the polymerization activity of cyclic olefin terpolymers can be significantly improved compared to existing methods, thus solving the problem of difficult industrial production of cyclic olefin terpolymers. Furthermore, the prepared cyclic olefin terpolymers possess both high refractive index and high toughness.

[0034] In addition, the prepared cyclic olefin terpolymer also has a certain glass transition temperature and retains other excellent properties of cyclic olefin resin, such as high thermal stability, high Abbe number, high light transmittance, and low water absorption. Attached Figure Description

[0035] Figure 1 The cyclic olefin terpolymer of Example 26 13 C-NMR spectrum.

[0036] Figure 2 The TGA curve of the cyclic olefin terpolymer of Example 26 is shown.

[0037] Figure 3 The visible light transmittance spectrum of the cyclic olefin terpolymer of Example 26 is shown. Detailed Implementation

[0038] The following detailed description, in conjunction with specific embodiments, illustrates the cyclic olefin terpolymer, its preparation method, and optical elements of this application. This application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of this application.

[0039] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0040] As used herein, the terms “and / or,” “or / and,” and “and / or” may include any one of two or more of the related listed items, as well as any and all combinations of the related listed items, including any two related listed items, any more related listed items, or a combination of all the related listed items.

[0041] In this article, "one or more" refers to any one, two or more of the listed items.

[0042] In this application, terms such as "first aspect," "second aspect," "third aspect," and "fourth aspect" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, terms such as "first," "second," "third," and "fourth" serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0043] In this application, the technical features described in an open-ended manner include both closed technical solutions consisting of the listed features and open technical solutions that include the listed features.

[0044] In this application, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0045] Unless otherwise specified, the percentage content mentioned in this application refers to mass percentage for solid-liquid mixtures and solid-phase-solid mixtures, and volume percentage for liquid-phase-liquid mixtures.

[0046] Unless otherwise specified, all percentage concentrations mentioned in this application refer to the final concentration. The final concentration refers to the proportion of the added component in the system after the addition of that component.

[0047] Unless otherwise specified, the temperature parameters in this application may be either constant temperature processing or processing within a certain temperature range. The constant temperature processing allows for temperature fluctuations within the precision range controlled by the instrument.

[0048] In this application, room temperature generally refers to 4℃~30℃, and preferably 20±5℃.

[0049] Unless otherwise specified, the pressure referred to in this application refers to gauge pressure.

[0050] Some embodiments of this application provide a method for preparing a cyclic olefin terpolymer, comprising the following steps:

[0051] The cyclic olefin terpolymer is prepared by mixing ethylene monomer, cyclic olefin monomer and conjugated aryl-substituted olefin monomer and carrying out polymerization reaction in the presence of catalyst and co-catalyst.

[0052] The conjugated aryl-substituted olefin monomers have the following structural features:

[0053] Where m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin;

[0054] The catalyst includes a metallocene catalyst;

[0055] The cocatalyst includes one or more of aluminum compounds and boron compounds;

[0056] The conditions for the polymerization reaction include a pressure of 2.2 MPa to 10 MPa.

[0057] Understandably, the pressure of the polymerization reaction can be controlled by filling the reaction solution with ethylene and continuously introducing ethylene.

[0058] Specifically, the pressure includes, but is not limited to: 2.2 MPa, 2.5 MPa, 2.8 MPa, 3 MPa, 3.2 MPa, 3.4 MPa, 4 MPa, 4.5 MPa, 5 MPa, 5.5 MPa, 6 MPa, 6.5 MPa, 7 MPa, 7.5 MPa, 8 MPa, 8.5 MPa, 9 MPa, 9.5 MPa, 10 MPa, or any range between the foregoing. Further, the polymerization reaction conditions include a pressure of 2.2 MPa to 6 MPa.

[0059] Specifically, m includes, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any two of the aforementioned ranges. Further, 2 ≤ m ≤ 8. Even further, 2 ≤ m ≤ 6.

[0060] In some embodiments, the metallocene catalyst includes one or more of Cat1 (ethyl-bridged bis(indene)zirconia catalyst), Cat2 (dimethylsilyl-bridged bis(indene)zirconia catalyst), Cat3 (isopropylidene-bridged fluorene-zirconia catalyst), Cat4 (dimethylsilyl-bridged restricted geometry titanium catalyst), Cat5 (di-tert-butylimine-based monotitanium catalyst), and Cat6 (trimethylsilyl-substituted cyclopentadienyl monotitanium catalyst). The specific structures are as follows:

[0061]

[0062] In some embodiments, the aluminum compound includes one or more of methylaluminoxane, modified methylaluminoxane, trialkylaluminum (such as triisobutylaluminum), dialkylaluminum chloride, monoalkylaluminum chloride, and trialkylaluminum trichloride.

[0063] In some embodiments, the boron compound includes one or more of N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetra(pentafluorophenyl)borate, N,N-di(hexadecyl)phenylammonium tetra(pentafluorophenyl)borate, tri(pentafluorophenyl)borate, triphenylcarbamonium tetra(pentafluorophenyl)borate, and triphenylmethyltetra(pentafluorophenyl)borate.

[0064] In some embodiments, the cyclic olefin monomer includes one or more of norbornene and tetracyclododecene.

[0065] In some embodiments, the molar ratio of the catalyst to the cyclic olefin monomer is 1:(500~40000). Specifically, the molar ratio of the catalyst to the cyclic olefin monomer includes, but is not limited to: 1:500, 1:800, 1:1000, 1:3000, 1:4000, 1:4500, 1:5000, 1:7000, 1:10000, 1:12600, 1:13000, 1:15000, 1:17000, 1:18600, 1:20000, 1:22400, 1:25000, 1:30000, 1:35000, 1:40000, or any range between the foregoing. Further, the molar ratio of the catalyst to the cyclic olefin monomer is 1:(800~30000). Furthermore, the molar ratio of the catalyst to the cyclic olefin monomer is 1:(4500~30000).

[0066] In some embodiments, the molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer is 1:(50~40000). Specifically, the molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer includes, but is not limited to: 1:50, 1:100, 1:150, 1:200, 1:500, 1:1000, 1:1800, 1:2000, 1:3000, 1:3600, 1:5000, 1:10000, 1:12000, 1:14000, 1:14400, 1:15000, 1:18000, 1:18900, 1:20000, 1:25000, 1:28000, 1:28800, 1:30000, 1:35000, 1:40000, or a range between any two of the foregoing. Further, the molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer is 1:(200~30000). Even further, the molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer is 1:(3600~30000).

[0067] In some embodiments, the molar ratio of the catalyst to the co-catalyst is 1:(1~5000). Specifically, the molar ratio of the catalyst to the co-catalyst includes, but is not limited to: 1:1, 1:5, 1:50, 1:100, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, 1:500, 1:550, 1:600, 1:650, 1:700, 1:750, 1:800, 1:850, 1:1000, 1:1500, 1:2000, 1:2500, 1:3000, 1:3500, 1:4000, 1:4500, 1:5000, or any range between the foregoing. Further, the molar ratio of the catalyst to the co-catalyst is 1:(1~3000). Furthermore, the molar ratio of the catalyst to the co-catalyst is 1:(1~1000).

[0068] In some embodiments, the polymerization reaction conditions further include a temperature of 0°C to 200°C. Specifically, this temperature includes, but is not limited to, 0°C, 5°C, 10°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 150°C, 200°C, or any range between the foregoing. Further, the polymerization reaction temperature is 50°C to 90°C.

[0069] In some embodiments, the polymerization reaction conditions further include a time of 5 min to 240 min. Specifically, the time includes, but is not limited to, 5 min, 10 min, 15 min, 20 min, 50 min, 100 min, 150 min, 200 min, 240 min, or any range between the two aforementioned.

[0070] Without limitation, the conjugated aryl-substituted olefin monomer includes one or more of the following compounds 1 to 10:

[0071] .

[0072] Using conjugated aryl-substituted olefin monomers with appropriate structures can further improve the refractive index of the prepared cyclic olefin copolymers and cyclic terpolymers.

[0073] In some embodiments, the cyclic olefin monomers include one or more of norbornene and tetracyclododecene. During copolymerization, these cyclic olefin monomers can provide suitable rigidity, resulting in cyclic olefin terpolymers with high glass transition temperatures and significant practical value.

[0074] In some embodiments, based on the total molar number of the ethylene monomer, the cyclic olefin monomer, and the conjugated aryl-substituted olefin monomer, the molar percentage of the ethylene monomer is 40% to 80%, the molar percentage of the cyclic olefin monomer is 19.9% ​​to 40%, and the molar percentage of the conjugated aryl-substituted olefin monomer is 0.1% to 20%. Specifically, the molar percentage of the ethylene monomer includes, but is not limited to: 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any two of the foregoing; the molar percentage of the cyclic olefin monomer includes, but is not limited to: 19.9%, 25%, 30%, 35%, 40%, or any two of the foregoing; and the molar percentage of the conjugated aryl-substituted olefin monomer includes, but is not limited to: 0.1%, 1%, 5%, 10%, 15%, 20%, or any two of the foregoing.

[0075] Without limitation, the ethylene monomer, the cyclic olefin monomer, and the conjugated aryl-substituted olefin monomer can be commercially available products or self-made products.

[0076] In some embodiments, the polymerization reaction is carried out in the presence of an inert solvent. Without limitation, the inert solvent includes one or more of straight-chain hydrocarbons, cyclic hydrocarbons, and aromatic hydrocarbons, optionally including benzene compounds, such as toluene.

[0077] Without limitation, post-processing steps are also included after the polymerization reaction is completed:

[0078] The reaction solution obtained from the polymerization reaction is mixed with an ethanol solution of hydrochloric acid to terminate the growth of the polymerization chain and obtain the reaction product; the reaction product is then subjected to solid-liquid separation and dried to obtain a cyclic olefin copolymer.

[0079] Understandably, there are no particular limitations on the method for terminating the growth of the polymerization chain. The above-mentioned method of mixing the reaction solution with an ethanol solution of hydrochloric acid can be used, wherein the volume percentage of the ethanol solution of hydrochloric acid can be 5% to 15%.

[0080] Understandably, there are no special restrictions on the method of solid-liquid separation. The reaction product can be separated into solid and liquid by means such as filtration, and the filtered product can be washed with acetone as the washing reagent, and the washing can be performed twice.

[0081] Understandably, there are no special restrictions on the drying method. Methods such as vacuum drying can be used, the drying temperature can be 50℃~80℃, and the drying time can be 16h~24h.

[0082] Other embodiments of this application provide a cyclic olefin terpolymer having the following structural features:

[0083] ,

[0084] in,

[0085] m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin;

[0086] p is 0 or 1;

[0087] 50≤n≤5000;

[0088] X: Y: Z=40%~80%: 19.9%~40%: 0.1%~20%.

[0089] Understandably, the sum of X, Y, and Z is 100%.

[0090] In some embodiments, the cyclic olefin terpolymer is a pure hydrocarbon polymer.

[0091] In some embodiments, the cyclic olefin terpolymer has one or more of the following characteristics:

[0092] (1) The weight-average molecular weight is 20kDa~900kDa, and can be selected as 60kDa~500kDa;

[0093] (2) The glass transition temperature is 120℃~200℃;

[0094] (3) Light transmittance ≥ 90%;

[0095] (4) Refractive index 1.56~1.65;

[0096] (5) Abbe number ≥ 21;

[0097] (6) Water absorption rate ≤ 0.01%;

[0098] (7) Elongation at break: 12%~25%.

[0099] In some embodiments, the insertion rate of the cyclic olefin monomer in the cyclic olefin terpolymer is adjustable between 24.8 mol% and 37.8 mol%, and the insertion rate of the conjugated aryl-substituted olefin monomer is adjustable between 3.8 mol% and 18.2 mol%.

[0100] In some embodiments, the cyclic olefin terpolymer is prepared by the preparation method described above, which has similar technical solutions and advantages, and will not be repeated here.

[0101] Without limitation, the cyclic olefin terpolymer includes one or more of the following polymers a to l:

[0102] .

[0103] Without limitation, the cyclic olefin terpolymers prepared by the preparation method described above or the cyclic olefin terpolymers described above can be used in the fields of optics, medical devices, packaging, electronic communications, etc., especially as optical components.

[0104] Some embodiments of this application provide an optical element, including a cyclic olefin terpolymer prepared by the preparation method described above or a cyclic olefin terpolymer as described above.

[0105] For experimental parameters not specified in the following specific embodiments, please refer to the guidelines given in this application document first, or refer to experimental manuals or other experimental methods known in the art, or refer to the experimental conditions recommended by the manufacturer.

[0106] The raw materials and reagents involved in the following specific embodiments can be obtained commercially or prepared by those skilled in the art using known methods.

[0107] The main raw material information involved in the examples and comparative examples is shown in Table 1 below.

[0108] Table 1

[0109]

[0110] The methods for structural identification and performance testing of the prepared cyclic olefin terpolymers are as follows:

[0111] The molecular structure of the cyclic olefin terpolymer was determined by nuclear magnetic resonance spectroscopy.

[0112] The melting temperature of the cyclic olefin terpolymer was determined using differential thermal analysis (DSC).

[0113] The molecular weight and molecular weight distribution index of cyclic olefin terpolymers were determined by gel permeation chromatography.

[0114] Among them, nuclear magnetic resonance spectroscopy refers to the polymer's 1 H NMR and 13 C10 NMR spectra were measured using a Bruker AV400 nuclear magnetic resonance spectrometer at 110 °C, with deuterated tetrachloroethane as the solvent.

[0115] Differential thermal analysis refers to the glass transition temperature (Tg) of the polymer, which is determined by a Mettler TOPEM DSC (Mettler-Toledo, Zurich, Switzerland) differential scanning calorimeter at a heating / cooling rate of 10℃ / min.

[0116] Thermogravimetric analysis (TGA) was performed using a Mettler-Toledo TGA2 instrument at a heating rate of 20 °C / min, where T... d,5% This is the real-time temperature at which the polymer loses 5% of its weight due to thermal decomposition during the test.

[0117] Transmittance was measured using a Shimadzu UV-3600 UV-Vis-NIR spectrophotometer at wavelengths of 400–800 nm.

[0118] The refractive index and Abbe number were measured at 20°C using an Abbe refractometer (DR-M4, Atago Co. Ltd., Tokyo, Japan) without the use of a contact liquid.

[0119] The molecular weight and molecular weight distribution index of the polymer were determined by gel permeation chromatography (GPC) using a PL-GPC 220 gel permeation chromatograph with 1,2,4-trichlorobenzene as the solvent, at a test temperature of 150°C and a flow rate of 1.0 mL / min, relative to a polystyrene standard.

[0120] The water absorption rate was tested according to the national standard GB / T 1034-2008, and the result was the 24-hour water absorption rate.

[0121] Elongation at break was determined by a universal testing machine at room temperature using a standard dumbbell-shaped specimen, with a test rate of 5 mm / min.

[0122] Example 1

[0123] This embodiment describes the preparation of pure hydrocarbon conjugated aryl-substituted olefin monomer 1, and the steps are as follows:

[0124]

[0125] 9-Bromophenanthrene (20.0 g) was dissolved in anhydrous tetrahydrofuran (300 mL) and stirred at -78 °C for 30 min. Then, under nitrogen protection, a solution of n-butyllithium (62.5 mL, 2.4 M, n-hexane as solvent) was slowly added dropwise, and the reaction was continued at this temperature for 5 h to generate the corresponding phenanthrene lithium salt intermediate. Subsequently, 5-bromo-1-pentene (22.3 g) was slowly added under nitrogen atmosphere. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h to complete the reaction. The reaction was terminated by pouring in a saturated ammonium chloride solution. The reaction mixture was extracted with diethyl ether, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The resulting product was purified by silica gel column chromatography (eluent: petroleum ether) and recrystallized in n-hexane to give a white solid product in 70% yield.

[0126] Example 2

[0127] This embodiment describes the preparation of pure hydrocarbon conjugated aryl-substituted olefin monomer 2, and the steps are as follows:

[0128]

[0129] 9-Bromoanthracene (20.0 g) was dissolved in anhydrous tetrahydrofuran (300 mL), and stirred at -78 °C for 30 min. Then, under nitrogen protection, a solution of n-butyllithium (62.5 mL, 2.4 M, n-hexane as solvent) was slowly added dropwise, and the reaction was continued at this temperature for 5 h to generate the corresponding phenanthrene lithium salt intermediate. Subsequently, 5-bromo-1-pentene (22.3 g) was slowly added under nitrogen atmosphere. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h to complete the reaction. The reaction was terminated by pouring in a saturated ammonium chloride solution. The reaction mixture was extracted with diethyl ether, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The resulting product was purified by silica gel column chromatography (eluent: petroleum ether) and recrystallized in n-hexane to give a white solid product in 58% yield.

[0130] Example 3

[0131] This embodiment describes the preparation of pure hydrocarbon conjugated aryl-substituted olefin monomer 3, and the steps are as follows:

[0132]

[0133] 1-Bromopyrene (21.8 g) was dissolved in anhydrous tetrahydrofuran (300 mL) and stirred at -78 °C for 30 min. Then, under nitrogen protection, a solution of n-butyllithium (62.5 mL, 2.4 M, n-hexane as solvent) was slowly added dropwise, and the reaction was continued at this temperature for 5 h to generate the corresponding phenanthrene lithium salt intermediate. Subsequently, 5-bromo-1-pentene (22.3 g) was slowly added under nitrogen atmosphere. After the addition was complete, the mixture was brought to room temperature and stirred for 12 h to complete the reaction. The reaction was terminated by pouring in a saturated ammonium chloride solution. The reaction mixture was extracted with diethyl ether, dried over anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation. The resulting product was purified by silica gel column chromatography (eluent: petroleum ether) and recrystallized in n-hexane to give a pale green liquid product in 65% yield.

[0134] Examples 4-17

[0135] Examples 4-17 illustrate the preparation of cyclic olefin terpolymers, with the following steps:

[0136]

[0137] A 100 mL reactor connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, specific molar amounts of toluene solutions of pure hydrocarbon conjugated aryl-substituted olefin monomers prepared in Examples 1-3 and specific molar amounts of toluene solutions of tetracyclododecene monomers were added to the reactor, totaling 24 mL. 2.0 mL of a triisobutylaluminum hexane solution (1.0 M, 2 mmol) was added, followed by the injection of 10.0 μmol of Cat 6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium titanate catalyst) and 10.5 μmol of triphenylmethyltetra(pentafluorophenyl)borate dissolved in 4 mL of toluene into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at a certain pressure. After 10 min, the reactor was emptied, and 400 mL of hydrochloric acid-ethanol (1 wt% hydrochloric acid) was poured in for quenching. The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 2.

[0138] Table 2

[0139]

[0140] Note: All data are based on results from at least two parallel experiments (unless otherwise stated). The concentrations of cyclic olefin monomers and pure hydrocarbon conjugated aryl-substituted olefin monomers refer to their concentrations in the total reaction system. Activity: expressed in 10... 6 g mol -1 h -1 Units are used for the insertion rate of monomers. 13 Obtained by C-NMR analysis.

[0141] Table 2 shows that increasing the concentration of pure hydrocarbon conjugated aryl-substituted olefin monomers gradually decreases the insertion rate of cyclic olefin monomers, while increasing the insertion rate of conjugated aryl-substituted olefin monomers, resulting in a certain improvement in activity. Examples 4, 5, and 9-12 show that when the tetracyclododecene monomer concentration is 1.5M and the polymerization temperature is 70℃, monomers 1 and 3 exhibit better activity than monomer 2 during polymerization. Examples 4, 6, 7, and 8 show that when the polymerization ethylene pressure is increased from 2.5 MPa to 4.5 MPa, 6.0 MPa, and 10 MPa, the higher ethylene pressure results in better polymerization activity; however, with increasing pressure, more monomers are needed to obtain cyclic olefin resins with a certain insertion rate. Examples 13-15 show that when the polymerization temperature is increased to 90℃, the polymerization activity of all monomers decreases to varying degrees. As can be seen from Example 16, the polymerization activity is significantly improved when the polymerization temperature is reduced to 50°C. As can be seen from Example 17, the insertion rates of conjugated aryl-substituted olefin monomers and cyclic olefin monomers in the copolymer are mutually restrictive; however, when both concentrations increase simultaneously, the insertion rate of the conjugated aryl-substituted olefin monomers increases relatively significantly. To obtain cyclic olefin copolymers with specific glass transition temperatures and molecular weights, more cyclic olefin monomers need to be added during low-temperature polymerization.

[0142] Examples 18-21

[0143] Examples 18-21 illustrate the preparation of cyclic olefin terpolymers, with the following steps:

[0144] A 100 mL reactor connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, a specific molar amount of toluene solution of the pure hydrocarbon conjugated aryl-substituted olefin monomer prepared in Example 1 and a specific molar amount of toluene solution of tetracyclododecene were added to the reactor, along with a 1.5 M toluene solution of methylaluminoxane (MAO) at a quantitative multiple relative to the catalyst (Cat6), bringing the total solution volume in the reactor to 20 mL. Subsequently, 10.0 μmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium titanate catalyst) was dissolved in 10 mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at a certain pressure. After 10 min, the reactor was emptied, and 400 mL of hydrochloric acid-ethanol (1 wt% hydrochloric acid) was poured in for quenching. The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0145] Examples 22-24

[0146] Examples 22-24 describe the preparation of cyclic olefin terpolymers, and the steps are as follows:

[0147] A 100 mL reactor connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, a specific molar amount of toluene solution of the pure hydrocarbon conjugated aryl-substituted olefin monomer prepared in Example 1 and a specific molar amount of toluene solution of tetracyclododecene were added to the reactor, along with a 1.5 M toluene solution of methylaluminoxane (MAO) at a ratio of 500 times that of the catalyst (Cat6), bringing the total solution volume in the reactor to 20 mL. Subsequently, 10.0 μmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium titanate catalyst) was dissolved in 10 mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at a certain pressure. After 10 min, the reactor was emptied, and 400 mL of hydrochloric acid-ethanol (1 wt% hydrochloric acid) was poured in for quenching. The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0148] Example 25

[0149] Example 25 describes the scale-up preparation of cyclic olefin terpolymers, and the steps are as follows:

[0150] A 1L reactor connected to the gas pipeline was vacuum dried at 110°C for 1 hour. Then, under an inert atmosphere, a toluene solution containing a specific molar amount of the pure hydrocarbon conjugated aryl-substituted olefin monomer prepared in Example 1 and a specific molar amount of tetracyclododecene in toluene were added to the reactor. A toluene solution (1.5 M) of methylaluminoxane (MAO) at 500 times the amount of the catalyst (Cat6) was added, bringing the total solution volume in the reactor to 220 mL. Subsequently, 100.0 μmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium catalyst) dissolved in 80 mL of toluene was injected into the polymerization system via a feed tank. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at 2.2 MPa. After 10 min, the reactor was emptied, and the polymerization reaction was quenched by adding hydrochloric acid-ethanol (1 wt% hydrochloric acid). The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0151] Example 26

[0152] Example 26 describes the scale-up preparation of cyclic olefin terpolymers, with the following steps:

[0153] The 5 L reaction vessel connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, a specific molar amount of toluene solution of the pure hydrocarbon conjugated aryl-substituted olefin monomer prepared in Example 1 and a specific molar amount of toluene solution of tetracyclododecene were added to the reactor, along with a 1.5 M toluene solution of methylaluminoxane (MAO) at a ratio of 500 times that of the catalyst (Cat6), bringing the total solution volume in the reactor to 2700 mL. Subsequently, 1.0 mmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium catalyst) dissolved in 300 mL of toluene was added to the polymerization system via a feeder. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at 2.2 MPa. After 10 min, the reactor was emptied, and the polymerization reaction was quenched by adding hydrochloric acid-ethanol (1 wt% hydrochloric acid). The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0154] Among them, the cyclic olefin terpolymer of Example 26 13 C-NMR spectrum, TGA curve spectrum and visible light transmittance curve spectrum, such as Figure 1 , Figure 2 and Figure 3 As shown.

[0155] Comparative Example 1

[0156] Comparative Example 1 illustrates the preparation of a cyclic olefin terpolymer, following these steps:

[0157] A 100 mL reactor connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, a specific molar amount of toluene solution of the pure hydrocarbon conjugated aryl-substituted olefin monomer prepared in Example 1 and a specific molar amount of toluene solution of tetracyclododecene were added to the reactor, along with a 1.5 M toluene solution of methylaluminoxane (MAO) at a ratio of 500 times that of the catalyst (Cat6), bringing the total solution volume in the reactor to 20 mL. Subsequently, 10.0 μmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium titanate catalyst) was dissolved in 10 mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at a certain pressure. After 10 min, the reactor was emptied, and 400 mL of hydrochloric acid-ethanol (1 wt% hydrochloric acid) was poured in for quenching. The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0158] Comparative Example 2

[0159] Comparative Example 2 illustrates the preparation of a cyclic olefin terpolymer, following these steps:

[0160] A 100 mL reactor connected to the gas line was vacuum dried at 110 °C for 1 h. Then, under an inert atmosphere, a specific molar amount of α-olefin monomers containing five carbon chain lengths and carbazole groups (…) was… A toluene solution of methylaluminoxane (MAO) and a specific molar amount of tetracyclododecene in toluene were added to the reactor, along with a 1.5M toluene solution of methylaluminoxane (MAO) at a ratio of 500 times that of the catalyst (Cat6), bringing the total solution volume in the reactor to 20 mL. Subsequently, 10.0 μmol of Cat6 (trimethylsilyl-substituted cyclopentadienyl monocerammonium titanate catalyst) was dissolved in 10 mL of toluene and injected into the polymerization system via a syringe. Ethylene was introduced under rapid stirring (1000 rpm) and maintained at a certain pressure. After 10 min, the reactor was emptied, and 400 mL of hydrochloric acid-ethanol (1 wt% hydrochloric acid) was added for quenching. The polymer was filtered and dried to constant weight in a vacuum oven. Specific reaction conditions and results are shown in Table 3.

[0161] Table 3

[0162]

[0163] Note: All data are based on results from at least two parallel experiments (unless otherwise stated). The concentrations of cyclic olefin monomers and pure hydrocarbon conjugated aryl-substituted olefin monomers refer to their concentrations in the total reaction system. Activity: expressed in 10... 7 g mol -1 h -1 Units are used for the insertion rate of monomers. 13 The results were obtained from C-NMR analysis. α is an α-olefin monomer containing a carbazole group with a five-carbon chain length.

[0164] As shown in Table 3, under high temperature and high pressure polymerization, the polymerization system with MAO as a co-catalyst exhibits significantly increased catalytic activity, reaching a polymerization activity as high as 9.8 x 10⁻⁶. 7 g mol -1 h -1The above is a summary. Examples 18-21 show that when the polymerization temperature is 90°C, the insertion rate of cyclic olefin monomers significantly increases with the increase of MAO content. Examples 22-24 show that when the polymerization temperature is 90°C, with the increase of ethylene pressure in the polymerization system, more cyclic olefin monomers and conjugated aryl-substituted olefin monomers need to be added to achieve the desired effect, in order to meet the requirement of a certain monomer insertion rate in the obtained polymer. Examples 25 and 26 show that based on the conditions of Example 19, scaling up polymerization proportionally (from 100 ml, 1 L to 5 L reactors), under constant temperature and ethylene pressure, increasing the amounts of catalyst, co-catalyst, and the two monomers by 10 times and 100 times respectively, to obtain a polymer with a certain monomer insertion rate is feasible. Comparative Example 1, a normal-pressure polymerization of ternary copolymers, significantly reduced the amount of comonomers used, but the activity was only 0.04 x 10⁻⁴. 7 g mol -1 h -1 Comparative Example 2 is a ternary copolymerization of ethylene, cyclic olefin monomers, and α-olefin monomers containing five carbon chains with carbazole groups. Under these conditions, a polymer with a certain monomer insertion rate can be obtained, with a polymerization activity of 0.51 x 10⁻⁶. 7 g mol -1 h -1 Compared with Comparative Examples 1 and 2, the method in this embodiment has a significant improvement in polymerization activity and has certain prospects for scale-up or industrialization.

[0165] The thermal and optical properties of the cyclic olefin terpolymers in the examples and comparative examples were tested, and the results are shown in Table 4.

[0166] Table 4

[0167]

[0168] Note: All data are based on results from at least two parallel trials (unless otherwise stated). M w , are the weight-average molecular weights of the polymer. a is an α-olefin monomer with a carbazole group containing five carbon chains.

[0169] As shown in Table 4, the terpolymer prepared in the examples has high heat resistance (5% thermal decomposition temperature greater than 420℃), a significantly improved refractive index (1.56-1.65), good optical properties (light transmittance greater than 90%), and certain toughness (elongation at break 12%-25%). Its water absorption rate is ≤0.01%, showing good application prospects.

[0170] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0171] The embodiments described above are merely illustrative of several implementation methods of this application, intended to facilitate a detailed understanding of the technical solutions of this application, but should not be construed as limiting the scope of protection of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the scope of protection of this application. It should be understood that technical solutions obtained by those skilled in the art based on the technical solutions provided in this application through logical analysis, reasoning, or limited experimentation are all within the scope of protection of the appended claims. Therefore, the scope of protection of this patent application should be determined by the content of the appended claims, and the specification can be used to interpret the content of the claims.

Claims

1. A method for preparing a cyclic olefin terpolymer, characterized in that, Includes the following steps: The cyclic olefin terpolymer is prepared by mixing ethylene monomer, cyclic olefin monomer and conjugated aryl-substituted olefin monomer and carrying out polymerization reaction in the presence of catalyst and co-catalyst. The conjugated aryl-substituted olefin monomers have the following structural features: Where m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin; The catalyst includes a metallocene catalyst; The cocatalyst includes one or more of aluminum compounds and boron compounds; The conditions for the polymerization reaction include a pressure of 2.2 MPa to 10 MPa.

2. The method for preparing the cyclic olefin terpolymer according to claim 1, characterized in that, The conditions for the polymerization reaction include a pressure of 2.2 MPa to 5 MPa.

3. The method for preparing the cyclic olefin terpolymer according to claim 1, characterized in that, The metallocene catalyst comprises one or more of the following: ethyl-bridged bis(indene) zirconium chloride catalyst, dimethylsilyl-bridged bis(indene) zirconium chloride catalyst, isopropylidene-bridged fluorene zirconium chloride catalyst, dimethylsilyl-bridged restricted geometry titanium catalyst, di-tert-butylimine-based monotitanium catalyst, and trimethylsilyl-substituted cyclopentadienyl monotitanium catalyst; and / or, The aluminum compound includes one or more of methylaluminoxane, modified methylaluminoxane, trialkylaluminum, dialkylaluminum chloride, monoalkylaluminum dichloride, and trialkylaluminum trichloride; and / or, The boron compound includes one or more of N,N-dimethylphenylamine tetra(pentafluorophenyl)borate, N,N-diethylphenylamine tetra(pentafluorophenyl)borate, N,N-di(hexadecyl)phenylamine tetra(pentafluorophenyl)borate, tri(pentafluorophenyl)borate, triphenylcarbazide tetra(pentafluorophenyl)borate, and triphenylmethyltetra(pentafluorophenyl)borate; and / or, The cyclic olefin monomers include one or more of norbornene and tetracyclododecene.

4. The method for preparing the cyclic olefin terpolymer according to any one of claims 1 to 3, characterized in that, The molar ratio of the catalyst to the cyclic olefin monomer is 1:(500~40000), optionally 1:(800~30000); and / or, The molar ratio of the catalyst to the conjugated aryl-substituted olefin monomer is 1:(50~40000), optionally 1:(200~30000); and / or, The molar ratio of the catalyst to the co-catalyst is 1:(1~5000), and can be optionally 1:(1~3000).

5. The method for preparing the cyclic olefin terpolymer according to any one of claims 1 to 3, characterized in that, The conditions for the polymerization reaction also include a temperature of 0℃ to 200℃, which can be selected as 50℃ to 90℃.

6. The method for preparing the cyclic olefin terpolymer according to any one of claims 1 to 3, characterized in that, The conjugated aryl-substituted olefin monomers include one or more of the following compounds 1 to 10: 。 7. The method for preparing the cyclic olefin terpolymer according to any one of claims 1 to 3, characterized in that, Based on the total molar number of the ethylene monomer, the cyclic olefin monomer, and the conjugated aryl-substituted olefin monomer, the molar percentage of the ethylene monomer is 40% to 80%, the molar percentage of the cyclic olefin monomer is 19.9% ​​to 40%, and the molar percentage of the conjugated aryl-substituted olefin monomer is 0.1% to 20%.

8. A cyclic olefin terpolymer, characterized in that, It has the following structural features: ， in, m is an integer from 1 to 10, and R1 is naphthyl, anthraceneyl, phenanthryl, pyrene, acenaphthene, or tretinoin; p is 0 or 1; 50≤n≤5000； X: Y: Z=40%~80%: 19.9%~40%: 0.1%~20%.

9. The cyclic olefin terpolymer according to claim 8, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 7.

10. An optical element, characterized in that, This includes the cyclic olefin terpolymer prepared by the preparation method according to any one of claims 1 to 7, or the cyclic olefin terpolymer according to any one of claims 8 to 9.

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