Thermoplastic resin, and preparation method therefor and use thereof

Abstract

The present application belongs to the field of optical resins, and provides a thermoplastic resin, and a preparation method therefor and the use thereof. The preparation raw materials of the thermoplastic resin comprise at least one of a carbonate diester or a dicarboxylic acid compound, and a dihydroxy compound. By making the content of a specific triptycene framework compound in the raw materials lower than a certain specific value, a thermoplastic resin having excellent optical performance, low fluidity and low yellowness is prepared.

Description

A thermoplastic resin and its preparation method and application Technical Field

[0001] The present invention relates to the field of optical resins, and in particular to a thermoplastic resin and its preparation method and application. Background Art

[0002] Optical plastic, also known as optical resin, is a traditional optical material with excellent optical, mechanical, thermal and chemical properties. It has simple synthesis and processing processes and low manufacturing costs. It has become one of the three basic materials for optical lenses that can compete with optical glass. At present, optical lenses made of optical plastics have occupied half of the market, especially in the field of small and micro lenses.

[0003] Currently, optical resin materials mainly include cycloolefin polymers and optical polycarbonates. Among them, optical polycarbonate occupies an extremely important position in the field of optical lenses due to its unique advantages such as lightweight, excellent optical and mechanical properties, and easy processing and molding.

[0004] CN109476835A discloses a polycarbonate using 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl as monomers. The introduction of 9,9-bis[6-(2-hydroxyethoxy)naphthyl]fluorene and 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl significantly increases the refractive index of the polycarbonate, but results in high viscosity of the reaction system and increased rigidity of the polymer, which affects practical processing and molding. CN113667110A discloses the introduction of nitrogen and a benzene ring structure into a polycarbonate resin to increase the refractive index of the polycarbonate, and the introduction of a spirocyclic structure to improve the moldability of the polycarbonate, but the yellowness of the polycarbonate is poor. CN115725063A discloses a polymer having a triptycene skeleton, 1,4-dihydroxyethoxytriptycene (DHTC). The resin containing the triptycene skeleton has a higher refractive index than the fluorene skeleton resin and is suitable for application in optical materials, but has problems with its fluidity and yellowness.

[0005] Therefore, there is an urgent need to develop a thermoplastic resin with high refractive index, low fluidity and low yellowness in this field. Summary of the Invention

[0006] The present application provides a thermoplastic resin, a preparation method and an application thereof. The thermoplastic resin has a high refractive index, low fluidity and low yellowness.

[0007] In a first aspect, the present application provides a thermoplastic resin, wherein the raw materials for preparing the thermoplastic resin include at least one of a carbonic acid diester or a dicarboxylic acid compound, and a dihydroxy compound;

[0008] The dihydroxy compound comprises: a dihydroxy compound represented by the following formula (1); and

[0009] Any one or a combination of at least two of the compound represented by the following formula (A), the compound represented by the following formula (B), or the compound represented by the following formula (C).

[0010] In formula (1), formula (A), formula (B) and formula (C), R1 and R2 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), an alkoxy group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), a 17, 18, 19, 20) cycloalkyl group having 5 to 20 carbon atoms (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), cycloalkoxy group having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), aryl group having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), or aryloxy group having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20).

[0011] The total weight of the compound represented by formula (A), the compound represented by formula (B) and the compound represented by formula (C) relative to 100 parts by weight of the dihydroxy compound represented by formula (1) is 1500 ppm or less, for example, it can be 1500 ppm, 1450 ppm, 1400 ppm, 1350 ppm, 1300 ppm, 1250 ppm, 1200 ppm, 1150 ppm, 1100 ppm, 1050 ppm, 1000 ppm, 900 ppm, 800 ppm, 700 ppm, 600 ppm, 500 ppm, etc.

[0012] Thermoplastic resins containing compound structural units derived from a triptycene skeleton represented by formula (1) have a high refractive index and are suitable for optical materials. During the synthesis process, it was discovered that the compounds represented by formulas (A), (B), and / or (C) can act as plasticizers to improve the fluidity of the thermoplastic resin. Furthermore, reducing the content of the compound represented by formula (C) in the raw materials can significantly reduce the yellowness of the thermoplastic resin.

[0013] In the synthesis process of the dihydroxy compound shown in formula (1), the compounds shown in formula (A), formula (B) and formula (C) are used as impurity by-products. Generally, in chemical reactions including polymerization reactions, the higher the purity of the raw materials, the better. However, when the thermoplastic resin contains a trace amount of the compound shown in formula (A), formula (B) and / or formula (C), a resin with excellent fluidity can be obtained. It is worth noting that excessively increasing the amount of the compound shown in formula (A), formula (B) and / or formula (C) will cause the glass transition temperature and molecular weight of the thermoplastic resin to be substandard, the product to become brittle, the mechanical properties to deteriorate, and the yellowness to increase. Therefore, it is necessary to balance the content between the above formula (1) and the compounds shown in formula (A), formula (B) and formula (C).

[0014] In addition, a variety of by-product compounds having a triptycene structure are contained as by-product impurities during the synthesis process. By-product compounds other than the compounds represented by formula (A), formula (B) and formula (C) are shown in the following formula:

[0015] During the synthesis experiment, impurities should be completely removed, especially the compounds represented by the above formula (A) and formula (B) which will affect the fluidity of the resin. Limiting their content to a certain level can improve the properties of the thermoplastic resin.

[0016] There is no particular limitation on the method for setting the content of the compound represented by formula (A), formula (B) and / or formula (C) to a certain amount in the dihydroxy compound. For example, the compound represented by formula (A), formula (B) and / or formula (C) may be added to the dihydroxy compound as a raw material to control the content of the compound represented by formula (A), formula (B) and / or formula (C); or a method of using a low-purity dihydroxy compound containing a certain amount of the compound represented by formula (A), formula (B) and / or formula (C); or adjusting the content of the dihydroxy compound represented by formula (1). The synthesis conditions of the base compound, for example, setting the reaction temperature and reaction time to 150-200°C and 1-10 hours respectively; changing the melt polymerization to different solution polymerization, such as N-methylpyrrolidone (NMP), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc.; adjusting the refining conditions after synthesis, such as adjusting the number of water washings; adjusting the solvent during water washing, such as tetrahydrofuran (THF), dichloromethane; setting the temperature of the water used for water washing to 50-90°C, and controlling the crystallization precipitation rate after the reaction, etc.

[0017] Preferably, the weight of the compound represented by formula (A) relative to 100 parts by weight of the dihydroxy compound represented by formula (1) is less than 800 ppm, for example, it can be 800 ppm, 790 ppm, 780 ppm, 770 ppm, 750 ppm, 700 ppm, 600 ppm, 500 ppm, 400 ppm, 300 ppm, 200 ppm, 100 ppm, 50 ppm, 10 ppm, 5 ppm, 1 ppm, etc.

[0018] Preferably, the weight of the compound represented by formula (B) relative to 100 parts by weight of the dihydroxy compound represented by formula (1) is less than 300 ppm, for example, it can be 300 ppm, 290 ppm, 280 ppm, 270 ppm, 260 ppm, 250 ppm, 200 ppm, 150 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, 1 ppm, etc.

[0019] Preferably, the weight of the compound represented by formula (C) relative to 100 parts by weight of the dihydroxy compound represented by formula (1) is less than 200 ppm, for example, it can be 200 ppm, 190 ppm, 180 ppm, 170 ppm, 160 ppm, 150 ppm, 140 ppm, 130 ppm, 120 ppm, 110 ppm, 100 ppm, 50 ppm, 40 ppm, 30 ppm, 20 ppm, 10 ppm, 5 ppm, 1 ppm, etc.

[0020] Preferably, based on the mass of the dihydroxy compound as 100 mol%, the proportion of the dihydroxy compound represented by formula (1) is 1 to 99.9 mol%, for example, it can be 1 mol%, 5 mol%, 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%, 99.9 mol%, etc., preferably 45 to 99.9 mol%, more preferably 55 to 99.9 mol%.

[0021] Preferably, the dihydroxy compound further comprises a dihydroxy compound selected from the following formula (2) and / or a dihydroxy compound selected from the following formula (3);

[0022] In formula (2), X is independently an alkylene group having 1 to 4 carbon atoms (e.g., 1, 2, 3, 4);

[0023] In formula (3), R3 and R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), an alkoxy group having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20), a a cycloalkyloxy group having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20); an aryloxy group having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20); and a halogen atom;

[0024] Y is selected from an alkylene group having 1 to 8 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8), a cycloalkylene group having 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, 10), and an arylene group having 6 to 10 carbon atoms (e.g., 6, 7, 8, 9, 10), and n is an integer from 0 to 5 (e.g., 0, 1, 2, 3, 4, 5);

[0025] L is selected from a single bond or any one of the following groups;

[0026] R5, R6, R9~R 12 Each is independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10), and a phenyl group;

[0027] R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., 1, 2, 3, 4, 5).

[0028] Preferably, the molar ratio of the dihydroxy compound represented by formula (1) to the dihydroxy compound represented by formula (2) is (20:80) to (99.9:0.1), for example, it can be 20:80, 25:75, 30:70, 35:65, 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 90:10, 95:5, 99.9:0.1, etc., preferably (30:70) to (99.5:0.5), and more preferably (40:60) to (99:1).

[0029] Preferably, the number average molecular weight of the thermoplastic resin is 10,000 to 50,000, for example, 10,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, etc., preferably 15,000 to 25,000, and more preferably 17,500 to 20,000.

[0030] Controlling the number average molecular weight of the thermoplastic resin within the range of 10,000 to 50,000 can prevent the molded body from being too brittle and unable to be molded, and the melt viscosity will not become too high. The resin can be easily removed from the mold during molding, and the fluidity is good, making it suitable for injection molding in a molten state.

[0031] Preferably, the glass transition temperature of the thermoplastic resin is 95 to 180°C, for example, it can be 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, etc., preferably 110 to 170°C, more preferably 130 to 160°C, and particularly preferably 140 to 150°C.

[0032] When the glass transition temperature of a thermoplastic resin exceeds 180°C, the melting temperature of the resin becomes high, and the resin is easily decomposed or colored. In addition, when the glass transition temperature of the resin is too high, the difference between the mold temperature and the glass transition temperature of the resin increases in a conventional mold temperature controller.

[0033] Preferably, the phenol content in the thermoplastic resin is 0.1 to 1000 ppm, for example, it can be 0.1 ppm, 1 ppm, 10 ppm, 50 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, etc., preferably 0.1 to 500 ppm, and more preferably 0.1 to 300 ppm.

[0034] Preferably, the carbonic acid diester is any one of diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dicyclohexyl carbonate, or a combination of at least two thereof.

[0035] Preferably, the dicarboxylic acid compound is selected from the group consisting of 2,7-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,8-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2-methyl terephthalic acid, biphenyl dicarboxylic acid, tetranaphthalene dicarboxylic acid, fluorene-9,9-dipropionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Any one or a combination of at least two of sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decahydronaphthalene dicarboxylic acid, norbornane dicarboxylic acid, tricyclodecane dicarboxylic acid, pentacyclododecanedicarboxylic acid, 3,9-bis(1,1-dimethyl-2-carboxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 5-carboxy-5-ethyl-2-(1,1-dimethyl-2-carboxyethyl)-1,3-dioxane or dimer acid.

[0036] Preferably, relative to 1 mol of the dihydroxy compound, the total amount of at least one of the carbonic acid diester and the dicarboxylic acid compound is 0.97 to 1.20 mol, for example, it can be 0.97 mol, 0.98 mol, 0.99 mol, 1.00 mol, 1.05 mol, 1.10 mol, 1.15 mol, 1.20 mol, etc., preferably 0.98 to 1.10 mol.

[0037] Preferably, the thermoplastic resin further comprises an antioxidant, a processing stabilizer, a light stabilizer, a polymeric metal deactivator, a flame retardant, a lubricant, an antistatic agent, a surfactant, an antibacterial agent, a release agent, an ultraviolet absorber, a plasticizer or a solubilizer.

[0038] Preferably, the antioxidant is triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, any one or a combination of at least two of the following: 1,2-dimethyl-2-[13-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, ....

[0039] Preferably, the content of the antioxidant is 0.001 to 0.1 parts by weight relative to 100 parts by weight of the thermoplastic resin, for example, it can be 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, or 0.1 parts by weight.

[0040] Preferably, the processing stabilizer is a phosphorus-based processing heat stabilizer and / or a sulfur-based processing heat stabilizer.

[0041] Preferably, the phosphorus-based processing heat stabilizer is triphenyl phosphite, tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, tri-octadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl) octyl phosphite, bis(nonylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, bis(2 any one or a combination of at least two of the following: dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,3-biphenyl diphosphite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenyl diphosphite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphite or bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphite.

[0042] Preferably, the content of the phosphorus-based processing heat stabilizer is 0.001 to 0.1 parts by weight relative to 100 parts by weight of thermoplastic resin, for example, it can be 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, or 0.1 parts by weight.

[0043] Preferably, the sulfur-based processing heat stabilizer is any one of pentaerythritol-tetrakis (3-lauryl thiopropionate), pentaerythritol-tetrakis (3-myristyl thiopropionate), pentaerythritol-tetrakis (3-stearyl thiopropionate), dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate or distearyl-3,3'-thiodipropionate, or a combination of at least two thereof.

[0044] Preferably, the content of the sulfur-based processing heat stabilizer is 0.001 to 0.1 parts by weight relative to 100 parts by weight of the thermoplastic resin, for example, 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.02 parts by weight, 0.03 parts by weight, 0.04 parts by weight, 0.05 parts by weight, 0.06 parts by weight, 0.07 parts by weight, 0.08 parts by weight, 0.09 parts by weight, 0.1 parts by weight, etc.

[0045] Preferably, more than 90% by weight of the release agent is ester.

[0046] Preferably, the ester is prepared by reacting a fatty acid and an alcohol.

[0047] Preferably, the alcohol includes a monohydric alcohol having 1 to 20 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20) and / or a polyhydric alcohol having 1 to 25 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25).

[0048] Preferably, the fatty acid is a saturated fatty acid having 10 to 30 carbon atoms (e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30).

[0049] Preferably, the content of the release agent is 0.005 to 1.5 parts by weight relative to 100 parts by weight of the thermoplastic resin, for example, it can be 0.005 parts by weight, 0.01 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, etc., preferably 0.01 to 0.6 parts by weight, and more preferably 0.05 to 0.1 parts by weight.

[0050] Preferably, the ultraviolet absorber includes any one or a combination of at least two of a benzotriazole ultraviolet absorber, a benzophenone ultraviolet absorber, a triazine ultraviolet absorber, a cyclic imine ester ultraviolet absorber or a nitroacrylate ultraviolet absorber.

[0051] Preferably, the content of the ultraviolet absorber is 0.01 to 3.0 parts by weight relative to 100 parts by weight of the thermoplastic resin, for example, it can be 0.01 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1.0 parts by weight, 1.5 parts by weight, 2.0 parts by weight, 2.5 parts by weight, 3.0 parts by weight, etc., preferably 0.05 to 1.5 parts by weight, more preferably 0.1 to 0.5 parts by weight. By controlling the ultraviolet absorber within the above range, excellent weather resistance can be imparted to the thermoplastic resin.

[0052] Preferably, the thermoplastic resin is any one of polyester resin, polyester carbonate resin or polycarbonate resin, or a combination of at least two of them. In consideration of heat resistance and hydrolysis resistance, polycarbonate resin is preferred.

[0053] Optical properties such as refractive index, Abbe number, and birefringence are significantly affected by the chemical structure of the structural units, and are less affected by whether the chemical bonds between the structural units are ester or carbonate. Furthermore, the presence of impurities can increase saturated water absorption or decrease polymerization rates, which are significantly affected by the chemical structure of the resin structural units and less affected by differences in the chemical bonds between the structural units.

[0054] In a second aspect, the present application provides a method for preparing the thermoplastic resin according to the first aspect, the preparation method comprising the following steps:

[0055] The raw materials for preparing the thermoplastic resin are mixed and reacted to obtain the thermoplastic resin.

[0056] Preferably, the reaction is carried out in the presence of a catalyst.

[0057] Preferably, the catalyst is selected from any one or a combination of at least two of alkali metal compounds, alkaline earth metal compounds or nitrogen-containing compounds.

[0058] Preferably, the alkali metal compound is any one of sodium hydroxide, potassium hydroxide, sodium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium phenyl boronate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenyl phosphate, disodium salt, dipotassium salt, dicesium salt or dilithium salt of bisphenol A, sodium salt, potassium salt, cesium salt or lithium salt of phenol, or a combination of at least two thereof, and more preferably sodium hydroxide and / or sodium bicarbonate.

[0059] Preferably, the amount of the catalyst is such that the molar ratio of the sum of the compounds having the structure shown in formula (1) to the catalyst is 1:(10 -7 ~10 -5 ).

[0060] Preferably, the reaction conditions of the reaction are as follows: heating the mixture to 150-190°C (e.g., 150°C, 160°C, 170°C, 180°C, 190°C, etc.) under normal pressure, reacting for 5-15 min (e.g., 5 min, 10 min, 15 min, etc.), then reducing the pressure to 20-30 kPa (e.g., 20 kPa, 25 kPa, 30 kPa, etc.), and continuing the reaction for 20-40 min (e.g., 20 min, 30 min, 40 min, etc.); then heating to 200-220°C (e.g., 200°C, 210°C, 220°C, etc.), reducing the pressure to 10-18 kPa (e.g., 10 kPa, 14 kPa, 18 kPa, etc.), and reacting for 15-25 min (e.g., 15 min, 20 min, 25 min, etc.); then heating to 230-270° C. (e.g., 230° C., 250° C., 270° C., etc.), the pressure is reduced to 3-6 kPa (e.g., 3 kPa, 4 kPa, 5 kPa, 6 kPa, etc.), and the reaction is carried out for 10-25 min (e.g., 10 min, 15 min, 20 min, 25 min, etc.); then the temperature is raised to 240-290° C. (e.g., 250° C., 260° C., 270° C., 280° C., 290° C., etc.), the pressure is further reduced to 0.05-0.5 kPa (e.g., 0.1 kPa, 0.2 kPa, 0.3 kPa, 0.4 kPa, 0.5 kPa, etc.), and the reaction is continued for 50-90 min (e.g., 50 min, 60 min, 70 min, 80 min, 90 min, etc.). After the reaction is completed, heating is stopped and nitrogen is introduced to obtain the thermoplastic resin.

[0061] Under an inert gas atmosphere, a dihydroxy compound and a carbonic acid diester are heated and stirred until melted, and then polymerized while distilling off the generated alcohol or phenol. The reaction temperature is typically 120-350°C, depending on the boiling point of the generated alcohol or phenol. Initially, the reaction is decompressed to distill off the generated alcohol or phenol. A transesterification catalyst may also be used to accelerate the reaction. The reaction can be carried out continuously or batchwise.

[0062] In a third aspect, the present application provides a molded body, which is obtained by molding the thermoplastic resin described in the first aspect, and the molded body includes a lampshade, an automobile lamp lens, a signboard, a laser printing film or a display light.

[0063] The thermoplastic resin of the present application can be manufactured into a molded body by methods such as injection molding, compression molding, extrusion molding, or solution casting.

[0064] In a fourth aspect, the present application provides an optical material, wherein the raw materials for preparing the optical material include the thermoplastic resin described in the first aspect.

[0065] In a fifth aspect, the present application provides an optical lens, wherein the raw materials for preparing the optical lens include the thermoplastic resin described in the first aspect.

[0066] The thermoplastic resin of the present application can be used to prepare optical lenses through injection molding, compression molding or injection-compression molding.

[0067] In a sixth aspect, the present application provides an optical film, which is prepared from the thermoplastic resin described in the first aspect.

[0068] Compared with the related art, this application has at least the following beneficial effects:

[0069] By adding a specific amount of a triptycene skeleton compound to a dihydroxy compound having a specific triptycene skeleton, the optical properties of the thermoplastic resin, such as the refractive index, Abbe number and birefringence, are not affected, and the fluidity and yellowness of the thermoplastic resin are significantly improved. DETAILED DESCRIPTION

[0070] To facilitate understanding of the present application, the present application lists the following examples. Those skilled in the art should understand that the examples are only provided to help understand the present application and should not be considered as specific limitations of the present application.

[0071] Preparation Example 1

[0072] This preparation example provides a dihydroxy compound. 12.1 g (112 mmol) of anthracene, 10 g (56 mmol) of benzoquinone, and 100 mL of toluene were added to a glass reactor equipped with a stirrer, nitrogen insufflation tube, thermometer, and reflux condenser. The mixture was stirred at 110°C under reflux for 3 hours. After the reaction, the mixture was filtered, and the filtrate was collected and crystallized with ethanol to obtain a white powder, 1,4-dihydroxytriptycene. This was then transesterified with ethylene carbonate to obtain white crystals. 150 mL of toluene was added to the white crystals, and the crystals were washed twice with 100 g of alkaline solution at 80°C. The mixture was slowly cooled to room temperature, and the precipitated crystals were filtered and dried to obtain white crystalline 1,4-dihydroxyethoxytriptycene (DHTC-1). LC-MS analysis showed that the purity of DHTC-1 was 99.5%, with a content of 800 ppm of formula (A), 450 ppm of formula (B), and 200 ppm of formula (C).

[0073] Preparation Example 2

[0074] This preparation example provides a dihydroxy compound. 12.1 g (112 mmol) of anthracene, 10 g (56 mmol) of benzoquinone, and 100 mL of toluene were added to a glass reactor equipped with a stirrer, nitrogen insufflation tube, thermometer, and reflux condenser. The mixture was stirred at 110°C under reflux for 3 hours. After the reaction, the mixture was filtered, and the filtrate was collected and crystallized with ethanol to obtain a white powder, 1,4-dihydroxytriptycene. This was then transesterified with ethylene carbonate to obtain white crystals. 150 mL of toluene was added to the white crystals, and the mixture was washed five times with 100 g of alkali solution at 80°C. After filtration, the mixture was added to 500 mL of dichloromethane and precipitated with excess n-hexane. The precipitated crystals were filtered and dried to obtain white crystals of DHTC-2. LC-MS analysis showed that the purity of DHTC-2 was 99.7%, with a content of 500 ppm of formula (A), 250 ppm of formula (B), and 200 ppm of formula (C).

[0075] Preparation Example 3

[0076] This preparation example provides a dihydroxy compound. 12.1 g (112 mmol) of anthracene, 10 g (56 mmol) of benzoquinone, and 100 mL of toluene were added to a glass reactor equipped with a stirrer, nitrogen insufflation tube, thermometer, and reflux condenser. The mixture was stirred at 110°C under reflux for 3 hours. After the reaction, the mixture was filtered, and the filtrate was collected and crystallized with ethanol to obtain a white powder, 1,4-dihydroxytriptycene. This was then transesterified with ethylene carbonate to obtain white crystals. 150 mL of toluene was added to the white crystals, and the mixture was washed five times with 100 g of alkali solution at 80°C. The mixture was slowly cooled to room temperature, and the precipitated crystals were filtered and dried to obtain white crystals of DHTC-3. LC-MS analysis showed that the purity of DHTC-3 was 99.9%, with a content of 400 ppm of formula (A), 200 ppm of formula (B), and 100 ppm of formula (C).

[0077] Comparative Preparation Example 1

[0078] This comparative preparation example provides a dihydroxy compound. 12.1 g (112 mmol) of anthracene, 10 g (56 mmol) of benzoquinone, and 100 mL of toluene were added to a glass reactor equipped with a stirrer, a nitrogen insufflation tube, a thermometer, and a condenser reflux. The mixture was stirred at 110°C for 3 hours. After the reaction was completed, the mixture was filtered, and the filtrate was collected and added to ethanol for crystallization to obtain a white powder of 1,4-dihydroxytriptycene. The white powder DHTC-4 was obtained by transesterification with ethylene carbonate, dissolving and recrystallizing the mixture. Liquid chromatography-mass spectrometry (LC-MS) analysis showed that the purity of DHTC-4 was 97.7%, the content of formula (A) was 5700 ppm, the content of formula (B) was 4300 ppm, and the content of formula (C) was 2500 ppm.

[0079] Example 1

[0080] This embodiment provides a thermoplastic resin. 1037.3 g (3.3 mol) of DHTC-3, 749.8 g (3.5 mol) of diphenyl carbonate (DPC), and sodium bicarbonate as a catalyst are placed in a stainless steel reactor equipped with a stirrer and a distillation device. The reactor is maintained at atmospheric pressure. The temperature in the reactor is raised to 170° C. over 20 minutes, the reaction is continued for 10 minutes, and the pressure in the reactor is subsequently reduced to 25 kPa over 5 minutes, and the reaction is continued for 30 minutes. Next, the temperature in the reactor is raised to 210° C. over 10 minutes, the pressure in the reactor is reduced to 15 kPa, and the reaction is continued for 20 minutes. Then, the temperature in the reactor is raised to 240° C. over 10 minutes, the pressure in the reactor is reduced to 5 kPa, and the reaction is continued for 20 minutes. Finally, the temperature in the reactor is raised to 260° C. over 10 minutes, the pressure in the reactor is reduced to 0.1 kPa, and the reaction is continued for 60 minutes. Nitrogen is introduced into the reactor to return the reaction system to atmospheric pressure, thereby producing a thermoplastic resin.

[0081] Example 2

[0082] This example provides a thermoplastic resin. 902.4 g (2.871 mol) of DHTC-3, 91.9 g (0.429 mol) of 2,2-bis(4-hydroxyphenyl)propane (BPA), 728.4 g (3.4 mol) of diphenyl carbonate, and sodium bicarbonate as a catalyst were placed in a stainless steel reactor equipped with a stirrer and a distillation device. The reactor was maintained at atmospheric pressure and the temperature was raised to 190°C over 20 minutes. The reaction was continued for 15 minutes. Subsequently, the pressure was reduced to 20 kPa over 5 minutes, and the reaction was continued for another 20 minutes. Next, the temperature was raised to 200°C over 10 minutes, the pressure was reduced to 12 kPa, and the reaction was continued for 25 minutes. Finally, the temperature was raised to 250°C over 10 minutes, the pressure was reduced to 6 kPa, and the reaction was continued for 15 minutes. Finally, the temperature in the kettle was raised to 280°C within 10 minutes, and the pressure in the kettle was reduced to 0.2 kPa. The reaction was continued for 80 minutes. Nitrogen was introduced into the reactor to restore the reaction system to normal pressure to obtain a thermoplastic resin.

[0083] Example 3

[0084] This example provides a thermoplastic resin. 902.4 g (2.871 mol) of DHTC-3, 188.1 g (0.429 mol) of 9,9-bis[4-(2-hydroxyethoxy)-3-phenyl]fluorene (BPEF), 642.7 g (3 mol) of diphenyl carbonate, and sodium bicarbonate as a catalyst were placed in a stainless steel reactor equipped with a stirrer and a distillation device. The reactor was maintained at atmospheric pressure and the temperature was raised to 180°C over 20 minutes. The reaction was continued for 15 minutes. Subsequently, the pressure was reduced to 20 kPa over 5 minutes, and the reaction was continued for 35 minutes. Subsequently, the temperature was raised to 215°C over 10 minutes, the pressure was reduced to 18 kPa, and the reaction was continued for 25 minutes. Finally, the temperature was raised to 230°C over 10 minutes, the pressure was reduced to 3 kPa, and the reaction was continued for 10 minutes. Finally, the temperature in the kettle was raised to 240°C within 10 minutes, and the pressure in the kettle was reduced to 0.05 kPa. The reaction was continued for 50 minutes. Nitrogen was introduced into the reactor to restore the reaction system to normal pressure to obtain a thermoplastic resin.

[0085] Example 4

[0086] This embodiment provides a thermoplastic resin, which differs from the embodiment 1 only in that DHTC-1 is used, and other conditions are the same as those of the embodiment 1.

[0087] Example 5

[0088] This embodiment provides a thermoplastic resin, which differs from embodiment 2 only in that DHTC-1 is used, and other conditions are the same as those in embodiment 2.

[0089] Example 6

[0090] This embodiment provides a thermoplastic resin, which differs from the embodiment 3 only in that DHTC-1 is used, and other conditions are the same as those of the embodiment 3.

[0091] Example 7

[0092] This embodiment provides a thermoplastic resin, which differs from the embodiment 1 only in that DHTC-2 is used, and other conditions are the same as those of the embodiment 1.

[0093] Example 8

[0094] This embodiment provides a thermoplastic resin, which differs from embodiment 2 only in that DHTC-2 is used, and other conditions are the same as those of embodiment 2.

[0095] Example 9

[0096] This embodiment provides a thermoplastic resin, which differs from the embodiment 3 only in that DHTC-2 is used, and other conditions are the same as those of the embodiment 3.

[0097] Comparative Example 1

[0098] This comparative example provides a thermoplastic resin, which differs from Example 1 only in that DHTC-4 is used, and other conditions are the same as those of Example 1.

[0099] Comparative Example 2

[0100] This comparative example provides a thermoplastic resin, which differs from Example 2 only in that DHTC-4 is used, and other conditions are the same as those in Example 2.

[0101] Comparative Example 3

[0102] This comparative example provides a thermoplastic resin, which differs from Example 3 only in that DHTC-4 is used, and other conditions are the same as those of Example 3.

[0103] Application Example 1

[0104] The thermoplastic resin of Example 2 was dissolved in dichloromethane to prepare a resin solution having a solid content of 5 wt %. This resin solution was poured into a mold for forming a casting film, and after the dichloromethane evaporated, the mold was peeled off and dried to prepare a casting film with a thickness of 0.1 mm.

[0105] Application Example 2

[0106] The thermoplastic resin of Example 3 was dissolved in dichloromethane to prepare a resin solution having a solid content of 5 wt %. This resin solution was poured into a mold for forming a casting film, and after the dichloromethane evaporated, the mold was peeled off and dried to prepare a casting film with a thickness of 0.1 mm.

[0107] Comparative Application Example 1

[0108] A thermoplastic resin (Mitsubishi Chemical EP5000) was dissolved in dichloromethane to prepare a resin solution with a solid content of 5 wt%. This resin solution was poured into a casting film mold, and after the dichloromethane evaporated, the mold was peeled off and dried to produce a casting film with a thickness of 0.1 mm.

[0109] Performance Testing

[0110] The test method is as follows:

[0111] (1) Melt Volume Flow Rate (MVR): MVR is an indicator of the fluidity of a resin or resin composition. A larger value indicates higher fluidity. The thermoplastic resin is vacuum-dried at 120°C for 4 hours and measured using an Instron melt indexer at 260°C and a load of 2160 g.

[0112] (2) Purity and impurity content: 20 mg of DHTC was dissolved in 10 mL of methanol and filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 0.20 μm. The compounds were identified using a liquid chromatography-mass spectrometer (LC-MS). The purity was calculated from the ratio of the peak area of ​​each compound to the total peak area.

[0113] (3) Tensile Strength: A thermoplastic resin was dissolved in dichloromethane at a concentration of 5 wt% and cast onto a horizontal casting plate. The solvent was then evaporated while adjusting the evaporation rate from the casting solution to obtain a transparent film with a thickness of approximately 100 μm. The film was then thoroughly dried in a vacuum dryer at a temperature below the glass transition temperature. The film was tested using a universal tensile testing machine in accordance with ASTM D882-61T.

[0114] (4) Yellowness: Yellowness was measured using a CS-820N desktop spectrophotometer.

[0115] (5) Total light transmittance and haze: The total light transmittance and haze were measured using a HAM-200 haze meter from Yuanfang Photoelectric.

[0116] (6) Glass transition temperature: measured using a differential scanning calorimeter (DSC).

[0117] (7) Refractive index: The refractive index of a film having a thickness of 0.1 mm was measured at a wavelength of 589 nm at 23°C using an Abbe refractometer.

[0118] (8) Abbe number: The refractive index of a film having a thickness of 0.1 mm was measured at wavelengths of 486 nm, 589 nm, and 656 nm at 23° C. using an Abbe refractometer, and the Abbe number was calculated using the following formula.

[0119] v=(n D -1) / (n F -n C )

[0120] n D : Refractive index at a wavelength of 589nm

[0121] n C : Refractive index at a wavelength of 656nm

[0122] n F : Refractive index at a wavelength of 486nm

[0123] Test results

[0124] Table 1

[0125] From the analysis of the data in Table 1, it can be seen that, taking Examples 1 to 9 as an example, the number average molecular weight of the thermoplastic resin described in this application is 15500 to 18000, and the MVR is 43 to 50 cm 3 / 10min, yellowness is 1.12~5.03.

[0126] Analysis of Comparative Examples 1 to 3 and Example 1 shows that Comparative Examples 1 to 3 use raw materials containing 12500 ppm of compounds of formula (A) to (C), and the MVR of the thermoplastic resin increases from 45 cm 3 / 10min increased to 77cm 3 / 10min, the yellowness increased from 1.19 to 12.36.

[0127] Analysis of Examples 1 to 9 shows that the total content of the compounds of formula (A) to (C) in Examples 7 to 9 is less than 1000 ppm, and the MVR of the thermoplastic resin is 47 to 48 cm 3 / 10min, yellowness is 2.83-2.87; the total content of the compounds of formula (A)-(C) in Examples 4-6 is less than 1500ppm, and the MVR of the thermoplastic resin is 45-50cm 3 / 10min, yellowness is 5.00-5.03; the total content of the compounds of formula (A)-(C) in Examples 1-3 is less than 800ppm, and the MVR of the thermoplastic resin is 43-46cm 3 / 10min, the yellowness is 1.12-1.19, and reducing the total content of the compounds of formula (A) to (C) in the thermoplastic resin can significantly improve the melt volume flow rate and yellowness of the thermoplastic resin.

[0128] Table 2

[0129] Analysis of the data in Table 2 shows that, compared with the existing optical thermoplastic resin in Comparative Application Example 1, the films made of the thermoplastic resins in Application Examples 1 and 2 of the present application have a high refractive index, high heat resistance and low Abbe number.

[0130] The applicant declares that the above is only a specific implementation method of the present application, but the protection scope of the present application is not limited thereto. Technical personnel in the relevant technical field should understand that any changes or substitutions that can be easily thought of by technical personnel in the relevant technical field within the technical scope disclosed in this application fall within the protection scope and disclosure scope of this application.

Claims

1. A thermoplastic resin, the raw materials for its preparation comprising at least one of a dicarbonate or a dicarboxylic acid compound, and a dihydroxy compound; The dihydroxy compound includes: the dihydroxy compound represented by the following formula (1); and Any one or a combination of at least two of the compounds represented by the following formula (A), the compounds represented by the following formula (B), or the compounds represented by the following formula (C); In formula (1), formula (A), formula (B) and formula (C), R1 and R2 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms; Based on 100 parts by weight of the dihydroxy compound represented by formula (1), the total weight of the compound represented by formula (A), the compound represented by formula (B) and the compound represented by formula (C) is 1500 ppm or less.

2. The thermoplastic resin according to claim 1, wherein, Based on 100 parts by weight of the dihydroxy compound represented by formula (1), the weight of the compound represented by formula (A) is 800 ppm or less; Based on 100 parts by weight of the dihydroxy compound represented by formula (1), the weight of the compound represented by formula (B) is 300 ppm or less; Based on 100 parts by weight of the dihydroxy compound represented by formula (1), the weight of the compound represented by formula (C) is 200 ppm or less; Based on 100 mol% of the dihydroxy compound, the proportion of the dihydroxy compound represented by formula (1) is 1 to 99.9 mol%.

3. The thermoplastic resin according to claim 1, wherein, The dihydroxy compound also contains a dihydroxy compound selected from the dihydroxy compounds represented by the following formula (2) and / or a dihydroxy compound represented by the following formula (3); In formula (2), X is an alkylene group having 1 to 4 carbon atoms; In formula (3), R3 and R4 are each independently selected from a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms or a halogen atom; Y is selected from an alkylene group having 1 to 8 carbon atoms, a cycloalkylene group having 6 to 10 carbon atoms or an arylene group having 6 to 10 carbon atoms, and n is an integer from 0 to 5; L is selected from a single bond or any one of the following groups; R5, R6, R9 to R 12 are each independently selected from a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group; R7 and R8 are each independently selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; The molar ratio of the dihydroxy compound represented by formula (1) to the dihydroxy compound represented by formula (2) is 20 / 80 to 99.9 / 0.

1.

4. The thermoplastic resin according to claim 1, wherein The number average molecular weight of the thermoplastic resin is 10,000 to 50,000; The glass transition temperature of the thermoplastic resin is 95 to 180 °C; The phenol content in the thermoplastic resin is 0.1 to 1000 ppm.

5. The thermoplastic resin according to claim 1, wherein The dicarbonate is any one or a combination of at least two of diphenyl carbonate, dimethylxylene carbonate, bis(chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate or dicyclohexyl carbonate; The dicarboxylic acid compound is any one or a combination of at least two of 2,7-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 2-methylterephthalic acid, biphenyldicarboxylic acid, tetrahydronaphthalenedicarboxylic acid, fluorene-9,9-dipropionic acid, oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, cyclohexanedicarboxylic acid, decahydronaphthalenedicarboxylic acid, norbornanedicarboxylic acid, tricyclodecanedicarboxylic acid, pentacyclododecanedicarboxylic acid, 3,9-bis(1,1-dimethyl-2-carboxyethyl)-2,4,8,10-tetraoxaspiro[5.5]undecane, 5-carboxy-5-ethyl-2-(1,1-dimethyl-2-carboxyethyl)-1,3-dioxane or dimer acid; The total amount of at least one of the carbonic acid diester and the dicarboxylic acid compound is 0.97 to 1.20 moles relative to 1 mole of the dihydroxy compound.

6. A method for preparing a thermoplastic resin according to any one of claims 1 to 5, which comprises the following steps: Mixing and reacting the raw materials for preparing the thermoplastic resin to obtain the thermoplastic resin.

7. The preparation method according to claim 6, wherein, The reaction is carried out in the presence of a catalyst; The catalyst is selected from any one or a combination of at least two of alkali metal compounds, alkaline earth metal compounds or nitrogen-containing compounds; The amount of the catalyst used is such that the molar ratio of the sum of the compounds having the structure shown in formula (1) to the catalyst is 1:(10 -8 ~10 -4 ).

8. The preparation method according to claim 6, wherein, The reaction conditions of the reaction are as follows: heating the mixture to 150-190°C under atmospheric pressure and reacting for 5-15 min, then reducing the pressure to 20-30 kPa and continuing to react for 20-40 min; then heating to 200-220°C, reducing the pressure to 10-18 kPa and reacting for 15-25 min; then heating to 230-270°C, reducing the pressure to 3-6 kPa and reacting for 10-25 min; then heating to 240-290°C, continuing to reduce the pressure to 0.05-0.5 kPa and continuing to react for 50-90 min. After the reaction is completed, heating is stopped and nitrogen is introduced to obtain the thermoplastic resin.

9. A molded article formed from the thermoplastic resin according to any one of claims 1 to 5; The molded article includes a lamp shade, an automotive lamp lens, a sign board, a laser printing film or a display lamp.

10. An optical material, the raw materials for preparing which include the thermoplastic resin according to any one of claims 1 to 5.

11. An optical lens, the raw materials for preparing which include the thermoplastic resin according to any one of claims 1 to 5.

12. An optical film prepared from the thermoplastic resin according to any one of claims 1 to 5.

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