A polycarbonate resin, a method for preparing the same, and an application thereof

Abstract

Provided is a polycarbonate resin, a method for producing the same, and use thereof. The polycarbonate resin includes a structural unit A represented by the following formula (1), and at least one selected from a structural unit B represented by the following formula (2) and a structural unit C represented by the following formula (3). The polycarbonate resin of the present application has a high refractive index, a low birefringence, and has high scratch resistance and high total light transmittance.

Description

Technical Field

[0001] This application belongs to the field of polymer materials technology, and relates to a polycarbonate resin, its preparation method and application. Background Technology

[0002] Traditionally, polycarbonate resins are prepared by reacting 2,2-bis(4-hydroxyphenyl)propane (commonly known as bisphenol A) with carbonates such as phosgene or diphenyl carbonate. Due to its high transparency, excellent heat resistance, and impact resistance, it has long been used in optical components such as optical discs. However, this material suffers from drawbacks such as high birefringence and susceptibility to surface scratches, limiting its application range. Meanwhile, with the increasing demand for thinner and higher-performance optical devices, the market's demand for materials with high refractive index and low birefringence is becoming increasingly urgent.

[0003] As a method to increase refractive index and reduce birefringence, related literature reports copolymers of bisphenols with fluorene structures in the side chains (Japanese Patent Application Laid-Open No. 7-109342 and Japanese Patent Application Laid-Open No. 10-101787). However, due to their low surface hardness, they are easily damaged, which poses problems for their applications.

[0004] Furthermore, polycarbonate resins with a structure derived from bisphenol C are known to have a tendency to exhibit high scratch resistance (Japanese Patent Application Publication No. Sho 64-069625, Japanese Patent Application Publication No. Hei 08-183852, Japanese Patent Application Publication No. 2017-110180). While this polycarbonate resin exhibits improved surface hardness, it does not meet the requirements for high refractive index and low birefringence, and it also suffers from poor heat resistance.

[0005] As a resin composition copolymerized from bisphenols with fluorene side chains and bisphenol C, methods for polycarbonate or copolycarbonate with 2,2-bis(4-hydroxy-3-methylphenyl)fluorene as a constituent unit have been proposed (Japanese Patent Application Publication No. 2002-117580, Japanese Patent No. 3768903, International Publication No. 2017 / 073508) and methods for polycarbonate or copolycarbonate with 9,9-bis(6-hydroxy-2-naphthyl)fluorene as a constituent unit (International Publication No. 2024 / 090157), showing effectiveness in achieving high pencil hardness and heat resistance. However, if structural units with rigid structures are introduced to improve scratch resistance, the glass transition temperature increases, and the moldability decreases. Therefore, it is not possible to introduce them at a high ratio, or if the introduction ratio is increased, the moldability decreases significantly, making it impossible to mold complex shapes. It is difficult to achieve a product with a balanced high refractive index, low birefringence, and good moldability. Summary of the Invention

[0006] In view of the shortcomings of the prior art, the purpose of this application is to provide a polycarbonate resin, its preparation method and application.

[0007] To achieve this objective, the present application adopts the following technical solution: On the one hand, this application provides a polycarbonate resin, the polycarbonate resin comprising structural unit A as shown in formula (1) below, and at least one structural unit selected from structural unit B derived from the compound shown in formula (2) below and structural unit C derived from the compound shown in formula (3) below; ; In formula (1), R1 and R2 are independently alkyl or halogen atoms with 1 to 6 carbon atoms (e.g., 1, 2, 3, 4, 5 or 6). X1 is a single bond, a substituted or unsubstituted alkylene group with 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), a substituted or unsubstituted alkylidene group with 1 to 10 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10), a sulfur atom or an oxygen atom; ; R3 through R6 are each independently selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms (e.g., 1, 3, 5, 7, 9, 11, 13, 15, 17, or 20), alkoxy groups having 1 to 20 carbon atoms (e.g., 1, 3, 5, 7, 9, 11, 13, 15, 17, or 20), cycloalkyl groups having 5 to 20 carbon atoms (e.g., 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 20), cycloalkoxy groups having 5 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or groups having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 20), cycloalkoxy groups having 5 to 20 carbon atoms, aryl ... or cycloalkoxy groups having 5 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms (e.g., 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20) of aryloxy groups; X2 and X3 are each independently selected from alkylene groups having 2 to 8 carbon atoms (e.g., 2, 3, 4, 5, 6, 7 or 8), cycloalkylene groups having 5 to 12 carbon atoms (e.g., 6, 7, 8, 9, 10, 11 or 12), and arylene groups having 6 to 20 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20); m1 and m2 are each independently integers from 1 to 5 (e.g., 1, 2, 3, 4 or 5); ;; In formula (3), Y1 and Y2 are each independently an alkylene group with 1 to 8 carbon atoms (e.g., 2, 3, 4, 5, 6, 7 or 8); n1 and n2 are each independently an integer from 1 to 5 (e.g., 1, 2, 3, 4 or 5).

[0008] In structural unit A represented by formula (1), R1 and R2 are each preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms, and most preferably both R1 and R2 in formula (1) are methyl groups. X1 is preferably a single bond, a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 10 carbon atoms, more preferably a substituted or unsubstituted alkylene group having 1 to 5 carbon atoms, or a substituted or unsubstituted alkylidene group having 1 to 5 carbon atoms.

[0009] In some embodiments, structural unit A is a structural unit derived from a diphenol. Examples of diphenols include 2,2-bis(4-hydroxy-3-methylphenyl)propane (hereinafter referred to as bisphenol C), 2,2-bis(4-hydroxy-3-isopropylphenyl)propane, and 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane. Bisphenol C is preferred.

[0010] In the polycarbonate resin, the molar percentage of structural unit A, calculated relative to all structural units at 100 mol%, is 10–50 mol%; for example: 10 mol%, 20 mol%, 30 mol%, 40 mol%, 50 mol%, etc. If the molar percentage of structural unit A is less than 10 mol%, the pencil hardness decreases, and scratch resistance is not improved. If the molar percentage of structural unit A is greater than 50 mol%, damage resistance is improved, but the refractive index decreases and the birefringence increases significantly, resulting in deteriorated optical properties.

[0011] In structural unit B derived from formula (2), R3 to R6 are each preferably hydrogen atoms, alkyl groups with 1 to 20 carbon atoms, or aryl groups with 6 to 20 carbon atoms, more preferably hydrogen atoms, alkyl groups with 1 to 10 carbon atoms, or aryl groups with 6 to 10 carbon atoms. X2 and X3 are each preferably alkylene groups with 2 to 8 carbon atoms, and preferably both X2 and X3 in formula (2) are ethylenes; m1 and m2 are each preferably integers of 1 to 3, more preferably integers of 1 to 2. In some embodiments, m1 and m2 in formula (2) are both 1.

[0012] In some embodiments, the structural unit B is a structural unit derived from 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene or 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

[0013] In the structural unit C represented by formula (3), Y1 and Y2 are each independently alkylene groups having 1 to 6 carbon atoms, more preferably alkylene groups having 1 to 3 carbon atoms, and most preferably Y1 and Y2 in formula (3) are both ethylenes; n1 and n2 are each independently preferably integers of 1 to 3, more preferably integers of 1 to 2, and further in some embodiments, n1 and n2 in formula (3) are both 1.

[0014] In some embodiments, the structural unit C is a structural unit derived from at least one of 2,2'-dicarboxy-1,1'-binaphthyl, 2,2'-bis(carboxymethoxy)-1,1'-binaphthyl, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl, and 2,2'-bis(3-carboxypropoxy)-1,1'-binaphthyl, preferably 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl.

[0015] In polycarbonate resin, the molar percentage of structural units B and C, calculated relative to 100 mol% of all structural units, is 50–90 mol%; for example: 50 mol%, 60 mol%, 70 mol%, 80 mol%, 90 mol%, etc. If the molar percentage of structural units B and C is less than 50 mol%, the refractive index decreases and the birefringence increases significantly, resulting in deteriorated optical properties; if the molar percentage of structural units B and C is greater than 90 mol%, the optical properties are good, but the damage resistance decreases.

[0016] In this application, all structural units include structural unit A, structural unit B, and structural unit C.

[0017] In some embodiments, the viscosity-average molecular weight of the polycarbonate resin is 15,000 to 40,000 (e.g., 15,000, 17.5,000, 20,000, 22.5,000, 25,000, 27.5,000, 30,000, 32.5,000, 35,000, or 40,000), preferably 16,000 to 30,000, and more preferably 18,000 to 28,000. When the viscosity-average molecular weight of the polycarbonate resin is less than 15,000, its toughness and fracture resistance are poor. On the other hand, when the viscosity-average molecular weight of the polycarbonate resin exceeds 40,000, high molding processing temperatures or special molding methods are required, resulting in poor versatility. Moreover, the injection speed dependence can easily increase due to the increase in melt viscosity, leading to poor appearance and a decrease in yield.

[0018] Secondly, this application provides a method for preparing the polycarbonate resin as described above. The method for preparing the polycarbonate resin provided in this application is carried out by melt polycondensation. The polycarbonate resin is obtained by reacting a dihydroxy compound having the structure shown in Formula I, and a dihydroxy compound selected from those having the structure shown in Formula II and / or those having the structure shown in Formula III with a diester under heating conditions for transesterification and removing byproducts.

[0019] Formula I; In Equation I, R1~R2 and X1 each independently have the same defined range as in Equation (1); Formula II; In Equation II, R3~R6, X2~X3, and m1~m2 each independently have the same range of limitation as in Equation (2); Formula III; In equation (III), Y1, Y2, n1 and n2 each have the same range of limitation as in equation (3).

[0020] In some embodiments, the molar ratio of the sum of the dihydroxy compound having the structure shown in Formula I, the dihydroxy compound having the structure shown in Formula II, and the dihydroxy compound having the structure shown in Formula III to the diester carbonate is 1:(1~1.1), for example 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, or 1:1.1, and more preferably 1:(1.03~1.07).

[0021] In some embodiments, the carbonate includes any one or a combination of at least two of diphenyl carbonate, dimethyl carbonate, dimethyl carbonate, or diethyl carbonate, more preferably diphenyl carbonate.

[0022] In some embodiments, the polycondensation reaction is carried out in the presence of an alkaline catalyst.

[0023] In some embodiments, the alkaline catalyst includes lithium hydroxide, sodium hydroxide, magnesium hydroxide, potassium hydroxide, calcium hydroxide, cesium hydroxide, strontium hydroxide, barium hydroxide, lithium carbonate, sodium bicarbonate, magnesium bicarbonate, sodium carbonate, magnesium carbonate, potassium carbonate, calcium bicarbonate, calcium carbonate, cesium carbonate, strontium carbonate, barium carbonate, lithium acetate, sodium acetate, magnesium acetate, potassium acetate, calcium acetate, strontium acetate, barium acetate, sodium stearate, magnesium stearate, potassium stearate, calcium stearate, lithium benzoate, sodium benzoate, potassium benzoate, and benzoic acid. The combination of any one or at least two of the following: calcium, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, disodium phenyl phosphate, magnesium phenyl phosphate, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylbenzylammonium hydroxide, diethylamine, triethylamine, dimethylbenzylamine, triphenylamine, tetramethylborohydride, tetrabutylborohydride, tetrabutyltetraphenylborate, or tetraphenyltetraphenylborate, is more preferably a combination of any one or at least two of the following: sodium hydroxide, sodium bicarbonate, or sodium carbonate.

[0024] In some embodiments, the molar ratio of the sum of the dihydroxy compound having the structure shown in Formula I, the dihydroxy compound having the structure shown in Formula II, and the dihydroxy compound having the structure shown in Formula III to the basic catalyst is 1:(10) -3 ~10 -8 For example, 1:10 -3 1:10 -4 1:10 -5 1:10 -6 1:10 -7 Or 1:10 -8 Etc., further preferably 1:(10 -4 ~10 -6 ).

[0025] Thirdly, this application provides a resin composition comprising the polycarbonate resin described above.

[0026] In some embodiments, the resin composition further includes at least one of the following additives: antioxidant, processing stabilizer, light stabilizer, dye, flame retardant, lubricant, antistatic agent, surfactant, antibacterial agent, mold release agent, ultraviolet absorber, plasticizer, and compatibilizer.

[0027] As antioxidants, examples include 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-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenyl)propionate. The combination of any one or at least two of the following: benzylbenzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrogenated cinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzyl phosphate-diethyl ester, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, and 3,9-bis{1,1-dimethyl-2-[13-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro(5,5)undecane.

[0028] In some embodiments, the antioxidant content is 0.001 to 0.1 parts by weight relative to 100 parts by weight of the resin composition, 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, or 0.1 parts by weight.

[0029] In some embodiments, the processing stabilizer is a phosphorus-based processing heat stabilizer and / or a sulfur-based processing heat stabilizer.

[0030] As heat stabilizers for phosphorus-based processing, examples include 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, and bis... (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenylmono-o-biphenyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate, dimethyl phenylphosphonate, diethyl phenylphosphonate, dipropyl phenylphosphonate, tetra(2,4-di-tert-butylphenyl)-4,4'-biphenyl diphosphite, tetra(2,4-di-tert-butylphenyl)-4,3-biphenyl diphosphite, tetra(2,4-di-tert-butylphenyl)-3,3'-biphenyl diphosphite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphite, and bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphite.

[0031] In some embodiments, 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 the resin composition, 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, or 0.1 parts by weight.

[0032] As a sulfur-based processing heat stabilizer, examples include any one or a combination of at least two 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.

[0033] In some embodiments, 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 resin composition, 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.

[0034] As a release agent, it is composed of esters, which account for more than 90% by weight.

[0035] In some embodiments, the ester is prepared by reacting fatty acids and alcohols.

[0036] In some embodiments, the alcohol comprises monohydric alcohols 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 polyhydric alcohols 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).

[0037] In some embodiments, the fatty acid is a saturated fatty acid with 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).

[0038] In some embodiments, the content of the release agent is 0.005 to 1.5 parts by weight relative to 100 parts by weight of the resin composition, for example, 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.

[0039] As ultraviolet absorbers, examples include any one or a combination of at least two of benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, triazine ultraviolet absorbers, cyclic imine ester ultraviolet absorbers, or nitrogen-based acrylate ultraviolet absorbers.

[0040] In some embodiments, the content of the ultraviolet absorber is 0.01 to 3.0 parts by weight relative to 100 parts by weight of the resin composition, 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, and more preferably 0.1 to 0.5 parts by weight. Controlling the ultraviolet absorber within the above range can impart excellent weather resistance to the resin composition.

[0041] Examples of flame retardants include, for example, sulfonate metal salt flame retardants, halogenated compound flame retardants, phosphorus-containing compound flame retardants, and silicon-containing compound flame retardants. Among these, sulfonate metal salt flame retardants are preferred. The amount of flame retardant incorporated is generally 0.01 to 1 part by weight, more preferably 0.05 to 1 part by weight, relative to 100 parts by weight of the resin composition.

[0042] Fourthly, this application also provides a molded article comprising the above-described resin composition. The target molded article can be obtained by methods such as injection molding, extrusion molding, or blow molding.

[0043] The molded body of this application can be used as an optical thin film or an optical lens, improving its scratch resistance while maintaining high refractive index and low birefringence characteristics.

[0044] Compared with the prior art, this application has the following advantages: The polycarbonate resin of this application has a high refractive index (above 1.6), a low birefringence (below 4), and high scratch resistance. Its pencil hardness reaches H or F grade, and its total light transmittance is above 86%. Detailed Implementation

[0045] The technical solution of this application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely to help understand this application and should not be regarded as specific limitations on this application.

[0046] The measured values ​​in the examples were determined using the following methods or apparatus.

[0047] (1) Glass transition temperature (Tg): Measured by dynamic differential thermal analysis (DSC) according to the method provided in ASTM E1356.

[0048] (2) Refractive index (nD): Under the condition of 1.0 mm film thickness, the refractive index nD at 25℃ and wavelength 589 nm are determined using an arsenic refraction plate.

[0049] (3) Abbe number (v): v = (nD-1) / (nF-nC), where nD refers to the refractive index at wavelength 589nm, nC refers to the refractive index at wavelength 656nm, and nF refers to the refractive index at wavelength 486nm.

[0050] (4) Birefringence (Δn): The polymer is molded into a film with a thickness of 1 mm, and the birefringence Δn is measured using an ellipsometer.

[0051] (5) Total light transmittance: The transmittance was measured using a haze meter according to the method of ASTM D1003, with a sample thickness of 0.1 mm.

[0052] (6) Pencil hardness: Based on GB / T 6739-2022, in a greenhouse with an ambient temperature of 23°C, the pencil is held at a 45-degree angle relative to the surface of the resin board and a 750g load is applied while drawing lines, and the surface condition is visually evaluated.

[0053] Example 1 The method for preparing polycarbonate resin provided in this embodiment includes the following steps: (1) At room temperature, add 0.90 kg (4.20 mol) of diphenyl carbonate (hereinafter referred to as "DPC"), 0.10 kg (0.40 mol) of 2,2-bis(3-methyl-4-hydroxyphenyl)propane (hereinafter referred to as "BPC"), and 1.56 kg (3.56 mol) of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene (hereinafter referred to as "BPEF") to a 5 L reactor equipped with a thermometer, stirrer, and reflux condenser, so that the molar ratio of BPC to BPEF is 10:90, and then add 3.17 × 10 -4 g (7.92×10 - 6 The air in the reactor was replaced with nitrogen five times with sodium hydroxide (mol) to maintain atmospheric pressure inside the reactor.

[0054] (2) Within 20 minutes, raise the temperature inside the reactor to 190°C, allow it to react for 10 minutes, then within 5 minutes, reduce the pressure inside the reactor to 25 kPa, and continue the reaction for another 50 minutes.

[0055] (3) Increase the temperature inside the reactor to 210°C within 10 minutes, reduce the pressure inside the reactor to 15 kPa, and react for 60 minutes.

[0056] (4) Increase the temperature inside the reactor to 230°C within 10 minutes, reduce the pressure inside the reactor to 5 kPa, and react for 50 minutes.

[0057] (5) Increase the temperature inside the reactor to 260°C within 10 minutes, reduce the pressure inside the reactor to 0.1 kPa, and continue the reaction for 60 minutes.

[0058] (6) After the reaction is complete, nitrogen gas is introduced and the reactants are discharged from the outlet at the bottom of the reactor. After being cooled with water, they are made into granules for collection.

[0059] (7) The collected particles were vacuum dried at 80°C for 4 hours to obtain the target polycarbonate resin. The MVR value measured at 260°C and 2.16 kg load was 32 cm. 3 / 10 min.

[0060] Example 2 Except for changing BPC to 0.31 kg (1.19 mol), BPEF to 1.22 kg (2.77 mol), and setting the molar ratio of BPC to BPEF to 30:70, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 33 cm⁻¹. 3 / 10 minutes.

[0061] Example 3 Except for changing BPC to 0.51 kg (1.98 mol), BPEF to 0.87 kg (1.98 mol), and setting the molar ratio of BPC to BPEF to 50:50, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 35 cm⁻¹. 3 / 10 minutes.

[0062] Example 4 Except for changing BPC to 0.10 kg (0.40 mol), BPEF to 0.70 kg (1.58 mol), and adding 0.72 kg (1.98 mol) of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthyl (hereinafter referred to as "BHEBN") to make the molar ratio of BPC, BPEF, and BHEBN 10:40:50, the same operation as in Example 1 was performed. The resulting polycarbonate resin had an MVR of 31 cm⁻¹. 3 / 10 min.

[0063] Example 5 Except for changing BPC to 0.31 kg (1.19 mol), BPEF to 0.52 kg (1.19 mol), and BHEBN to 0.57 kg (1.58 mol), and maintaining the molar ratio of BPC, BPEF, and BHEBN at 30:30:40, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 33 cm⁻¹. 3 / 10 minutes.

[0064] Example 6 Except for changing BPC to 0.51 kg (1.98 mol), BPEF to 0.35 kg (0.79 mol), and BHEBN to 0.43 kg (1.19 mol), and maintaining the molar ratio of BPC, BPEF, and BHEBN at 50:20:30, the same procedures as in Example 1 were performed, resulting in a polycarbonate resin with an MVR of 34 cm⁻¹. 3 / 10 min.

[0065] Example 7 Except for the use of 1.87 kg (3.17 mol) of 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene (hereinafter referred to as "BEPF"), 0.10 kg (0.40 mol) of BPC, and 0.14 kg (0.40 mol) of BHEBN, with a molar ratio of BPC, BEPF, and BHEBN of 10:80:10, the same operation as in Example 1 was performed, and the resulting polycarbonate resin had an MVR of 30 cm⁻¹. 3 / 10 min.

[0066] Example 8 Except for changing BPC to 0.31 kg (1.19 mol), BEPF to 0.94 kg (1.58 mol), and BHEBN to 0.43 kg (1.19 mol), and maintaining the molar ratio of BPC, BEPF, and BHEBN at 30:40:30, the same procedures as in Example 1 were performed, resulting in a polycarbonate resin with an MVR of 32 cm⁻¹. 3 / 10 min.

[0067] Example 9 Except for changing BPC to 0.51 kg (1.98 mol), BEPF to 0.70 kg (1.19 mol), and BHEBN to 0.29 kg (0.79 mol), and maintaining the molar ratio of BPC, BEPF, and BHEBN at 50:30:20, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 33 cm⁻¹. 3 / 10 minutes.

[0068] Comparative Example 1 The monomer was changed to only 1.74 kg (3.96 mol) of BPEF, and homopolymerization was carried out. The polymerization conditions were the same as in Example 1. The resulting polycarbonate resin had an MVR of 32 cm⁻¹. 3 / 10 min.

[0069] Comparative Example 2 Except for changing BPC to 0.71 kg (2.77 mol), BPEF to 0.52 kg (1.19 mol), and setting the molar ratio of BPC to BPEF to 70:30, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 37 cm⁻¹. 3 / 10 min.

[0070] Comparative Example 3 The monomer was changed to include only 1.02 kg (3.96 mol) of BPC, and homopolymerization was carried out. The polymerization conditions were the same as in Example 1. The resulting polycarbonate resin had an MVR of 40 cm⁻¹. 3 / 10 min.

[0071] Comparative Example 4 The monomer was changed to include only 2.34 kg (3.96 mol) of BEPF, and homopolymerization was carried out. The polymerization conditions were the same as in Example 1. The resulting polycarbonate resin had an MVR of 31 cm⁻¹. 3 / 10 min.

[0072] Comparative Example 5 The monomer was changed to include only 1.44 kg (3.96 mol) of BHEBN, and homopolymerization was carried out. The polymerization conditions were the same as in Example 1. The resulting polycarbonate resin had an MVR of 31 cm⁻¹. 3 / 10 min.

[0073] Comparative Example 6 Except for changing BPC to 0.71 kg (2.77 mol), BEPF to 0.70 kg (1.19 mol), and the molar ratio of BPC to BEPF to 70:30, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 35 cm⁻¹. 3 / 10 minutes.

[0074] Comparative Example 7 Except for changing BPC to 0.71 kg (2.77 mol), BHEBN to 0.43 kg (1.19 mol), and setting the molar ratio of BPC to BHEBN to 70:30, the same procedures as in Example 1 were performed. The resulting polycarbonate resin had an MVR of 34 cm⁻¹. 3 / 10 min.

[0075] The prepared polycarbonate resin was subjected to performance tests, and the test results are shown in Tables 1 and 2.

[0076] Table 1 Table 2 The applicant declares that this application illustrates the polycarbonate resin, its preparation method, and its application through the above embodiments, but this application is not limited to the above embodiments, that is, it does not mean that this application must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of the raw materials used in this application, additions of auxiliary components, and selection of specific methods, etc., all fall within the protection scope and disclosure scope of this application.

Claims

1. A polycarbonate resin, characterized in that, The polycarbonate resin includes structural unit A as shown in formula (1) and at least one selected from structural unit B as shown in formula (2) and structural unit C as shown in formula (3). ； In formula (1), R1 and R2 are independently alkyl or halogen atoms with 1 to 6 carbon atoms; X1 is a single bond, a substituted or unsubstituted alkylene group with 1 to 10 carbon atoms, a substituted or unsubstituted alkylidene group with 1 to 10 carbon atoms, a sulfur atom or an oxygen atom. ； R3 to R6 are each independently selected from hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, cycloalkyl groups having 5 to 20 carbon atoms, cycloalkoxy groups having 5 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aryloxy groups having 6 to 20 carbon atoms; X2 and X3 are each independently selected from alkylene groups having 2 to 8 carbon atoms, cycloalkylene groups having 5 to 12 carbon atoms, and arylene groups having 6 to 20 carbon atoms; m1 and m2 are each independently integers from 1 to 5. ； In formula (3), Y1 and Y2 are each independently alkylene groups with 1 to 8 carbon atoms; n1 and n2 are each independently integers from 1 to 5.

2. The polycarbonate resin according to claim 1, characterized in that, In structural unit A represented by formula (1), R1 and R2 are each independently an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and more preferably both R1 and R2 are methyl groups; Preferably, X1 is a single bond, an alkylene group with 1 to 10 substituted or unsubstituted carbon atoms, or an alkylidene group with 1 to 10 substituted or unsubstituted carbon atoms; more preferably, it is an alkylene group with 1 to 5 substituted or unsubstituted carbon atoms, or an alkylidene group with 1 to 5 substituted or unsubstituted carbon atoms. Preferably, the structural unit A is a structural unit derived from 2,2-bis(4-hydroxy-3-methylphenyl)propane.

3. The polycarbonate resin according to claim 1 or 2, characterized in that, The molar percentage of structural unit A accounts for 10 to 50 mol of all structural units of the polycarbonate resin.

4. The polycarbonate resin according to any one of claims 1-3, characterized in that, In the structural unit B represented by formula (2), R3 to R6 are each independently a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, or an aryl group with 6 to 20 carbon atoms, more preferably a hydrogen atom, an alkyl group with 1 to 10 carbon atoms, or an aryl group with 6 to 10 carbon atoms; Preferably, X2 and X3 are each independently an alkylene group having 2 to 8 carbon atoms; more preferably, both X2 and X3 are ethylene groups. Preferably, m1 and m2 are each independently an integer from 1 to 3, more preferably an integer from 1 to 2, and even more preferably both m1 and m2 are 1; Preferably, the structural unit B is a structural unit derived from 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene or 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)fluorene.

5. The polycarbonate resin according to any one of claims 1-4, characterized in that, In the structural unit C represented by formula (3), Y1 and Y2 are each independently an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably both Y1 and Y2 are ethylene groups; Preferably, n1 and n2 are each an integer from 1 to 3, more preferably an integer from 1 to 2, and even more preferably both n1 and n2 are 1.

6. The polycarbonate resin according to any one of claims 1-5, characterized in that, The structural unit C is a structural unit derived from 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthylene; Preferably, the total molar percentage of structural unit B and structural unit C accounts for 50 to 90 mol of all structural units.

7. The polycarbonate resin according to any one of claims 1-6, characterized in that, The polycarbonate resin has a viscosity-average molecular weight of 15,000 to 40,000, preferably 16,000 to 30,000, and more preferably 18,000 to 28,000.

8. A resin composition, characterized in that, The resin composition comprises the polycarbonate resin according to any one of claims 1-6; Preferably, the resin composition further includes at least one of the following additives: antioxidant, processing stabilizer, light stabilizer, heavy metal passivator, flame retardant, lubricant, antistatic agent, surfactant, antibacterial agent, mold release agent, ultraviolet absorber, plasticizer, and compatibilizer.

9. A molded body, characterized in that, The molded body comprises the resin composition of claim 8.

10. The use of the resin composition according to claim 8 in optical films or optical lenses.

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