WO2022077450A1 - 聚碳酸酯及其制备方法和应用 - Google Patents

聚碳酸酯及其制备方法和应用 Download PDF

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WO2022077450A1
WO2022077450A1 PCT/CN2020/121550 CN2020121550W WO2022077450A1 WO 2022077450 A1 WO2022077450 A1 WO 2022077450A1 CN 2020121550 W CN2020121550 W CN 2020121550W WO 2022077450 A1 WO2022077450 A1 WO 2022077450A1
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polycarbonate
independently selected
formula
bis
substituted
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PCT/CN2020/121550
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English (en)
French (fr)
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赵欣
黎雷
靳少华
曾伟
王磊
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万华化学集团股份有限公司
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Priority to PCT/CN2020/121550 priority Critical patent/WO2022077450A1/zh
Publication of WO2022077450A1 publication Critical patent/WO2022077450A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics

Definitions

  • the present application belongs to the technical field of polymer materials, and in particular relates to a polycarbonate and a preparation method and application thereof.
  • optical glass has high cost, poor material forming and processing performance, and poor hydrothermal stability, thus limiting its large-scale application in optical lenses and lenses.
  • optical resins have the advantages of low cost, easy processing, and thinning, and have broader application prospects.
  • Polycarbonate is an engineering plastic with good comprehensive properties. It not only has good dimensional stability, heat resistance and mechanical properties, but also is colorless and transparent. It is a widely used optical resin.
  • the applications of polycarbonate in optical lenses include multilayer diffusers, light reflective films and vision correction lenses.
  • the refractive index of the polycarbonate obtained by homopolymerization of bisphenol A is about 1.58, and the optical properties are more excellent than that of polymethyl methacrylate or polystyrene. Therefore, the development of polycarbonate-based optical resins is a current research focus.
  • CN104769007A discloses a polycarbonate resin, its manufacturing method and an optical molded body.
  • the polycarbonate resin contains a structural unit represented by the general formula (A) Wherein, X is an alkylene group with 1-4 carbon atoms; the refractive index of the polycarbonate resin can reach 1.66, and the Abbe number is lower than 24.
  • CN111094389A discloses a polycarbonate resin, its manufacturing method and optical lens.
  • the general formula is contained in the polycarbonate resin
  • the structural unit shown has a refractive index of up to 1.71 and an Abbe number below 20.
  • the purpose of the present application is to provide a polycarbonate and its preparation method and application, by designing a specific structural unit with a dithionaphthalene group, so that the polycarbonate has both high refractive index, High Abbe number and excellent hydrothermal stability can fully meet the performance requirements of polycarbonate as an optical resin in optical components.
  • the application provides a polycarbonate comprising a repeating unit having a structure as shown in formula I:
  • X 1 and X 2 are each independently selected from C1-C8 linear or branched alkylene groups.
  • the C1-C8 linear or branched alkylene groups include C1, C2, C3, C4, C5, C6, C7 or C8 linear or branched alkylene groups, exemplarily including but not limited to: methylene , ethylene, 1,2-ethylene, propylene or butylene, etc.
  • R 1 and R 2 are each independently selected from halogen, substituted or unsubstituted C1-C6 (such as C1, C2, C3, C4, C5 or C6) straight or branched chain alkyl, substituted or unsubstituted C2-C6 (e.g. C2, C3, C4, C5 or C6) alkenyl, substituted or unsubstituted C1-C6 (e.g.
  • C6-C30 such as C6, C8, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.
  • C3-C30 such as C3, C4, C5 , C6, C8, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.
  • halogen mentioned in the present application includes fluorine, chlorine, bromine or iodine, and the same description is referred to below, and all have the same meaning.
  • a and b are each independently selected from an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • n 1 and n 2 are each independently selected from an integer from 0 to 4, such as 0, 1, 2, 3 or 4.
  • the polycarbonate provided in this application contains repeating units of the structure shown in formula I, and the repeating units contain specific dithionaphthalene groups
  • the above-mentioned specific structural units endow the polycarbonate with high refractive index and high Abbe number, high glass transition temperature, excellent hydrothermal stability, and can meet the requirements of subsequent high-temperature processing and harsh environments stability requirements in use.
  • the optical lens comprising the polycarbonate has the characteristics of lightness and thinness, low chromatic aberration and low dispersion, and provides more selectivity for the combination of optical systems.
  • the substituted substituents in R 1 and R 2 are each independently selected from cyano, mercapto, hydroxyl, C1-C6 (eg C1, C2, C3, C4, C5 or C6) linear or branched alkanes base, C1-C6 (such as C1, C2, C3, C4, C5 or C6) alkoxy, C6-C18 (such as C6, C8, C9, C10, C12, C14, C16 or C18, etc.) aryloxy, C6 ⁇ C18 (such as C6, C8, C9, C10, C12, C14, C16 or C18, etc.) arylthio, C6 ⁇ C18 (such as C6, C8, C9, C10, C12, C14, C16 or C18, etc.) aryl or At least one of C3-C18 (eg C3, C4, C5, C6, C8, C9, C10, C12, C14, C16 or C18, etc.) heteroaryl.
  • the X 1 and X 2 are each independently selected from C1-C3 linear or branched alkylene groups, more preferably ethylene groups, and even more preferably 1,2-ethylene groups.
  • the a and b are each independently selected from an integer from 1 to 4, such as 1, 2, 3 or 4.
  • the R 1 and R 2 are each independently selected from substituted or unsubstituted C6-C18 aryl groups, substituted or unsubstituted C3-C18 heteroaryl groups; the substituted substituents are each independently selected from cyano at least one of C1-C4 (eg C1, C2, C3 or C4) straight or branched chain alkyl, C1-C3 (eg C1, C2 or C3) alkoxy group.
  • C1-C4 eg C1, C2, C3 or C4 straight or branched chain alkyl
  • C1-C3 eg C1, C2 or C3 alkoxy group.
  • the C6-C18 aryl groups include C6, C8, C9, C10, C12, C14, C16 or C18 aryl groups, exemplarily including but not limited to: phenyl, biphenyl, naphthyl, Anthracenyl or fluorenyl, etc.
  • the C3-C18 heteroaryl groups include C3, C4, C5, C6, C8, C9, C10, C12, C14, C16 or C18 heteroaryl groups, wherein the heteroatoms include O, S or N etc.; exemplarily including but not limited to: furanyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, indolyl, isoindolyl, carbazolyl, pyridyl, quinolinyl, isoquinolinyl , benzofuranyl, dibenzofuranyl, naphthofuranyl, benzopyrazolyl, naphthopyridyl, benzothienyl or dibenzothienyl and the like.
  • n 1 and n 2 are each independently selected from an integer from 0 to 2, such as 0, 1 or 2.
  • R 1 and R 2 are each independently selected from any one of the following groups, or any one of the following groups substituted by substituents:
  • the dotted line represents the attachment site of the group
  • the substituent is selected from cyano group, mercapto group, hydroxyl group, C1-C4 (eg C1, C2, C3 or C4) straight or branched chain alkyl, C1-C3 (eg C1, C2 or C3) alkoxy group any kind.
  • the R 1 and R 2 are each independently selected from phenyl, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-mercaptophenyl, 3-mercaptophenyl group, 4-mercaptophenyl, 1-naphthyl, 2-naphthyl, 3-naphthyl, 2-cyanonaphthyl, 3-cyanonaphthyl, 4-cyanonaphthyl, 2-mercaptonaphthyl, Any one of 3-mercaptonaphthyl, 4-mercaptonaphthyl, thienyl or benzothienyl.
  • the polycarbonate comprises any one or a combination of at least two of the following repeating units 1a-1m:
  • the molar percentage of repeating units having the structure shown in formula I in the polycarbonate is 10-100%, for example, 12%, 15%, 18%, 20%, 22%, 25%, 28% %, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85%, 88%, 90%, 92%, 95% or 98%, as well as specific point values between the above point values, limited by space and For the sake of simplicity, the present application does not exhaustively list the specific point values included in the range, and it is more preferably 20% to 90%.
  • the polycarbonate also includes a repeating unit having a structure as shown in formula II:
  • Y 1 and Y 2 are each independently selected from C1-C4 (eg C1, C2, C3 or C4) linear or branched alkylene groups.
  • Z is selected from single bond, O, S, C1-C5 (such as C1, C2, C3, C4 or C5) linear or branched alkylene, In either, the dotted line represents the attachment site of the group.
  • R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydroxyl, C1-C20 (eg, C1, C3, C5, C7, C9, C10, C12, C14, C16, C18, or C19 etc.) straight or branched chain alkyl, C1-C20 (such as C1, C3, C5, C7, C9, C10, C12, C14, C16, C18 or C19, etc.) alkoxy, C3-C20 (such as C4, C5 , C7, C9, C10, C12, C14, C16, C18 or C19, etc.) cyclic hydrocarbon group, C3-C20 (such as C4, C5, C7, C9, C10, C12, C14, C16, C18 or C19, etc.) cyclic hydrocarbon oxygen base, C6-C20 (such as C6, C8, C9, C10, C12, C14, C16 or C18, etc
  • the cyclic hydrocarbon group includes a cycloalkyl group or an unsaturated non-aromatic cyclic hydrocarbon group.
  • n 1 and m 2 are each independently selected from an integer from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • n 3 , m 4 , m 7 , and m 8 are each independently selected from an integer from 0 to 4, such as 0, 1, 2, 3, or 4.
  • n 5 and m 6 are each independently selected from an integer from 0 to 5, for example, 0, 1, 2, 3, 4 or 5.
  • the Y 1 and Y 2 are each independently selected from C1-C3 (eg C1, C2 or C3) linear or branched alkylene groups, more preferably ethylene groups, and still more preferably 1,2- Ethylene.
  • C1-C3 eg C1, C2 or C3 linear or branched alkylene groups, more preferably ethylene groups, and still more preferably 1,2- Ethylene.
  • the Z is selected from S, methylene, In either, the dotted line represents the attachment site of the group.
  • said R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydroxyl, C1-C5 (eg C1, C2, C3, C4 or C5) linear or branched alkanes base, C6-C18 (such as C6, C8, C9, C10, C12, C14, C16 or C18, etc.) aryl or C3-C18 (such as C3, C4, C5, C6, C8, C9, C10, C12, C14, C16 or C18 etc.) any of the heteroaryl groups.
  • C1-C5 eg C1, C2, C3, C4 or C5
  • C6-C18 such as C6, C8, C9, C10, C12, C14, C16 or C18, etc.
  • aryl or C3-C18 such as C3, C4, C5, C6, C8, C9, C10, C12, C14, C16 or C18 etc.
  • the repeating unit of the structure shown in the formula II comprises any one or a combination of at least two of the repeating units having the structure shown in the formula II-1, the formula II-2 or the formula II-3:
  • Y 1 , Y 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , m 1 , m 2 , m 3 , m 4 , m 5 , m 6 , m 7 , and m 8 respectively independently have the same defined ranges as in Formula II.
  • the m 1 and m 2 are each independently selected from an integer from 1 to 3, such as 1, 2 or 3.
  • the m 3 , m 4 , m 5 , m 6 , m 7 and m 8 are each independently selected from an integer from 0 to 3, such as 0, 1, 2 or 3.
  • the repeating unit of the structure represented by the formula II comprises any one or a combination of at least two of the following repeating units 2a-2h:
  • the molar percentage of repeating units having the structure shown in formula II in the polycarbonate is 10-90%, for example, 12%, 15%, 18%, 20%, 22%, 25%, 28% %, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, 78%, 80%, 82%, 85% or 88%, as well as specific point values between the above-mentioned point values, limited by space and for the sake of brevity, this application will not list exhaustively
  • the specific point value included in the range is more preferably 20 to 80%.
  • the refractive index of the polycarbonate is 1.65-1.75, such as 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73 or 1.74, and the specific point values between the above point values are limited by space and For the sake of brevity, the present application does not exhaustively enumerate the specific point values included in the range.
  • the refractive index of the polycarbonate is 1.65-1.75, more preferably 1.675-1.735, still more preferably 1.680-1.710, still more preferably 1.6850-1.715.
  • the refractive index is measured at 25°C and a wavelength of 589 nm.
  • the high refractive index of the polycarbonate can significantly reduce the spherical aberration of the lens, thereby shortening the focal length of the lens.
  • the Abbe number of the polycarbonate is 20-40, such as 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38 or 39, as well as specific point values between the above-mentioned point values, due to space limitations and for the sake of brevity, the present application will not exhaustively list the specific point values included in the range.
  • the glass transition temperature of the polycarbonate is 135-200°C, such as 138°C, 140°C, 145°C, 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185° C., 190° C. or 195° C., as well as specific point values between the above-mentioned point values, limited by space and for the sake of brevity, this application will not exhaustively list the specific point values included in the range.
  • the glass transition temperature of the polycarbonate is 135-200° C., and the glass transition temperature (T g ) is measured at a heating rate of 20° C./min. If the T g of the polycarbonate is too low, its heat resistance is not good, which affects the performance of the polycarbonate as an optical material; if the T g is too high, its melt viscosity becomes high, which increases the processing and molding process. Difficulty handling.
  • the spectral transmittance of the polycarbonate is ⁇ 80%, more preferably ⁇ 81%, even more preferably ⁇ 82%; the transmittance is obtained by measuring a formed plate with a thickness of 0.1 mm at a wavelength of 395 nm .
  • the index of the heat and humidity resistance of the polycarbonate is: the retention rate of specific viscosity after standing for 2000 hours under the conditions of 85° C. and 85% relative humidity (RH), preferably more than 80%, more preferably 85% Above, more preferably 90% or more. If the specific viscosity retention rate is 80% or more, the color tone will not deteriorate and the strength of the molded product will not decrease even when used in a humid and hot environment, and the use environment of polycarbonate is not limited; if the specific viscosity retention rate is less than 80%, the As the specific viscosity decreases, the strength decreases, and cracks and deformations tend to occur, resulting in poor color tone.
  • RH relative humidity
  • the polycarbonate also includes additives; the additives can improve the excellent properties of the polycarbonate, and do not affect the refractive index, Abbe number, hydrothermal stability, etc. necessary for the material.
  • the additives include any one or at least two of antioxidants, mold release agents, heat stabilizers, ultraviolet absorbers, bluing agents, antistatic agents, flame retardants, plasticizers or fillers The combination.
  • the heat stabilizer includes any one or a combination of at least two of a phosphorus-based heat stabilizer, a sulfur-based heat stabilizer, or a hindered phenol-based heat stabilizer.
  • the phosphorus-based heat stabilizer includes tris(2,4-di-tert-butylphenyl) phosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite ester or tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphite, or a combination of at least two.
  • the content of the phosphorus-based heat stabilizer is 0.001 to 0.2 parts by weight.
  • the sulfur-based heat stabilizer includes pentaerythritol-tetrakis(3-lauryl thiopropionate).
  • the content of the sulfur-based heat stabilizer is 0.001-0.2 parts by weight.
  • the hindered phenol-based heat stabilizer includes octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and/or pentaerythritol-tetra[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate].
  • the content of the hindered phenol-based heat stabilizer is 0.001-0.3 parts by weight.
  • the ultraviolet absorber includes a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a cyclic imidate-based ultraviolet absorber or a cyanoacrylate-based ultraviolet absorber Any one or a combination of at least two of the UV absorbers.
  • the content of the ultraviolet absorber is 0.01-3.0 parts by weight, which can impart good weather resistance to the polycarbonate composition.
  • the antioxidant comprises triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol -Bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoic acid ester], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate or its salt, 1,3,5-trimethyl-2,4,6-tri (3,5-Di-tert-butyl-4-hydroxybenzyl)benzene, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), 3,5- Di-tert-butyl-4-hydroxy-benzylphosphonate
  • the content of the antioxidant is 0.001-0.3 parts by weight.
  • the present application provides a method for preparing polycarbonate according to the first aspect, the preparation method comprising: performing a polycondensation reaction between a dihydroxy monomer having the structure shown in formula 1A and a carbonic diester compound , to obtain the polycarbonate;
  • X 1 , X 2 , R 1 , R 2 , a, b, n 1 , n 2 each independently have the same defined ranges as in formula I.
  • the dihydroxy monomer having the structure shown in formula 1A includes any one or a combination of at least two of the following compounds:
  • the dihydroxy monomer having the structure shown in formula 1A is synthesized by the following method: the mixed solution of 2-naphthol, toluene and ethyl acetate is stirred and dissolved, and under ice bath conditions, dichloride is slowly added dropwise. The temperature of the reaction system was controlled at about 15°C.
  • 1,1-thiobis(2-naphthol) was obtained by crystallization, washing and filtration; 1,1-thiobis(2-naphthol) is used as a raw material, and is reacted with alkylene oxide or alkylene carbonate to obtain a dihydroxy monomer having a structure as shown in formula 1A.
  • the carbonic diester compounds include diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, m-tolyl carbonate, dimethyl carbonate, diethyl carbonate, and dibutyl carbonate Or any one or a combination of at least two of dicyclohexyl carbonate.
  • the polycondensation reaction is a melt polycondensation reaction.
  • the preparation method also includes a dihydroxy monomer having a structure as shown in formula IIA:
  • Y 1 , Y 2 , Z, R 3 , R 4 , m 1 , m 2 , m 3 , m 4 each independently have the same defined ranges as in formula II.
  • the dihydroxy monomer having the structure shown in formula IIA includes any one or at least two dihydroxy monomers having the structure shown in formula IIA-1, formula IIA-2 or formula IIA-3 Combination of species:
  • the dihydroxy monomer having the structure shown in formula IIA-2 comprises any one or a combination of at least two of the following compounds: 10,10-bis-(4-hydroxyethoxyphenyl) -9,9-bisphenol tetrahydroanthracene, 10,10-bis-(4-hydroxyethoxyphenyl)-9,9-bisphenyltetrahydroanthracene, 10,10-bis-(4-hydroxyethyl) oxyphenyl)-9,9-bis-o-cresol tetrahydroanthracene, 10,10-bis-(4-hydroxyethoxyphenyl)-9,9-bisphenyltetrahydroanthracene, 10,10- Bis-(4-hydroxyethoxyphenyl)-9,9-bisethylphenyltetrahydroanthracene, 10,10-bis-(4-hydroxyethoxyphenyl)-9,9-bisethylphenyltetrahydroanthracene
  • the dihydroxy monomer having the structure shown in formula IIA-2 is synthesized and obtained by the following method: under the action of an acid catalyst, the phenoxy alcohol compound is first subjected to a condensation reaction with the ketone group of 9-anthrone. , to obtain intermediate product A; in the presence of oxygen atmosphere and oxidant, intermediate product A is oxidized to intermediate product B containing ketone group; under the action of acid catalyst, cyclic hydrocarbon compounds continue to form with the ketone group on intermediate product C The condensation reaction produces a dihydroxy monomer having the structure shown in formula IIA-2.
  • the dihydroxy monomer having the structure shown in formula IIA-3 comprises any one or a combination of at least two of the following compounds: 9,9-bis[4-(2-hydroxyethoxy) Phenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-methylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3, 5-Dimethylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-tert-butylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethyl) Oxy)-3-isopropylphenyl]fluorene, 9,9-bis[4-(2-hydroxyethoxy)-3-cyclohexylphenyl]fluorene, 9,9-bis[4-(2 -Hydroxyethoxy)-3-phenylphenyl]fluorene, 9,9-bis[4-(2-hydroxyeth
  • the amount of the carbonic diester compound is 0.97 ⁇ 1.2mol, such as 0.99mol, 1mol, 1.01mol, 1.03mol, 1.05mol, 1.07mol, 1.09mol, 1.1mol, 1.11mol, 1.13mol, 1.15mol, 1.17mol or 1.19mol, etc.
  • the polycondensation reaction is carried out in the presence of a catalyst.
  • the catalyst comprises any one or a combination of at least two of an alkali metal compound, an alkaline earth metal compound or a nitrogen-containing compound.
  • the alkali metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkali metals, and more preferably sodium acetate, potassium acetate, cesium acetate, lithium acetate, hydroxide Sodium, Potassium Hydroxide, Cesium Hydroxide, Lithium Hydroxide, Sodium Bicarbonate, Sodium Carbonate, Potassium Carbonate, Cesium Carbonate, Lithium Carbonate, Sodium Stearate, Potassium Stearate, Cesium Stearate, Lithium Stearate, Sodium Borohydride, Sodium Phenyl Borate, Sodium Benzoate, Potassium Benzoate, Cesium Benzoate, Lithium Benzoate, Disodium Hydrogen Phosphate, Dipotassium Hydrogen Phosphate, Dilithium Hydrogen Phosphate, Disodium Phenyl Phosphate, Bisphenol A Disodium salt, dipotassium salt, di
  • the alkaline earth metal compounds include organic acid salts, inorganic salts, oxides, hydroxides, hydrides or alkoxides of alkaline earth metals, and more preferably magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydroxide Barium, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, stearic acid Calcium, calcium benzoate or magnesium phenyl phosphate, etc.
  • magnesium hydroxide calcium hydroxide, strontium hydroxide
  • hydroxide Barium, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate,
  • the nitrogen-containing compound includes quaternary ammonium hydroxide and its salts and/or amines, etc., more preferably tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylhydrogen Ammonium oxide, trimethylbenzylammonium hydroxide, triethylamine, dimethylbenzylamine, triphenylamine and other tertiary amines, diethylamine, dibutylamine and other secondary amines, propylamine, butylamine, 2-methylamine imidazoles such as imidazole, 2-phenylimidazole, benzimidazole, ammonia, tetramethylammonium borohydride, tetrabutylammonium borohydride, tetrabutyltetraphenylammonium borate, tetraphenyltetrapheny
  • the amount of the catalyst used is 1 ⁇ 10 ⁇ 9 to 1 ⁇ 10 -3 mol, more preferably 1 ⁇ 10 -7 to 1 ⁇ 10 -4 mol.
  • the preparation method specifically includes: in a protective atmosphere (eg nitrogen), dihydroxy monomers with the structure shown in formula 1A, carbonic diester compounds and optional dihydroxyl monomers with the structure shown in formula IIA Hydroxy monomers are mixed, and in the presence of a catalyst, a polycondensation reaction is carried out under reduced pressure; the step-by-step decompression method is adopted to finally make the pressure below 100Pa, and the generated alcohols are distilled off to the outside of the system to obtain the polycarbonate ester.
  • a protective atmosphere eg nitrogen
  • dihydroxy monomers with the structure shown in formula 1A carbonic diester compounds and optional dihydroxyl monomers with the structure shown in formula IIA Hydroxy monomers
  • a catalyst e.g nitrogen
  • a polycondensation reaction is carried out under reduced pressure
  • the step-by-step decompression method is adopted to finally make the pressure below 100Pa, and the generated alcohols are distilled off to the outside of the system to obtain the polycarbonate ester.
  • the temperature of the polycondensation reaction is 150-300°C, such as 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C °C, 280 °C or 290 °C, etc.
  • the time of the polycondensation reaction is 1-4h, for example, 1.2h, 1.5h, 1.8h, 2h, 2.2h, 2.5h, 2.8h, 3h, 3.2h, 3.5h or 3.8h and the like.
  • the reaction device used in the preparation method may be a vertical device equipped with an anchor-type stirring paddle, a MAXBLEND stirring paddle, a ribbon-type stirring paddle, etc., or a horizontal type equipped with a paddle-type blade, a lattice blade, a spectacle-type blade, etc. Apparatus; It is preferable to implement using a reaction apparatus in which these reaction apparatuses are appropriately combined in consideration of the viscosity of the polymer.
  • the catalyst in order to maintain the thermal stability and hydrolytic stability of the polycarbonate, the catalyst may be removed or deactivated after the polycondensation reaction is completed.
  • the deactivation method includes adding a known acidic substance as a deactivating agent;
  • the acidic substance is preferably esters such as butyl benzoate, aromatic sulfonic acids such as p-toluenesulfonic acid; p-toluenesulfonic acid Aromatic sulfonic acid esters such as butyl ester and hexyl p-toluenesulfonate; phosphoric acid such as phosphorous acid, phosphoric acid, and phosphonic acid; triphenyl phosphite, monophenyl phosphite, diphenyl phosphite, diethyl phosphite , Di-n-propyl phosphite, di-n-butyl phosphite, di-n-hexyl phosphite, dioctyl phosphite, mono-octyl phosphite and other
  • the amount of the acidic substance is 0.01-50 mol, more preferably 0.3-20 mol. If the added amount of the acidic substance is too low, the deactivation effect will be insufficient; if the added amount of the acidic substance is too high, the heat resistance of the polycarbonate may be reduced, and it is easy to be colored in subsequent applications.
  • the present application provides an application of the polycarbonate according to the first aspect in optical components, electronic products, electrical equipment, packaging materials, medical devices or building materials.
  • the optical components include optical lenses such as automotive front lighting lenses, Fresnel lenses, f-theta lenses for laser printers, camera lenses or projection lenses, as well as optical discs, optical system components for image display media, optical Optical moldings such as films, optical bases, optical filters, or prisms.
  • optical lenses such as automotive front lighting lenses, Fresnel lenses, f-theta lenses for laser printers, camera lenses or projection lenses, as well as optical discs, optical system components for image display media, optical Optical moldings such as films, optical bases, optical filters, or prisms.
  • the present application provides an optical lens comprising the polycarbonate of the first aspect.
  • the optical lens can be obtained by processing the polycarbonate as described in the first aspect; the processing and molding include injection molding, compression molding, injection compression molding or casting molding. Among them, when an optical lens is produced by injection molding, it is preferable to perform molding under the conditions of a barrel temperature of 230 to 350°C and a mold temperature of 70 to 180°C.
  • the optical lens is implemented using the shape of an aspherical lens as required. Since the aspherical lens can make spherical aberration practically zero with one lens, it is not necessary to remove spherical aberration by combining a plurality of spherical lenses, and it is possible to reduce the weight and the molding cost. Therefore, aspherical lenses are particularly useful as camera lenses among optical lenses.
  • the polycarbonate provided by the present application has high molding fluidity, it is particularly suitable as a material for an optical lens with a thin wall and a small size and a complicated shape.
  • the thickness of the central portion of the optical lens is 0.05-3.0 mm, preferably 0.05-2.0 mm, more preferably 0.1-2.0 mm; the diameter of the optical lens is 1.0-20.0 mm, preferably 1.0-10.0 mm , more preferably 3.0 to 10.0 mm.
  • the optical lens is a meniscus lens with a convex side and a concave side.
  • a coating layer such as an antireflection layer or a hard coat layer may be provided on the surface of the optical lens.
  • the anti-reflection layer is a single layer or multiple layers; the material of the anti-reflection layer can be organic and/or inorganic, preferably inorganic. Specifically, the material of the anti-reflection layer includes any one or a combination of at least two of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, ceria, magnesium oxide or magnesium fluoride.
  • optical lens described in the present application may be formed by any method such as mold forming, cutting, polishing, laser machining, electrical discharge machining, and etching, and preferably, mold forming.
  • the polycarbonate provided by the present application contains specific repeating units including dithionaphthalene groups, so that the polycarbonate has both high refractive index, high Abbe number and excellent hydrothermal stability, and can fully meet the needs of polycarbonate As the performance requirements of optical resins in optical components.
  • the refractive index of the polycarbonate is as high as 1.66-1.75, the Abbe number is 20-40, the glass transition temperature reaches 120-200°C, and the total light transmittance is ⁇ 86%.
  • the pass rate is still ⁇ 86%, with high transparency, high refractive index, high Abbe number and excellent hydrothermal stability, which can fully meet the application requirements of polycarbonate materials in high-performance optical components.
  • the samples used for performance evaluation were prepared by the following methods:
  • the molding temperature was set to Tg +110°C, and the mold temperature was set to Tg -10°C, and injection molding was performed using a SE30DU injection molding machine manufactured by Sumitomo Heavy Industries, Ltd.
  • the polycarbonate obtained after melt-kneading was measured for the cast film at a temperature increase rate of 20°C/min using DSC-60A manufactured by Shimadzu Corporation.
  • the refractive index in 25 degreeC of the film produced by the method of (a) was measured using the DR-M2 Abbe refractometer made by ATAGO, and the wavelength was 589 nm.
  • the produced resin was injection-molded to obtain a rectangular plate with a thickness of 3 mm, a length and a width of 2 cm and 1 cm, respectively, and the measurement was carried out using the SE2000 type spectrophotometer according to the method in standard JIS-K-7361-1.
  • ⁇ sp specific viscosity retention rate
  • ⁇ sp 0 specific viscosity before the test
  • ⁇ sp 1 specific viscosity after the test.
  • BPEF 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene
  • BPPEF 9,9-bis[4-(2-hydroxyethyl) oxy)-3-phenylphenyl]fluorene
  • the synthetic route is as follows:
  • the temperature was raised to 100°C, after most of the solvent was distilled off, it was put into the refrigerator for 1 hour, and a solid was precipitated, filtered, recrystallized from anhydrous ethanol, filtered and dried to obtain 6,6-dibromo-1,1-dithionaphthalene phenol.
  • the 6,6-dibromo-1,1-dithionaphthalene 1mol obtained in step (1) and 2mol of phenylboronic acid are dissolved in toluene/ethanol mixed solution (the mass ratio of toluene and ethanol is 4:1) in 500 mL, and then further adding 0.01 mol of tetrakis(triphenylphosphine) palladium and 100 mL of 1.5 mol/L potassium carbonate aqueous solution, stirring at 75° C. for 2 h to complete the reaction, and reducing the obtained reaction solution.
  • the molar ratio of the 6,6-diphenyl-1,1-dithionaphthol, sodium hydroxide and ethylene oxide obtained in step (2) is 4:0.005:1 , and then add ⁇ -5°C absolute ethanol and dimethylformamide DMF to it, seal and stir at 70°C, cool down after reacting for 12 hours, then wash with water to obtain a white solid, then recrystallize from methanol, pump Filter and dry to obtain the target product BINSL-2EO.
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 8.07(d, 2H), 7.95(t, 2H), 7.86(d, 2H), 7.55(m, 2H) ), 7.52(m, 4H), 7.51(m, 4H), 7.41(d, 2H), 6.85(d, 2H), 4.43(t, 4H), 3.69(m, 4H), 3.65(m, 2H) .
  • the synthetic route is as follows:
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 8.55(t, 2H), 8.42(t, 2H), 8.08-8.04(m, 6H), 7.95(t , 2H), 7.86 (d, 2H), 7.61-7.55 (m, 8H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H).
  • the synthetic route is as follows:
  • the temperature was raised to 100°C, after most of the solvent was distilled off, it was placed in the refrigerator for 1 hour, and a solid was precipitated, filtered, recrystallized from anhydrous ethanol, filtered and dried to obtain dithionaphthol.
  • step (1) (2) in the reaction kettle, the added molar ratio of the dithionaphthol, sodium hydroxide, and ethylene oxide obtained in step (1) is 4:0.005:1, and then anhydrous ⁇ -5°C is added therein.
  • Ethanol and DMF were sealed and stirred at 70°C, reacted for 12 hours, cooled and cooled, then washed with water to obtain a white solid, then recrystallized from methanol, filtered and dried to obtain the target product BNSE.
  • the synthetic route is as follows:
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 8.11(d, 2H), 8.00(m, 4H), 7.95-7.92(m, 4H), 7.86(d , 2H), 7.73 (t, 2H), 7.59-7.55 (m, 8H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H).
  • the synthetic route is as follows:
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 8.11(d, 2H), 7.95(d, 2H), 7.88-7.69(m, 10H), 7.55(d , 2H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H).
  • the synthetic route is as follows:
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 10.1(s, 2H), 8.12-8.07(m, 6H), 7.95(d, 2H), 7.87-7.86 (t, 4H), 7.63-7.50 (m, 6H), 7.35-7.29 (m, 4H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H) ).
  • the synthetic route is as follows:
  • step (1) 1010-bis(4-hydroxyethoxyphenyl)-9-hydro-anthracene obtained in step (1) was prepared with a total of 700 g of methanol solution with a mass concentration of 30%, and 63 g of concentrated nitric acid was added dropwise thereto, Oxygen was continuously introduced for 2 hours, and the flow rate was 100 L/h. After the reaction was completed, 10,10-bis(4-hydroxyethoxyphenyl)anthrone was obtained by cooling and crystallization.
  • the synthetic route is as follows:
  • the NMR results of the target product are as follows: 1 H-NMR (400MHz, CDCl 3 ) ⁇ / ⁇ 10 -6 : 8.45-8.41(m, 4H), 8.20(d, 2H), 8.07(t, 2H), 7.98-7.95 (m, 4H), 7.86 (d, 2H), 7.58-7.50 (m, 8H), 6.85 (d, 2H), 4.43 (t, 4H), 3.69 (m, 4H), 3.65 (m, 2H).
  • a polycarbonate containing repeating units The preparation method is as follows:
  • the jacket was kept at this temperature, the pressure was reduced to below 100 Pa within 60 min, and the polycondensation reaction was carried out under the conditions of 270° C. and below 100 Pa until the reaction reached a torque of 20 N ⁇ m. Pelletizing to obtain pellets of the polycarbonate.
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 2;
  • Preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 2;
  • Preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 5;
  • Preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 5;
  • Preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 8;
  • Preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 8;
  • Preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 18;
  • Preparation method is as follows:
  • a kind of polycarbonate, the kind of repeating unit is identical with embodiment 18;
  • Preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a polycarbonate containing repeating units The preparation method is as follows:
  • a kind of polycarbonate its difference with embodiment 6 is only in that repeating unit wherein replaced by equimolar
  • the difference between the preparation method and Example 6 is only that the dihydroxy monomer BINSL-2EO is used in an equimolar amount of 2,2-bis(2-hydroxyethoxy)-6,6-diphenyl-binaphthyl (BINOL-2EO) to obtain pellets of the polycarbonate.
  • the dihydroxy monomer components used in the above Examples 1 to 25 and their corresponding molar percentages (%, based on the total amount of dihydroxy monomers as 100%) are shown in Table 1.
  • the fractional content corresponds to the mole percent content of repeating units in the polycarbonates provided in the examples.
  • the polycarbonates with specific repeating units provided by the present application have significantly improved refractive index and Abbe number compared to the polycarbonates in the prior art, and also increased the glass transition temperature and Heat resistance, the refractive index of the polycarbonate is as high as 1.66 to 1.75, the Abbe number is 20 to 40, the glass transition temperature reaches 120 to 200 ° C, and the total light transmittance is ⁇ 86%.
  • the transmittance of the polycarbonate mentioned above, the total light transmittance after the humidity and heat resistance test is still ⁇ 86%, with high transparency, high refractive index, high Abbe number and excellent hydrothermal stability.

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Abstract

一种聚碳酸酯及其制备方法和应用，所述聚碳酸酯包含具有特定结构的重复单元，所述重复单元中包括联硫萘基团，使所述聚碳酸酯兼具高折射率、高阿贝数和优异的水热稳定性，能够充分满足聚碳酸酯作为光学树脂在光学部件中的性能要求。

Description

聚碳酸酯及其制备方法和应用 技术领域
本申请属于聚合物材料技术领域，具体涉及一种聚碳酸酯及其制备方法和应用。
背景技术
如今光学镜头中的镜片朝着轻薄化的方向发展。常用的镜片材料包括光学玻璃和光学树脂。其中，光学玻璃成本较高，材料成型加工性能差，耐水热稳定性欠佳，因此限制了其在光学镜头和镜片中的大规模应用。相比之下，光学树脂具有成本较低、易加工成型、轻薄化的优点，应用前景更加广阔。
随着电子数码产品的轻薄化发展，对光学树脂的性能也提出了新的要求，包括折射率、阿贝数和稳定性等。聚碳酸酯是一种综合性能较好的工程塑料，不仅具有良好的尺寸稳定性、耐热性和机械性能，而且无色透明，是一种广泛使用的光学树脂。聚碳酸酯在光学镜片中的应用包括多层扩散片、光反射膜和视力矫正镜片等。由双酚A均聚得到的聚碳酸酯的折射率在1.58左右，相比于聚甲基丙烯酸甲酯或聚苯乙烯，光学性能更加优异。因此，开发基于聚碳酸酯的光学树脂是目前的研究热点。
CN104769007A公开了一种聚碳酸酯树脂、其制造方法及光学成形体。所述聚碳酸酯树脂含有通式(A)所示的结构单元
Figure PCTCN2020121550-appb-000001
其中，X为碳原子数1～4的亚烷基；该聚碳酸酯树脂的折射率可达到1.66，阿贝数低于24。
CN111094389A公开了一种聚碳酸酯树脂、其制造方法和光学透镜。所述聚碳酸酯树脂中含有该通式
Figure PCTCN2020121550-appb-000002
所示的结构单元，其折射率最高可达到1.71，阿贝数低于20。
研究表明，光学镜片的折射率越高，镜片就越轻越薄。因此，现有技术一直致力于高折射率的聚碳酸酯研究。而镜片的折射率越高，阿贝数也就越低，色散越明显，色差较大。在照相机的光学系统中，通常通过多片凹透镜和凸透镜的组合来进行色差的修正，使光学系统的镜片构成十分复杂。目前，聚碳酸酯类光学树脂的折射率还具有较大的提升空间，在提高折射率的同时不降低光学树脂的阿贝数，使光学系统的组合具有更多的选择性，是光学树脂的一个重要研究方向。同时，基于加工性和使用稳定性的考虑，提高光学树脂的水热稳定性也很有必要。
因此，开发一种兼具高折射率、高阿贝数和高水热稳定性的聚碳酸酯，以满足其在高性能光学部件中的应用要求，是本领域的研究重点。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
针对现有技术的不足，本申请的目的在于提供一种聚碳酸酯及其制备方法和应用，通过设计具有联硫萘基团的特定结构单元，使所述聚碳酸酯兼具高折射率、高阿贝数和优异的水 热稳定性，能够充分满足聚碳酸酯作为光学树脂在光学部件中的性能要求。
为达此目的，本申请采用以下技术方案：
第一方面，本申请提供一种聚碳酸酯，所述聚碳酸酯包含具有如式I所示结构的重复单元：
Figure PCTCN2020121550-appb-000003
式I中，X 1、X 2各自独立地选自C1～C8直链或支链亚烷基。
所述C1～C8直链或支链亚烷基包括C1、C2、C3、C4、C5、C6、C7或C8的直链或支链亚烷基，示例性地包括但不限于：亚甲基、亚乙基、1,2-亚乙基、亚丙基或亚丁基等。
式I中，R 1、R 2各自独立地选自卤素、取代或未取代的C1～C6(例如C1、C2、C3、C4、C5或C6)直链或支链烷基、取代或未取代的C2～C6(例如C2、C3、C4、C5或C6)烯烃基、取代或未取代的C1～C6(例如C1、C2、C3、C4、C5或C6)烷氧基、取代或未取代的C6～C30(例如C6、C8、C9、C10、C12、C14、C16、C18、C20、C22、C24、C26或C28等)芳基、取代或未取代的C3～C30(例如C3、C4、C5、C6、C8、C9、C10、C12、C14、C16、C18、C20、C22、C24、C26或C28等)杂芳基。
本申请所述卤素包括氟、氯、溴或碘，下文涉及到相同描述，均具有相同含义。
式I中，a、b各自独立地选自1～10的整数，例如1、2、3、4、5、6、7、8、9或10。
式I中，n 1、n 2各自独立地选自0～4的整数，例如0、1、2、3或4。
本申请提供的聚碳酸酯中含有如式I所示结构的重复单元，所述重复单元中含有特定的联硫萘基团
Figure PCTCN2020121550-appb-000004
通过上述特定的结构单元，赋予了所述聚碳酸酯高的折射率和高的阿贝数，且玻璃化转变温度高，具有优异的水热稳定性，能够满足后续高温加工的要求以及苛刻环境中的使用稳定性要求。包含所述聚碳酸酯的光学透镜兼具轻薄、低色差和低色散的特性，为光学系统的组合提供更多的选择性。
优选地，R 1、R 2中所述取代的取代基各自独立地选自氰基、巯基、羟基、C1～C6(例如C1、C2、C3、C4、C5或C6)直链或支链烷基、C1～C6(例如C1、C2、C3、C4、C5或C6)烷氧基、C6～C18(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳氧基、C6～C18(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳硫基、C6～C18(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳基或C3～C18(例如C3、C4、C5、C6、C8、C9、C10、C12、C14、C16或C18等)杂芳基中的至少一种。
优选地，所述X 1、X 2各自独立地选自C1～C3直链或支链亚烷基，进一步优选为亚乙基，进一步优选为1,2-亚乙基。
优选地，所述a、b各自独立地选自1～4的整数，例如1、2、3或4。
优选地，所述R 1、R 2各自独立地选自取代或未取代的C6～C18芳基、取代或未取代的C3～C18杂芳基；所述取代的取代基各自独立地选自氰基、巯基、羟基、C1～C4(例如C1、C2、C3或C4)直链或支链烷基、C1～C3(例如C1、C2或C3)烷氧基中的至少一种。
本申请中，所述C6～C18芳基包括C6、C8、C9、C10、C12、C14、C16或C18等的芳 基，示例性地包括但不限于：苯基、联苯基、萘基、蒽基或芴基等。
本申请中，所述C3～C18杂芳基包括C3、C4、C5、C6、C8、C9、C10、C12、C14、C16或C18等的杂芳基，其中的杂原子包括O、S或N等；示例性地包括但不限于：呋喃基、噻吩基、吡咯基、咪唑基、吡唑基、吲哚基、异吲哚基、咔唑基、吡啶基、喹啉基、异喹啉基、苯并呋喃基、二苯并呋喃基、萘并呋喃基、苯并吡唑基、萘并吡啶基、苯并噻吩基或二苯并噻吩基等。
优选地，所述n 1、n 2各自独立地选自0～2的整数，例如0、1或2。
优选地，所述R 1、R 2各自独立地选自如下基团中的任意一种，或被取代基取代的如下基团中的任意一种：
Figure PCTCN2020121550-appb-000005
其中，虚线表示基团的连接位点；
所述取代基选自氰基、巯基、羟基、C1～C4(例如C1、C2、C3或C4)直链或支链烷基、C1～C3(例如C1、C2或C3)烷氧基中的任意一种。
示例性地，所述R 1、R 2各自独立地选自苯基、2-氰基苯基、3-氰基苯基、4-氰基苯基、2-巯基苯基、3-巯基苯基、4-巯基苯基、1-萘基、2-萘基、3-萘基、2-氰基萘基、3-氰基萘基、4-氰基萘基、2-巯基萘基、3-巯基萘基、4-巯基萘基、噻吩基或苯并噻吩基中的任意一种。
优选地，所述聚碳酸酯包含如下重复单元1a～1m中的任意一种或至少两种的组合：
Figure PCTCN2020121550-appb-000006
Figure PCTCN2020121550-appb-000007
优选地，所述聚碳酸酯中具有如式I所示结构的重复单元的摩尔百分含量为10～100％，例如12％、15％、18％、20％、22％、25％、28％、30％、32％、35％、38％、40％、42％、45％、48％、50％、52％、55％、58％、60％、62％、65％、68％、70％、72％、75％、78％、80％、82％、85％、88％、90％、92％、95％或98％，以及上述点值之间的具体点值，限于篇幅及出 于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为20～90％。
本申请中，所述聚碳酸酯还包含具有如式II所示结构的重复单元：
Figure PCTCN2020121550-appb-000008
式II中，Y 1、Y 2各自独立地选自C1～C4(例如C1、C2、C3或C4)直链或支链亚烷基。
式II中，Z选自单键、O、S、C1～C5(例如C1、C2、C3、C4或C5)直链或支链亚烷基、
Figure PCTCN2020121550-appb-000009
中的任意一种，虚线代表基团的连接位点。
R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自羟基、C1～C20(例如C1、C3、C5、C7、C9、C10、C12、C14、C16、C18或C19等)直链或支链烷基、C1～C20(例如C1、C3、C5、C7、C9、C10、C12、C14、C16、C18或C19等)烷氧基、C3～C20(例如C4、C5、C7、C9、C10、C12、C14、C16、C18或C19等)环烃基、C3～C20(例如C4、C5、C7、C9、C10、C12、C14、C16、C18或C19等)环烃氧基、C6～C20(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳基或C3～C20(例如C3、C4、C5、C6、C8、C9、C10、C12、C14、C16或C18等)杂芳基中的任意一种。
所述环烃基包括环烷基或不饱和非芳香族环烃基。
m 1、m 2各自独立地选自1～10的整数，例如1、2、3、4、5、6、7、8、9或10。
m 3、m 4、m 7、m 8各自独立地选自0～4的整数，例如0、1、2、3或4。
m 5、m 6各自独立地选自0～5的整数，例如0、1、2、3、4或5。
所述m 3≥2时，2个或2个以上的R 3彼此相同或不同；同理，所述m 4、m 5、m 6、m 7、m 8各自独立地≥2时，2个或2个以上的R 4、R 5、R 6、R 7、R 8彼此相同或不同。
优选地，所述Y 1、Y 2各自独立地选自C1～C3(例如C1、C2或C3)直链或支链亚烷基，进一步优选为亚乙基，更进一步优选为1,2-亚乙基。
优选地，所述Z选自S、亚甲基、
Figure PCTCN2020121550-appb-000010
Figure PCTCN2020121550-appb-000011
中的任意一种，虚线代表基团的连接位点。
优选地，所述R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自羟基、C1～C5(例如C1、C2、C3、C4或C5)直链或支链烷基、C6～C18(例如C6、C8、C9、C10、C12、C14、C16或C18等)芳基或C3～C18(例如C3、C4、C5、C6、C8、C9、C10、C12、C14、C16或C18等)杂芳基中的任意一种。
优选地，所述式II所示结构的重复单元包含具有如式II-1、式II-2或式II-3所示结构的重复单元中的任意一种或至少两种的组合：
Figure PCTCN2020121550-appb-000012
其中，Y 1、Y 2、R 3、R 4、R 5、R 6、R 7、R 8、m 1、m 2、m 3、m 4、m 5、m 6、m 7、m 8各自独立地具有与式II中相同的限定范围。
优选地，所述m 1、m 2各自独立地选自1～3的整数，例如1、2或3。
优选地，所述m 3、m 4、m 5、m 6、m 7、m 8各自独立地选自0～3的整数，例如0、1、2或3。
优选地，所述式II所示结构的重复单元包含如下重复单元2a～2h中的任意一种或至少两种的组合：
Figure PCTCN2020121550-appb-000013
Figure PCTCN2020121550-appb-000014
优选地，所述聚碳酸酯中具有如式II所示结构的重复单元的摩尔百分含量为10～90％，例如12％、15％、18％、20％、22％、25％、28％、30％、32％、35％、38％、40％、42％、45％、48％、50％、52％、55％、58％、60％、62％、65％、68％、70％、72％、75％、78％、80％、82％、85％或88％，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值，进一步优选为20～80％。
本申请中，所述聚碳酸酯的折射率为1.65～1.75，例如1.66、1.67、1.68、1.69、1.70、1.71、1.72、1.73或1.74，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
作为本申请的优选技术方案，所述聚碳酸酯的折射率为1.65～1.75，进一步优选为1.675～1.735，更进一步优选为1.680～1.710，进一步优选为1.6850～1.715的范围。所述折射率在25℃、波长589nm下测定。所述聚碳酸酯的高折射率能够显著降低透镜的球面像差，进而可缩短透镜的焦点距离。
优选地，所述聚碳酸酯的阿贝数为20～40，例如21、22、23、24、25、26、27、28、29、30、31、32、33、34、35、36、37、38或39，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
作为本申请的优选技术方案，所述聚碳酸酯的阿贝数(v)为20～40，所述阿贝数由25℃、波长分别为486nm、589nm、656nm下的折射率通过公式v＝(nD－1)/(nF－nC)计算得到，其中，nD为波长589nm下的折射率，nF为波长656nm下的折射率，nC为波长486nm下的折射率。
优选地，所述聚碳酸酯的玻璃化转变温度为135～200℃，例如138℃、140℃、145℃、150℃、 155℃、160℃、165℃、170℃、175℃、180℃、185℃、190℃或195℃，以及上述点值之间的具体点值，限于篇幅及出于简明的考虑，本申请不再穷尽列举所述范围包括的具体点值。
作为本申请的优选技术方案，所述聚碳酸酯的玻璃化转变温度为135～200℃，玻璃化转变温度(T g)以升温速度20℃/min测定得到。如果聚碳酸酯的T g过低，则其耐热性欠佳，影响所述聚碳酸酯作为光学材料的使用性能；如果T g过高，则其熔融粘度变高，增加了加工成型时的处理难度。
优选地，所述聚碳酸酯的分光透过率≥80％，进一步优选为≥81％，更进一步优选为≥82％；所述透过率通过在波长395nm下测定厚度0.1mm的成形板得到。
优选地，所述聚碳酸酯的耐湿热性的指标为：85℃、85％相对湿度(RH)的条件下放置2000小时后的比粘度保持率，优选为80％以上，更优选为85％以上，进一步优选为90％以上。若比粘度保持率为80％以上，则即使在湿热环境下使用时也没有色调变差和成形品的强度降低，聚碳酸酯的使用环境没有限制；若比粘度保持率低于80％，则强度伴随比粘度降低而降低，容易产生裂纹和变形，色调变差。
优选地，所述聚碳酸酯中还包括添加剂；所述添加剂能够提高聚碳酸酯的优良特性，且不影响材料所必须的折射率、阿贝数和水热稳定性等。
优选地，所述添加剂包括抗氧剂、脱模剂、热稳定剂、紫外线吸收剂、上蓝剂、防静电剂、阻燃剂、增塑剂或填充剂中的任意一种或至少两种的组合。
优选地，所述热稳定剂包括磷系热稳定剂、硫系热稳定剂或受阻酚系热稳定剂中的任意一种或至少两种的组合。
优选地，所述磷系热稳定剂包括三(2,4-二叔丁基苯基)亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯或四(2,4-二叔丁基苯基)-4,4'-亚联苯基二亚磷酸酯中的任意一种或至少两种的组合。
优选地，以所述聚碳酸酯的含量为100重量份计，所述磷系热稳定剂的含量为0.001～0.2重量份。
优选地，所述硫系热稳定剂包括季戊四醇-四(3-月桂基硫代丙酸酯)。
优选地，以所述聚碳酸酯的含量为100重量份计，所述硫系热稳定剂的含量为0.001～0.2重量份。
优选地，所述受阻酚系热稳定剂包括十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯和/或季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
优选地，以所述聚碳酸酯的含量为100重量份计，所述受阻酚系热稳定剂的含量为0.001～0.3重量份。
优选地，所述紫外线吸收剂包括苯并三唑系紫外线吸收剂、二苯甲酮系紫外线吸收剂、三嗪系紫外线吸收剂、环状亚氨酸酯系紫外线吸收剂或氰基丙烯酸酯系紫外线吸收剂中的任意一种或至少两种的组合。
优选地，以所述聚碳酸酯的含量为100重量份计，所述紫外线吸收剂的含量为0.01～3.0重量份，能够赋予所述聚碳酸酯组合物良好的耐候性。
优选地，所述抗氧剂包括二缩三乙二醇-双[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸酯]、1,6-己二醇-双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、十八烷基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯或其盐、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、N,N-六亚甲基双(3,5-二叔丁基-4-羟基-氢化肉桂酰胺)、3,5-二叔丁基-4-羟基-苄基膦酸酯-二乙酯、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯或3,9-双{1,1-二甲基-2-[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基]乙基}-2,4,8,10-四噁螺(5,5)十一烷中的任意一种或至少两种的组合，进一步优选为季戊四醇-四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
优选地，以所述聚碳酸酯的含量为100重量份计，所述抗氧剂的含量为0.001～0.3重量份。
另一方面，本申请提供一种如第一方面所述的聚碳酸酯的制备方法，所述制备方法包括： 具有如式1A所示结构的二羟基单体与碳酸二酯类化合物进行缩聚反应，得到所述聚碳酸酯；
Figure PCTCN2020121550-appb-000015
式IA中，X 1、X 2、R 1、R 2、a、b、n 1、n 2各自独立地具有与式I中相同的限定范围。
优选地，所述具有如式1A所示结构的二羟基单体包括如下化合物中的任意一种或至少两种的组合：
2,2-双(2-羟基乙氧基)-6,6-二苯基-1,1-联硫萘(BINSL-2EO)
Figure PCTCN2020121550-appb-000016
2,2-双(2-羟基乙氧基)-6,6-二(萘-1-基)-1,1-联硫萘(1DNBINSL-2EO)
Figure PCTCN2020121550-appb-000017
2,2-双(2-羟基乙氧基)-1,1-联硫萘(BNSE)
Figure PCTCN2020121550-appb-000018
2,2-双(2-羟基乙氧基)-6,6-二(萘-2-基)-1,1-联硫萘(2DNBINSL-2EO)
Figure PCTCN2020121550-appb-000019
2,2-双(2-羟基乙氧基)-6,6-二(3-氰基苯基)-1,1-联硫萘(CN-BNS)
Figure PCTCN2020121550-appb-000020
2,2-双(2-羟基乙氧基)-6,6-二(二苯并吡咯-4-基)-1,1-联硫萘(PYR-BNS)
Figure PCTCN2020121550-appb-000021
2,2-双(2-羟基乙氧基)-6,6-二(二苯并噻吩-4-基)-1,1-联硫萘(THI-BNS)
Figure PCTCN2020121550-appb-000022
示例性地，所述具有如式1A所示结构的二羟基单体通过如下方法合成：将2-萘酚和甲苯与乙酸乙酯的混合溶液搅拌溶解，冰浴条件下，缓慢滴加二氯化硫，控制反应体系的温度在15℃左右，滴加完成后，继续反应3h；将溶剂蒸出，通过结晶、洗涤、过滤，得到1,1-硫代双(2-萘酚)；以1,1-硫代双(2-萘酚)为原料，与环氧烷或者亚烷基碳酸酯类进行反应，得到具有如式1A所示结构的二羟基单体。
优选地，所述碳酸二酯类化合物包括碳酸二苯酯、碳酸二甲苯酯、碳酸二(氯苯基)酯、间甲苯基碳酸酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯或碳酸二环己酯中的任意一种或至少两种的组合。
优选地，所述缩聚反应为熔融缩聚反应。
优选地，所述制备方法中还包括具有如式IIA所示结构的二羟基单体：
Figure PCTCN2020121550-appb-000023
式IIA中，Y 1、Y 2、Z、R 3、R 4、m 1、m 2、m 3、m 4各自独立地具有与式II中相同的限定范围。
优选地，所述具有如式IIA所示结构的二羟基单体包括具有如式IIA-1、式IIA-2或式IIA-3所示结构的二羟基单体中的任意一种或至少两种的组合：
Figure PCTCN2020121550-appb-000024
优选地，所述具有如式IIA-2所示结构的二羟基单体包括如下化合物中的任意一种或至少两种的组合：10,10-双-(4-羟乙氧基苯基)-9,9-双酚四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双联苯四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双邻甲酚四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双苯基四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双乙苯基四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双二甲苯四氢蒽、10,10-双-(4-羟乙氧基苯基)-9,9-双萘酚四氢蒽。
示例性地，所述具有如式IIA-2所示结构的二羟基单体通过如下方法合成得到：酸催化剂作用下，使苯氧基醇类化合物先与9-蒽酮的酮基发生缩合反应，得到中间产物A；在氧气氛围与氧化剂的存在下，将中间产物A氧化为含酮基的中间产物B；在酸催化剂作用下，使环烃类化合物继续与中间产物C上的酮基发生缩合反应，生成具有如式IIA-2所示结构的二羟基单体。
优选地，所述具有如式IIA-3所示结构的二羟基单体包括如下化合物中的任意一种或至少两种的组合：9,9-双[4-(2-羟乙氧基)苯基]芴、9,9-双[4-(2-羟乙氧基)-3-甲基苯基]芴、9,9-双[4-(2-羟乙氧基)-3，5-二甲基苯基]芴、9,9-双[4-(2-羟乙氧基)-3-叔丁基苯基]芴、9,9-双[4-(2-羟乙氧基)-3-异丙基苯基]芴、9,9-双[4-(2-羟乙氧基)-3-环己基苯基]芴、9,9-双[4-(2-羟乙氧基)-3-苯基苯基]芴、9,9-双[4-(2-羟乙氧基)苯基]-1,8-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-甲基苯基]-1,8-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-苯基苯基]-1,8-二苯基芴、9,9-双[4-(2-羟乙氧基)苯基]-2,7-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-甲基苯基]-2,7-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-苯基苯基]-2,7-二苯基芴、9,9-双[4-(2-羟乙氧基)苯基]-3,6-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-甲基苯基]-3,6-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-苯基苯基]-3,6-二苯基芴、9,9-双[4-(2-羟乙氧基)苯基]-4,5-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-甲基苯基]-4,5-二苯基芴、9,9-双[4-(2-羟乙氧基)-3-苯基苯基]-4,5-二苯基芴。
优选地，以所述具有如式1A所示结构的二羟基单体和具有如式IIA所示结构的二羟基单 体的总量为1mol计，所述碳酸二酯类化合物的用量为0.97～1.2mol，例如0.99mol、1mol、1.01mol、1.03mol、1.05mol、1.07mol、1.09mol、1.1mol、1.11mol、1.13mol、1.15mol、1.17mol或1.19mol等。
优选地，所述缩聚反应在催化剂存在下进行。
优选地，所述催化剂包括碱金属化合物、碱土金属化合物或含氮化合物中的任意一种或至少两种的组合。
优选地，所述碱金属化合物包括碱金属的有机酸盐、无机盐、氧化物、氢氧化物、氢化物或醇盐等，进一步优选为乙酸钠、乙酸钾、乙酸铯、乙酸锂、氢氧化钠、氢氧化钾、氢氧化铯、氢氧化锂、碳酸氢钠、碳酸钠、碳酸钾、碳酸铯、碳酸锂、硬脂酸钠、硬脂酸钾、硬脂酸铯、硬脂酸锂、硼氢化钠、苯基化硼钠、苯甲酸钠、苯甲酸钾、苯甲酸铯、苯甲酸锂、磷酸氢二钠、磷酸氢二钾、磷酸氢二锂、苯基磷酸二钠、双酚A的二钠盐、双酚A的二钾盐、双酚A的二铯盐、双酚A的二锂盐、苯酚的钠盐、苯酚的钾盐、苯酚的铯盐、苯酚的锂盐等。综合考虑催化剂的催化性能和市场价格等因素，优选碳酸钠和/或碳酸氢钠。
优选地，所述碱土金属化合物包括碱土金属的有机酸盐、无机盐、氧化物、氢氧化物、氢化物或醇盐等，进一步优选为氢氧化镁、氢氧化钙、氢氧化锶、氢氧化钡、碳酸氢镁、碳酸氢钙、碳酸氢锶、碳酸氢钡、碳酸镁、碳酸钙、碳酸锶、碳酸钡、乙酸镁、乙酸钙、乙酸锶、乙酸钡、硬脂酸镁、硬脂酸钙、苯甲酸钙或苯基磷酸镁等。
优选地，所述含氮化合物包括季铵氢氧化物及其盐和/或胺类等，进一步优选为四甲基氢氧化铵、四乙基氢氧化铵、四丙基氢氧化铵、四丁基氢氧化铵、三甲基苄基氢氧化铵、三乙胺、二甲基苄胺、三苯胺等叔胺类、二乙胺、二丁胺等仲胺类、丙胺、丁胺、2-甲基咪唑、2-苯基咪唑、苯并咪唑等咪唑类、氨、四甲基硼氢化铵、四丁基硼氢化铵、四丁基四苯基硼酸铵、四苯基四苯基硼酸铵等。
优选地，以所述具有如式1A所示结构的二羟基单体和具有如式IIA所示结构的二羟基单体的总量为1mol计，所述催化剂的用量为1×10 -9～1×10 -3mol，进一步优选为1×10 -7～1×10 -4mol。
优选地，所述制备方法具体包括：在保护气氛(例如氮气)中将具有如式1A所示结构的二羟基单体、碳酸二酯类化合物和任选的具有如式IIA所示结构的二羟基单体混合，在催化剂存在下、在减压条件下进行缩聚反应；采用逐段减压方式进行，最终使压力为100Pa以下，将生成的醇类蒸馏除去至体系外，得到所述聚碳酸酯。
优选地，所述缩聚反应的温度为150～300℃，例如160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃或290℃等。
优选地，所述缩聚反应的时间为1～4h，例如1.2h、1.5h、1.8h、2h、2.2h、2.5h、2.8h、3h、3.2h、3.5h或3.8h等。
所述制备方法中使用的反应装置可以是具备锚型搅拌桨、MAXBLEND搅拌桨、螺带型搅拌桨等的立式装置，也可以是具备桨式叶片、格子叶片、眼镜式叶片等的卧式装置；优选使用考虑了聚合物的粘度而将这些反应装置适当组合的反应装置来实施。
所述制备方法中，为了保持所述聚碳酸酯的热稳定性和水解稳定性，可以在缩聚反应结束后将催化剂去除或者使其失活。
优选地，所述失活的方法包括通过添加公知的酸性物质作为失活剂；所述酸性物质优选为苯甲酸丁酯等酯类、对甲苯磺酸等芳香族磺酸类；对甲苯磺酸丁酯、对甲苯磺酸己基等芳香族磺酸酯类；亚磷酸、磷酸、膦酸等磷酸类；亚磷酸三苯酯、亚磷酸单苯酯、亚磷酸二苯酯、亚磷酸二乙酯、亚磷酸二正丙酯、亚磷酸二正丁酯、亚磷酸二正己酯、亚磷酸二辛酯、亚磷酸单辛酯等亚磷酸酯类；磷酸三苯酯、磷酸二苯酯、磷酸单苯基、磷酸二丁酯、磷酸二辛酯、磷酸单辛酯等磷酸酯类；二苯基膦酸、二辛基膦酸、二丁基膦酸等膦酸类；苯基膦酸二乙酯等膦酸酯类；三苯基膦、双(二苯基膦基)乙烷等膦类；硼酸、苯基硼酸等硼酸类；十 二烷基苯磺酸四丁基鏻盐等芳香族磺酸盐类；硬脂酰氯、苯甲酰氯、对甲苯磺酰氯等有机卤化物；二甲基硫酸等烷基硫酸；氯化苄等有机卤化物等。
优选地，以所述催化剂的用量为1mol计，所述酸性物质的用量为0.01～50mol，进一步优选为0.3～20mol。如果酸性物质的添加量过低，则导致失活效果不充分；如果酸性物质的添加量过高，则可能导致聚碳酸酯的耐热性降低，易于在后续应用中着色。
另一方面，本申请提供一种如第一方面所述的聚碳酸酯在光学部件、电子产品、电器设备、包装材料、医疗器械或建筑材料中的应用。
优选地，所述光学部件包括汽车用前照明透镜、菲涅尔透镜、激光打印机用f-θ透镜、相机透镜或投影透镜等光学透镜，以及光盘、用于影像显示介质的光学系元件、光学膜、光学底座、光学滤波器或棱镜等光学成型品。
另一方面，本申请提供一种光学透镜，所述光学透镜包含如第一方面所述的聚碳酸酯。
优选地，所述光学透镜可通过如第一方面所述的聚碳酸酯加工成型得到；所述加工成型包括注射成型、压缩成型、注射压缩成型或浇筑成型。其中，在利用注射成型制造光学透镜的情况下，优选在料筒温度230～350℃、模具温度70～180℃的条件下进行成型。
优选地，所述光学透镜根据需要使用非球面透镜的形状而实施。非球面透镜由于可以用1片透镜使球面像差实际上为零，因此不需要利用多个球面透镜的组合除去球面像差，能够轻型化和降低成型成本。因此，非球面透镜在光学透镜中特别作为照相机透镜是有用的。
另外，本申请提供的聚碳酸酯于成型流动性高，因此尤其适用于作为薄壁小型且复杂形状的光学透镜的材料。具体地，所述光学透镜的中心部厚度为0.05～3.0mm，优选为0.05～2.0mm，进一步优选为0.1～2.0mm；所述光学透镜的直径为1.0～20.0mm，优选为1.0～10.0mm，进一步优选为3.0～10.0mm。
优选地，所述光学透镜为一面为凸、一面为凹的凹凸透镜。
另外，也可以根据需要所述光学透镜的表面设置防反射层或硬涂层等涂布层。
优选地，所述防反射层为单层或多层；所述防反射层的材料可以为有机物和/或无机物，优选为无机物。具体而言，所述防反射层的材料包括氧化硅、氧化铝、氧化锆、氧化钛、氧化铈、氧化镁或氟化镁中的任意一种或至少两种的组合。
另外，本申请所述光学透镜也可以通过模具成形、切削、研磨、激光加工、放电加工、蚀刻等任意的方法进行成形，优选为模具成形。
相对于现有技术，本申请具有以下有益效果：
本申请提供的聚碳酸酯中含有包括联硫萘基团的特定重复单元，使所述聚碳酸酯兼具高折射率、高阿贝数和优异的水热稳定性，能够充分满足聚碳酸酯作为光学树脂在光学部件中的性能要求。所述聚碳酸酯的折射率高达1.66～1.75，阿贝数为20～40，玻璃化转变温度达到120～200℃，全光线透过率≥86％，经过耐湿热特性测试后的全光线透过率仍然≥86％，具有高透明度、高折射率、高阿贝数和优异的水热稳定性，能够充分满足聚碳酸酯材料在高性能光学部件中的应用要求。
在阅读并理解了详细描述后，可以明白其他方面。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
1、性能评价使用的样品用以下方法制得：
(a)膜
使得到的聚碳酸酯3g溶解于50mL二氯甲烷中，浇注于玻璃皿上；在室温下充分干燥后，在120℃以下的温度下干燥8小时，制成厚度约100μm的膜。
(b)球面透镜
将得到的聚碳酸酯在120℃下真空干燥8小时后，使成形温度为T g+110℃，使模具温度 为T g-10℃，使用住友重机械(株)制SE30DU注射成形机注射成形厚度0.2mm、凸面曲率半径5mm、凹面曲率半径4mm、Φ5mm的透镜。
(c)成形片
与上述(b)同样地注射成形宽度2.5cm、长度5cm、厚度分别为1mm、2mm、3mm的成形片。
2、评价用以下方法进行：
(1)玻璃化转变温度(T g)
浇注膜利用株式会社岛津制作所制DSC-60A以升温速度20℃/min来测定熔融混炼后得到的聚碳酸酯。
(2)折射率(nD)
使用ATAGO制DR-M2阿贝折射计对利用(a)的方法制成的膜，测定25℃下的折射率，波长为589nm。
(3)阿贝数(v)
按照(2)中折射率的测试方法分别测试25℃、波长分别为486nm、589nm、656nm下的折射率，通过公式v＝(nD－1)/(nF－nC)计算得到，其中，nD为波长589nm下的折射率，nF为波长656nm下的折射率，nC为波长486nm下的折射率。
(4)重均分子量M w
使用凝胶渗透色谱(GPC)，将四氢呋喃作为展开溶剂，使用已知分子量(分子量分布＝1)的标准聚苯乙烯制作标准曲线。基于该标准曲线，由GPC的保留时间算出M w。
(5)全光线透过率
将制造的树脂进行注射成型，得到厚度为3mm，长和宽分别为2cm和1cm的长方形板，使用SE2000型分光式色差计，以标准JIS-K-7361-1中的方法进行测定。
(6)PCT测试
将厚度为1mm的成形片置于85℃、85％湿度(RH)的条件下2000小时后，将该成形片0.7g溶解于100mL二氯甲烷中，测定该溶液在20℃下的比粘度(ηsp)，求出湿热试验后的比粘度保持率(分子量保持率)。将该比粘度保持率率(分子量保持率)设为耐湿热性的指标；计算公式如下：
Δηsp＝(ηsp 1/ηsp 0)×100％；
其中，Δηsp：比粘度保持率；ηsp 0：试验前的比粘度；ηsp 1：试验后的比粘度。
3、本申请以下实施例及对比例中所使用的原料及其制备方法如下：
9,9-双[4-(2-羟乙氧基)苯基]芴(BPEF)，购自黄骅市信诺立兴精细化工有限公司；9,9-双[4-(2-羟乙氧基)-3-苯基苯基]芴(BPPEF)，购自黄骅市信诺立兴精细化工有限公司。
制备例1
2,2-双(2-羟基乙氧基)-6,6-二苯基-1,1-联硫萘(BINSL-2EO)
合成路线如下：
Figure PCTCN2020121550-appb-000025
(1)在装有磁力搅拌器、温度计、恒压滴液漏斗以及冷凝回流管的四口烧瓶中，依次加入6-溴2-萘酚(武汉荣灿生物制药)223g(1mol)和甲苯与乙酸乙酯的混合溶液500mL(甲 苯与乙酸乙酯的质量比为3:2)，搅拌使其溶解，冰浴条件下，缓慢滴加二氯化硫53g(0.52mol)，控制反应体系温度在15℃左右。滴完后，继续反应3h。升温至100℃，蒸馏出大部分溶剂后，放入冰箱冰冻1h，有固体析出，过滤，无水乙醇重结晶，过滤、烘干，得到6,6-二溴-1,1-联硫萘酚。
(2)在反应釜中，将步骤(1)得到的6,6-二溴-1,1-联硫萘1mol和苯基硼酸2mol溶于甲苯/乙醇混合溶液(甲苯与乙醇的质量比为4:1)500mL中，然后进一步添加四(三苯基膦)钯0.01mol和1.5mol/L的碳酸钾水溶液100mL之后，在75℃条件下搅拌2h后结束反应，将得到的反应液进行减压浓缩，除去溶剂后，将得到的固体中加入0.5mol/L的氢氧化钠水溶液，利用氯仿进行萃取，将有机层进行重结晶，滤取析出的固体，通过干燥得到6,6-二苯基-1,1-联硫萘酚。
(3)在反应釜中，将步骤(2)得到的6,6-二苯基-1,1-联硫萘酚、氢氧化钠、环氧乙烷的添加摩尔比为4:0.005:1，然后向其中加入<-5℃的无水乙醇和二甲基甲酰胺DMF，在70℃条件下密封搅拌，反应12h后冷却降温，然后水洗涤后得到白色固体，再进行甲醇重结晶，抽滤烘干得到目标产物BINSL-2EO。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.07(d，2H)，7.95(t，2H)，7.86(d，2H)，7.55(m，2H)，7.52(m，4H)，7.51(m，4H)，7.41(d，2H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例2
2,2-双(2-羟基乙氧基)-6,6-二(萘-1-基)-1,1-联硫萘(1DNBINSL-2EO)
合成路线如下：
Figure PCTCN2020121550-appb-000026
具体制备方法与制备例1的区别仅在于，将步骤(2)中的苯基硼酸用等摩尔量的1-萘基硼酸(濮阳惠成科技)替换；其他反应步骤均与制备例1相同，得到目标产物1DNBINSL-2EO。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.55(t，2H)，8.42(t，2H)，8.08-8.04(m，6H)，7.95(t，2H)，7.86(d，2H)，7.61-7.55(m，8H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例3
2,2-双(2-羟基乙氧基)-1,1-联硫萘(BNSE)
合成路线如下：
Figure PCTCN2020121550-appb-000027
(1)在装有磁力搅拌器、温度计、恒压滴液漏斗以及冷凝回流管的四口烧瓶中，依次加入2-萘酚(江苏手性化工)144g(1mol)和甲苯与乙酸乙酯的混合溶液500mL(甲苯与乙酸乙酯的质量比为3:2)，搅拌使其溶解，冰浴条件下，缓慢滴加二氯化硫53g(0.52mol)， 控制反应体系温度在15℃左右。滴完后，继续反应3h。升温至100℃，蒸馏出大部分溶剂后，放入冰箱冰冻1h，有固体析出，过滤，无水乙醇重结晶，过滤、烘干，得到联硫萘酚。
(2)在反应釜中，将步骤(1)得到的联硫萘酚、氢氧化钠、环氧乙烷的添加摩尔比为4:0.005:1，然后向其中加入<-5℃的无水乙醇和DMF，在70℃条件下密封搅拌，反应12h后冷却降温，然后水洗涤后得到白色固体，再进行甲醇重结晶，抽滤烘干得到目标产物BNSE。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.05-8.01(m，4H)，7.55(m，4H)，7.44(m，2H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例4
2,2-双(2-羟基乙氧基)-6,6-二(萘-2-基)-1,1-联硫萘(2DNBINSL-2EO)
合成路线如下：
Figure PCTCN2020121550-appb-000028
具体制备方法与制备例1的区别仅在于，将步骤(2)中的苯基硼酸用等摩尔量的2-萘基硼酸(濮阳惠成科技)替换；其他反应步骤均与制备例1相同，得到目标产物2DNBINSL-2EO。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.11(d，2H)，8.00(m，4H)，7.95-7.92(m，4H)，7.86(d，2H)，7.73(t，2H)，7.59-7.55(m，8H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例5
2,2-双(2-羟基乙氧基)-6,6-二(3-氰基苯基)-1,1-联硫萘(CN-BNS)
合成路线如下：
Figure PCTCN2020121550-appb-000029
具体制备方法与制备例1的区别仅在于，将步骤(2)中的苯基硼酸用等摩尔量的苯甲腈硼酸替换；其他反应步骤均与制备例1相同，得到目标产物CN-BNS。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.11(d，2H)，7.95(d，2H)，7.88-7.69(m，10H)，7.55(d，2H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例6
2,2-双(2-羟基乙氧基)-6,6-二(二苯并吡咯-4-基)-1,1-联硫萘(PYR-BNS)
合成路线如下：
Figure PCTCN2020121550-appb-000030
具体制备方法与制备例1的区别仅在于，将步骤(2)中的苯基硼酸用等摩尔量的二苯并吡咯-4-硼酸替换；其他反应步骤均与制备例1相同，得到目标产物PYR-BNS。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：10.1(s，2H)，8.12-8.07(m，6H)，7.95(d，2H)，7.87-7.86(t，4H)，7.63-7.50(m，6H)，7.35-7.29(m，4H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
制备例7
10,10-双(4-羟乙氧基苯基)-9,9-双联苯四氢蒽(2BPL-ANT)
合成路线如下：
Figure PCTCN2020121550-appb-000031
(1)将1L的三口烧瓶置于恒温油浴中，分别加入194g蒽酮、260g苯氧乙醇进行缩合反应(摩尔比为1:2.1)，催化剂为10g浓硫酸，助剂为2.12g巯基丙酸，反应温度为40℃，搅拌4h后结束反应，将得到的反应液加入200g甲醇，超声溶解，然后加入200g去离子水，有大量的固体析出，在该温度下继续搅拌2h，降温抽滤得到固体粗产物；将粗产物加入到200g异丙醇中，搅拌、升温至完全溶解，继续加入粗产物直至接近饱和溶解度(粗产物:异丙醇质量比为1:1.6)，继续搅拌30min后，降温结晶得到纯品10,10-双(4-羟乙氧基苯基)-9-氢-蒽。
(2)将步骤(1)得到的10,10-双(4-羟乙氧基苯基)-9-氢-蒽配制质量浓度30％的甲醇溶液共700g，向其中滴加浓硝酸63g，连续通入氧气2h，流量为100L/h，反应结束后，降温结晶得到10,10-双(4-羟乙氧基苯基)蒽酮。
(3)以步骤(2)得到的10,10-双(4-羟乙氧基苯基)蒽酮为原料，按照10,10-双(4-羟乙氧基苯基)蒽酮：联苯：巯基乙酸：HCl的摩尔比为1:6:0.2:0.05进行混合反应，压力0.2MPa， 反应温度20℃，经过3h后结束反应。经碱(氢氧化钠)中和后，去离子水洗涤、抽滤，得到目标产物2BPL-ANT。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)：δ7.52(d,J＝8Hz,4H)，7.51(d,J＝8Hz,4H)，7.41(d,J＝8Hz,2H)，7.33(d,J＝8Hz,4H)，7.31(d,J＝8Hz,4H),7.29(d,J＝8Hz,4H),7.19(d,J＝8Hz,4H),7.12(d,J＝8Hz,4H),6.87(d,J＝8Hz,4H),4.33(t,J＝8Hz,4H),3.69(t,J＝10Hz,4H),3.65(s,2H)。
制备例8
2,2-双(2-羟基乙氧基)-6,6-二(二苯并噻吩-4-基)-1,1-联硫萘(THI-BNS)
合成路线如下：
Figure PCTCN2020121550-appb-000032
具体制备方法与制备例1的区别仅在于，将步骤(2)中的苯基硼酸用等摩尔量的二苯并噻吩-4-硼酸替换；其他反应步骤均与制备例1相同，得到目标产物THI-BNS。
目标产物的核磁结果如下： 1H-NMR(400MHz，CDCl 3)δ/×10 -6：8.45-8.41(m，4H)，8.20(d，2H)，8.07(t，2H)，7.98-7.95(m，4H)，7.86(d，2H)，7.58-7.50(m，8H)，6.85(d，2H)，4.43(t，4H)，3.69(m，4H)，3.65(m，2H)。
实施例1
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000033
制备方法如下：
将3.35kg(6mol)2,2-双(2-羟基乙氧基)-6,6-二苯基-1,1-联硫萘(BINSL-2EO)、1.35kg(6.3mol)碳酸二苯酯(DPC)、0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，进行五次氮气置换，之后将夹套加热到180℃，使原料熔融，完全熔解后，用20min减压至20KPa，同时将夹套升温至270℃，进行酯交换反应。随后将夹套保持在该温度下，在60min内减压至100Pa以下，在270℃、100Pa以下的条件下进行缩聚反应，直至反应达到20N·m的扭矩，反应结束后，将生成的树脂进行造粒，得到所述聚碳酸酯的粒料。
实施例2
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000034
Figure PCTCN2020121550-appb-000035
制备方法如下：
将0.837kg(1.5mol)BINSL-2EO、3.294kg(4.5mol)10,10-双(4-羟乙氧基苯基)-9,9-双联苯四氢蒽(2BPL-ANT)、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例3
一种聚碳酸酯，重复单元的种类与实施例2相同；制备方法如下：
将1.674kg(3mol)BINSL-2EO、2.196kg(3mol)2BPL-ANT、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例4
一种聚碳酸酯，重复单元的种类与实施例2相同；制备方法如下：
将2.511kg(4.5mol)BINSL-2EO、1.098kg(1.5mol)2BPL-ANT、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例5
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000036
Figure PCTCN2020121550-appb-000037
制备方法如下：
将0.837kg(1.5mol)BINSL-2EO、1.91kg(4.5mol)9,9-双[4-(2-羟乙氧基)苯基]芴(BPEF)、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例6
一种聚碳酸酯，重复单元的种类与实施例5相同；制备方法如下：
将1.674kg(3mol)BINSL-2EO、1.27kg(3mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例7
一种聚碳酸酯，重复单元的种类与实施例5相同；制备方法如下：
将2.511kg(4.5mol)BINSL-2EO、0.63kg(1.5mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例8
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000038
制备方法如下：
将0.837kg(1.5mol)BINSL-2EO、2.59kg(4.5mol)9,9-双[4-(2-羟乙氧基)-3-苯基苯基]芴(BPPEF)、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例9
一种聚碳酸酯，重复单元的种类与实施例8相同；制备方法如下：
将1.674kg(3mol)BINSL-2EO、1.72kg(3mol)BPPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例10
一种聚碳酸酯，重复单元的种类与实施例8相同；制备方法如下：
将2.511kg(4.5mol)BINSL-2EO、0.86kg(1.5mol)BPPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例11
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000039
Figure PCTCN2020121550-appb-000040
制备方法如下：
将2.764kg(4.2mol)2,2-双(2-羟基乙氧基)-6,6-二(萘-1-基)-1,1-联硫萘(1DNBINSL-2EO)、0.76kg(1.8mol)BPEF、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例12
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000041
Figure PCTCN2020121550-appb-000042
制备方法如下：
将1.096kg(2.7mol)2,2-双(2-羟基乙氧基)-1,1-联硫萘(BNSE)、0.837kg(1.5mol)BINSL-2EO、1.318kg(1.8mol)2BPL-ANT、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例13
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000043
Figure PCTCN2020121550-appb-000044
制备方法如下：
将0.487kg(1.2mol)BNSE、2.009kg(3.6mol)BINSL-2EO、0.510kg(1.2mol)BPEF、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例14
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000045
Figure PCTCN2020121550-appb-000046
制备方法如下：
将0.487kg(1.2mol)BNSE、2.009kg(3.6mol)BINSL-2EO、0.690kg(1.2mol)BPPEF、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例15
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000047
Figure PCTCN2020121550-appb-000048
制备方法如下：
将1.218kg(3mol)BNSE、0.592kg(0.9mol)1DNBINSL-2EO、1.537kg(2.1mol)2BPL-ANT、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例16
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000049
Figure PCTCN2020121550-appb-000050
制备方法如下：
将0.731kg(1.8mol)BNSE、0.789kg(1.2mol)1DNBINSL-2EO、1.725kg(3mol)BPPEF、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例17
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000051
Figure PCTCN2020121550-appb-000052
制备方法如下：
将0.731kg(1.8mol)BNSE、1.184kg(1.8mol)1DNBINSL-2EO、1.01kg(2.4mol)BPEF、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例18
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000053
Figure PCTCN2020121550-appb-000054
制备方法如下：
将3.355kg(5.1mol)2,2-双(2-羟基乙氧基)-6,6-二(萘-2-基)-1,1-联硫萘(2DNBINSL-2EO)、0.38kg(0.9mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例19
一种聚碳酸酯，重复单元的种类与实施例18相同；制备方法如下：
将1.973kg(3mol)2DNBINSL-2EO、1.27kg(3mol)BPEF、1.35kg(6.3mol)DPC 和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例20
一种聚碳酸酯，重复单元的种类与实施例18相同；制备方法如下：
将0.592kg(0.9mol)2DNBINSL-2EO、2.15kg(5.1mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例21
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000055
Figure PCTCN2020121550-appb-000056
制备方法如下：
将1.098kg(1.8mol)2,2-双(2-羟基乙氧基)-6,6-二(3-氰基苯基)-1,1-联硫萘(CN-BNS)、1.84kg(4.2mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例22
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000057
Figure PCTCN2020121550-appb-000058
制备方法如下：
将1.331kg(1.8mol)2,2-双(2-羟基乙氧基)-6,6-二(二苯并吡咯-4-基)-1,1-联硫萘(PYR-BNS)、1.84kg(4.2mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例23
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000059
Figure PCTCN2020121550-appb-000060
制备方法如下：
将1.521kg(1.8mol)2,2-双(2-羟基乙氧基)-6,6-二(二苯并噻吩-4-基)-1,1-联硫萘(THI-BNS)、1.84kg(4.2mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例24
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000061
制备方法如下：
将3.58kg(6mol)BNSE、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
实施例25
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000062
Figure PCTCN2020121550-appb-000063
制备方法如下：
1.521kg(1.8mol)的THI-BNS、1.05kg(4.2mol)的双酚硫醚，1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
对比例1
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000064
制备方法如下：
将4.392kg(6mol)2BPL-ANT、1.35kg(6.3mol)的DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
对比例2
一种聚碳酸酯，含有重复单元
Figure PCTCN2020121550-appb-000065
制备方法如下：
将2.52kg(6mol)BPEF、1.35kg(6.3mol)DPC和0.0051g(1×10 -5mol)碳酸氢钠放入带有搅拌机和馏出装置的反应釜，按照实施例1中的熔融缩聚方法进行反应，得到所述聚碳酸酯的粒料。
对比例3
一种聚碳酸酯，其与实施例6的区别仅在于，将其中的重复单元
Figure PCTCN2020121550-appb-000066
替换为等摩尔量的
Figure PCTCN2020121550-appb-000067
制备方法与实施例6的区别仅在于，将其中的二羟基单体BINSL-2EO用等摩尔量的2,2-双(2-羟基乙氧基)-6,6-二苯基-联萘(BINOL-2EO)替换，得到所述聚碳酸酯的粒料。
上述实施例1～25中所使用的二羟基单体组分及其对应的摩尔百分含量(％，以二羟基单体总量为100％计)如表1所示，单体的摩尔百分含量与实施例提供的聚碳酸酯中重复单元的摩尔百分含量相对应。
表1
Figure PCTCN2020121550-appb-000068
Figure PCTCN2020121550-appb-000069
测试实施例1～25、对比例1～3提供的聚碳酸酯的物性，包括重均分子量M w、玻璃化转变温度T g、折射率、阿贝数、全光线透过率和经过PCT测试后的全光线透过率，测试数据如表2所示。
表2
Figure PCTCN2020121550-appb-000070
Figure PCTCN2020121550-appb-000071
通过表2的测试结果可知，本申请提供的具有特定重复单元的聚碳酸酯，相对于现有技术中的聚碳酸酯，折射率和阿贝数显著提高，同时还提高了玻璃化转变温度和耐热性，所述聚碳酸酯的折射率高达1.66～1.75，阿贝数为20～40，玻璃化转变温度达到120～200℃，全光线透过率≥86％，湿热处理不会影响所述聚碳酸酯的透过率，经过耐湿热特性测试后的全光线透过率仍然≥86％，具有高透明度、高折射率、高阿贝数和优异的水热稳定性。
比较实施例1～25、对比例1～3的测试数据可知，如果聚碳酸酯中不含有特定的联硫萘结构单元，会使其折射率和阿贝数降低，透明度下降，无法满足光学部件中的应用要求。

Claims (10)

  1. 一种聚碳酸酯，其包含具有如式I所示结构的重复单元：
    Figure PCTCN2020121550-appb-100001
    其中，X 1、X 2各自独立地选自C1～C8直链或支链亚烷基；
    R 1、R 2各自独立地选自卤素、取代或未取代的C1～C6直链或支链烷基、取代或未取代的C2～C6烯烃基、取代或未取代的C1～C6烷氧基、取代或未取代的C6～C30芳基、取代或未取代的C3～C30杂芳基；
    a、b各自独立地选自1～10的整数；
    n 1、n 2各自独立地选自0～4的整数。
  2. 根据权利要求1所述的聚碳酸酯，其中，R 1、R 2中所述取代的取代基各自独立地选自氰基、巯基、羟基、C1～C6直链或支链烷基、C1～C6烷氧基、C6～C18芳氧基、C6～C18芳硫基、C6～C18芳基或C3～C18杂芳基中的至少一种。
  3. 根据权利要求1或2所述的聚碳酸酯，其中，所述X 1、X 2各自独立地选自C1～C3直链或支链亚烷基，优选为亚乙基；
    优选地，所述a、b各自独立地选自1～4的整数；
    优选地，所述R 1、R 2各自独立地选自取代或未取代的C6～C18芳基、取代或未取代的C3～C18杂芳基；所述取代的取代基各自独立地选自氰基、巯基、羟基、C1～C4直链或支链烷基、C1～C3烷氧基中的至少一种；
    优选地，所述n 1、n 2各自独立地选自0～2的整数；
    优选地，所述R 1、R 2各自独立地选自如下基团中的任意一种，或被取代基取代的如下基团中的任意一种：
    Figure PCTCN2020121550-appb-100002
    其中，虚线表示基团的连接位点；
    所述取代基选自氰基、巯基、羟基、C1～C4直链或支链烷基、C1～C3烷氧基中的任意一种；
    优选地，所述聚碳酸酯包含如下重复单元1a～1m中的任意一种或至少两种的组合：
    Figure PCTCN2020121550-appb-100003
    Figure PCTCN2020121550-appb-100004
    优选地，所述聚碳酸酯中具有如式I所示结构的重复单元的摩尔百分含量为10～100％，进一步优选为20～90％。
  4. 根据权利要求1～3任一项所述的聚碳酸酯，其还包含具有如式II所示结构的重复单元：
    Figure PCTCN2020121550-appb-100005
    其中，Y 1、Y 2各自独立地选自C1～C4直链或支链亚烷基；
    Z选自单键、O、S、C1～C5直链或支链亚烷基、
    Figure PCTCN2020121550-appb-100006
    Figure PCTCN2020121550-appb-100007
    中的任意一种，虚线代表基团的连接位点；
    R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自羟基、C1～C20直链或支链烷基、C1～C20烷氧基、C3～C20环烃基、C3～C20环烃氧基、C6～C20芳基或C3～C20杂芳基中的任意一种；
    m 1、m 2各自独立地选自1～10的整数；
    m 3、m 4、m 7、m 8各自独立地选自0～4的整数；
    m 5、m 6各自独立地选自0～5的整数。
  5. 根据权利要求4所述的聚碳酸酯，其中，所述Y 1、Y 2各自独立地选自C1～C3直链或支链亚烷基，优选为亚乙基；
    优选地，所述Z选自S、亚甲基、
    Figure PCTCN2020121550-appb-100008
    Figure PCTCN2020121550-appb-100009
    中的任意一种，虚线代表基团的连接位点；
    优选地，所述R 3、R 4、R 5、R 6、R 7、R 8各自独立地选自羟基、C1～C5直链或支链烷基、C6～C18芳基或C3～C18杂芳基中的任意一种；
    优选地，所述式II所示结构的重复单元包含具有如式II-1、式II-2或式II-3所示结构的重复单元中的任意一种或至少两种的组合：
    Figure PCTCN2020121550-appb-100010
    Figure PCTCN2020121550-appb-100011
    其中，Y 1、Y 2、R 3、R 4、R 5、R 6、R 7、R 8、m 1、m 2、m 3、m 4、m 5、m 6、m 7、m 8各自独立地具有与式II中相同的限定范围。
  6. 根据权利要求4或5所述的聚碳酸酯，其中，所述m 1、m 2各自独立地选自1～3的整数；
    优选地，所述m 3、m 4、m 5、m 6、m 7、m 8各自独立地选自0～3的整数；
    优选地，所述式II所示结构的重复单元包含如下重复单元2a～2h中的任意一种或至少两种的组合：
    Figure PCTCN2020121550-appb-100012
    Figure PCTCN2020121550-appb-100013
    优选地，所述聚碳酸酯中具有如式II所示结构的重复单元的摩尔百分含量为10～90％，进一步优选为20～80％。
  7. 根据权利要求1～6任一项所述的聚碳酸酯，其中，所述聚碳酸酯的折射率为1.65～1.75；
    优选地，所述聚碳酸酯的阿贝数为20～40；
    优选地，所述聚碳酸酯的玻璃化转变温度为135～200℃。
  8. 一种如权利要求1～7任一项所述的聚碳酸酯的制备方法，其包括：具有如式1A所示结构的二羟基单体与碳酸二酯类化合物进行缩聚反应，得到所述聚碳酸酯；
    Figure PCTCN2020121550-appb-100014
    其中，X 1、X 2、R 1、R 2、a、b、n 1、n 2各自独立地具有与式I中相同的限定范围；
    优选地，所述碳酸二酯类化合物包括碳酸二苯酯、碳酸二甲苯酯、碳酸二(氯苯基)酯、间甲苯基碳酸酯、碳酸二甲酯、碳酸二乙酯、碳酸二丁酯或碳酸二环己酯中的任意一种或至少两种的组合；
    优选地，所述缩聚反应为熔融缩聚反应；
    优选地，所述制备方法中还包括具有如式IIA所示结构的二羟基单体：
    Figure PCTCN2020121550-appb-100015
    Figure PCTCN2020121550-appb-100016
    其中，Y 1、Y 2、Z、R 3、R 4、m 1、m 2、m 3、m 4各自独立地具有与式II中相同的限定范围；
    优选地，以所述具有如式1A所示结构的二羟基单体和具有如式IIA所示结构的二羟基单体的总量为1mol计，所述碳酸二酯类化合物的用量为0.97～1.2mol。
  9. 一种如权利要求1～7任一项所述的聚碳酸酯在光学部件、电子产品、电器设备、包装材料、医疗器械或建筑材料中的应用。
  10. 一种光学透镜，其包含如权利要求1～7任一项所述的聚碳酸酯。
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1130647A (zh) * 1994-12-28 1996-09-11 通用电气公司 聚碳酸酯的制造方法
WO2000073387A1 (fr) * 1999-05-27 2000-12-07 Teijin Limited Composition a base de resine de polycarbonate, support d'enregistrement optique et substrat afferent
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