CN115703881B - Polycarbonate optical resin and preparation method and application thereof - Google Patents
Polycarbonate optical resin and preparation method and application thereof Download PDFInfo
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Abstract
The application provides a polycarbonate optical resin, a preparation method and application thereof, wherein the polycarbonate comprises a repeating unit with a structure shown as a formula (I):
Description
Technical Field
The application relates to the field of optical materials, in particular to a polycarbonate optical resin and a preparation method and application thereof.
Background
The polycarbonate is used as one of five thermoplastic engineering plastics, has excellent weather resistance, insulativity, no toxicity and dimensional stability, and has been widely applied to the fields of electronics, construction, automobile manufacturing, aerospace and the like. Particularly, compared with glass, the polycarbonate has the advantages of unique weight and light weight, excellent optical and mechanical properties and easy processing and forming, and as an optical resin, the polycarbonate optical resin occupies an extremely important position in the field of optical lenses, and can be applied to various fields of optical products, such as spectacle lens materials, cameras, microscopes, telescopes, projectors, various prisms, optical test instruments and the like by replacing glass with the polycarbonate optical resin, so that the polycarbonate has a wide application prospect.
However, with the iteration of the technology, the refractive index of the traditional bisphenol a type polycarbonate is 1.58, and the optical performance is more excellent than that of polymethyl methacrylate or polystyrene, but the technology cannot meet the light and thin development of products such as new-generation glasses, electronic products and the like, and higher requirements are put forward on the performance of the polycarbonate optical resin, so that the development of new-generation high-performance novel polycarbonate optical resin materials has important significance. The main means for improving the optical performance of the polycarbonate at present is to introduce a comonomer with a fluorenyl structure, but the refractive index of the obtained polycarbonate is about 1.64, the refractive index product is currently eliminated in the market, and other novel optical comonomers disclosed and reported in some patents are complicated in structure, extremely complex in synthesis, expensive in monomer cost and difficult to realize large-scale industrialization, and the polycarbonate with the refractive index of more than 1.7, low dispersion, low birefringence and excellent thermodynamic performance is rarely researched and has room for improvement at present, so that the polycarbonate with the high refractive index, low dispersion, low birefringence and high thermal stability is developed to meet the application requirements of the polycarbonate in high-performance optical components, and is the research focus in the field.
Disclosure of Invention
The application provides a polycarbonate optical resin which has excellent performances of high refractive index, low dispersion, low birefringence, high thermal stability and the like, and the refractive index can reach 1.765 at the highest, so that the polycarbonate optical resin can meet the performance requirement of the polycarbonate as the optical resin in optical parts; the preparation method takes carbonic diester and dihydroxyl compound as raw materials, and the carbonic diester and dihydroxyl compound undergo melt transesterification reaction under the action of a catalyst, so that the polycarbonate optical resin is produced by polycondensation; the preparation method can easily obtain the polycarbonate optical resin with high refractive index, high thermal stability and adjustable molecular weight, the catalyst consumption is small, the reaction condition is mild, the reaction process does not cause environmental pollution, the product does not contain toxic substances, the process is simple, the large-scale production is convenient, and the preparation method is an efficient and environment-friendly polycarbonate optical resin preparation process; also disclosed is an optical article which can be made from the synthesized polycarbonate and which has excellent properties such as high refractive index and high thermal stability.
In order to achieve the aim of the application, the application adopts the following technical scheme:
a polycarbonate optical resin comprising a repeating unit having a structure as shown in formula (I):
in the formula (I), W 1 、W 2 Each independently selecting O or S; x is X 1 、X 2 Each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; r is R 1 、R 2 Each independently represents hydrogen, halogen, hydroxyl, ester, cyano, amino, thiol, substituted or unsubstituted straight or branched alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted aryl or fused ring aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl or fused ring heteroaryl having 3 to 30 carbon atoms, or an atom or group of atoms which may be substituted for the above groups; p1 and p2 are each independently selected from integers of 1 to 3; a. b are each independently selected from integers from 0 to 5.
Specifically, in the application, the structural unit shown in the formula (I) contains a benzanthracene cardo ring structure, is a multi-aromatic ring planar structure, has better heat resistance, is in a side-hanging state with the main polymer chain of the formed polycarbonate optical resin, can well eliminate the birefringence phenomenon, and ensures that the polymer material has better anisotropism; the planar structure of the benzanthracene type cardo ring structure ensures that the steric hindrance of an active site in the catalytic process is small, the monomer synthesis activity is high, the yield is high, the selectivity is good, the monomer cost is reduced, and the preparation and the production of large-scale monomers are facilitated; in addition, in the polycarbonate structure, groups with high molar refraction degree and relatively small molar volume such as heteroatom sulfur, halogen and the like are introduced, the refractive index of the material can be effectively improved, the electronegativity (2.5) of the heteroatom sulfur is equivalent to that of a carbon atom (2.5) and is smaller than that of oxygen (3.5), when sulfur is substituted in an aromatic ring, the acting force is weak, the plane action of the aromatic ring is not damaged, and the refractive index of the polycarbonate can be remarkably improved by combining with the higher molar refractive index. In this case, the polycarbonate of the present application may have a high refractive index, low birefringence and high thermal stability.
The polycarbonate optical resin according to the present application has a content ratio of the structural unit selected from the group consisting of the structural units represented by the formula (I) of 5mol% to 100mol% based on the total mole number of all the repeating structural units of the polycarbonate optical resin. (specifically, the content of structural units derived from the dihydroxy compound represented by formula (I) constituting the polycarbonate optical resin is 5mol% to 100mol% based on the total mole number of all structural units derived from the dihydroxy compound)
Preferably, the structural formula of the polycarbonate optical resin is any one of the formulas (I-1) to (I-13), but is not limited to the following structural formula:
the polycarbonate optical resin further comprises a repeating unit having a structure represented by formula (II) or formula (III):
in the formula (II) of the present application,Y 1 、Y 2 each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; c. d is each independently selected from integers from 0 to 5; m is M 1 Independently represents a single bond, O, S, a linear or linear alkylene group having 1 to 5 carbon atoms, a catalyst system,The dotted line represents the attachment site of the group; r is R 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight or branched alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted aryl or fused ring aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or fused ring heteroaryl; p3, p4, p5, p6 are each independently selected from integers from 1 to 3;
in the formula (III), M 2 Independently represents a single bond, O, S; z is Z 1 、Z 2 Each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; e. f are each independently selected from integers from 0 to 5; r is R 7 、R 8 Each independently selected from hydrogen, hydroxy, substituted or unsubstituted straight or branched alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted aryl or fused ring aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or fused ring heteroaryl; p7 and p8 are each independently selected from integers of 1 to 3.
Preferably, the structural formula of the polycarbonate optical resin includes any one of the formulas (II-1) to (II-3) and the formulas (III-1) to (III-2), but is not limited to the following structural formula:
the content ratio of the structural unit selected from the group consisting of the structural unit represented by the formula (I) is 30 to 85mol% and the content ratio of at least one structural unit selected from the group consisting of the structural unit represented by the formula (II) and the structural unit represented by the formula (III) is 15 to 70mol% with respect to the total mole number of all the repeating structural units of the polycarbonate optical resin. (specifically, the content of structural units of the dihydroxy compound represented by formula (I) constituting the polycarbonate optical resin is 30 to 85mol% relative to the total mole number of all structural units of the dihydroxy compound, and the content of structural units of at least one dihydroxy compound from structural units represented by formula (II) and structural units represented by formula (III) is 15 to 70mol% relative to the total mole number of all structural units of the dihydroxy compound.)
The refractive index of the polycarbonate optical resin can reach 1.647-1.765, and the glass transition temperature is 135-200 ℃, and further preferably 140-175 ℃. The polycarbonates of the application have further increased refractive index and heat resistance.
The preparation method of the polycarbonate optical resin takes dihydroxyl compound and carbonic diester as raw materials, wherein at least one dihydroxyl compound selected from the dihydroxyl compounds shown in the formulas (1), (2) and (3) is synthesized into polycarbonate through melt transesterification polycondensation reaction in nitrogen atmosphere under normal pressure; after the raw materials are melted, heating to 120-190 ℃ of transesterification temperature, adding a catalyst, and carrying out transesterification reaction for 0.2-5 h to obtain polycarbonate prepolymer; then gradually heating to the polycondensation temperature of 200-260 ℃, the pressure of a reaction system is less than 50pa, and obtaining the polycarbonate copolymer after the polycondensation reaction for 0.2-5 h and the weightAverage molecular weight of 3.07×10 4 ～18.0×10 4 g/mol。
Wherein W is 1 、W 2 、X 1 、X 2 、R 1 、R 2 Each of p1, p2, a, b independently has the same defined range as in formula (I);
wherein M is 1 、Y 1 、Y 2 、R 3 、R 4 P3, p4, c, d each independently have the same defined range as formula (II);
wherein M is 2 、Z 1 、Z 2 、R 7 、R 8 P7, p8, e, f each independently have the same defined range as formula (III);
specifically, any of the formulae (1-1) to (1-13), the formulae (2-1) to (2-3), and the formulae (3-1) to (3-2) may be used, but the present application is not limited to the following structural formulae:
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the catalyst is selected from an ionic liquid catalyst or a metal catalyst, wherein cations in the ionic liquid catalyst are selected from any one of imidazole cations, quaternary ammonium cations, quaternary phosphonium cations, piperidine cations and pyridine cations; the metal catalyst is at least one of lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, zinc acetylacetonate, dibutyl tin oxide, tetrabutyl titanate, tetraisopropyl titanate, carbonate, acetate, alkali metal, alkaline earth metal, TBD or DBU; the catalyst is used in an amount of 1×10 of the amount of the carbonic acid diester compound material -7 ～5×10 -4 。
The carbonic acid diester compound comprises any one or a combination of at least two of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate; the dihydroxyl compound comprises any one or a combination of at least two selected from the group consisting of formula (1), formula (2), formula (3), isosorbide, isomannide, isoidide, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 3-cyclopentanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, hydrogenated dioleyl glycol, 1, 5-decalin dimethanol, 2, 5-norbornane dimethanol, and 4, 8-bis (hydroxymethyl) tricyclodecane; the ratio of the amounts of the dihydroxy compound and the carbonic acid diester is 1 (0.97 to 5).
The polycarbonate optical resin described in the present application may optionally further include additives, examples of which include, but are not limited to: antioxidants, plasticizers, anti-aging agents, heat stabilizers, fillers, dyes, light stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, mold release agents, antibacterial agents. These additives may be used singly or in any combination of two or more. The content of the additive can be added in proper amount according to the requirement.
The preparation method can easily obtain the polycarbonate optical resin with high refractive index, low birefringence, high thermal stability and adjustable molecular weight, has the advantages of less catalyst consumption, mild reaction conditions, no environmental pollution in the reaction process, no toxic substances in the product, simple process, convenient mass production and high efficiency and environment friendliness, and is an efficient and environment-friendly preparation process for the polycarbonate optical resin.
The polycarbonate optical resin is applied to optical parts, electronic products, electrical equipment, packaging materials, medical devices or building materials.
An optical article comprising the polycarbonate optical resin prepared according to the present application.
The beneficial effects of the application are as follows: the polycarbonate optical resin provided by the application has excellent performances such as high refractive index and high thermal stability, and the optical lens with better performance can be prepared by processing the polycarbonate, so that the polycarbonate optical resin can be applied to the fields of optical parts, electronic products, electrical equipment, packaging materials, medical appliances or building materials and the like.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without any inventive effort, are intended to be within the scope of the application.
1. Samples used for performance evaluation were prepared by the following method:
(a) Film: 1g of the obtained polycarbonate was dissolved in 10mL of methylene chloride and poured onto a glass dish; after sufficiently drying at room temperature, the film was dried at 60℃or lower for 12 hours to give a film having a thickness of about 100. Mu.m.
2. The evaluation test method is as follows:
(a) Weight average molecular weight (M) w ): using a gel permeation chromatograph PL-GPC 50 manufactured by Agilent Technologies, N-Dimethylformamide (DMF) was used as a developing solvent, and monodisperse polystyrene of a known molecular weight was used as a standard curve, M was obtained from the retention time of GPC based on the standard curve w 。
(b) Refractive index (n) D )
The refractive index of the film produced by the method of (a) was measured at 25℃using a DR-M2 Abbe refractometer manufactured by ATAGO, and the wavelength was 589nm.
(c) Abbe number (V) D )
The refractive index at 25℃and at wavelengths of 486nm, 589nm and 656nm, respectively, was measured according to the method for measuring refractive index in (b) and was calculated by the formula V D ＝(n D －1)/(n F －n C ) Calculated, where n D Refractive index at wavelength of 589nm, n F Is refractive index at 656nm, n C Is refractive index at wavelength 486 nm.
3. The raw materials used in the following examples and comparative examples of the present application and the preparation methods thereof are as follows:
2, 2-bis (4-hydroxyphenyl) propane (BPA), 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene (BPEF), 1 '-bis [4- (2-hydroxyethoxy) phenyl ] cyclohexane (BPEZ), 2-bis (2-hydroxyethoxy) -1,1' -thiobis (2-naphthol) (S-BNE) and the like.
Preparation example 1
7, 7-bis [4- (2-hydroxyethoxy) phenyl ] benzanthracene (BPEBA), synthetic route:
0.050mol of benzanthrone, 0.300mol of phenoxyethanol and 0.004g of beta-mercaptopropionic acid are weighed, the reaction system is kept in a nitrogen atmosphere, firstly, the mixture is stirred at 40 ℃ until the benzanthrone is completely dissolved, then 10.900mL of concentrated sulfuric acid is added dropwise, titration is completed within 0.5-1 h, then the temperature is raised to 65 ℃ and the reaction is kept for 5h. After the reaction is finished, 100mL of toluene dissolved product is added, stirring is carried out for 1h at 50 ℃, warm water is used for repeatedly washing for more than 3 times, then the organic phase is decompressed, distilled and concentrated, 150mL of methanol is poured into the mixture, stirring is carried out for 1h, then the mixture is left stand, a large amount of precipitate is separated out, the mixture is filtered, and the crude product of diether benzanthracene is obtained, and then the mixture is recrystallized by using a mixed solvent of toluene and acetone, thus obtaining a purer target product.
Preparation example 2
7, 7-bis [ 3-bromo-4- (2-hydroxyethoxy) phenyl ] benzanthracene (Br-BPEBA), synthetic route:
BPEBA 0.300mol and 200mL chloroform were added to a 1000mL reaction flask, and stirred, the flask was equipped with a calcium chloride tube and a dropping funnel, and a mixed solvent of 0.06mol of bromine and 100mL of chloroform was added dropwise to the resulting suspension at room temperature over 20 minutes. After the completion of the dropping, the mixture was further stirred at room temperature for 30 minutes, then 50mL of deionized water was added, the supernatant was removed by a separating funnel, a saturated aqueous sodium sulfite solution was added to the organic layer, the separation was performed twice, the organic layer was further washed with distilled water, anhydrous sodium sulfate was added to the organic layer to dry, and finally the mixture was filtered and dried under reduced pressure to obtain the objective product.
Preparation example 3
7, 7-bis [4- (2-hydroxyethylthio) phenyl ] benzanthracene (S-BPEBA), synthetic route:
the same operations as in production example 1 were performed except that phenoxyethanol as the raw material in production example 1 was replaced with 2-thiophenylethanol.
Preparation example 4
7, 7-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] benzanthracene (BNEBA), synthetic route:
0.050mol of benzanthrone, 0.200mol of 2-naphthol, 0.04 g of beta-mercaptopropionic acid and 100mL of toluene are weighed as reaction solvents, a nitrogen atmosphere is maintained in a reaction system, firstly, the mixture is uniformly stirred at 60 ℃, then 5.450mL of concentrated sulfuric acid is added dropwise, titration is completed within 0.5-1 h, the temperature is raised to 80 ℃ after that, and heat preservation reaction is carried out for 5h under a micro negative pressure condition. After the reaction is finished, 80mL of toluene and 150mL of deionized water are added, stirring is continued for 1h, then toluene organic phase is obtained through separation and washed for more than 3 times by warm water, the organic phase is reserved, then reduced pressure distillation and concentration are carried out, 150mL of methanol is poured into the mixture for stirring for 1h, the crude product is obtained after filtration, and then the recrystallization is carried out by isopropanol, thus obtaining a purer product.
0.020mol of crude product was taken, 0.044mol of Ethylene Carbonate (EC), 100mL of N, N-Dimethylformamide (DMF) was added as solvent, 0.002mol of K 2 CO 3 Heating the catalyst to reflux, reacting for 3 hours, cooling to room temperature, adding 150mL of deionized water, standing, precipitating a large amount of precipitate, filtering, washing with water, and placing in a vacuum drying oven at 60 ℃ for 24 hours to obtain a crude product. Toluene is used for recrystallization to obtain a purer target product.
Preparation example 5
7, 7-bis [6- (2-hydroxyethylthio) naphthalen-2-yl ] benzanthracene (S-BNEBA), synthetic route:
the same operations as in production example 4 were performed except that 2-naphthol as the raw material in production example 4 was replaced with 2-naphthalenethiol.
Example 1
The preparation steps of the polycarbonate optical resin are as follows:
at room temperature, 0.030mol of diphenyl carbonate (DPC) and 0.030mol of BPEBA are added into a 250ml three-neck flask, the raw materials are melted under the protection of nitrogen atmosphere, the temperature is raised to 150 ℃ after the transesterification temperature, and then sodium hydroxide catalyst is added, wherein the catalyst dosage is 0.005mol% of the diphenyl carbonate dosage. Stirring at 150 ℃ to perform transesterification reaction for 3 hours to obtain a polycarbonate prepolymer; then gradually heating and gradually reducing the temperature to 240 ℃ until the pressure of a reaction system is less than 50pa, maintaining the temperature for 0.5h through polycondensation reaction, introducing nitrogen into the reactor after the reaction is finished, and recovering the pressure to normal pressure. And then obtaining the polycarbonate material through dichloro dissolution and methanol precipitation.
Example 2
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were conducted except that 0.030mol of DPC, 0.021mol of BPEBA, 0.0045mol of BPA and 0.0045mol of S-BNE were used as the raw materials.
Example 3
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were performed except that 0.030mol of DPC, 0.024mol of Br-BPEBA and 0.006mol of BPEF were used as the raw materials.
Example 4
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were carried out except that 0.030mol of DPC, 0.018mol of BNEBA, 0.006mol of BPEZ and 0.006mol of S-BNE were used as the starting materials.
Example 5
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were performed except that 0.030mol of DPC, 0.021mol of S-BPEBA, 0.0045mol of BPEF and 0.0045mol of S-BNE were used as the raw materials.
Example 6
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were carried out except that 0.030mol of DPC and 0.030mol of S-BNEBA were used as the starting materials.
Example 7
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were carried out except that 0.030mol of DPC, 0.018mol of S-BNEF, 0.006mol of BPEF and 0.006mol of S-BNE were used as the starting materials.
Example 8
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were carried out except that 0.030mol of DPC, 0.018mol of S-BNEF, 0.006mol of BPEF and 0.006mol of S-BNE were used as the starting materials, the transesterification temperature was adjusted to 190℃and the transesterification time was adjusted to 5 hours.
Example 9
The preparation steps of the polycarbonate optical resin are as follows:
the same operations as in example 1 were carried out except that 0.030mol of DPC, 0.018mol of S-BNEF, 0.006mol of BPEF and 0.006mol of S-BNE were used as the starting materials, the transesterification temperature was adjusted to 190℃and the transesterification time was adjusted to 5 hours, and tetraethylammonium hydroxide was used as the catalyst.
Comparative example 1
The same operations as in example 1 were carried out except that 0.030mol of DPC and 0.300mol of BPA were used as the raw materials.
Comparative example 2
The same operations as in example 1 were performed except that 0.030mol of DPC and 0.300mol of BPEF were used as the raw materials and tetraethylammonium hydroxide was used as the catalyst.
Comparative example 3
The same operations as in example 1 were performed except that 0.030mol of DPC and 0.300mol of BPEZ were used as the raw materials and tetraethylammonium hydroxide was used as the catalyst.
The polycarbonates provided in examples 1 to 9 and comparative examples 1 to 3 were tested for physical properties including weight average molecular weight Mw, refractive index and Abbe number, and the test data are shown in Table 1.
As can be seen from the test results in Table 1, the polycarbonate provided by the application has a significantly improved refractive index compared with the polycarbonate in the prior art, the refractive index of the polycarbonate is as high as 1.647-1.765, the Abbe number is 15-20, no obvious birefringence phenomenon exists, and the polycarbonate has excellent optical properties.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (11)
1. A polycarbonate optical resin comprising a repeating unit having a structure according to formula (I):the compound of formula (I),
in the formula (I), W 1 、W 2 Each independently selected from O or S; x is X 1 、X 2 Each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; r is R 1 、R 2 Each independently represents hydrogen, halogen, hydroxyl, ester, cyano, amino, thiol, substituted or unsubstituted straight or branched alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms, substituted or unsubstituted alkenyl having 2 to 6 carbon atoms, substituted or unsubstituted alkoxy having 1 to 6 carbon atoms, substituted or unsubstituted aryl or fused ring aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms or fused ring heteroaryl; p1 and p2 are each independently selected from integers of 1 to 3; a. b are each independently selected from integers from 1 to 5.
2. The polycarbonate optical resin according to claim 1, wherein: the content ratio of the structural unit selected from the group consisting of the structural units represented by the formula (I) is 5mol% to 100mol% with respect to the total mole number of all the repeating structural units of the polycarbonate optical resin.
3. The polycarbonate optical resin according to claim 2, wherein: the polycarbonate optical resin further comprises a repeating unit having a structure represented by formula (II) or formula (III):the compound of formula (II),
in the formula (II), Y 1 、Y 2 Each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; c. d is each independently selected from integers from 0 to 5; m is M 1 Independently represents a single bond, O, S, a linear or branched alkylene group having 1 to 5 carbon atoms, a catalyst,Or->The dotted line represents the attachment site of the group; r is R 3 、R 4 、R 5 、R 6 Each independently selected from the group consisting of hydrogen, halogen, hydroxy, ester, cyano, amino, thiol, substituted or unsubstituted straight or branched alkyl of 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl of 3 to 10 carbon atoms, substituted or unsubstituted alkenyl of 2 to 6 carbon atoms, substituted or unsubstituted alkoxy of 1 to 6 carbon atoms, substituted or unsubstituted aryl or fused ring aryl of 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl of 3 to 30 carbon atoms, and fused ring heteroaryl; p3, p4, p5, p6 are each independently selected from integers of 1 to 3;
formula (III),
in the formula (III), M 2 Independently represents a single bond, O, S; z is Z 1 、Z 2 Each independently represents a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 8 carbon atoms; e. f are each independently selected from integers from 0 to 5; r is R 7 、R 8 Each independently selected from the group consisting of hydrogen, halogen, hydroxy, ester, cyano, amino, thiol, substituted or unsubstituted straight or branched alkyl having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 carbon atoms,A substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms or a condensed ring aryl group, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms or a condensed ring heteroaryl group; p7 and p8 are each independently selected from integers of 1 to 3.
4. The polycarbonate optical resin according to claim 3, wherein: the content ratio of the structural unit selected from the group consisting of the structural unit represented by the formula (I) is 30 to 85mol% and the content ratio of at least one structural unit selected from the group consisting of the structural unit represented by the formula (II) and the structural unit represented by the formula (III) is 15 to 70mol% with respect to the total mole number of all the repeating structural units of the polycarbonate optical resin.
5. The polycarbonate optical resin according to claim 4, wherein: the refractive index of the polycarbonate optical resin can reach 1.647-1.765, and the glass transition temperature is 135-200 ℃.
6. A preparation method of polycarbonate optical resin is characterized in that a dihydroxyl compound and carbonic diester are used as raw materials, wherein the dihydroxyl compound comprises a dihydroxyl compound shown in a formula (1), and polycarbonate is obtained through melt transesterification polycondensation reaction under nitrogen atmosphere and normal pressure; after the raw materials are melted, heating to 120-190 ℃ of transesterification temperature, adding a catalyst, and carrying out transesterification reaction by 0.2-5 h to obtain polycarbonate prepolymer; then gradually heating to the polycondensation temperature of 200-260 ℃, the pressure of a reaction system is less than 50pa, and obtaining the polycarbonate copolymer after the polycondensation reaction of 0.2-5 h and the weight average molecular weight of 3.07 multiplied by 10 4 ～18.0×10 4 g/mol；
(1),
wherein W is 1 、W 2 、X 1 、X 2 、R 1 、R 2 Each of p1, p2, a, b independently has the same definition as claim 1.
7. The preparation method according to claim 6, wherein a dihydroxy compound and a carbonic acid diester are used as raw materials, wherein the dihydroxy compound further comprises a dihydroxy compound represented by formula (2) and/or formula (3), and the polycarbonate is synthesized by melt transesterification polycondensation under nitrogen atmosphere and normal pressure; after the raw materials are melted, heating to 120-190 ℃ of transesterification temperature, adding a catalyst, and carrying out transesterification reaction by 0.2-5 h to obtain polycarbonate prepolymer; then gradually heating to the polycondensation temperature of 200-260 ℃, the pressure of a reaction system is less than 50pa, and obtaining the polycarbonate copolymer after the polycondensation reaction of 0.2-5 h and the weight average molecular weight of 3.07 multiplied by 10 4 ～18.0×10 4 g/mol；
(2),
wherein M is 1 、Y 1 、Y 2 、R 3 、R 4 P3, p4, c, d each independently have the same defined range as claim 3;
(3),
wherein M is 2 、Z 1 、Z 2 、R 7 、R 8 P7, p8, e, f each independently have the same definition as claim 3.
8. The production method according to claim 6 or 7, wherein the catalyst is selected from an ionic liquid catalyst or a metal catalyst, wherein the cation in the ionic liquid catalyst is selected from any one of an imidazole-based cation, a quaternary ammonium-based cation, a quaternary phosphine-based cation, a piperidine-based cation, and a pyridine-based cation; the metal catalyst is lithium acetylacetonate,At least one of sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, calcium acetylacetonate, zinc acetylacetonate, dibutyl tin oxide, tetrabutyl titanate, tetraisopropyl titanate, carbonate, acetate, alkali metal, and alkaline earth metal; the catalyst is used in an amount of 1×10 of the amount of the carbonic acid diester compound material -7 ～5×10 -4 。
9. The production method according to claim 6 or 7, wherein the carbonic acid diester compound comprises any one or a combination of at least two of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate, and dioctyl carbonate; the dihydroxy compound further includes any one or a combination of at least two of isosorbide, isomannide, isoidide, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 3-cyclopentanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, 1, 4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, hydrogenated dioleyldiol, 1, 5-decalin dimethanol, 2, 5-norbornane dimethanol, or 4, 8-bis (hydroxymethyl) tricyclodecane; the ratio of the amount of the dihydroxy compound to the amount of the carbonic acid diester is 1 (0.97-5).
10. The use of the polycarbonate optical resin prepared by the preparation method of claim 6 in optical parts, electronic products, electrical equipment, packaging materials, medical devices or building materials.
11. An optical article comprising the polycarbonate optical resin according to any one of claims 1 to 5 or the polycarbonate optical resin produced by the production method according to any one of claims 6 to 8.
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