CN115703881A - 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 invention provides a polycarbonate optical resin, a preparation method and an application thereof, wherein the polycarbonate comprises a repeating unit with a structure shown as a formula (I):
Description
Technical Field
The invention relates to the field of optical materials, in particular to a polycarbonate optical resin and a preparation method and application thereof.
Background
Polycarbonate is one of five thermoplastic engineering plastics, has excellent weather resistance, insulativity, nontoxicity and dimensional stability, and is widely applied to the fields of electronic and electric appliances, buildings, automobile manufacturing, aerospace and the like. Particularly, compared with glass, polycarbonate has the advantages of light weight, excellent optical and mechanical properties and easy processing and forming due to unique quality, and the polycarbonate is taken as an optical resin and plays an extremely important role in the field of optical lenses.
However, with the iteration of the technology, the refractive index of the traditional bisphenol a polycarbonate is 1.58, and although the optical performance is more excellent compared with polymethyl methacrylate or polystyrene, the optical performance is not yet satisfied with the thinning development of the products of the new generation of 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 the new generation of high-performance novel polycarbonate optical resin material has important significance. At present, a main means for improving the optical performance of polycarbonate is to introduce a comonomer with a fluorenyl structure, but the refractive index of the obtained polycarbonate is about 1.64, the product with the refractive index is currently about to be eliminated in the market, and some patent publications report that a novel optical comonomer is expensive in monomer cost and difficult to realize large-scale industrialization due to the complex structure, extremely complex synthesis and few improvement spaces exist for optical polycarbonate with the refractive index of more than 1.7, low dispersion, low birefringence and excellent thermodynamic performance, so that the development of the polycarbonate with the high refractive index, the low dispersion, the low birefringence and the high thermal stability is a research focus in the field to meet the application requirements of the polycarbonate in high-performance optical parts.
Disclosure of Invention
The invention provides a polycarbonate optical resin, which has excellent performances of high refractive index, low dispersion, low birefringence, high thermal stability and the like, the refractive index can reach 1.765 at most, and the polycarbonate optical resin can meet the performance requirements of the polycarbonate as the optical resin in optical components; also provides a preparation method of the polycarbonate optical resin, which takes carbonic diester and dihydroxy compound as raw materials to carry out melt transesterification reaction under the action of a catalyst and carry out polycondensation to generate the polycarbonate optical resin; the preparation method can easily obtain the polycarbonate optical resin with high refractive index, high thermal stability and adjustable molecular weight, the dosage of the catalyst 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, green and environment-friendly preparation process for the polycarbonate optical resin; also disclosed is an optical article which can be produced by synthesizing a polycarbonate and has excellent properties such as a high refractive index and high thermal stability.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polycarbonate optical resin comprising a repeating unit having a structure represented by formula (I):
in the formula (I), W 1 、W 2 Each independently selected from O or S; x 1 、X 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; r 1 、R 2 Each independently represents hydrogen, halogen, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl or condensed ring aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl or condensed ring heteroaryl group having 3 to 30 carbon atoms, or an atom or atom group which may substitute for the above groups; p1 and p2 are each independently selected from integers of 1 to 3; a. each b is independently selected from integers of 0 to 5.
Specifically, in the application, the structural unit shown in formula (I) contains a benzanthracene type cardo ring structure, is a planar structure of multiple aromatic rings, has better heat resistance, is in a side-perpendicular state with a formed polymer main chain of the polycarbonate optical resin due to spatial arrangement, can well eliminate a birefringence phenomenon, and enables a polymer material to have better anisotropy; 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 the large-scale monomer are facilitated; in addition, in the structure of the polycarbonate, groups with high molar refraction and relatively small molar volume such as heteroatom sulfur, halogen and the like are introduced, so that 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 planar action of the aromatic ring cannot be destroyed, and the higher molar refraction index is combined, so that the refractive index of the polycarbonate can be obviously improved. In this case, the polycarbonate of the present application can combine high refractive index, low birefringence, and high thermal stability.
The polycarbonate optical resin of the present invention contains the structural unit represented by the formula (I) in a proportion of 5 to 100mol% based on the total number of moles of all repeating structural units in the polycarbonate optical resin. (specifically, the content of the structural unit derived from the dihydroxy compound represented by formula (I) constituting the polycarbonate optical resin is 5 to 100mol% based on the total number of moles of all structural units derived from the dihydroxy compound.)
Preferably, the structural formula of the polycarbonate optical resin is any one of formulas (I-1) to (I-13), but is not limited to the following structural formula:
the polycarbonate optical resin also comprises a repeating unit with a structure shown in a formula (II) or a formula (III):
in the formula (II), Y 1 、Y 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; c. d is each independently selected from an integer of 0 to 5; m is a group of 1 Independently represents a single bond, O, S, a linear or branched alkylene group having 1 to 5 carbon atoms,
The dotted line represents the attachment site of the group; r 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, hydroxyl, substituted or unsubstituted straight chain or branched chain alkyl with 1-6 carbon atoms, substituted or unsubstituted cycloalkyl with 3-10 carbon atoms, substituted or unsubstituted alkenyl with 2-6 carbon atoms, substituted or unsubstituted alkoxy with 1-6 carbon atoms, substituted or unsubstituted aryl or condensed ring aryl with 6-30 carbon atoms, substituted or unsubstituted heteroaryl or condensed ring heteroaryl with 3-30 carbon atoms; p3, p4, p5 and p6 are independently selected from integers of 1-3;
in the formula (III), M 2 Independently represent a single bond, O, S; z 1 、Z 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; e. each f is independently selected from an integer of 0 to 5; r 7 、R 8 Each independently selected from hydrogen, hydroxyl, substituted or unsubstituted C1-6 linear or branched alkyl, substituted or unsubstituted CA cycloalkyl group 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 or condensed ring aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl or condensed ring heteroaryl group having 3 to 30 carbon atoms; 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 formulas (II-1) to (II-3) and 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 structural units represented by the formula (I) is 30 to 85mol%, and the content ratio of at least one structural unit selected from the structural units represented by the formula (II) and the structural units represented by the formula (III) is 15 to 70mol%, based on the total number of moles of all repeating structural units of the polycarbonate optical resin. Specifically, the content of the structural unit derived from the dihydroxy compound represented by formula (I) is 30 to 85mol% based on the total number of moles of all structural units derived from the dihydroxy compound, and the content of at least one structural unit derived from the structural unit represented by formula (II) and the structural unit represented by formula (III) is 15 to 70mol% based on the total number of moles of all structural units derived from the dihydroxy compound, which constitute the polycarbonate optical resin
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 polycarbonate of the present invention has a further increased refractive index and heat resistance.
The preparation method of the polycarbonate optical resin takes a dihydroxy compound and a carbonic diester as raw materials, wherein dihydroxy isAt least one compound selected from dihydroxy compounds shown in formula (1), formula (2) and formula (3) is synthesized into polycarbonate through melt ester exchange polycondensation reaction under nitrogen atmosphere and normal pressure; after the raw materials are melted, heating the raw materials to the ester exchange temperature of 120-190 ℃, adding a catalyst into the raw materials to perform ester exchange reaction for 0.2-5 hours to obtain a polycarbonate prepolymer; then gradually heating to the polycondensation temperature of 200-260 ℃, the pressure of the reaction system is less than 50pa, and carrying out polycondensation reaction for 0.2-5 h to obtain the polycarbonate copolymer with the weight average molecular weight of 3.07 multiplied by 10 4 ～18.0×10 4 g/mol。
Wherein, W 1 、W 2 、X 1 、X 2 、R 1 、R 2 P1, p2, a, b each independently have the same limits as in formula (I);
wherein, M 1 、Y 1 、Y 2 、R 3 、R 4 P3, p4, c, d each independently have the same limitations as formula (II);
wherein, M 2 、Z 1 、Z 2 、R 7 、R 8 P7, p8, e, f each independently have the same limitations as formula (III);
specifically, the compound may be any one of formulas (1-1) to (1-13), formulas (2-1) to (2-3), and formulas (3-1) to (3-2), but is not limited to the following structural formula:
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 phosphine 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, dibutyltin oxide, tetrabutyl titanate, tetraisopropyl titanate, carbonate, acetate, alkali metal, alkaline earth metal, TBD or DBU; the amount of the catalyst used is 1X 10 times the amount of the carbonic acid diester compound substance -7 ～5×10 -4 。
The carbonic acid diester compound comprises any one of diphenyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dipentyl carbonate and dioctyl carbonate or the combination of at least two of the diphenyl carbonate, the dimethyl carbonate, the diethyl carbonate, the dipropyl carbonate, the dibutyl carbonate, the dipentyl carbonate and the dioctyl carbonate; the dihydroxy 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-decalindianol, 2, 5-norbornanedimethanol 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 herein may also optionally include additives, examples of which include, but are not limited to: antioxidant, plasticizer, anti-aging agent, heat stabilizer, filler, dye, light stabilizer, ultraviolet absorber, flame retardant, antistatic agent, mold release agent and antibacterial agent. These additives may be used alone or in any combination of two or more. The content of the additive can be added 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 and convenience for large-scale production, and is an efficient, green and environment-friendly preparation process for the polycarbonate optical resin.
The polycarbonate optical resin is applied to optical components, electronic products, electrical equipment, packaging materials, medical instruments or building materials.
An optical article comprising the polycarbonate optical resin prepared according to the present invention.
The beneficial effects of the invention are: the polycarbonate optical resin disclosed by the invention has excellent performances such as high refractive index, high thermal stability and the like, can be processed and used to prepare an optical lens with better performance, and can be applied to the fields of optical components, electronic products, electrical equipment, packaging materials, medical instruments or building materials and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
1. Performance evaluation the samples used were prepared as follows:
(a) Film formation: 1g of the obtained polycarbonate was dissolved in 10mL of methylene chloride and poured on a glass dish; after sufficient drying at room temperature, the film was dried at a temperature of 60 ℃ or lower for 12 hours to obtain 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 ): the M was obtained from the retention time of GPC based on a standard curve prepared using a PL-GPC 50 gel permeation chromatograph manufactured by Agilent Technologies, N-Dimethylformamide (DMF) as a developing solvent and monodisperse polystyrene having a known molecular weight as a standard w 。
(b) Refractive index (n) D )
The film produced by the method (a) was measured for its refractive index at 25 ℃ and its wavelength was 589nm using a DR-M2 Abbe refractometer (manufactured by ATAGO).
(c) Abbe number (V) D )
Respectively measuring refractive indexes at 25 deg.C and 486nm, 589nm and 656nm at wavelength according to the method for measuring refractive index in (b), and passing through formula V D ＝(n D －1)/(n F －n C ) Is calculated to obtain, wherein n D Refractive index at a wavelength of 589nm, n F Refractive index at a wavelength of 656nm, n C Is the refractive index at a wavelength of 486 nm.
3. The raw materials used in the following examples and comparative examples of the present invention and the preparation method thereof were 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:
weighing 0.050mol of benzanthrone, 0.300mol of phenoxyethanol and 0.004g of beta-mercaptopropionic acid, keeping a reaction system in a nitrogen atmosphere, firstly stirring at 40 ℃ until the benzanthrone is completely dissolved, then dropwise adding 10.900mL of concentrated sulfuric acid, completing titration within 0.5-1 h, then heating to 65 ℃ of reaction temperature, and carrying out heat preservation reaction for 5h. And after the reaction is finished, adding 100mL of toluene to dissolve the product, stirring for 1h at 50 ℃, repeatedly washing for more than 3 times by using warm water, then distilling and concentrating the organic phase under reduced pressure, pouring 150mL of methanol, stirring for 1h, standing, precipitating a large amount of precipitate, filtering to obtain a crude product of the diether benzanthracene, and then recrystallizing by using a mixed solvent of toluene and acetone to obtain 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 of chloroform were added to a 1000mL reaction flask equipped with a calcium chloride tube and a dropping funnel and stirred, and a mixed solvent of 0.06mol of bromine and 100mL of chloroform was added dropwise to the resulting suspension over 20 minutes at room temperature. After the completion of the dropwise addition, the mixture was further stirred for 30 minutes while maintaining the room temperature, then 50mL of deionized water was added, the supernatant was removed with a separatory funnel, a saturated aqueous sodium sulfite solution was added to the organic layer, and liquid separation was performed twice, the organic layer was further washed with distilled water, anhydrous sodium sulfate was added to the organic layer and dried, 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), scheme:
the same operation as in production example 1 was carried out, except that phenoxyethanol as a raw material in production example 1 was replaced with 2-phenylthioethanol.
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, 0.004g of beta-mercaptopropionic acid and 100mL of toluene are weighed as reaction solvents, a reaction system maintains nitrogen atmosphere, the materials are firstly stirred uniformly at 60 ℃, then 5.450mL of concentrated sulfuric acid is dripped, the titration is completed within 0.5 to 1h, then the temperature is raised to 80 ℃ of reaction temperature, and the heat preservation reaction is carried out for 5h under the condition of micro negative pressure. And after the reaction is finished, adding 80mL of toluene and 150mL of deionized water, continuously stirring for 1h, separating to obtain a toluene organic phase, washing with warm water for more than 3 times, retaining the organic phase, carrying out reduced pressure distillation, concentrating, pouring 150mL of methanol, stirring for 1h, filtering to obtain a crude product, and then recrystallizing with isopropanol to obtain a purer product.
0.020mol of crude product is taken, 0.044mol of Ethylene Carbonate (EC), 100mL of N, N-Dimethylformamide (DMF) are added as solvent, and 0.002mol of K 2 CO 3 Heating the catalyst to reflux, reacting for 3h, 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 24h to obtain a crude product. And (4) recrystallizing by using toluene 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 operation as in production example 4 was carried out, except that 2-naphthol as the raw material in production example 4 was replaced with 2-naphthylthiol.
Example 1
The preparation steps of the polycarbonate optical resin are as follows:
0.030mol of diphenyl carbonate (DPC) and 0.030mol of BPEBA were charged into a 250ml three-necked flask at room temperature, the flask was purged with nitrogen, the raw materials were melted, and then heated to 150 ℃ for transesterification, and then a sodium hydroxide catalyst was added in an amount of 0.005mol% based on the amount of diphenyl carbonate. Stirring at 150 ℃ to perform ester exchange reaction for 3h to obtain polycarbonate prepolymer; then gradually raising the temperature and gradually reducing the pressure until the polycondensation temperature is 240 ℃ and the pressure of the reaction system is less than 50pa, keeping the reaction for 0.5h through the polycondensation reaction, and introducing nitrogen into the reactor after the reaction is finished to restore the normal pressure. And then the polycarbonate material can be obtained through dichlorolysis and methanol precipitation.
Example 2
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was carried out, except that 0.030mol of DPC, 0.021mol of BPEBA, 0.0045mol of BPA and 0.0045mol of S-BNE were used as raw materials.
Example 3
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was carried out, except that 0.030mol of DPC, 0.024mol of Br-BPEBA and 0.006mol of BPEF were used as raw materials.
Example 4
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was 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 raw materials.
Example 5
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was carried out, except that 0.030mol of DPC, 0.021mol of S-BPEBA, 0.0045mol of BPEF, and 0.0045mol of S-BNE were used as raw materials.
Example 6
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was carried out, except that 0.030mol of DPC and 0.030mol of S-BNEBA were used as raw materials.
Example 7
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was 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 raw materials.
Example 8
The preparation steps of the polycarbonate optical resin are as follows:
the same operation as in example 1 was 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 raw 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 operation as in example 1 was 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 raw materials, the transesterification temperature was adjusted to 190 ℃, the transesterification time was adjusted to 5 hours, and the catalyst was tetraethylammonium hydroxide.
Comparative example 1
The same operation as in example 1 was carried out, except that 0.030mol of DPC and 0.300mol of BPA were used as raw materials.
Comparative example 2
The same operation as in example 1 was carried out except that 0.030mol of DPC, 0.300mol of BPEF was used as a raw material and the catalyst was tetraethylammonium hydroxide.
Comparative example 3
The same operation as in example 1 was carried out except that 0.030mol of DPC, 0.300mol of BPEZ were used as the raw material and the catalyst was tetraethylammonium hydroxide.
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.
The test results in table 1 show that the polycarbonate with specific repeating units provided by the invention 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 above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A polycarbonate optical resin, comprising a repeating unit having a structure represented by formula (I):
in the formula (I), W 1 、W 2 Each independently selected from O or S; x 1 、X 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; r is 1 、R 2 Each independently represents hydrogen, halogen, a hydroxyl group, an ester group, a cyano group, an amino group, a thiol group, a substituted or unsubstituted straight-chain or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkylene 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 or condensed ring aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group or condensed ring heteroaryl group having 3 to 30 carbon atoms, or an atom or atomic group which may substitute for the above groups; p1 and p2 are each independently selected from integers of 1 to 3; a. each b is independently selected from integers of 0 to 5.
2. The polycarbonate optical resin according to claim 1, wherein: the content ratio of the structural unit selected from the structural units represented by the formula (I) is 5 to 100mol% relative to the total number of moles of all repeating structural units of the polycarbonate optical resin.
3. The polycarbonate optical resin according to claim 2, wherein: the polycarbonate optical resin also comprises a repeating unit with a structure shown in a formula (II) or a formula (III):
in the formula (II), Y 1 、Y 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; c. d is each independently selected from an integer of 0 to 5; m 1 Independently represents a single bond, O, S, a C1-5 linear or branched alkylene group,
The dotted line represents the attachment site of the group; r 3 、R 4 、R 5 、R 6 Each independently selected from hydrogen, halogen, hydroxyl, ester group, cyano, amino, thiol group, a substituted or unsubstituted straight or branched alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, a substituted or unsubstituted alkylene group having 2 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl or fused ring aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl or fused ring heteroaryl group having 3 to 30 carbon atoms, or an atom or atom group which may substitute the above groups; p3, p4, p5 and p6 are independently selected from integers of 1-3;
in the formula (III), M 2 Independently represent a single bond, O, S; z 1 、Z 2 Each independently represents a substituted or unsubstituted, linear or branched alkylene group having 1 to 8 carbon atoms; e. each f is independently selected from an integer of 0 to 5; r 7 、R 8 Each independently selected from hydrogen, halogen, hydroxyl, ester group, cyano, amino, thiol, substituted or unsubstituted straight or branched alkyl group having 1 to 6 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 10 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 6 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, substituted or unsubstituted aryl or condensed ring aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl or condensed ring heteroaryl group having 3 to 30 carbon atoms, or atom group which may substitute the above group; p7 and p8 are each independently selected from integers of 1 to 3.
4. The polycarbonate optical resin of claim 3, wherein: the content ratio of the structural unit selected from the structural units represented by the formula (I) is 30 to 85mol%, and the content ratio of at least one structural unit selected from the structural units represented by the formula (II) and the structural units represented by the formula (III) is 15 to 70mol%, based on the total number of moles of all repeating structural units of the polycarbonate optical resin.
5. The polycarbonate optical resin according to claim 2, 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 method for producing a polycarbonate optical resin, characterized in that a polycarbonate is synthesized by a melt transesterification polycondensation reaction in a nitrogen atmosphere at normal pressure using a dihydroxy compound and a carbonic acid diester as raw materials, wherein at least one of the dihydroxy compounds is selected from the group consisting of dihydroxy compounds represented by formula (1), formula (2), and formula (3); original sourceAfter the materials are melted, heating the materials to the ester exchange temperature of 120-190 ℃, adding a catalyst into the materials to carry out ester exchange reaction for 0.2-5 h to obtain a polycarbonate prepolymer; then gradually heating to the polycondensation temperature of 200-260 ℃, the pressure of the reaction system is less than 50pa, and carrying out polycondensation reaction for 0.2-5 h to obtain the polycarbonate copolymer with the weight average molecular weight of 3.07 multiplied by 10 4 ～18.0×10 4 g/mol；
Wherein, W 1 、W 2 、X 1 、X 2 、R 1 、R 2 P1, p2, a, b each independently have the same limits 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 ranges as formula (II);
wherein M is 2 、Z 1 、Z 2 、R 7 、R 8 P7, p8, e, f each independently have the same limitations as in formula (III).
7. The preparation method according to claim 6, 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 imidazole type cations, quaternary ammonium type cations, quaternary phosphine type cations, piperidine type cations and pyridine type cations; the metal catalyst is lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, and acetylacetoneAt least one of ketomagnesium, 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 1X 10 times the amount of the carbonic acid diester compound substance -7 ～5×10 -4 。
8. The method according to claim 6, 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 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-decalindianol, 2, 5-norbornanedimethanol 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).
9. The polycarbonate optical resin prepared by the preparation method of claim 6, which is used in optical parts, electronic products, electrical equipment, packaging materials, medical devices or building materials.
10. 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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