CN113667110A - Optical polycarbonate resin and preparation method thereof - Google Patents
Optical polycarbonate resin and preparation method thereof Download PDFInfo
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- CN113667110A CN113667110A CN202111036256.4A CN202111036256A CN113667110A CN 113667110 A CN113667110 A CN 113667110A CN 202111036256 A CN202111036256 A CN 202111036256A CN 113667110 A CN113667110 A CN 113667110A
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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
- C08G64/305—General preparatory processes using carbonates and alcohols
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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
- C08G64/04—Aromatic polycarbonates
- C08G64/06—Aromatic polycarbonates not containing aliphatic unsaturation
- C08G64/08—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen
- C08G64/12—Aromatic polycarbonates not containing aliphatic unsaturation containing atoms other than carbon, hydrogen or oxygen containing nitrogen
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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
- C08G64/307—General preparatory processes using carbonates and phenols
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- 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
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Abstract
The invention provides an optical polycarbonate resin and a preparation method thereof. The resin introduces nitrogen and benzene ring structures to improve the refractive index of the polycarbonate, introduces a spiro structure to improve the moldability of the polycarbonate, and the combination of the nitrogen and benzene ring structures can enable the polycarbonate to have high refractive index and easy moldability. The invention also provides a preparation method of the resin. The resin is useful for the manufacture of optical lenses and optical articles such as optical lens compositions.
Description
Technical Field
The invention relates to the field of polymers, in particular to an optical polycarbonate resin and a preparation method thereof.
Background
The optical lens is made of optical glass at first, has the advantages of high refractive index, stable chemical property, difficult environmental influence and the like, has more obvious defects at the same time, is mainly high in processing difficulty, high in production cost, heavier in weight and easy to break, and although the glass lens has a plurality of advantages along with the development of electronic information technology, the defects of the glass lens are overcome due to the appearance of optical polycarbonate, and the optical resin has the advantages of easiness in forming, high production efficiency, light weight and the like relative to the optical glass.
With the rapid development of the times, especially the development of electronic information technology for over ten years, optical-grade polycarbonate has more application fields, such as mobile phone lenses, security lenses, VR and other fields, and the lens is developed towards the trend of light weight, thin thickness and low dispersion by the needs of manufacturers and consumers, so that the parameters of refractive index, chromatic aberration, easy molding and the like of an optical system meet the application requirements while meeting the requirements of lightness and thinness. Therefore, the optical lens material with high refractive index can meet the application requirement of lightness and thinness, and simultaneously has the performances of high Abbe number, easy molding and the like.
Patent CN201080006995.2 discloses a method for preparing a copolymer polycarbonate with high refractive index by copolymerizing a dihydroxy compound having a fluorene structure with a dihydroxy compound having a thioester bond, wherein the dihydroxy compound having a thioester bond is introduced to improve the refractive index of the polymer, but the synthesis of the copolymer polycarbonate is complicated and the light transmittance of the product is poor.
Patent CN 201810165983.2 discloses a method for synthesizing high refractive index polycarbonate by using 2, 2-bis- (2-hydroxyethoxy) -1, 1-binaphthyl as comonomer, wherein the refractive index of the obtained polycarbonate can only reach 1.668 at most, and the refractive index is difficult to meet the market demand.
Patent CN109476835A discloses a high-refraction polycarbonate using 9, 9-bis (6- (2-hydroxyethoxy) naphthalene-2-yl) fluorene and 2, 2-bis (2-hydroxyethoxy) -1, 1-binaphthyl as monomers, and the introduction of 9, 9-bis (6- (2-hydroxyethoxy) naphthalene-2-yl) fluorene and 2, 2-bis (2-hydroxyethoxy) -1, 1-binaphthyl greatly improves the refractive index of the polycarbonate, but leads to high reaction system viscosity and enhanced rigidity of the polymer, and influences practical processing and forming.
In summary, the trend of optical lenses is toward the development of light weight, high image quality, and further improvement of refractive index and abbe number of optical resin, and high flowability and easy moldability, and how to design and manufacture an optical resin with high refractive index, high abbe number, easy moldability and industrial prospect is a problem to be solved in the industry.
Disclosure of Invention
The invention aims to provide an optical polycarbonate resin which has high refractive index, easy molding, high Abbe number, simple manufacturing method and industrial prospect, and can meet the use requirement of an optical lens.
In order to achieve the purpose, the invention adopts the following technical scheme:
a polycarbonate resin comprising a structural unit represented by formula (1) and/or a structural unit represented by formula (2):
wherein X represents an alkylene group having 1 to 4 carbon atoms,
in the present invention, the resin optionally contains a structural unit represented by formula (3):
wherein Y represents an alkylene group having 1 to 8 carbon atoms, and R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-6 carbon atoms, aryl or aryloxy with 6-12 carbon atoms and heterocycloalkyl with 5-20 carbon atoms; preferably, Y represents an alkylene group having 1 to 6 carbon atoms, R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-3 carbon atoms, aryl or aryloxy with 6-10 carbon atoms and heterocycloalkyl with 5-16 carbon atoms; more preferably, Y represents one of methylene, ethylene and propylene, and R represents3～R4Each independently represents one or two of methyl, ethyl, propyl, phenyl, naphthyl, dibenzothienyl, thienyl, dibenzofuryl and furyl.
In the present invention, the introduction of the nitrogen element in the formula (1) and the introduction of the polyphenolic ring structure in the formula (3) can improve the refractive index of the polycarbonate, but the introduction of the polyphenolic ring structure can improve the rigidity of the polycarbonate and is disadvantageous to the moldability, and the introduction of the spiro ring structure in the formula (2) can improve the moldability of the polycarbonate, and the combination of the three can make the polycarbonate have both a high refractive index and moldability.
In the present invention, when the resin contains the structural units represented by the formulae (1) to (3), the proportion of the structural unit represented by the formula (1) is 10 to 75 mol%, preferably 20 to 70 mol%, the proportion of the structural unit represented by the formula (2) is 15 to 70 mol%, preferably 15 to 60 mol%, the proportion of the structural unit represented by the formula (3) is 10 to 25 mol%, preferably 15 to 20 mol%, based on 100 mol% of the total amount of the structural units represented by the formulae (1), (2), and (3).
In the present invention, when the resin contains the structural units represented by the formulae (1) to (2), the proportion of the structural unit represented by the formula (1) is 30 to 90 mol%, preferably 40 to 90 mol%, and the proportion of the structural unit represented by the formula (2) is 10 to 70 mol%, preferably 10 to 60 mol%, based on 100 mol% of the total amount of the structural units represented by the formulae (1) and (2).
In the present invention, when the resin contains the structural units represented by the formulae (1) and (3), the proportion of the structural unit represented by the formula (1) is 60 to 99 mol%, preferably 70 to 95 mol%, and the proportion of the structural unit represented by the formula (3) is 1 to 40 mol%, preferably 5 to 30 mol%, based on 100 mol% of the total amount of the structural units represented by the formulae (1) and (3).
In the present invention, the resin has an Abbe number of 30 to 40, a refractive index (nD) at 23 ℃ and a wavelength of 589nm of 1.68 to 1.72, and a film having a thickness of 0.1mm is measured by a method of JIS K-7142 using an Abbe refractometer, and the resin has a high refractive index and is suitable for an optical lens material and an optical lens composition.
In the invention, the melt index MFR of the resin at the temperature of 280 ℃ and under the load of 1.2barG is 25-35 g/10 min.
In the present invention, the polycarbonate resin has a weight average molecular weight (Mw) of 12,000 to 130,000, preferably 22,000 to 100,000, and more preferably 30,000 to 40,000. When Mw is more than 130,000, the increase in melt viscosity leads to deterioration in fluidity, and injection molding in a molten state is difficult. When Mw is less than 12,000, the molded article becomes brittle.
It is known in the art that an auxiliary agent such as an antioxidant, a mold release agent, an ultraviolet absorber, a flow improver, a crystal nucleating agent, a reinforcing agent, a dye, an antistatic agent, or an antibacterial agent may be added to the polycarbonate resin as needed.
Another object of the present invention is to provide a method for preparing the polycarbonate resin.
A production method for producing the polycarbonate resin, which comprises subjecting a dihydroxy compound comprising formula (4) and/or formula (5), and optionally formula (6), to a polycondensation reaction with a carbonic acid diester to obtain:
wherein X represents an alkylene group having 1 to 4 carbon atoms,
wherein Y represents an alkylene group having 1 to 8 carbon atoms, and R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-6 carbon atoms, aryl or aryloxy with 6-12 carbon atoms and heterocycloalkyl with 5-20 carbon atoms; preferably, Y represents an alkylene group having 1 to 6 carbon atoms, R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-3 carbon atoms, aryl or aryloxy with 6-10 carbon atoms and heterocycloalkyl with 5-16 carbon atoms; more preferably, Y represents one of methylene, ethylene and propylene, and R represents3～R4Each independently represents one or two of methyl, ethyl, propyl, phenyl, naphthyl, dibenzothienyl, thienyl, dibenzofuryl and furyl.
Preferably, the dihydroxy compound represented by formula (4) is:
preferably, the dihydroxy compound represented by formula (5) is:
preferably, the dihydroxy compound represented by formula (6) is one or more of the following phenanthroline ether alcohol derivatives:
in the present invention, the above-mentioned carbonic acid diester is one or more selected from diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and dicyclohexyl carbonate, and diphenyl carbonate is preferable.
In the present invention, the molar ratio of the total molar amount of the dihydroxy compounds of formulae (4), (5), and (6) to the carbonic acid diester in the above method is 1 (0.8 to 1.5), preferably 1 (0.9 to 1.3), and more preferably 1 (1 to 1.1).
In the present invention, the dihydroxy compound and the carbonic acid diester are produced by a melt transesterification polycondensation method in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst of both of them or in the absence of a catalyst.
In the invention, the catalyst is one or more of an alkaline earth metal compound, an alkali metal compound, organic amine and a rare earth metal compound, preferably one or more of magnesium hydroxide, calcium hydroxide, sodium bicarbonate, magnesium bicarbonate, tetraethylammonium hydroxide, triethylamine and lanthanum acetylacetonate.
In the present invention, the molar ratio of the total amount of the catalyst added to the total amount of the dihydroxy compounds is 1X 10-6～1×10-2The preferred ratio is 1X 10-5～1×10-4。
In one embodiment of the invention, the preparation method of the polycarbonate comprises the steps of adding the dihydroxy compound shown in the formula (4) and/or (5), the optional dihydroxy compound shown in the formula (6), a catalyst, a carbonic diester and an optional auxiliary agent into a reactor with stirring, keeping the materials in a nitrogen atmosphere, heating the materials in the reactor to 180-250 ℃ within 1h, starting stirring after the materials are molten, raising the temperature to the transesterification reaction temperature of 200-290 ℃, keeping the stage for 60-200 min, and controlling the pressure to be 500-30000 Pa (A). The next stage enters a polycondensation stage, the system pressure of the stage is 50-100 Pa (A), the reaction temperature is 250-320 ℃, and the retention time is 30-90 min. After the reaction, the reactor was pressurized, and the produced polycarbonate resin was taken out while being pelletized.
The blends of the present invention can be obtained by blending the different polycarbonates obtained by polymerization in equipment such as extruders, kneaders, mixers and the like.
Still another object of the present invention is to provide a use of the polycarbonate resin.
Use of the polycarbonate resin for optical articles, preferably for optical lenses and/or optical lens compositions.
Compared with the prior art, the invention has the advantages that: the abbe number of the polycarbonate resin is high, the refractive index of the polycarbonate resin is 30-40, the fluidity (melting index is 25-35 g/10min), and the refractive index can reach more than 1.68, under the refractive index, the prepared optical resin is thinner, and the light transmittance can reach more than 88%.
Detailed Description
The present invention will now be described with reference to specific embodiments. The examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as any insubstantial modifications and variations thereof in accordance with the teachings of the present invention are intended to be covered thereby.
1) Weight average molecular weight (Mw): a calibration curve was prepared using standard polystyrene of a known molecular weight (molecular weight distribution of 1) using Gel Permeation Chromatography (GPC) with tetrahydrofuran as a developing solvent. Based on the standard curve, Mw was calculated from the retention time of GPC.
2) Refractive index (n)D) Abbe number: the film produced by the method (a) was measured for the refractive index (wavelength: 589nm) and Abbe number (calculated from the refractive indices at wavelengths of 486nm, 589nm, and 656nm using a DR-M2 Abbe refractometer manufactured by ATAGO, using the following formula).
ν ═ n d-1)/(nF-nC), where nD means the refractive index at a wavelength of 589nm, nC means the refractive index at a wavelength of 656nm, and nF means the refractive index at a wavelength of 486 nm.
3) Melt index (MFR): reference international standard ISO 1133-1: 2011 (high Ford MI4 for the test instrument, 1.2barG pressure at 280 ℃).
The raw material sources are as follows:
synthesis raw material (4): dissolving 1mol of isophthaloyl dichloride in a small amount of N, N-dimethylformamide, completely mixing 2.5mol of p-aminophenol and 2.5mol of triethylamine, placing the mixture in a nitrogen atmosphere at the temperature of-20 ℃, then dripping isophthaloyl dichloride solution into a mixed system of p-aminophenol and triethylamine in a dripping mode, continuously stirring the mixture for 2 hours in the nitrogen atmosphere after the complete dripping is finished, precipitating the reaction system by using water after the reaction is finished, drying the reaction system to obtain a diphenol monomer, adding the diphenol monomer, sodium hydroxide and ethylene oxide into a reaction kettle to obtain a molar ratio of 6:0.006:1.5, then adding absolute ethyl alcohol into the reaction kettle, sealing and stirring the reaction kettle at the temperature of 55 ℃, cooling and cooling the reaction kettle after 8 hours, then washing the reaction kettle to obtain a white solid, recrystallizing the white solid by using methanol, and drying the white solid to obtain a target product (4). The nuclear magnetic results of the target product are as follows:1H-NMR(400MHz，CDCl3)δ/×10-6：9.15(s，2H)，8.50(d，1H)，8.28(t，2H)，7.51(m，4H)，6.97(t，4H)，4.34(t，4H)，3.69(m，4H)，3.65(m，2H)。
raw material (5): 6,6 ', 7, 7' -tetrahydroxy-4, 4,4 '-tetramethyl-bis-2, 2' -spirochroman, reagent pure, Michalin reagents, Inc.
Raw material BFNP/THI-FNP/NFNP: the reagent is pure, and the Hebei company is neutralized.
Example 1
41.2g (0.1mol) of BPNP as a raw material, 22.684g (0.106mol) of diphenyl carbonate, 48.87. mu.g (1.5X 10 mol)- 6Putting mol) cesium carbonate into a 200ml four-neck flask with a stirrer and a distillation device, replacing 5 times with nitrogen, heating to 180 ℃ under a nitrogen atmosphere of 101KPa (A), starting heating for 40min, then confirming that the raw materials are completely dissolved, starting stirring, adjusting the pressure to 20KPa (A), simultaneously heating to 220 ℃ at a speed of 30 ℃/hr, confirming that phenol generated as a byproduct starts distilling, maintaining the temperature at 220 ℃ for reaction for 120min, then heating to 260 ℃ at a speed of 60 ℃/hr, after the temperature reaches 260 ℃, gradually reducing the pressure to 50Pa (A) within 1 hour, stirring and reacting for 40min under the condition, and finishing the reaction. After the reaction, nitrogen gas was introduced into the four-neck flask to return to normal pressure, and the resulting polycarbonate resin was pelletized while being extruded, and the properties were evaluated, and the measured physical properties of the obtained polycarbonate were as shown in Table 1.
Example 2
4.12g (0.01mol) of BPNP as a raw material, 16.78g (0.02mol) of THI-FNP as a raw material, 23.83g (0.07mol) of BSD as a raw material, 21.614g (0.101mol) of diphenyl carbonate, and 325.8. mu.g (1X 10 mol)-5The same operations as in example 1 were carried out except that mol) cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were as shown in Table 1.
Example 3
30.9g (0.085mol) of BPNP as a raw material, 7.27g (0.01mol) of NFNP as a raw material, 5.1g (0.015mol) of BSD as a raw material, 21.828g (0.102mol) of diphenyl carbonate, and 325.8. mu.g (1X 10 mol)-5The same operations as in example 1 were carried out except that mol) cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were as shown in Table 1.
Example 4
20.6g (0.05mol) of BPNP as a raw material, 15.67g (0.025mol) of BFNP as a raw material, 8.5g (0.025mol) of BSD as a raw material, 22.042g (0.103mol) of diphenyl carbonate, and 58. mu.g (1X 10 mol)-5Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Example 5
12.36g (0.03mol) of BPNP as a raw material, 58.73g (0.07mol) of THI-FNP as a raw material, 21.4g (0.1mol) of diphenyl carbonate, and 580. mu.g (1X 10 mol) of diphenyl carbonate-4Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Example 6
35.02g (0.085mol) of BPNP as a starting material, 9.39g (0.015mol) of BFNP as a starting material, 21.828g (0.102mol) of diphenyl carbonate, and 325.8. mu.g (1X 10 mol) of BPNP as a starting material-5The same operations as in example 1 were carried out except that mol) cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were as shown in Table 1.
Example 7
18.54g (0.045mol) of BPNP as a starting material, 39.98g (0.055mol) of NFNP as a starting material, 22.47g (0.105mol) of diphenyl carbonate, and 580. mu.g (1X 10 mol) of BPNP as a starting material-4Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Example 8
37.08g (0.09mol) of BPNP as a raw material, 8.39g (0.01mol) of THI-FNP as a raw material, 22.256g (0.104mol) of diphenyl carbonate, and 580. mu.g (1X 10 mol) of diphenyl carbonate were mixed together-4Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Example 9
28.84g (0.07mol) of BPNP as a raw material, 18.80g (0.03mol) of BFNP as a raw material, 22.684g (0.106mol) of diphenyl carbonate, and 325.8. mu.g (1X 10 mol)-5Poly (arylene sulfide) obtained in the same manner as in example 1 except that mol) of cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatusThe physical properties of the carbonates are shown in Table 1.
Example 10
37.08g (0.09mol) of BPNP as a starting material, 3.4g (0.01mol) of BSD as a starting material, 21.614g (0.101mol) of diphenyl carbonate, and 3.258mg (1X 10 mol)-4The same operations as in example 1 were carried out except that mol) cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were as shown in Table 1.
Example 11
24.72g (0.06mol) of BPNP as a raw material, 13.6g (0.04mol) of BSD as a raw material, 23.54g (0.11mol) of diphenyl carbonate, and 580. mu.g (1X 10 mol) of BPNP as a raw material-4Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Example 12
26.78g (0.065mol) of BPNP as a raw material, 11.92g (0.035mol) of BSD as a raw material, 22.684g (0.106mol) of diphenyl carbonate, and 325.8. mu.g (1X 10 mol)-5The same operations as in example 1 were carried out except that mol) cesium carbonate was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were as shown in Table 1.
Comparative example 1
It differs from example 4 in that it does not contain BPNP and BSD.
61.68g (0.05mol) of BFNP as a raw material, 22.042g (0.103mol) of diphenyl carbonate, and 58. mu.g (1X 10 mol) of diphenyl carbonate were mixed-5Table 1 shows physical properties of polycarbonates obtained by performing the same operations as in example 1 except that mol) of magnesium hydroxide was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus.
Comparative example 2
It differs from example 1 in that BPNP is replaced with bisphenol A.
22.8g (0.1mol) of bisphenol A as a raw material, 22.684g (0.106mol) of diphenyl carbonate, 48.87. mu.g (1.5X 10 mol)- 6mol) of cesium carbonate, was charged in a 200ml four-necked flask equipped with a stirrer and a distillation apparatus, and the physical properties of the obtained polycarbonate were measured in the same manner as in example 1The parameters are shown in table 1.
TABLE 1
As can be seen from the comparison between the above examples and comparative examples, the present invention can improve the refractive index of the polycarbonate by introducing the nitrogen element in the formula (1) and the polyphenolic structure in the formula (3), but the introduction of the polyphenolic structure can improve the rigidity of the polycarbonate and is disadvantageous to the moldability, and the introduction of the spiro structure in the formula (2) can improve the moldability of the polycarbonate, and the combination of the three can make the polycarbonate have both high refractive index and moldability.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A polycarbonate resin, characterized in that the resin contains a structural unit represented by formula (1) and/or a structural unit represented by formula (2):
wherein X represents an alkylene group having 1 to 4 carbon atoms,
2. the polycarbonate resin of claim 1, wherein the resin optionally comprises structural units represented by formula (3):
wherein Y represents an alkylene group having 1 to 8 carbon atoms, and R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-6 carbon atoms, aryl or aryloxy with 6-12 carbon atoms and heterocycloalkyl with 5-20 carbon atoms;
preferably, Y represents an alkylene group having 1 to 6 carbon atoms, R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-3 carbon atoms, aryl or aryloxy with 6-10 carbon atoms and heterocycloalkyl with 5-16 carbon atoms;
more preferably, Y represents one of methylene, ethylene and propylene, and R represents3～R4Each independently represents one or two of methyl, ethyl, propyl, phenyl, naphthyl, dibenzothienyl, thienyl, dibenzofuryl and furyl.
3. The polycarbonate resin according to claim 1 or 2, wherein when the resin comprises the structural units represented by the formulae (1) to (3), the proportion of the structural unit represented by the formula (1) is 10 to 75 mol%, preferably 20 to 70 mol%, the proportion of the structural unit represented by the formula (2) is 15 to 70 mol%, preferably 15 to 60 mol%, and the proportion of the structural unit represented by the formula (3) is 10 to 25 mol%, preferably 15 to 20 mol%, based on 100 mol% of the total amount of the structural units represented by the formulae (1), (2) and (3).
4. The polycarbonate resin according to any one of claims 1 to 3, wherein when the resin comprises the structural units represented by the formulae (1) to (2), the proportion of the structural unit represented by the formula (1) is 30 to 90 mol%, preferably 40 to 90 mol%, and the proportion of the structural unit represented by the formula (2) is 10 to 70 mol%, preferably 10 to 60 mol%, based on 100 mol% of the total amount of the structural units represented by the formulae (1) and (2).
5. The polycarbonate resin according to any one of claims 1 to 4, wherein when the resin comprises structural units represented by formulae (1) and (3), the proportion of the structural unit represented by formula (1) is 60 to 99 mol%, preferably 70 to 95 mol%, and the proportion of the structural unit represented by formula (3) is 1 to 40 mol%, preferably 5 to 30 mol%, based on 100 mol% of the total amount of the structural units represented by formulae (1) and (3).
6. The polycarbonate resin according to any one of claims 1 to 5, wherein the resin has an Abbe number of 30 to 40 and a refractive index of 1.68 to 1.72;
and/or the melt index MFR of the resin at the temperature of 280 ℃ and under the load of 1.2barG is 25-35 g/10 min.
7. A method for preparing the polycarbonate resin according to any one of claims 1 to 6, wherein the method comprises the step of subjecting a dihydroxy compound comprising structural formula (4) and/or formula (5), and optionally formula (6), to polycondensation with a carbonic acid diester to obtain:
wherein X represents an alkylene group having 1 to 4 carbon atoms,
wherein Y represents an alkylene group having 1 to 8 carbon atoms, and R3～R4Independently represent one or two of hydrogen atom, alkyl with 1-6 carbon atoms, aryl or aryloxy with 6-12 carbon atoms and heterocycloalkyl with 5-20 carbon atoms;
preferably, Y represents an alkylene group having 1 to 6 carbon atoms, R3～R4Each independently represents a hydrogen atom or a carbon atomOne or two of 1 to 3 alkyl, 6 to 10 carbon atoms aryl or aryloxy, and 5 to 16 carbon atoms heterocycloalkyl;
more preferably, Y represents one of methylene, ethylene and propylene, and R represents3～R4Each independently represents one or two of methyl, ethyl, propyl, phenyl, naphthyl, dibenzothienyl, thienyl, dibenzofuryl and furyl.
8. The method of claim 7, wherein the carbonic acid diester is one or more of diphenyl carbonate, ditolyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and dicyclohexyl carbonate, preferably diphenyl carbonate.
9. The method for producing a polycarbonate resin according to claim 7, wherein the molar ratio of the total molar amount of the dihydroxy compounds of formulae (4), (5), and (6) to the carbonic acid diester is 1 (0.8 to 1.5), preferably 1 (0.9 to 1.3), more preferably 1 (1 to 1.1).
10. Use of a polycarbonate resin according to any one of claims 1 to 6, or prepared by a method according to any one of claims 7 to 9, in an optical article, preferably in an optical lens and/or an optical lens composition.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114085369A (en) * | 2021-12-01 | 2022-02-25 | 万华化学集团股份有限公司 | Optical polycarbonate and preparation method and application thereof |
| JP7465956B2 (en) | 2020-04-28 | 2024-04-11 | 帝人株式会社 | Thermoplastic resin and optical components |
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| CN1564819A (en) * | 2001-08-24 | 2005-01-12 | 拜尔材料科学股份公司 | Polyester polycarbonates from special diphenols |
| JP2005068012A (en) * | 2003-08-21 | 2005-03-17 | Tosoh Corp | Aromatic amide-dihydroxy compound and method for producing the same |
| CN112961336A (en) * | 2021-04-09 | 2021-06-15 | 万华化学集团股份有限公司 | Polycarbonate resin with stable high refractive index, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1564819A (en) * | 2001-08-24 | 2005-01-12 | 拜尔材料科学股份公司 | Polyester polycarbonates from special diphenols |
| JP2005068012A (en) * | 2003-08-21 | 2005-03-17 | Tosoh Corp | Aromatic amide-dihydroxy compound and method for producing the same |
| CN112961336A (en) * | 2021-04-09 | 2021-06-15 | 万华化学集团股份有限公司 | Polycarbonate resin with stable high refractive index, preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7465956B2 (en) | 2020-04-28 | 2024-04-11 | 帝人株式会社 | Thermoplastic resin and optical components |
| CN114085369A (en) * | 2021-12-01 | 2022-02-25 | 万华化学集团股份有限公司 | Optical polycarbonate and preparation method and application thereof |
| CN114085369B (en) * | 2021-12-01 | 2023-09-19 | 万华化学集团股份有限公司 | Optical polycarbonate and preparation method and application thereof |
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