CN113956458A - Copolycarbonates having a high refractive index, high heat resistance and high weathering resistance, method for the production and use thereof - Google Patents
Copolycarbonates having a high refractive index, high heat resistance and high weathering resistance, method for the production and use thereof Download PDFInfo
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- CN113956458A CN113956458A CN202111173993.9A CN202111173993A CN113956458A CN 113956458 A CN113956458 A CN 113956458A CN 202111173993 A CN202111173993 A CN 202111173993A CN 113956458 A CN113956458 A CN 113956458A
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- 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
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Abstract
The invention relates to a copolycarbonate with high refractive index, high heat resistance and high weather resistance, a preparation method and application thereof, wherein the copolycarbonate comprises the following structure: dihydroxy compounds derived from compounds containing a heteronaphthalene biphenyl structure
Structural unit of (4), dihydroxy compound derived from a polyphenylene ring structure
Structural unit of (a), and dihydroxy compound derived from naphthol structure
Description
Technical Field
The invention relates to the technical field of polycarbonate copolymers, in particular to copolycarbonate with high refractive index, high heat resistance and high weather resistance, a preparation method and application thereof.
Background
In the application field of optical-grade Polycarbonate (PC), the usage amount of mobile phone lenses, security lenses, vehicle-mounted lenses, VR lenses and the like is gradually increased, and stricter requirements are provided for corresponding materials. Although the conventional polycarbonate has better transparency, the conventional polycarbonate has lower refractive index and poorer heat resistance, and cannot be used after being exposed to outdoor environment for a long time, and the PC material with the current performance can not meet the requirements of the lens industry far away.
At present, Mitsubishi gas chemistry is used for producing industrial high-refractive-index polycarbonate, and the highest refractive index can reach 1.68. However, this brand of polycarbonate is inferior in heat resistance and weather resistance, and cannot be used at high temperatures and in outdoor environments for a long period of time. Meanwhile, with the development of the trend of lightness and thinness in the mobile phone industry, higher requirements are put forward on the refractive index of the material. According to the Lorentz-Lorenz equation, a monomer with high molar refractive index is introduced, so that the refractive index of the polymer is favorably improved; but also has the problem of poor polymer processability due to the higher rigidity of the monomer.
For example, chinese patent application CN109476835A describes high refractive index polycarbonates comprising 9, 9-bis [6- (2-hydroxyethoxy) naphthalen-2-yl ] fluorene, 2 '-bis (2-hydroxyethoxy) -1, 1' -binaphthyl, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene and 9, 9-bis [4- (2-hydroxyethoxy) -3-phenyl ] fluorene, each monomer being more rigid and detrimental to polymer processing, while the patent does not mention whether or not it is advantageous to improve heat resistance.
Chinese patent CN101805501B describes a high refractive polycarbonate containing 9, 9-bis [4- (2-hydroxyethoxy) phenyl ] fluorene, which has a low refractive index and is not satisfactory for current applications.
Chinese patent CN101506267B describes a highly weatherable polycarbonate comprising resorcinol and polysiloxane, which, although improving the weatherability of the polymer, tend to cause phase separation during the post-processing injection molding process, and furthermore, the addition of polysiloxane is not favorable for improving the refractive index and heat resistance.
Therefore, there is a need for a polycarbonate having a high refractive index, high heat resistance and high weather resistance.
Disclosure of Invention
The object of the present invention is to provide copolycarbonates having a high refractive index, high heat resistance and high weathering resistance, which have the advantages of both low haze and good transparency.
Another object of the present invention is to provide a process for the preparation of copolycarbonates having the above-mentioned properties.
It is a further object of the present invention to provide the use of copolycarbonates having the above-described properties.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a copolycarbonate having a high refractive index, high heat resistance, and high weatherability comprising the structure:
1) structural units derived from dihydroxy compounds of formula (I)
Wherein, X1、X2Each independently represents C1-C10Alkylene of (C)6-C20Or only represents a chemical bond;
2) structural units derived from dihydroxy compounds of formula (II)
And 3) structural units derived from dihydroxy compounds of formula (III)
In a preferred embodiment, the dihydroxy compound of formula (I) has the structural formula:
in a specific embodiment, the molar ratio of the dihydroxy compound of formula (I) to the dihydroxy compound of formula (II) is 1:99 to 99:1, and the molar ratio of the total amount of formula (I) and formula (II) to the dihydroxy compound of formula (III) is 100:1 to 30.
In a particular embodiment, the copolycarbonate has a refractive index of 1.60 to 1.75.
In a specific embodiment, the copolycarbonate has a melt index of 3 to 60g/10min and a Vicat temperature of 120-.
In a specific embodiment, the copolycarbonate has a light transmission of 85 to 91% and a haze of 0.4 to 5%; preferably, after the copolycarbonate is subjected to an ultraviolet lamp aging test, the yellowness index YI is below 10, and the ball pressure hardness is 115-180N/mm2。
In a particular embodiment, from 0 to 5 wt.%, based on the total weight of copolycarbonate, of at least one or two of the following components selected from the group consisting of: the coating comprises a release agent, a flow additive, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorbent, a flame retardant, an antistatic agent, a pigment and a reinforcing filler.
On the other hand, the above-mentioned method for producing a copolycarbonate comprises a step of preparing a copolycarbonate by a melt transesterification method between a dihydroxy compound of the formula (I), a dihydroxy compound of the formula (II), and a dihydroxy compound of the formula (III) and diphenyl carbonate.
In a specific embodiment, the molar ratio of diphenyl carbonate to dihydroxy compounds of formula (I), formula (II), and formula (III) is 0.99 to 1.20.
On the other hand, the copolycarbonate or the copolycarbonate prepared by the method is applied to the field of optical lenses, such as mobile phone lenses, security lenses, vehicle-mounted lenses, VR (virtual reality) and other fields.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through selecting the compounds of the formula (I), the formula (II) and the formula (III) for combined design, preferably three dihydroxy compounds of the formula (II), the formula (III) and the formula (IV) and diphenyl carbonate are subjected to a molten transesterification method, the copolycarbonate with high refractive index, high heat resistance and high weather resistance can be obtained, and meanwhile, the copolycarbonate also has low haze, good transparency and processability, and can be applied to the field of lenses with higher requirements on refractive index, heat resistance and weather resistance.
According to the copolycarbonate, the refractive index of the polymer can be remarkably improved by introducing the structure of the heteronaphthalene biphenyl, and meanwhile, the heat resistance of the polymer can be remarkably improved by the rigid nitrogen heterocyclic structure; meanwhile, by introducing a bisphenol A structure, the rigidity of a polymer chain can be reduced, and the processability is improved. In addition, the introduction of the naphthol structure chain unit can enable the polymer to have an obvious shielding effect on ultraviolet rays, and the hardness of the polymer can be synergistically enhanced when the polymer is copolymerized with a heteronaphthalene biphenyl structure.
Detailed Description
The following examples will further illustrate the method provided by the present invention in order to better understand the technical solution of the present invention, but the present invention is not limited to the listed examples, and should also include any other known modifications within the scope of the claims of the present invention.
A copolycarbonate comprising the structure:
1) a structural unit derived from a dihydroxy compound represented by formula (I):
2) a structural unit derived from a dihydroxy compound represented by formula (II):
3) a structural unit derived from a dihydroxy compound represented by formula (III):
wherein, in the dihydroxy compound represented by formula (I), X1、X2Each independently represents C1-C10Alkylene of (C)6-C20Or an arylene radical representing only a chemical bond, e.g. X1、X2Each independently selected from methylene, ethylene, and the like, but not limited thereto. In a preferred embodiment, X is1、X2All represent only chemical bonds, and correspondingly, the dihydroxy compound represented by formula (I) may be a compound of formula (IV) having the following structural formula:
in the sources of the structural units of the copolycarbonate of the present invention, the molar ratio of the dihydroxy compound represented by formula (I) to the dihydroxy compound represented by formula (II) is 1:99 to 99:1, including, but not limited to, 1: 99. 5: 95. 10: 90. 15: 80. 20: 80. 30: 70. 40: 60. 50: 50. 60: 40. 70: 30. 80: 20. 90: 10. 99:1, the molar ratio of the total molar ratio of formula (I) and formula (II) to the dihydroxy compound represented by formula (III) is 100:1 to 30, including but not limited to 100: 1. 100, and (2) a step of: 5. 100, and (2) a step of: 10. 100, and (2) a step of: 15. 100, and (2) a step of: 20. 100, and (2) a step of: 25. 100, and (2) a step of: 30.
in the present invention, the copolycarbonate may be prepared by a melt transesterification method known to those skilled in the art. The melt transesterification method is a method for producing a polycarbonate by melt-reacting a dihydroxy compound and a carbonic acid diester in the presence of a basic compound catalyst, an ester exchange catalyst or a mixed catalyst of both of them. The carbonic acid diester, the catalyst, the reaction conditions, and the like can be the process conditions described in CN103257376A, but are not limited thereto. In a preferred embodiment, the molar ratio of the carbonic acid diester to all dihydroxy compounds in the present invention is 0.99 to 1.20, including but not limited toThe molar ratio is 0.99, 1.0, 1.05, 1.1, 1.15 and 1.2; the molar ratio of the catalyst used to all dihydroxy compounds was 1X 10-8～1×10-1Preferably 1X 10-7～1×10-3。
The melt transesterification method is a method of performing polycondensation by using the above-mentioned raw materials and catalyst under heating conditions and by carrying out transesterification under normal pressure or reduced pressure while removing by-products. The reaction is generally carried out in two or more stages. Specifically, the transesterification reaction is carried out, for example, at a temperature of 130 to 220 ℃, preferably 160 to 210 ℃ for 0.1 to 5 hours, preferably 2 to 3 hours. Then, the reaction of the dihydroxy compound and the carbonic acid diester is carried out at an elevated temperature while increasing the degree of pressure reduction of the reaction system, and finally, the reaction is carried out at a reduced pressure of 133.32Pa or less and at a temperature of 250 to 280 ℃ for 0.1 to 2 hours. Such a reaction may be carried out continuously or batchwise. The reaction apparatus used for carrying out the reaction may be a vertical type equipped with an anchor type paddle, a MAXBLEND type paddle, a ribbon type paddle, or the like, a horizontal type equipped with a paddle blade, a lattice blade, a spectacle-shaped blade, or the like, or an extruder type equipped with a screw, and it is preferable to use a reaction apparatus in which these are appropriately combined in consideration of the viscosity of the polymer.
After the polymerization reaction is completed, the catalyst is removed or deactivated in order to maintain the thermal stability and hydrolytic stability of the polymer. As the catalyst deactivator, there may be used known acidic substances, preferably esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid, and these may be used alone or in combination.
The amount of the catalyst deactivator to be used may be 0.1 to 50 times, preferably 1 to 25 times, and more preferably 2 to 10 times the amount of the catalyst used. The above-mentioned transesterification methods are well known to those skilled in the art, and the key to the present invention is the use of different dihydroxy compounds and different molar ratios of dihydroxy compound to carbonic acid diester.
The copolycarbonates prepared in the present invention preferably have a weight average molecular weight of 600000 (weight average molecular weight, determined by volume exclusion gel chromatography after calibration with PS or polycarbonate calibration substances), more preferably of 15000-70000, still more preferably of 20000-50000.
The copolycarbonates prepared according to the present invention have a melt index of 3 to 60g/10min, including, but not limited to, 3g/10min, 5g/10min, 8g/10min, 10g/10min, 15g/10min, 20g/10min, 25g/10min, 30g/10min, 35g/10min, 40g/10min, 45g/10min, 50g/10min, 55g/10min, 60g/10 min.
The copolycarbonates of the invention may additionally comprise various conventional additives commonly added to thermoplastic resins. The proportion of additives is from 0 to 5% by weight, preferably from 0 to 2.5% by weight, particularly preferably from 0 to 2% by weight, based on the total weight of the copolycarbonate. Conventional additives include, for example, at least one or more of the following: the coating comprises a release agent, a flow additive, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorbent, a flame retardant, an antistatic agent, a pigment and a reinforcing filler.
The copolycarbonates according to the invention and the above-mentioned additives can be prepared by means of compounding. Can be prepared by the following method: the components are mixed in a known manner and melt-compounded and melt-extruded at temperatures of from 250 ℃ to 330 ℃ in customary apparatuses such as internal mixers, extruders and twin-screw kneaders, and granulated by means of a granulator.
According to Lorentz-Lorenz equation, the introduction of a polyphenyl ring structure in the copolymerization structure is beneficial to improving the refractive index of the copolycarbonate. The introduction of the structure of the heteronaphthalene biphenyl can realize the obvious improvement of the refractive index. In addition, experiments show that the rigid nitrogen heterocyclic structure can improve the refractive index and the thermal property of the polymer, but has strong rigidity and poor processability. It is also found that the introduction of the naphthol structure of formula (III) can make the polymer have obvious shielding effect on ultraviolet rays, and can obviously enhance the weather resistance of the polymer.
The monomer represented by the formula (II) is introduced into the copolymerization structure, so that the rigidity of the copolymerization structure can be reduced, and the processability of the polymer can be obviously improved, particularly when small articles such as mobile phone lenses and the like are manufactured. Through the combined design of the structures, the prepared copolycarbonate has low haze, good transparency and processability while having high refractive index, heat resistance and weather resistance.
The refractive index of the terpolymer system containing (I), (II) and (III), preferably (II), (III) and (IV) of the present invention may vary from 1.60 to 1.75 depending on the monomer ratio. The transmittance of the copolycarbonate can reach more than 91 percent, and the Tg of the corresponding copolymer is 110-200 ℃. The above-mentioned ternary copolymer system can combine the refractive index and Tg in more ways within the above-mentioned range by adjusting the monomer ratio, for example, higher or lower Tg can be designed at the same refractive index, so that the heat resistance or processability of the polymer can be adjusted more conveniently.
The copolycarbonate or the composition thereof can be used for preparing any type of formed parts, has good designability, can adapt to forming processes such as injection molding, extrusion, blow molding and the like, and can meet the design requirements of molds.
Preferred applications of the copolycarbonates according to the invention or of the compositions thereof are transparent/translucent or colored injection-molded parts, extrudates, such as sheets, film laminates, profiles, semi-finished products, and cast films made of high molecular weight polycarbonates.
The copolycarbonates according to the invention or the compositions thereof may optionally be blended with other thermoplastic polymers and/or conventional additives for processing into any shaped parts/extrudates, all where known polycarbonates, polyester carbonates and polyesters have been used. Wherein the other thermoplastic polymer is selected from one or more of bisphenol A type copolycarbonate, polymethyl methacrylate, polyethylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polyamide copolymer, and polystyrene.
The invention is further illustrated, but not limited, by the following more specific examples.
The sources of the starting monomers in the examples are as follows:
the monomer shown in the formula (II), namely the Aradine, the bisphenol A (BPA), has the purity of 98 percent;
the monomer shown in the formula (III), namely the alatin and the 1, 3-dihydroxy naphthalene (m-naphthalenediol), has the purity of 99 percent;
the monomer represented by the formula (IV) was synthesized by the method described in CN 111704581A.
The performance test method of each sample is as follows:
weight average molecular weight, determined by volume exclusion gel chromatography after pre-calibration with PS or polycarbonate calibration substances.
And (3) injection molding the copolycarbonate resin granules into 40 multiplied by 20 multiplied by 3.2(mm) test pieces and 80 multiplied by 10 multiplied by 4(mm) sample strips, placing part of the test pieces and the sample strips in an ultraviolet aging box, irradiating for 800 hours under 340nm light, taking out after the irradiation is finished, placing in a constant-temperature drying box, and storing in a dark place.
The copolycarbonates were characterized by means of Vicat temperature (Vicat), glass transition temperature (Tg), refractive index, yellowness index YI, light transmittance, haze, and melt index (MFR) tests.
Wherein Vicat is tested according to ISO306(B120) and Tg is measured by dynamic differential thermal analysis (DSC) according to ASTM E1356.
The refractive index, transmittance and haze were obtained by measuring a copolycarbonate film, wherein the film was obtained by dissolving a copolycarbonate resin in methylene chloride to prepare a 10 wt% solution and then spin-coating the solution to a thickness of 50 μm. Refractive index was measured according to ASTM D542, and transmittance and haze were measured according to ASTM D1003.
The yellowness index YI is measured according to ASTM D1925 and UV-aged bars are used.
Ball crush hardness was measured according to ISO 2039-1.
Melt index was measured by melt index meter according to ASTM D1238.
Example 1
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized in a formula (IV) to formula (II) molar ratio of 99:1, with the total formula (IV) to formula (II) molar ratio to formula (III) being 100: 1.
326.7g (0.99mol) of a compound of the formula (IV)2.28g (0.01mol) of the dihydroxy compound of the formula (II), 1.60g (0.01mol) of the dihydroxy compound of the formula (III), 227.07g (1.06mol) of diphenyl carbonate and 0.02g (5X 10)-4mol) sodium hydroxide was charged into a reactor equipped with a stirring and distilling device and melted by heating to 185 ℃ under normal pressure over 1 hour. Thereafter, the temperature was raised to 210 ℃ over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 15 minutes, and the mixture was held at 210 ℃ and 2KPa for 30 minutes to perform the transesterification reaction. The temperature was further raised to 260 ℃ at a rate of 50 ℃ per hour, and the temperature was maintained at 260 ℃ and 2Kpa for 30 minutes. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the temperature was maintained at 260 ℃ and 1Kpa for 1 hour. Then, the pressure was adjusted to 500Pa for 10 minutes, and the pressure was maintained at 260 ℃ and 500Pa for 30 minutes. The pressure was further reduced to 133Pa or less for 30 minutes, and the mixture was stirred at 260 ℃ and 133Pa or less for 15 minutes to effect polymerization. After the reaction, 2 times the molar amount of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressure, and the reaction tank was cooled in a water tank and cut with a pelletizer to obtain pellets. The resulting copolycarbonate resin was numbered A1, and had a weight average molecular weight of 45231.
Example 2
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized in a 90:10 molar ratio of formula (IV) to formula (II) and a 100:5 molar ratio of the total molar ratio of formula (IV) to formula (II) to formula (III).
A copolymerized polycarbonate resin was synthesized in accordance with example 1, code A2, weight-average molecular weight 46253, except that 297g (0.9mol) of the dihydroxy compound having the structure of formula (IV), 22.8g (0.1mol) of the dihydroxy compound having the structure of formula (II), and 8.01g (0.05mol) of the dihydroxy compound having the structure of formula (III) were used.
Example 3
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized in a 70:30 molar ratio of formula (IV) to formula (II), with the total molar ratio of formula (IV) to formula (II) to formula (III) being 100: 10.
A copolymerized polycarbonate resin was synthesized in accordance with example 1, except that 231g (0.7mol) of the dihydroxy compound having the structure of formula (IV), 68.4g (0.3mol) of the dihydroxy compound having the structure of formula (II), 16.02g (0.1mol) of the dihydroxy compound having the structure of formula (III), and 249.78g (1.17mol) of diphenyl carbonate were used, and the polycarbonate resin was numbered A3 and had a weight-average molecular weight of 44257.
Example 4
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized with a 50:50 molar ratio of formula (IV) to formula (II) and a 100:15 molar ratio of the total molar ratio of formula (IV) to formula (II) to formula (III).
A copolymerized polycarbonate resin was synthesized in accordance with example 1, except that 165g (0.5mol) of the dihydroxy compound having the structure of formula (IV), 114g (0.5mol) of the dihydroxy compound having the structure of formula (II), 24.03g (0.15mol) of the dihydroxy compound having the structure of formula (III), and 261.35g (1.22mol) of diphenyl carbonate were used, and the polycarbonate resin was numbered A4 and had a weight-average molecular weight of 44201.
Example 5
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized with a 30:70 molar ratio of formula (IV) to formula (II) and a 100:20 molar ratio of the total molar ratio of formula (IV) to formula (II) to formula (III).
A copolymerized polycarbonate resin was synthesized in accordance with example 1 except that 99g (0.3mol) of the dihydroxy compound having the structure of formula (IV), 159.6g (0.7mol) of the dihydroxy compound having the structure of formula (II), 32.03g (0.20mol) of the dihydroxy compound having the structure of formula (III), and 272.06g (1.27mol) of diphenyl carbonate were used, and the polycarbonate resin was numbered A5 and had a weight-average molecular weight of 43272.
Example 6
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II), and formula (III) were synthesized in a 10:90 molar ratio of formula (IV) to formula (II), with the total molar ratio of formula (IV) to formula (II) to formula (III) being 100: 25.
A copolymerized polycarbonate resin was synthesized in accordance with example 1, except that 33g (0.1mol) of the dihydroxy compound having the structure of formula (IV), 205.2g (0.9mol) of the dihydroxy compound having the structure of formula (II), 40.04g (0.25mol) of the dihydroxy compound having the structure of formula (III), and 284.91g (1.33mol) of diphenyl carbonate were used, and the polycarbonate resin was numbered A6 and had a weight-average molecular weight of 42523.
Example 7
Copolycarbonates prepared from dihydroxy compounds of formula (IV), formula (II) and formula (III) were synthesized in a 1:99 molar ratio of formula (IV) to formula (II) and a 100:30 molar ratio of the total molar ratio of formula (IV) to formula (II) to formula (III).
A copolymerized polycarbonate resin was synthesized in accordance with example 1, except that 3.3g (0.01mol) of the dihydroxy compound having the structure of formula (IV), 225.72g (0.99mol) of the dihydroxy compound having the structure of formula (II), 48.05g (0.30mol) of the dihydroxy compound having the structure of formula (III), and 295.62g (1.38mol) of diphenyl carbonate were used, and the polycarbonate resin was numbered A7 and had a weight-average molecular weight of 41923.
Comparative example 1
A polycarbonate prepared solely from the dihydroxy compound of formula (IV).
330g (1mol) of the dihydroxy compound of the formula (IV), 227.07(1.06mol) of diphenyl carbonate and 0.02g (5X 10)-4mol) sodium hydroxide was charged into a reactor equipped with a stirring and distilling device and melted by heating to 190 ℃ under normal pressure over 1 hour. Thereafter, the temperature was raised to 215 ℃ over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2Kpa for 15 minutes, and the mixture was held at 215 ℃ and 2Kpa for 30 minutes to effect transesterification. The temperature was further raised to 270 ℃ at a rate of 50 ℃ per hour, and the temperature was maintained at 270 ℃ and 2Kpa for 30 minutes. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the temperature was maintained at 270 ℃ and 1Kpa for 1 hour. Then, the pressure was adjusted to 500Pa for 10 minutes and maintained at 500Pa for 30 minutes at 270 ℃. The pressure was further reduced to 133Pa or less for 30 minutes, and the mixture was stirred at 270 ℃ and 133Pa or less for 15 minutes to effect polymerization. After the reaction, 2 times the molar amount of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressure, and the reaction tank was cooled in a water tank and cut with a pelletizer to obtain pellets. The resulting copolycarbonate resin was numbered 1, and had a weight-average molecular weight of 47201.
Comparative example 2
A polycarbonate prepared from a dihydroxy compound of formula (II).
228g (1mol) of the dihydroxy compound of the formula (II), 227.07(1.06mol) of diphenyl carbonate and 0.02g (5X 10)-4mol) sodium hydroxide is added into a reactor with a stirring and distilling device, andthe mixture was melted by heating to 160 ℃ under reduced pressure for 1 hour. Thereafter, the temperature was raised to 200 ℃ over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2Kpa for 15 minutes, and the mixture was held at 200 ℃ and 2Kpa for 30 minutes to effect transesterification. The temperature was further raised to 260 ℃ at a rate of 50 ℃ per hour, and the temperature was maintained at 260 ℃ and 2Kpa for 20 minutes. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the temperature was maintained at 260 ℃ and 1Kpa for 1 hour. Then, the pressure was adjusted to 500Pa for 10 minutes and maintained at 260 ℃ and 500Pa for 20 minutes. The pressure was further reduced to 133Pa or less for 30 minutes, and the mixture was stirred at 260 ℃ and 133Pa or less for 15 minutes to effect polymerization. After the reaction, 2 times the molar amount of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressure, and the reaction tank was cooled in a water tank and cut with a pelletizer to obtain pellets. The resulting copolycarbonate resin, No. 2, had a weight average molecular weight of 40125.
Comparative example 3
A polycarbonate prepared from a dihydroxy compound of formula (III).
160g (1mol) of the dihydroxy compound of the formula (III), 227.07(1.06mol) of diphenyl carbonate and 0.02g (5X 10)-4mol) sodium hydroxide was charged into a reactor equipped with a stirring and distilling device and melted by heating to 160 ℃ under normal pressure over 1 hour. Thereafter, the temperature was raised to 190 ℃ over 0.5 hour, and stirring was carried out. Then, the pressure was adjusted to 2Kpa for 15 minutes, and the mixture was held at 190 ℃ and 2Kpa for 30 minutes to effect transesterification. The temperature was further raised to 250 ℃ at a rate of 50 ℃ per hour, and the temperature was maintained at 250 ℃ and 2Kpa for 20 minutes. Then, the temperature was adjusted to 1Kpa for 10 minutes, and the temperature was maintained at 250 ℃ and 1Kpa for 1 hour. Then, the pressure was adjusted to 500Pa for 10 minutes and maintained at 500Pa for 20 minutes at 250 ℃. The pressure was further reduced to 133Pa or less for 30 minutes, and the mixture was stirred at 250 ℃ and 133Pa or less for 15 minutes to effect polymerization. After the reaction, 2 times the molar amount of butyl benzoate was added to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressure, and the reaction tank was cooled in a water tank and cut with a pelletizer to obtain pellets. The copolycarbonate resin thus obtained had number 3 and a weight-average molecular weight of 43259.
Comparative example 4
A copolycarbonate prepared from the dihydroxy compounds of formula (IV) and formula (II) was synthesized in a molar ratio of 50:50, referring to example 4, except that 165g (0.5mol) of the dihydroxy compound of formula (IV), 114g (0.5mol) of the dihydroxy compound of formula (II), and 261.35g (1.22mol) of diphenyl carbonate were used, and a copolycarbonate resin was synthesized, No. 4, and a weight average molecular weight of 44524.
Comparative example 5
A copolycarbonate prepared from the dihydroxy compounds of formula (II) and formula (III) was synthesized in a molar ratio of 50:15 according to example 4 except that 114g (0.5mol) of the dihydroxy compound of formula (II), 24.03g (0.15mol) of the dihydroxy compound of formula (III) and 261.35g (1.22mol) of diphenyl carbonate were used, and a copolycarbonate resin was synthesized, No. 5 and weight average molecular weight 45426.
Comparative example 6
A copolycarbonate prepared from the dihydroxy compounds of formula (IV) and formula (III) was synthesized in a molar ratio of 50:15, referring to example 4 except that 165g (0.5mol) of the dihydroxy compound of formula (IV), 24.03g (0.15mol) of the dihydroxy compound of formula (III) and 261.35g (1.22mol) of diphenyl carbonate were used, a copolycarbonate resin was synthesized, No. 6 and weight average molecular weight of 43528.
The results of the property tests of the copolycarbonates prepared in examples and comparative examples are shown in Table 1.
TABLE 1 Table of property data of copolycarbonates prepared in examples and comparative examples
As can be seen from the data in the table, by adjusting the proportion of the comonomer (example 4), the polycarbonate with excellent combination properties of refractive index, heat resistance and weather resistance, light transmittance, processability and the like can be obtained, and the practical application requirements can be met.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. 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 copolycarbonate having a high refractive index, high heat resistance, and high weatherability comprising the structure:
1) structural units derived from dihydroxy compounds of formula (I)
Wherein, X1、X2Each independently represents C1-C10Alkylene of (C)6-C20Or only represents a chemical bond;
2) structural units derived from dihydroxy compounds of formula (II)
And 3) structural units derived from dihydroxy compounds of formula (III)
2. The copolycarbonate of claim 1, wherein the dihydroxy compound of formula (I) has the formula:
3. the copolycarbonate according to claim 1 or 2, wherein the molar ratio of the dihydroxy compound of formula (I) to the dihydroxy compound of formula (II) is 1:99 to 99:1, and the molar ratio of the total amount of formula (I) and formula (II) to the dihydroxy compound of formula (III) is 100:1 to 30.
4. The copolycarbonate according to any of claims 1 to 3, wherein the refractive index of the copolycarbonate is between 1.60 and 1.75.
5. The copolycarbonate according to any one of claims 1 to 4, wherein the copolycarbonate has a melt index of 3 to 60g/10min and a Vicat temperature of 120-.
6. The copolycarbonate according to any of claims 1 to 5, wherein the copolycarbonate has a light transmittance of 85 to 91% and a haze of 0.4 to 5%; preferably, after the copolycarbonate is subjected to an ultraviolet lamp aging test, the yellowness index YI is below 10, and the ball pressure hardness is 115-180N/mm2。
7. The copolycarbonate according to any of claims 1 to 6, further comprising 0 to 5 wt% of at least one or two of the following components, based on the total weight of the copolycarbonate: the coating comprises a release agent, a flow additive, a heat stabilizer, a hydrolysis stabilizer, an antioxidant, a UV absorbent, a flame retardant, an antistatic agent, a pigment and a reinforcing filler.
8. The method of producing a copolycarbonate according to any one of claims 1 to 7, which comprises the step of melt transesterification of a dihydroxy compound of formula (I), formula (II), and formula (III) with diphenyl carbonate to produce the copolycarbonate.
9. The method according to claim 8, wherein the molar ratio of diphenyl carbonate to the dihydroxy compounds of formula (I), (II) and (III) is 0.99 to 1.20.
10. Use of a copolycarbonate according to any one of claims 1 to 7 or a copolycarbonate produced by the method according to any one of claims 8 to 9 in the field of optical lenses.
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