CN114349949B - Scratch-resistant copolycarbonate and preparation method and application thereof - Google Patents
Scratch-resistant copolycarbonate and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a copolycarbonate, which comprises a structural unit shown in a general formula (1) and a structural unit shown in a general formula (2),
Description
Technical Field
The application relates to the field of polycarbonate, in particular to copolycarbonate with high weather resistance and high scratch resistance, and a preparation method and application thereof.
Background
Polycarbonate (PC) is used as engineering plastic with excellent performance and has good application in the fields of automobiles, household appliances, electronic appliances and the like. It has good mechanical property, good impact toughness, creep resistance and good dimensional stability, the use temperature range is wide, and meanwhile, the electric insulation performance is good, and the electric insulation material is harmless to human bodies and accords with the sanitation and safety. The UL94V-2 weather resistance grade which can be achieved by the PC per se is not popular for general plastics, but can not meet the weather resistance requirement in some special occasions, and the PC per se can yellow, even degrade and become brittle after being exposed to ultraviolet rays for a long time, so that the service performance and the service life of the PC per se are affected.
In the prior art, the performance of polycarbonate is generally improved by adopting methods such as physical modification or chemical modification. Physical modification is achieved by adding other polymers such as ASA, polysiloxanes, or small molecule adjuvants such as benzophenones, benzotriazole uv absorbers, etc. to PC. The physical modification is simple to operate and easy to realize, but due to poor compatibility with a matrix, the light transmittance, the surface glossiness and the color saturation of the material can be reduced, the impact strength of the material can be reduced, and meanwhile, the added components can migrate out of the matrix in the long-term use process, so that the overall performance of the material is influenced, and the environment is also damaged. In this regard, there is a patent of an attempt to graft or end-cap ultraviolet absorbing groups on a PC molecular backbone in a chemical bond manner, for example, in the patent CN104193979B, an ultraviolet resistant polycarbonate resin and a preparation method thereof are provided, which are prepared by grafting an end-cap acid chloride polycarbonate oligomer with an ultraviolet absorbent under the catalysis of weak acid or weak base and further chain-extending and polycondensing, but the method can cause the reaction of active hydroxyl groups of the ultraviolet absorbent with phosgene or acid chloride groups of the end-cap acid chloride polycarbonate oligomer, thereby affecting the ultraviolet resistance, and the obtained ultraviolet resistant polycarbonate has only two absorption peaks with low peak intensity at 300-400 nm, and the ultraviolet resistant effect is very limited.
In addition, PC surface hardness is lower, and pencil hardness is only 1 ~ 2H grade, and easy scratch and scratch in the use are slightly poor to scratch resistance, thereby influence printing opacity and outward appearance effect. The method for improving the hardness of the polycarbonate is to add scratch resistant agents such as PMMA and siloxane, but the method can cause the decrease of the light transmittance of the material, the increase of the haze and even the pearl phenomenon, which affect the appearance and the strength of the product. For example, in patent CN201510413851.3, a maleic anhydride-styrene-methyl methacrylate terpolymer is used to improve the scratch resistance of PC, but the injection molding product has poor heat resistance, is easy to yellow and silver wire, and seriously affects the appearance and processability of the product.
Therefore, it is an important research in the art to develop a new structure of copolycarbonate having excellent weather resistance while having excellent mechanical properties such as high hardness, etc., to meet the application requirements in high-performance outdoor use parts.
Disclosure of Invention
Aiming at the defects of the prior art, the application aims to provide a copolycarbonate and a preparation method and application thereof, so that the polycarbonate has high weather resistance and high scratch resistance.
The application adopts the following technical scheme:
a copolycarbonate comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
wherein the structural unit represented by the general formula (1) is as follows:
in formula (1), R is 1 、R 2 Independently represent hydrogenAn atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms or a halogen atom.
The structural unit represented by the general formula (2) is as follows:
in the structural unit of the copolycarbonate of the present application, the molar ratio of the structural unit represented by the formula (1) to the structural unit represented by the formula (2) is 1:99 to 99:1, preferably 35:65 to 70:30, more preferably 55:45 to 60:40.
The application also provides a preparation method of the copolycarbonate, which is prepared by reacting the dihydroxy compound shown in the general formula (A) and the dihydroxy compound shown in the general formula (B) with carbonic diester.
As a preferable embodiment, the dihydroxy compound represented by general formula (a) has the following structural formula:
in formula (1), R is 1 、R 2 The definition is the same as the general formula (1).
Preferably, the dihydroxy compound represented by general formula (A) has the following binaphthyl ether alcohol derivative structure.
As a preferable embodiment, the dihydroxy compound represented by general formula (B) has the following structural formula:
in the present application, the copolycarbonates may be prepared by melt transesterification, which is well known to those skilled in the art.
The melt transesterification method of the present application is to prepare polycarbonate by a melt polycondensation reaction of a dihydroxy compound and a carbonic acid diester in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst comprising the two or in the absence of a catalyst.
Preferably, the carbonic acid diester includes diphenyl carbonate, xylene carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate and the like; among them, diphenyl carbonate is preferable. The molar ratio of the carbonic acid diester to the dihydroxy compound is 0.97 to 1.20, and more preferably 0.98 to 1.15.
Among the transesterification catalysts, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like can be particularly exemplified as the basic compound catalyst.
Examples of the alkali metal compound used in the present application include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and the like of alkali metals. Specifically, it is possible to use: sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium hydroxide, sodium bicarbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium carbonate, sodium acetate, potassium acetate, cesium acetate, lithium acetate, sodium stearate, potassium stearate, cesium stearate, lithium stearate, sodium borohydride, sodium boride benzoate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, disodium phenylphosphate, disodium, dipotassium or dilithium salts of bisphenol a, sodium, potassium, cesium or lithium salts of phenol, and the like.
Examples of the alkaline earth metal compound include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides, and the like of the alkaline earth metal compound. Specifically, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate, barium bicarbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, magnesium stearate, calcium benzoate, magnesium phenylphosphate, and the like can be used.
Examples of the nitrogen-containing compound include quaternary ammonium hydroxides, salts thereof, amines, and the like. Specifically, it is possible to use: quaternary ammonium hydroxides having an alkyl group, an aryl group, or the like, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and trimethylbenzylammonium hydroxide; tertiary amines such as triethylamine, dimethylbenzylamine and triphenylamine; secondary amines such as diethylamine and dibutylamine; primary amines such as propylamine and butylamine; imidazoles such as 2-methylimidazole, 2-phenylimidazole, and benzimidazole; or an alkali or basic salt such as ammonia, tetramethylammonium borohydride, tetrabutylammonium tetraphenylborate, or tetraphenylammonium tetraphenylborate.
As the transesterification catalyst, salts of zinc, tin, zirconium, lead, etc. are preferably used, and these may be used alone or in combination.
As the transesterification catalyst, specifically, zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyldimethoxytin, zirconium acetylacetonate, zirconium glycolate, zirconium tetrabutoxide, lead acetate, etc. can be used.
The molar ratio of the catalyst amount to the dihydroxy compound is 10 -8 ～10 -1 Molar ratio, preferably 10 -7 ～10 -3 。
The melt transesterification method is a method of performing polycondensation by transesterification under heating conditions using the above-mentioned raw materials and a catalyst, while removing by-products by the transesterification reaction under normal pressure or reduced pressure. The reaction is generally carried out in two or more stages.
For the transesterification, specifically, the reaction in the first stage is allowed to react at a temperature of 130 to 210 ℃, preferably 170 to 200 ℃ for 0.1 to 5 hours, preferably 1 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 reduced pressure of the reaction system, and finally, the reaction is carried out at a reduced pressure of 133.32Pa or less and a temperature of 230 to 270 ℃ for 0.1 to 2 hours. Such a reaction may be carried out continuously or batchwise.
The reaction apparatus used in the reaction may be a vertical type equipped with an anchor type stirring blade, a MAXBLEND type stirring blade, a ribbon type stirring blade, or the like, may be a horizontal type equipped with a paddle blade, a lattice blade, a spectacle type blade, or the like, may be an extruder type equipped with a screw, or may be preferably implemented by using a reaction apparatus appropriately combined with these 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 some known acidic substances, preferably esters such as butyl benzoate; aromatic sulfonic acids such as p-toluenesulfonic acid, which may be used alone or in combination.
The amount of the catalyst deactivator to be used may be 0.1 to 45 times by mol, preferably 1 to 20 times by mol, and more preferably 2 to 10 times by mol based on the catalyst. When the amount is less than 0.1 times by mol, the deactivation effect becomes insufficient. In addition, if the amount of the catalyst is more than 45 mol%, the heat resistance of the resin is lowered, and the molded article is liable to be colored, which is not preferable.
The copolycarbonates prepared according to the application have a weight average molecular weight of 5000 to 600000 (weight average molecular weight, determined by volume exclusion gel chromatography after pre-calibration with PS or polycarbonate calibration substances), preferably 15000 to 80000, more preferably 30000 to 70000.
The copolycarbonates according to the application may additionally contain various conventional additives which are customarily 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: mold release agents, flow aids, heat stabilizers, hydrolysis stabilizers, antioxidants, UV absorbers, flame retardants, antistatic agents, pigments, reinforcing fillers.
The copolycarbonates according to the application and the additives mentioned above can be prepared by compounding. Can be prepared by the following steps: the components are mixed in a known manner and melt compounded and melt extruded at a temperature of 270℃to 330℃in customary devices such as internal mixers, extruders and twin-screw kneaders, and granulated by means of a granulator.
The copolycarbonate or the copolycarbonate prepared by the method of the application can be used for preparing transparent, semitransparent or colored molded parts, extrudates and film laminates.
Copolycarbonates are materials having excellent physical properties such as high impact strength, high heat resistance, and the like, and are widely used in various fields. The UL94V-2 weathering grade which can be achieved by the polycarbonates per se is not trivial for general-purpose plastics, but does not meet the weathering requirements in certain special cases. Accordingly, there is a need for a copolycarbonate of new structure having improved weatherability while maintaining its inherent physical properties. As a result of continuous studies, the present inventors have found that when structural units of the general formula (1) and the general formula (2) are introduced in the preparation of copolycarbonates, the copolycarbonates can be provided with excellent weather resistance.
Therefore, when the copolycarbonate of the present application is applied to automobile interior/exterior materials, lamp housings, plastic exterior material products for construction, etc., excellent performance can be maintained even when exposed to light, high temperature and high pressure conditions during the manufacturing process of the products or the actual application of the products.
The application has the beneficial effects that:
according to the application, structural units of the formula (1) and the formula (2) are selected for combined design, benzene rings and carbonate groups exist in the structural units of the formula (1) and the formula (2), the rigid benzene rings block free rotation of molecular chains, and a large conjugated system is formed by the rigid benzene rings and the polar carbonate groups, so that the rigidity of the molecular chains is increased, and the polymer has higher tensile strength, rigidity and hardness. The carbonate group in the formula (2) is subjected to Fries rearrangement to be converted into an o-hydroxybenzoketone chain link when being irradiated by light, and the structure absorbs ultraviolet light to generate thermal vibration to cause hydrogen bond fracture and consume ultraviolet light energy, so that copolycarbonate with excellent weather resistance and scratch resistance can be obtained.
Detailed Description
The following examples are intended to illustrate the application, but the application is not limited to the scope of the examples, but includes any other modifications within the scope of the claims as claimed.
The raw material sources are as follows:
raw material BHAO: jinan chemical industry Co.Ltd
O-methylphenol: alatine
Dodecahydroanthrone (cas 52747-32-7): ji Biotech development Co.Ltd
O-phenylphenol: shanghai Yi En chemical technology Co.Ltd
O-naphthylphenol (cas 909004-74-6): dongying far chemical industry Co.Ltd
Preparation example 1
Synthesis of dihydroxy compound BCHA:
(1) Putting a 1L three-neck flask into a constant-temperature oil bath, adding 324g of o-methylphenol, 10g of ferrous sulfate and 2.2g of sodium persulfate into 500g of water, stirring for 4 hours at the reaction temperature of 80 ℃, and filtering, washing and drying to obtain an intermediate A;
(2) 235g of intermediate A and 206g of dodecahydroanthrone are added with 10g of concentrated sulfuric acid serving as a catalyst and 2.12g of mercaptopropionic acid serving as an auxiliary agent, the reaction temperature is 40 ℃, and the mixture is stirred for 4 hours to finish the reaction; 200g of deionized water is added, a large amount of solids are separated out, stirring is continued for 2 hours at the temperature, and the temperature is reduced and suction filtration is carried out to obtain a solid crude product. Adding the crude product into 300g of isopropanol, stirring, heating to dissolve completely, continuously adding the crude product until the crude product approaches to saturated solubility (the mass ratio of the crude product to the isopropanol is 1:1.5), continuously stirring for 30min, and cooling and crystallizing to obtain the pure BCHA.
Preparation example 2
Synthesis of dihydroxy compound BNPHA:
the reaction conditions were substantially the same as in preparation example 1 except that: 660g of o-naphthyl phenol is adopted to replace 324g of o-methylphenol, and an intermediate B is prepared; 372g of intermediate B is adopted to replace 235g of intermediate A, so that the target product BNPA is prepared.
Preparation example 3
Synthesis of dihydroxy compound BBPHA:
the reaction conditions were substantially the same as in preparation example 1 except that: 510g of o-phenylphenol is added to replace o-methylphenol in the step (1) to prepare an intermediate product C; 481g of intermediate C is added in the step (2), and the target product BBPHA is prepared.
Example 1
Copolycarbonates prepared from BCHA, BAHO were synthesized at a molar ratio of 99:1.
39.798g (0.099 mol) of BCHA,0.226g (0.001 mol) of BHAO of the structure of formula (B), 22.278 (0.104 mol) of diphenyl carbonate and 0.0002g (5X 10) -6 mol) sodium hydroxide was added to a reactor with stirring and distillation apparatus and heated to 160℃under normal pressure for 1 hour to melt. Thereafter, the temperature was raised to 200℃over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 10 minutes, and the reaction was kept at 200℃for 30 minutes under 2KPa to carry out transesterification. Then the temperature is raised to 260 ℃ at the speed of 50 ℃/hour, and the mixture is kept at 260 ℃ for 20 minutes at 2 KPa. Then, the temperature was adjusted to 1KPa for 10 minutes, and the temperature was maintained at 260℃for 1 hour at 1 KPa. Then adjusted to 500Pa for 10 minutes, and maintained at 260℃for 20 minutes at 500 Pa. The pressure was reduced to 133Pa or lower for 30 minutes, and the mixture was stirred at 260℃for 15 minutes under 133Pa or lower to carry out polymerization. After the reaction, butyl benzoate was added in an amount 2 times the amount of the catalyst to deactivate the catalyst, and the catalyst was discharged from the bottom of the reaction tank under nitrogen pressurization, and the mixture was cooled in the water tank and cut with a granulator to obtain granules. The physical properties of the obtained copolycarbonate resin, no. A1, and the obtained polycarbonate are shown in Table 1.
Example 2
Copolycarbonates prepared from BCHA, BAHO were synthesized at a molar ratio of 90:10.
The polycarbonate resin was synthesized in accordance with example 1, with the exception of using 36.18g (0.09 mol) of BCHA and 2.26g (0.01 mol) of BAHO, and the obtained polycarbonate was subjected to the physical properties shown in Table 1 under the reference number A2.
Example 3
Copolycarbonates prepared from BCHA, BAHO were synthesized at a molar ratio of 70:30.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A3, with reference to example 1 except that 28.14g (0.07 mol) of BCHA and 6.78g (0.03 mol) of BAHO were used are shown in Table 1.
Example 4
Copolycarbonates prepared from BCHA, BAHO were synthesized in a 50:50 molar ratio.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A4, with reference to example 1 except that 20.1g (0.05 mol) of BCHA and 11.3g (0.05 mol) of BAHO were used are shown in Table 1.
Example 5
Copolycarbonates prepared from BCHA, BAHO were synthesized at a molar ratio of 30:70.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A5, with reference to example 1 except that 12.06g (0.03 mol) of BCHA and 15.82g (0.07 mol) of BAHO were used are shown in Table 1.
Example 6
Copolycarbonates prepared from BCHA, BAHO were synthesized at a molar ratio of 10:90.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A6, with reference to example 1 except that 4.02g (0.01 mol) of BCHA and 20.34g (0.09 mol) of BAHO were used are shown in Table 1.
Example 7
Copolycarbonates prepared from BCHA and BAHO were synthesized at a molar ratio of 1:99.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A7, with reference to example 1, except that 0.402g (0.001 mol) of BCHA and 22.374g (0.099 mol) of BAHO were used are shown in Table 1.
Example 8
Copolycarbonates prepared from BNPA, BAHO were synthesized in a molar ratio of 70:30.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A8, with reference to example 1, except that 43.82g (0.07 mol) of BNPA and 6.78g (0.03 mol) of BAHO were used are shown in Table 1.
Example 9
Copolycarbonates prepared from BBPHA and BAHO were synthesized in a molar ratio of 70:30.
The physical properties of the polycarbonate obtained by synthesizing a copolymerized polycarbonate resin, no. A9, with reference to example 1, except that 36.82g (0.07 mol) of BBPHA and 6.78g (0.03 mol) of BAHO were used are shown in Table 1.
Comparative example 1
Copolycarbonates prepared from BCHA dihydroxy compound and bisphenol A in a molar ratio of 70:30.
The main difference between the present application and example 1 is that 28.14g (0.07 mol) of BCHA and 6.849g (0.03 mol) of bisphenol A were used to prepare copolycarbonates, and the rest was the same as in example 1. The physical properties of the obtained copolycarbonate resin, number B1, and the obtained polycarbonate are shown in table 1.
Comparative example 2
Copolycarbonates prepared from BAHO and bisphenol A in a molar ratio of 70:30.
The main difference between the present application and example 1 is that 15.82g (0.07 mol) of BAHO and 6.849g (0.03 mol) of bisphenol A are used to prepare copolycarbonates. The physical properties of the obtained copolycarbonate resin, number B2, and the obtained polycarbonate are shown in Table 1
The properties of the copolycarbonates prepared in examples and comparative examples were determined by the following methods. The results are shown in Table 1 below
Weight average molecular weight (Mw): using Gel Permeation Chromatography (GPC), tetrahydrofuran was used as a developing solvent, and a standard curve was prepared using standard polystyrene having a known molecular weight (molecular weight distribution=1). Based on the standard curve, mw was calculated from the retention time of GPC.
Weather resistance: the change in yellowness index (dYI) of the samples was measured over 250 hours, 500 hours using Sup>A QUV-A accelerated aging tester according to ASTM D630.
Scratch resistance: the iron needle was held at an angle of 90 ° to the test plane and a constant load of force down at 6 newtons, and then pulled across the surface of a series of test articles using a profilometer to measure the depth (in microns) at which scratches were made, as assessed according to the Erichson scratch test, using standard surface hardness scratch test methods.
Fluidity: melt volume rate is measured by ASTM D1238. The filled material was placed in a vertical cylinder with a small die of 2mm at the bottom and heated at the indicated temperature, then a indicated load was applied to the molten material and the material extruded through the die was collected and then the amount of material extruded after a given time was normalized to cc/10min.
TABLE 1
Claims (23)
1. A copolycarbonate comprising a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2),
wherein the structural unit represented by the general formula (1) is as follows:
in formula (1), R is 1 、R 2 Independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, a cycloalkoxy group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or a halogen atom;
the structural unit represented by the general formula (2) is as follows:
2. the copolycarbonate according to claim 1, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the structural units of the copolycarbonate is 1:99 to 99:1.
3. The copolycarbonate according to claim 2, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the structural units of the copolycarbonate is 35:65 to 70:30.
4. The copolycarbonate according to claim 3, wherein the molar ratio of the structural unit represented by formula (1) to the structural unit represented by formula (2) in the structural units of the copolycarbonate is 55:45 to 60:40.
5. The copolycarbonate according to claim 1, wherein the copolycarbonate has a weight average molecular weight of 5000 to 600000.
6. The copolycarbonate of claim 5, wherein the copolycarbonate has a weight average molecular weight of 15000 to 80000.
7. The copolycarbonate of claim 6, wherein the copolycarbonate has a weight average molecular weight of 30000 to 70000.
8. The method for producing a copolycarbonate according to any one of claims 1 to 3, wherein the copolycarbonate is produced by reacting a dihydroxy compound represented by general formula (a) and a dihydroxy compound represented by general formula (B) with a carbonic acid diester;
the dihydroxyl compound represented by the general formula (A) has the following structural formula:
in formula (1), R is 1 、R 2 The definition is the same as the general formula (1);
the dihydroxyl compound represented by the general formula (B) has the following structural formula:
9. the process according to claim 8, wherein the dihydroxy compound represented by general formula (A) is selected from the following binaphthyl ether alcohol derivative structures:
10. the method of claim 8 or 9, wherein the copolycarbonate is prepared by melt transesterification.
11. The method according to claim 10, wherein the melt transesterification method is a method of producing a polycarbonate by reacting a dihydroxy compound with a carbonic acid diester in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst comprising the two, or by melt polycondensation in the absence of a catalyst.
12. The method of claim 11, wherein the carbonic acid diester comprises diphenyl carbonate, xylenyl carbonate, m-cresol carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, or dicyclohexyl carbonate.
13. The method of claim 12, wherein the carbonic acid diester is diphenyl carbonate.
14. The process according to claim 11, wherein the molar ratio of carbonic acid diester to dihydroxy compound is 0.97 to 1.20.
15. The process according to claim 14, wherein the molar ratio of carbonic acid diester to dihydroxy compound is 0.98 to 1.15.
16. The method according to claim 8 or 9, wherein the basic compound catalyst is selected from the group consisting of alkali metal compounds, alkaline earth metal compounds and nitrogen-containing compounds.
17. The process according to claim 11, wherein the molar ratio of catalyst to dihydroxy compound is 10 -8 ～10 -1 。
18. The process according to claim 17, wherein the molar ratio of catalyst to dihydroxy compound is 10 -7 ～10 -3 。
19. The production method according to claim 11, wherein the melt transesterification method is a method in which polycondensation is performed under heating conditions under normal pressure or reduced pressure while removing by-products by transesterification.
20. The method according to claim 11, wherein the reaction is carried out in two or more steps.
21. The method according to claim 11, wherein the transesterification is carried out at a reaction temperature of 130 to 210 ℃ for 0.1 to 5 hours in the first stage; then, the reaction of the dihydroxy compound and the carbonic acid diester is carried out at an elevated temperature while increasing the reduced pressure of the reaction system, and finally, the reaction is carried out at a reduced pressure of 133.32Pa or less and a temperature of 230 to 270 ℃ for 0.1 to 2 hours.
22. The process according to claim 21, wherein the transesterification is carried out at a reaction temperature of 170 to 200 ℃ for 1 to 3 hours in the first stage.
23. Transparent, translucent or colored shaped parts, extrudates, film laminates prepared from copolycarbonates according to any of claims 1 to 7 or copolycarbonates prepared by the process according to any of claims 8 to 22.
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| WO2019009076A1 (en) * | 2017-07-07 | 2019-01-10 | 帝人株式会社 | Polycarbonate copolymer |
| CN112250853A (en) * | 2020-09-09 | 2021-01-22 | 万华化学集团股份有限公司 | Optical polycarbonate and manufacturing method and application thereof |
| CN113072694A (en) * | 2021-04-09 | 2021-07-06 | 万华化学集团股份有限公司 | Polycarbonate resin for temperature change resistant optical component and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019009076A1 (en) * | 2017-07-07 | 2019-01-10 | 帝人株式会社 | Polycarbonate copolymer |
| CN112250853A (en) * | 2020-09-09 | 2021-01-22 | 万华化学集团股份有限公司 | Optical polycarbonate and manufacturing method and application thereof |
| CN113072694A (en) * | 2021-04-09 | 2021-07-06 | 万华化学集团股份有限公司 | Polycarbonate resin for temperature change resistant optical component and preparation method and application thereof |
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