CN114349949A - Scratch-resistant copolycarbonate, and preparation method and application thereof - Google Patents
Scratch-resistant copolycarbonate, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114349949A CN114349949A CN202210045997.7A CN202210045997A CN114349949A CN 114349949 A CN114349949 A CN 114349949A CN 202210045997 A CN202210045997 A CN 202210045997A CN 114349949 A CN114349949 A CN 114349949A
- Authority
- CN
- China
- Prior art keywords
- general formula
- copolycarbonate
- carbonate
- dihydroxy compound
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention 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 invention relates to the field of polycarbonate, in particular to high-weather-resistance and high-scratch-resistance copolycarbonate and a preparation method and application thereof.
Background
Polycarbonate (PC) is used as an engineering plastic with excellent performance, and has good application in the fields of automobiles, household appliances, electronic appliances and the like. The composite material has the advantages of good mechanical property, good impact toughness, creep resistance, good dimensional stability, wide use temperature range, good electrical insulation, no harm to human bodies and sanitation and safety. PC can reach UL94V-2 weather resistance grade, which is not good for general plastics, but can not reach weather resistance requirements in some special occasions, and can yellow, even degrade and become brittle after being exposed to ultraviolet rays for a long time, thereby affecting the service performance and the service life of the PC.
In the prior art, the performance of polycarbonate is generally improved by physical modification or chemical modification. Physical modification is achieved by adding other polymers such as ASA, polysiloxane, or small molecule auxiliaries such as benzophenone, 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 gloss and the color saturation of the material can be reduced, the impact strength of the material can be reduced, and meanwhile, the additive 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 contrast, there is an attempt to graft or terminate an ultraviolet absorbing group onto a PC molecular backbone by a chemical bond, for example, in patent CN104193979B, an ultraviolet resistant polycarbonate resin is provided, which is prepared by performing a grafting reaction between an acid chloride-terminated polycarbonate oligomer and an ultraviolet absorber under the catalysis of a weak acid or a weak base, and then performing further chain extension and polycondensation, but this method may cause a reaction between a hydroxyl group of an active group of the ultraviolet absorber and an acid chloride group of phosgene or the acid chloride-terminated polycarbonate oligomer, thereby affecting the ultraviolet resistance thereof, and the obtained ultraviolet resistant polycarbonate has only two absorption peaks with lower peak strength at 300 to 400nm, and the ultraviolet resistant effect is very limited.
In addition, the surface hardness of the PC is low, the pencil hardness is only 1-2H grade, the pencil is easy to scratch and scratch in the using process, and the scratch resistance is slightly poor, so that the light transmission and the appearance effect are influenced. At present, the commonly used method for improving the hardness of polycarbonate is to add scratch-resistant agents such as PMMA, siloxane and the like, but the methods can cause the reduction of the light transmittance of the material, the increase of the haze and even the occurrence of the pearl phenomenon due to the compatibility problem, thereby influencing the appearance and the strength of the product. For example, in patent CN201510413851.3, maleic anhydride-styrene-methyl methacrylate terpolymer is used to improve scratch resistance of PC, but the injection molded product has poor heat resistance, is prone to yellowing and silver streaks, and seriously affects appearance and processability of the product.
Therefore, it is an important research in the art to develop a new structure of a copolymerized polycarbonate having excellent weather resistance together with excellent mechanical properties such as high hardness, etc. to meet the application requirements thereof in high-performance outdoor use parts.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a copolymerized polycarbonate, a preparation method and application thereof, so that the polycarbonate has high weather resistance and high scratch resistance.
The invention 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 the formula (1), wherein R1、R2Each independently represents 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 shown below:
in the structural units of the copolycarbonate according to the present invention, 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, and more preferably 55:45 to 60: 40.
The invention also provides a preparation method of the copolycarbonate, wherein the copolycarbonate is prepared by reacting the dihydroxy compound shown in the general formula (A) with the dihydroxy compound shown in the general formula (B) and a carbonic diester.
As a preferable embodiment, the dihydroxy compound represented by the general formula (A) has the following structural formula:
in the formula (1), wherein R1、R2The definition is the same as that of the general formula (1).
Preferably, the dihydroxy compound represented by the general formula (a) has the following binaphthyl ether alcohol derivative structure.
As a preferable embodiment, the dihydroxy compound represented by the general formula (B) has the following structural formula:
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 of the present invention is a method for producing a polycarbonate by reacting a dihydroxy compound and a carbonic acid diester by a melt 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.
Preferably, the carbonic acid diester includes diphenyl carbonate, ditolyl carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.; 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, the basic compound catalyst includes, in particular, alkali metal compounds, alkaline earth metal compounds, nitrogen-containing compounds, and the like.
Examples of the alkali metal compound used in the present invention include organic acid salts, inorganic salts, oxides, hydroxides, hydrides, alkoxides of alkali metals, and the like. 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 boratabenzate, sodium benzoate, potassium benzoate, cesium benzoate, lithium benzoate, disodium hydrogenphosphate, dipotassium hydrogenphosphate, dilithium hydrogenphosphate, disodium phenylphosphate, disodium salt, dipotassium salt, dicesium salt, or dilithium salt of bisphenol a, sodium salt, potassium salt, cesium salt, or lithium salt 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 hydrogencarbonate, calcium hydrogencarbonate, strontium hydrogencarbonate, barium hydrogencarbonate, 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 and salts thereof, and amines. 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, trimethylbenzylammonium hydroxide, or the like; 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 ammonium tetraphenylborate.
As the transesterification catalyst, salts of zinc, tin, zirconium, lead, and the like are preferably used, and these may be used alone or in combination.
Specific examples of the transesterification catalyst include zinc acetate, zinc benzoate, zinc 2-ethylhexanoate, tin chloride, tin acetate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dimethoxytin, zirconium acetylacetonate, zirconium glycolate, zirconium tetrabutoxide, and lead acetate.
The molar ratio of the amount of these catalysts to the dihydroxy compound was 10-8～10-1Molar ratio, preferably 10-7～10-3。
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 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 degree of pressure reduction of the reaction system, and finally, the reaction is carried out at 230 to 270 ℃ for 0.1 to 2 hours under a reduced pressure of 133.32Pa or less. 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 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 of the catalyst is less than 0.1 times mole, the deactivation effect becomes insufficient. Further, when the amount of the catalyst is more than 45 times by 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 in the present invention preferably have a weight average molecular weight of 5000-.
The copolycarbonates described in the present invention may additionally contain 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: 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 270 ℃ to 330 ℃ in customary apparatuses such as internal mixers, extruders and twin-screw kneaders, and granulated by means of a granulator.
Transparent, translucent or colored shaped parts, extrudates, film laminates are produced from the copolycarbonates according to the invention or from the copolycarbonates produced according to the method according to the invention.
Copolycarbonate is a material having excellent physical properties such as high impact strength and high heat resistance, and is widely used in various fields. Polycarbonate by itself can achieve a UL94V-2 weathering rating that is not uncommon for general purpose plastics, but does not meet weathering requirements in some special applications. Accordingly, there is a need for a copolycarbonate of a new structure having improved weather resistance while maintaining its inherent physical properties. As a result of extensive studies, the present inventors have found that when structural units of the general formulae (1) and (2) are introduced in the preparation of a copolycarbonate, the copolycarbonate can be provided with excellent weather resistance.
Therefore, when the copolycarbonate of the present invention is applied to automobile interior/exterior materials, lamp housings, plastic exterior material products for construction, and the like, excellent properties can be maintained even under exposure to light, high temperature, and high pressure conditions during the manufacturing process of the products or the practical use of the products.
The invention has the beneficial effects that:
according to the invention, the structural units of the formula (1) and the formula (2) are selected for combined design, wherein both the structural units of the formula (1) and the formula (2) have benzene rings and carbonate groups, rigid benzene rings prevent the free rotation of molecular chains, and the rigid benzene rings and the polar carbonate groups form a large conjugated system to increase the rigidity of the molecular chains, so that the polymer has higher tensile strength, rigidity and hardness. Fries rearrangement is carried out on the carbonate group in the formula (2) when the carbonate group is irradiated by light to be converted into an o-hydroxybenzophenone chain link, the structure absorbs thermal vibration generated by ultraviolet light to cause hydrogen bond breakage, and ultraviolet light energy is consumed, so that the copolycarbonate with excellent weather resistance and excellent scratch resistance can be obtained.
Detailed Description
The following examples are intended to illustrate the invention, which is not limited to the scope of the examples, but also includes any other modifications within the scope of the claims of the invention.
The raw material sources are as follows:
raw material BHAO: chemical Co Ltd of Jinan Chuangshi
O-methyl phenol: aladdin
Dodecahydroanthrone (cas 52747-32-7): such as Ji Biotech development Ltd
O-phenylphenol: shanghai Yi En chemical technology Co., Ltd
O-naphthylphenol (cas 909004-74-6): dongying Dada chemical Co Ltd
Preparation of 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 product A;
(2) adding 10g of concentrated sulfuric acid serving as a catalyst and 2.12g of thiopropionic acid serving as an auxiliary agent into 235g of the intermediate product A and 206g of dodecahydroanthrone, and stirring for 4 hours at the reaction temperature of 40 ℃ to finish the reaction; adding 200g of deionized water, precipitating a large amount of solid, continuously stirring for 2 hours at the temperature, and cooling and filtering to obtain a solid crude product. Adding the crude product into 300g of isopropanol, stirring, heating to completely dissolve, continuously adding the crude product until the crude product is close to the saturated solubility (the mass ratio of the crude product to the isopropanol is 1: 1.5), continuously stirring for 30min, and cooling to crystallize to obtain a pure BCHA product.
Preparation of example 2
Synthesis of dihydroxy compound BNPHA:
the reaction conditions were substantially the same as those in preparation example 1 except that: 660g of o-naphthyl phenol is adopted to replace 324g of o-methyl phenol to prepare an intermediate product B; and 372g of the intermediate product B is adopted to replace 235g of the intermediate product A, so that the target product BNPHA is prepared.
Preparation of example 3
Synthesis of dihydroxy compound BBPHA:
the reaction conditions were substantially the same as those in preparation example 1 except that: adding 510g of o-phenylphenol instead of o-methylphenol in the step (1) to prepare an intermediate product C; 481g of intermediate product C is added in the step (2) to prepare the target product BBPHA.
Example 1
Copolycarbonates prepared from BCHA, BAHO were synthesized in a molar ratio of 99: 1.
39.798g (0.099mol) of BCHA, 0.226g (0.001mol) of BHAO of the formula (B), 22.278(0.104mol) of diphenyl carbonate and 0.0002g (5X 10 mol) of diphenyl carbonate were mixed together-6mol) 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 200 ℃ over 0.5 hour, and stirring was performed. Then, the pressure was adjusted to 2KPa for 10 minutes, and the mixture was held at 200 ℃ and 2KPa for 30 minutes to perform the transesterification reaction. Then the temperature is raised to 260 ℃ at the speed of 50 ℃/hourThe temperature is kept at 260 ℃ and 2KPa for 20 minutes. Then, the temperature was adjusted to 1KPa over 10 minutes, and the mixture 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 physical properties of the resulting copolycarbonate resin, No. A1, are shown in Table 1.
Example 2
Copolycarbonates prepared from BCHA, BAHO were synthesized in a 90:10 molar ratio.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A2 in example 1 except for using 36.18g (0.09mol) of BCHA and 2.26g (0.01mol) of BAHO are shown in Table 1.
Example 3
Copolycarbonates prepared from BCHA, BAHO were synthesized in a molar ratio of 70: 30.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of example 1, No. A3, except for using 28.14g (0.07mol) of BCHA and 6.78g (0.03mol) of BAHO, are shown in Table 1.
Example 4
Copolycarbonates prepared from BCHA, BAHO were synthesized in a molar ratio of 50: 50.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A4 in example 1 except for using 20.1g (0.05mol) of BCHA and 11.3g (0.05mol) of BAHO are shown in Table 1.
Example 5
Copolycarbonates prepared from BCHA, BAHO were synthesized in a 30:70 molar ratio.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A5 in example 1 except for using 12.06g (0.03mol) of BCHA and 15.82g (0.07mol) of BAHO are shown in Table 1.
Example 6
Copolycarbonates prepared from BCHA, BAHO were synthesized in a molar ratio of 10: 90.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A6 in example 1 except for using 4.02g (0.01mol) of BCHA and 20.34g (0.09mol) of BAHO are shown in Table 1.
Example 7
Copolycarbonates prepared from BCHA, BAHO were synthesized in a 1:99 molar ratio.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A7 in example 1 except that 0.402g (0.001mol) of BCHA and 22.374g (0.099mol) of BAHO were used are shown in Table 1.
Example 8
Copolycarbonates prepared from BNPHA, BAHO were synthesized in a molar ratio of 70: 30.
Physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of example 1, No. A8, except that 43.82g (0.07mol) of BNPHA and 6.78g (0.03mol) of BAHO were used, are shown in Table 1.
Example 9
Copolycarbonates prepared from BBPHA, BAHO were synthesized in a molar ratio of 70: 30.
The physical properties of the polycarbonate resin obtained by synthesizing the copolymeric polycarbonate resin of No. A9 in example 1 were as shown in Table 1, except that 36.82g (0.07mol) of BBPHA and 6.78g (0.03mol) of BAHO were used.
Comparative example 1
A copolycarbonate prepared from a BCHA dihydroxy compound and bisphenol A in a molar ratio of 70: 30.
The invention differs from example 1 mainly in that 28.14g (0.07mol) of BCHA and 6.849g (0.03mol) of bisphenol A are used to prepare copolycarbonates, the rest being the same as in example 1. The physical properties of the resulting copolycarbonate resin, No. B1, are shown in Table 1.
Comparative example 2
Copolycarbonates prepared from BAHO and bisphenol a in a molar ratio of 70: 30.
The invention differs from example 1 essentially in that 15.82g (0.07mol) of BAHO and 6.849g (0.03mol) of bisphenol A are used to prepare copolycarbonates. The physical properties of the resulting copolycarbonate resin, No. B2, are shown in Table 1
The properties of the copolycarbonates prepared in examples and comparative examples were measured by the following methods. The results are shown in Table 1 below
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.
Weather resistance: the yellowness index change (dYI) of the samples was measured at 250 hours and 500 hours using a QUV-A accelerated weathering tester according to ASTM D630.
Scratch resistance: according to the Erichson scratch test evaluation, a stylus was held at an angle of 90 ° relative to the test plane and under a constant load of force down to 6 newtons using a standard surface hardness scratch test method, then dragged across a series of test article surfaces and the depth (in microns) at which scratches were made was measured using a profilometer.
Fluidity: melt volume rate is measured by ASTM D1238. The charged material was placed in a vertical cylinder having a 2mm small die at the bottom and heated at a specified temperature, then a specified load was applied to the molten material, and the material extruded through the die was collected, and then the amount of the extruded material after a given time was normalized to cc/10 min.
TABLE 1
Claims (9)
1. A copolycarbonate which is characterized by 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 the formula (1), wherein R1、R2Independently represents 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 shown below:
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, preferably 35:65 to 70:30, and more preferably 55:45 to 60: 40.
3. The polycarbonate of claim 1, wherein the polycarbonate has a weight average molecular weight of 5000-.
4. The method of 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 dihydroxy compound represented by the general formula (A) has the following structural formula:
in the formula (1), wherein R1、R2The definition is the same as that of the general formula (1);
the dihydroxy compound represented by the general formula (B) has the following structural formula:
5. the method according to claim 4, wherein the dihydroxy compound represented by the general formula (A) is selected from the following binaphthyl ether alcohol derivative structures:
6. the process according to claim 4 or 5, wherein the copolycarbonate is produced by a melt transesterification method;
preferably, the melt transesterification method is a method for producing a polycarbonate by reacting a dihydroxy compound and a carbonic acid diester by a melt polycondensation method in the presence of a basic compound catalyst, a transesterification catalyst or a mixed catalyst composed of both of them, or in the absence of a catalyst;
preferably, the carbonic acid diester includes diphenyl carbonate, ditolyl carbonate, m-cresyl carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, etc.; among them, diphenyl carbonate is preferable;
preferably, 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.
7. The production process according to any one of claims 4 to 6, wherein the basic compound catalyst in the transesterification catalyst is selected from the group consisting of an alkali metal compound, an alkaline earth metal compound and a nitrogen-containing compound;
preferably, the molar ratio of the amount of the catalyst to the dihydroxy compound is 10-8 to 10-1 mol, preferably 10-7 to 10-3.
8. The production process according to any one of claims 4 to 7, wherein the melt transesterification method is a method of conducting polycondensation under heating, under normal pressure or reduced pressure by transesterification while removing by-products;
preferably, the reaction is carried out in more than two stages;
preferably, the transesterification is carried out at a reaction temperature of 130-210 ℃ in the first stage, preferably at a temperature of 170-200 ℃ for 0.1-5 hours, preferably 1-3 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 230 to 270 ℃ for 0.1 to 2 hours under a reduced pressure of 133.32Pa or less.
9. Transparent, translucent or colored shaped parts, extrudates, film laminates prepared from copolycarbonates according to claims 1 to 3 or prepared by the process according to claims 4 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210045997.7A CN114349949B (en) | 2022-01-17 | 2022-01-17 | Scratch-resistant copolycarbonate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210045997.7A CN114349949B (en) | 2022-01-17 | 2022-01-17 | Scratch-resistant copolycarbonate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114349949A true CN114349949A (en) | 2022-04-15 |
| CN114349949B CN114349949B (en) | 2023-09-19 |
Family
ID=81091321
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210045997.7A Active CN114349949B (en) | 2022-01-17 | 2022-01-17 | Scratch-resistant copolycarbonate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114349949B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-01-17 CN CN202210045997.7A patent/CN114349949B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114349949B (en) | 2023-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106883575B (en) | Polycarbonate resin composition and molded article | |
| CN113956458B (en) | Copolycarbonate with high refractive index, high heat resistance and high weather resistance, preparation method and application thereof | |
| JP5332696B2 (en) | Polycarbonate resin composition and method for producing the same | |
| JP5617186B2 (en) | Polycarbonate resin composition | |
| KR101728181B1 (en) | Polycarbonate resin composition, process for producing molded article therefrom, and optical lens | |
| KR101602568B1 (en) | Terminal-modified polyoxyalkylene glycol and optically improved polycarbonate resin composition containing the same | |
| JP2010132782A (en) | Polycarbonate copolymer, method for producing the same and use thereof | |
| CN114763407A (en) | Copolycarbonate with high transmittance and low-temperature impact resistance, and preparation method and application thereof | |
| JP2013049847A (en) | Automotive interior | |
| EP3628699B1 (en) | Copolycarbonate and preparation method therefor | |
| CN114085369B (en) | Optical polycarbonate and preparation method and application thereof | |
| JP5655657B2 (en) | LED signal member | |
| JP2016156031A (en) | Polycarbonate resin composition and molded part | |
| CN114349949A (en) | Scratch-resistant copolycarbonate, and preparation method and application thereof | |
| KR101704896B1 (en) | Polyester carbonate resin, method for preparing the same and article comprising the same | |
| JP2004115609A (en) | Polycarbonate resin composition and molded article thereof | |
| JP5593865B2 (en) | Method for producing polycarbonate resin | |
| CN113968963B (en) | Polycarbonate and preparation method and application thereof | |
| CN113929893A (en) | Copolycarbonate with high refractive index and low birefringence | |
| CN114085368B (en) | Polycarbonate and preparation method and application thereof | |
| JPH07188539A (en) | Copolymerized polycarbonate resin composition | |
| JP2013049846A (en) | Sound-insulating member | |
| KR20180079065A (en) | Copolymerized polycarbonate resin having excellent weather resistance and method for preparing the same | |
| KR20190129893A (en) | Manufacturing method of thermoplastic resin | |
| JP6044058B2 (en) | Polycarbonate resin composition and molded product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |