CN112225885B - Copolyester and preparation method thereof - Google Patents
Copolyester and preparation method thereof Download PDFInfo
- Publication number
- CN112225885B CN112225885B CN202011121995.9A CN202011121995A CN112225885B CN 112225885 B CN112225885 B CN 112225885B CN 202011121995 A CN202011121995 A CN 202011121995A CN 112225885 B CN112225885 B CN 112225885B
- Authority
- CN
- China
- Prior art keywords
- formula
- copolyester
- reaction
- dihydro
- refractive index
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
The invention relates to a copolyester and a preparation method thereof, and the copolyesterPrepared from the following reaction raw materials: dihydroxy compound
And/or
And
and dicarboxylic acid compound
Description
Technical Field
The invention relates to a copolyester, in particular to a copolyester with high refractive index and low birefringence and a preparation method thereof.
Background
Optical glass or optical resin is mainly used as an optical lens material in optical systems such as mobile phone camera shooting, security protection, intelligent driving assistance, VR/AR and the like at present. Compared with optical glass, optical resin has the advantages of light weight, easy molding, easy mass production, low cost and the like, so that more and more optical lenses are made of the optical resin. At present, light, thin, short and small optical lens products are the mainstream trend, and the development of optical resins with higher refractive index is required.
Optical polyesters occupy an extremely important position in the field of optical applications. According to the Lorentz-Lorenz equation:
or
The refractive index n is determined by the structure of the polymer molecule, introducing a high [ R ]]The substituent with the value of/V0 can effectively improve the refractive index of the polymer. Therefore, the refractive index of the material can be improved by increasing the benzene ring structure in the polyester material.
Chinese patent CN200480005782 describes a high refractive index polyester obtained by polymerizing 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and its derivatives with aliphatic or aromatic dicarboxylic acids, the refractive index of which is up to 1.619. Chinese patent CN200480027704 describes optical resins obtained by blending polyester and polycarbonate described in patent CN200480005782, the refractive index of which is further reduced.
Chinese patent CN102471467B describes a high refractive index polyester comprising 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene and 2, 6-naphthalenedicarboxylic acid, the refractive index can reach 1.650. However, the polymer monomer 9, 9-bis (4- (2-hydroxyethoxy) phenyl) fluorene used in the patent has longer synthesis process, higher production cost and uses dangerous compound ethylene oxide.
In view of the defects of the optical polyesters reported in the patent and literature documents, there is an urgent need in the art to develop optical polyesters with high refractive index, low birefringence, and low cost, while simultaneously achieving other optical properties, such as low haze, low dispersion, etc.
Disclosure of Invention
The invention aims to provide a copolyester with high refractive index and low birefringence and a preparation method thereof, and simultaneously has the advantages of low haze and low dispersion.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a copolyester prepared from reaction raw materials comprising:
1) 9, 10-dihydro-9, 10-dihydroxyphenanthrene, derived from the dihydroxy compound of formula (I)
And/or
2) 9, 10-dihydro-9, 10-dihydroxyanthracene, a dihydroxy compound derived from formula (II):
and
3) a saturated linear dihydroxy compound derived from formula (III):
wherein n is 2-6;
and
4) a dicarboxylic acid compound derived from formula (iv):
in the present invention, the compound represented by formula (I) is obtained by hydrogenation of phenanthrenequinone, and preferably, the preparation method thereof is: taking 15-30 wt% phenanthrenequinone alcohol solution as a raw material, taking raney nickel as a catalyst, carrying out hydrogenation reaction in a batch kettle to obtain a 9, 10-dihydro-9, 10-dihydroxyphenanthrene reactant, and refining to obtain 9, 10-dihydro-9, 10-dihydroxyphenanthrene with the purity of 99.9%; wherein the addition amount of the catalyst is 2-3% of the mass ratio of the reaction substrate, the reaction time is 4-8 h, the reaction temperature is 120-160 ℃, the reaction pressure is 2-5 MPa, the low carbon alcohol (such as ethanol) is used as a solvent, and the selectivity of phenanthrene quinone is more than 99.9%, and the selectivity of 9, 10-dihydro-9, 10-dihydroxyphenanthrene is more than 99.9% under the conditions of stirring speed of 600-1000 r/min. The refining conditions are as follows: and (3) carrying out rotary evaporation at the temperature of 80-100 ℃ to remove the solvent ethanol to obtain the product 9, 10-dihydro-9, 10-dihydroxyl phenanthrene.
In the present invention, the compound represented by the formula (II) is obtained by hydrogenating anthraquinone, and preferably, it is prepared by: taking 15-25 wt% of anthraquinone ethyl acetate solution as a raw material, taking Raney nickel as a catalyst, carrying out hydrogenation reaction in a batch kettle to obtain a 9, 10-dihydro-9, 10-dihydroxyanthracene reactant, and refining to obtain the 9, 10-dihydro-9, 10-dihydroxyanthracene with the purity of more than 99.9%. Wherein the addition amount of the catalyst is 2.5-5% of the mass of the reaction substrate, the reaction time is 4-8 h, the reaction temperature is 50-60 ℃, the reaction pressure is 2-3 MPa, ethyl acetate is used as a solvent, and the stirring speed is 500-900 r/min. The refining conditions are as follows: and (3) performing rotary evaporation at the temperature of 80-100 ℃ to remove the ethyl acetate solvent to obtain the product 9, 10-dihydro-9, 10-dihydroxyanthracene.
In the present invention, the saturated linear dihydroxy compound represented by formula (III) may be ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol; ethylene glycol and/or 1, 3-propanediol are preferred.
In the present invention, the polymer composition formed by the dihydroxy compound and the dicarboxylic acid compound is: the molar ratio of the 9, 10-dihydro-9, 10-dihydroxyphenanthrene represented by the formula (I) and/or the 9, 10-dihydro-9, 10-dihydroxyanthracene represented by the formula (II) to the dihydroxy compound represented by the formula (III) is 60-95: 5-40, preferably 80-95: 5-20. When 9, 10-dihydro-9, 10-dihydroxyphenanthrene represented by formula (I) and 9, 10-dihydro-9, 10-dihydroxyanthracene represented by formula (II) are used, they may be mixed in an arbitrary ratio. The molar ratio of the total amount of dihydroxy compounds represented by formula (I), formula (II) and formula (III) to the dicarboxylic acid compound of formula (IV) is 1.01 to 1.1 to 1. In the invention, the saturated linear chain dihydroxy compound is indispensable in the copolyester, and if no saturated linear chain dihydroxy compound participates in the synthesis of the copolyester, the obtained polyester or copolyester is hard and brittle, has poor toughness and cannot meet the requirements of downstream application.
In the present invention, the copolyester can be prepared by a melt polycondensation method known to those skilled in the art, for example, see the literature or patent CN 104497290B.
In the invention, the melt polycondensation temperature of the copolyester is 300-350 ℃, the polycondensation time is 0.5-5 h, preferably 2-3.5 h, and the polycondensation vacuum degree is 100-2000 Pa.
In the invention, the catalyst used for melt polycondensation is one or a mixture of cesium carbonate, sodium bicarbonate and potassium bicarbonate, and the amount of the catalyst is 10 percent of the total weight of reactants-6～10-4And (4) doubling.
In the invention, the melt polycondensation comprises the following specific operation steps: firstly, adding the measured materials and the catalyst into a polycondensation reaction kettle, pumping the vacuum degree of a reaction system to a preset vacuum degree, then starting to heat the reaction system to a preset temperature, and carrying out polycondensation reaction for a certain time at the preset temperature.
After the melt polycondensation reaction is completed, the catalyst is deactivated in order to maintain the thermal stability and hydrolytic stability of the polymer. As the catalyst deactivator, there can be used known acidic substances, phosphoric acids such as phosphorous acid and phosphoric acid, and aromatic sulfonic acids such as toluenesulfonic acid, and these may be used alone or in combination. The amount of the catalyst deactivator used may be 1 to 10 times the molar amount of the catalyst.
In the invention, the weight average molecular weight Mw of the copolyester prepared by melt polycondensation is 30000-50000, and the refractive index is 1.600-1.650.
The invention has the beneficial effects that:
the invention introduces the polyphenyl ring dihydroxy compound formula (I), (II) and the polyphenyl ring dicarboxylic acid compound formula (IV) to melt and condense to improve the refractive index of the obtained polyester, and has low birefringence; meanwhile, linear dihydroxy compound copolymerization is introduced, so that the tensile property, impact resistance and other mechanical properties of the polymer are improved. The copolyester with high refractive index, low birefringence, low haze, low dispersion and low cost 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 test characterization methods in the examples and comparative examples are as follows:
the copolyesters were characterized by means of glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze, elongation at break tests.
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.
Tg was measured by dynamic differential thermal analysis (DSC) according to ASTM E1356.
Elongation at break: measured using an electronic universal tester.
The refractive index, light transmittance and haze were obtained by measuring a copolycarbonate film, the refractive index was measured according to ASTM D542, and the light transmittance and haze were measured according to ASTM D1003;
the copolymer film was prepared by dissolving the copolyester resin in methylene chloride to prepare a 10 wt% solution, and then spin-coating to a thickness of 50 μm.
Measurement of orientation birefringence: a casting film having a thickness of 100 μ M was cut into a length of 7cm in the casting direction and 1.5cm in the direction (width direction) perpendicular to the casting direction, the both ends in the longitudinal direction were clamped by a chuck (chuck interval 4.5cm), the casting direction was stretched 2 times at Tg +10 ℃ of the copolycarbonate resin, the phase difference (Re) at 589nm was measured by an ellipsometer M-220 manufactured by Nippon spectral Co., Ltd., and the oriented birefringence (. DELTA.n) was determined by the following equation.
Δ n — Re/d Δ n: oriented birefringence
Re: phase difference
d: thickness of
In the examples, the raw material sources are as follows:
2, 6-naphthalenedicarboxylic acid: xinnuolixing Fine chemical Co., Ltd
Ethylene glycol: shandong Xuchen chemical technology Co Ltd
1, 3-propanediol: suzhou Pu Lu chemical technology Co., Ltd
Anthraquinone: shunhun science and technology Co., Ltd
Phenanthrenequinone: jinan Walde chemical Co., Ltd
Raney nickel catalyst: jiangsu Renyi science and technology Co., Ltd
The preparation method of the 9, 10-dihydro-9, 10-dihydroxyl phenanthrene comprises the following steps: taking 20% phenanthrenequinone ethanol solution as a raw material, taking Raney nickel as a catalyst in a batch kettle, adding the catalyst in an amount which is 3% of the mass of a reaction substrate, carrying out hydrogenation reaction under the conditions of reaction time of 6 hours, reaction temperature of 120 ℃, reaction pressure of 4MPa and stirring speed of 1000 revolutions per minute to obtain 9, 10-dihydro-9, 10-dihydroxyphenanthrene ethanol reaction solution, wherein the conversion rate of phenanthrenequinone is more than 99.9%, and removing the solvent ethanol by rotary evaporation at 100 ℃ to obtain the product.
The preparation method of the 9, 10-dihydro-9, 10-dihydroxyanthracene comprises the following steps: taking 15% anthraquinone ethyl acetate as a raw material, taking Raney nickel as a catalyst in a batch kettle, adding the catalyst in an amount of 5% of the mass of a reaction substrate, carrying out hydrogenation reaction under the conditions of 6 hours of reaction time, 60 ℃ of reaction temperature, 2MPa of reaction pressure and 800 r/min of stirring speed to obtain a 9, 10-dihydro-9, 10-dihydroxyanthracene reactant, and refining to obtain the 9, 10-dihydro-9, 10-dihydroxyanthracene with the purity of more than 99.9%. Removing the solvent ethyl acetate by rotary evaporation at 85 ℃ to obtain the product.
Example 1
2120g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 155g of ethylene glycol, 2674g of 2, 6-naphthalenedicarboxylic acid and 0.12g of cesium carbonate were weighed, and these materials were put into a 10-L reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 800Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 2 hours when the temperature of the reaction system reaches 300 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.6g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-01. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 2
1060g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 1060g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 109.4g of ethylene glycol, 2443.5g of 2, 6-naphthalenedicarboxylic acid and 0.14g of sodium bicarbonate were weighed, and these materials were put into a 10L reactor, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 600Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 2.5h when the temperature of the reaction system reaches 315 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.8g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-02. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 3
2120g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 84.4g of propylene glycol, 2285.7g of 2, 6-naphthalenedicarboxylic acid and 0.22g of potassium hydrogen carbonate were weighed, and these materials were put into a 10L reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 500Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 330 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.9g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-03. The samples were characterized by molecular weight, glass transition temperature, Tg, refractive index, oriented birefringence, light transmittance, haze, elongation at break.
Example 4
1060g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 1060g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 68.9g of ethylene glycol, 2264.2g of 2, 6-naphthalenedicarboxylic acid and 0.24g of cesium carbonate were weighed, and these materials were charged into a 10L reactor, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 500Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 345 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 1g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-04. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 5
2120g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 68.9g of ethylene glycol, 2222.2g of 2, 6-naphthalenedicarboxylic acid and 0.26g of cesium carbonate were weighed, and these materials were charged into a 10-L reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 400Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3.5h when the temperature of the reaction system reaches 345 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.8g of catalyst deactivator toluenesulfonic acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-05. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 6
2120g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 32.6g of ethylene glycol, 2067g of 2, 6-naphthalenedicarboxylic acid and 0.29g of cesium carbonate were weighed, and these materials were charged into a 10-L reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 300Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 350 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.6g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-05. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 7
1060g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 1060g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 40g of propylene glycol, 2086g of 2, 6-naphthalenedicarboxylic acid and 0.33g of sodium bicarbonate were weighed, and these materials were put into a 10L reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 100Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 360 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.5g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-07. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Example 8
2120g of 9, 10-dihydro-9, 10-dihydroxyanthracene, 32.6g of ethylene glycol, 2165.4g of 2, 6-naphthalenedicarboxylic acid and 0.26g of potassium hydrogencarbonate were weighed, and these materials were put into a 10L reactor, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 200Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 350 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.5g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then pressed out with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer PDN-08. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Comparative example 1
2120g of 9, 10-dihydro-9, 10-dihydroxyphenanthrene, 1963g of 2, 6-naphthalenedicarboxylic acid and 0.29g of cesium carbonate were weighed, and these materials were charged into a 10-liter reaction vessel, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 300Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 3 hours when the temperature of the reaction system reaches 350 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.6g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then extruded with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer VPDN-00. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
Comparative example 2
632.4g of ethylene glycol, 2160g of 2, 6-naphthalenedicarboxylic acid and 0.29g of cesium carbonate were weighed, and these materials were put into a 10L reactor, which was then closed. Starting stirring (the stirring speed can be 20-60 r/min), starting a vacuum pump to vacuumize the reaction system to 300Pa, then starting a high-temperature circulating oil bath to heat the reaction kettle, and starting timing reaction for 2 hours when the temperature of the reaction system reaches 350 ℃. After the reaction is finished, the vacuum pump is stopped, nitrogen is introduced to break the vacuum, and 0.6g of catalyst deactivator phosphorous acid is added to react for 30 min. The copolyester in the reactor was then extruded with nitrogen, pulled into strands, and cut into pellets, which were designated as polymer VPDN-01. And (3) performing molecular weight, glass transition temperature Tg, refractive index, orientation birefringence, light transmittance, haze and elongation at break tests on the sample for characterization.
The results of the characterization of the polyester resins in the examples and comparative examples are shown in Table 1.
TABLE 1
As can be seen by comparing the examples with the comparative examples: only 9, 10-dihydro-9, 10-dihydroxyphenanthrene and naphthalenedicarboxylic acid are used for synthesizing polyester, the content of benzene rings in the polyester is high, the refractive index is high, but the oriented birefringence is high, the material is very brittle, and the elongation at break is low; and only ethylene glycol and naphthalenedicarboxylic acid are used for synthesizing the polyester, so that the material is low in refractive index, good in toughness and high in elongation at break.
Claims (7)
1. A copolyester prepared from reaction raw materials comprising:
1) 9, 10-dihydro-9, 10-dihydroxyphenanthrene derived from formula (I):
and/or
2) 9, 10-dihydro-9, 10-dihydroxyanthracene derived from formula (II):
and
3) a saturated linear dihydroxy compound derived from formula (III):
wherein n is 2-6;
and
4) a dicarboxylic acid compound derived from formula (iv):
the molar ratio of the 9, 10-dihydro-9, 10-dihydroxyphenanthrene represented by the formula (I) and/or the 9, 10-dihydro-9, 10-dihydroxyanthracene represented by the formula (II) to the dihydroxy compound represented by the formula (III) is 80-95: 5-20.
2. The copolyester of claim 1, wherein the molar ratio of the total amount of dihydroxy compounds represented by formula (I), formula (II) and formula (III) to the dicarboxylic acid compound of formula (iv) is 1.01 to 1.1: 1.
3. A copolyester according to claim 1 or 2, wherein n of the saturated linear dihydroxy compound of formula (III) is 2-3.
4. A process for preparing a copolyester according to any one of claims 1 to 3, characterized in that the process is a process for preparing a copolyester by melt polycondensation of raw materials comprising a compound of formula (I) and/or formula (II), and a dihydroxy compound corresponding to formula (III) with a dicarboxylic acid compound of formula (iv).
5. The method according to claim 4, wherein the melt polycondensation temperature is 300 to 360 ℃, the polycondensation time is 0.5 to 5 hours, and the polycondensation vacuum degree is 100 to 2000 Pa.
6. The process according to claim 4 or 5, wherein the catalyst used in the melt polycondensation is one or more of cesium carbonate, sodium bicarbonate and potassium bicarbonate, and the amount of the catalyst is 10% by weight based on the total weight of the reactants-6～10-4And (4) doubling.
7. The copolyester according to any one of claims 1 to 3 or the copolyester produced by the production method according to any one of claims 4 to 6, wherein the weight average molecular weight Mw of the copolyester is 30000 to 50000 and the refractive index is 1.600 to 1.650.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011121995.9A CN112225885B (en) | 2020-10-20 | 2020-10-20 | Copolyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011121995.9A CN112225885B (en) | 2020-10-20 | 2020-10-20 | Copolyester and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112225885A CN112225885A (en) | 2021-01-15 |
| CN112225885B true CN112225885B (en) | 2022-04-22 |
Family
ID=74119152
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011121995.9A Active CN112225885B (en) | 2020-10-20 | 2020-10-20 | Copolyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225885B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5941328A (en) * | 1982-09-01 | 1984-03-07 | Agency Of Ind Science & Technol | Aromatic polyester |
| DE3171069D1 (en) * | 1980-12-09 | 1985-07-25 | Asahi Chemical Ind | Polynuclear fused aromatic ring type polymer and preparation thereof |
| JP2010275236A (en) * | 2009-05-29 | 2010-12-09 | Kawasaki Kasei Chem Ltd | 1,4-dihydroanthracene-9,10-diether compound, and method for manufacturing the same |
| CN110691765A (en) * | 2017-05-17 | 2020-01-14 | 川崎化成工业株式会社 | High molecular photopolymerization sensitizer |
-
2020
- 2020-10-20 CN CN202011121995.9A patent/CN112225885B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3171069D1 (en) * | 1980-12-09 | 1985-07-25 | Asahi Chemical Ind | Polynuclear fused aromatic ring type polymer and preparation thereof |
| JPS5941328A (en) * | 1982-09-01 | 1984-03-07 | Agency Of Ind Science & Technol | Aromatic polyester |
| JP2010275236A (en) * | 2009-05-29 | 2010-12-09 | Kawasaki Kasei Chem Ltd | 1,4-dihydroanthracene-9,10-diether compound, and method for manufacturing the same |
| CN110691765A (en) * | 2017-05-17 | 2020-01-14 | 川崎化成工业株式会社 | High molecular photopolymerization sensitizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112225885A (en) | 2021-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Biobased amorphous polyesters with high T g: Trade-off between rigid and flexible cyclic diols | |
| TWI503349B (en) | Polycarbonate resin and transparency film containing the same | |
| KR102100099B1 (en) | Resin composition, stretched film , circularly polarizing plate, and image display device | |
| JP2006028441A (en) | Optical film comprising aliphatic polycarbonate | |
| KR101850169B1 (en) | Cyclic olefin ring-opening polymer, hydride thereof, composition of the hydride, and tricyclopentadiene | |
| EP1838770A1 (en) | Processes for making low color poly(ethylene-co-isosorbide) terephthalate polymers | |
| Seto et al. | Synthesis and property of 9, 9′-spirobifluorene-containing aromatic polyesters as optical polymers with high refractive index and low birefringence | |
| CN113072694A (en) | Polycarbonate resin for temperature change resistant optical component and preparation method and application thereof | |
| CN106188513A (en) | A kind of synthetic method of polyetherester block copolymer | |
| CN112250851A (en) | Optical polycarbonate resin and manufacturing method and application thereof | |
| CN113667110B (en) | Optical polycarbonate resin and preparation method thereof | |
| CN112225885B (en) | Copolyester and preparation method thereof | |
| CN107189043B (en) | Weak crystalline polyester of high molecular weight and its preparation method and application | |
| JP2843214B2 (en) | Polyester polymer and molded product thereof | |
| EP2918623B1 (en) | Polyformal resin copolymer and production method | |
| KR20220023967A (en) | Thermoplastic resin, optical film comprising same, diol compound, diester compound | |
| JP2011241277A (en) | Copolycarbonate | |
| CN111440299A (en) | Polycarbonate diol copolyester and preparation method thereof | |
| Hu et al. | Bio‐based aromatic copoly (ether ester) s with enhanced toughness and degradability: Influence of insertion of phenoxy‐ether linkage and eugenol‐derived composition on properties | |
| TW202037632A (en) | Thermoplastic resin and method for producing same, and optical lens comprising said thermoplastic resin | |
| CN109608626B (en) | Process for producing polyetherketoneketones | |
| KR102292023B1 (en) | Polycarbonate resin and method for preparing the same | |
| CN113968963B (en) | Polycarbonate and preparation method and application thereof | |
| CN115873226B (en) | Copolycarbonate and preparation method and application thereof | |
| AU2018225190B2 (en) | Process for preparing poly(alkylene furandicarboxylate) |
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 |