CN110317328B - Preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole - Google Patents
Preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole Download PDFInfo
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Abstract
The invention discloses a preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, and relates to a preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, aiming at solving the problems of high preparation difficulty and non-ideal mechanical property of liquid crystal polyarylate. The preparation method comprises the following steps: firstly, adding p-hydroxybenzoic acid, 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, acetic anhydride, 3-propylaminopyridine and an antioxidant into a polymerization kettle to prepare a prepolymer of thermotropic liquid crystal polyarylate through melt polycondensation; secondly, the prepolymer is placed in a rotary kiln to carry out solid-phase polycondensation reaction under the condition of nitrogen protection, so as to obtain high molecular weight polymer powder; thirdly, cooling and drafting the high molecular weight polymer powder after mixing to prepare nascent polyarylate; fourthly, carrying out heat treatment on the nascent polyarylate. The preparation method of the thermotropic liquid crystal polyarylate is simple to operate, and the stretching strength of the finally obtained polyarylate can reach 105-165 MPa.
Description
Technical Field
The invention relates to a preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole.
Background
The polyarylate is a non-crystalline polymer compound, the regularity of molecular chains of the polyarylate is high, the polyarylate molecular chains are always in a liquid crystal phase state in the process of melt processing, and the polyarylate molecular chains are easily regularly arranged under the action of external force to form a multilayer oriented structure. It can be formed by thermoplastic method, but has poor melt flowability. The polyarylate is acid-resistant and oil-resistant, but the performances of alkali resistance, stress cracking resistance, aromatic hydrocarbon resistance and ketone resistance are not ideal. In addition, it has excellent ultraviolet screening resistance, impact resistance, surface hardness and creep resistance, and shows high tensile strength in a wide temperature range.
TLCP has attracted considerable attention from a number of researchers because of its incomparably excellent properties and extremely wide range of applications compared to conventional polymers. However, in the industrial practice of TLCP, many technical problems are encountered, such as the polymerization of thermotropic liquid crystal polymer is not easy to control, the processing temperature window of the synthesized TLCP material is narrow, and the solution of these problems requires a lot of basic research for application. Domestic patent 200410054025.6 reports a solid-state preparation method of liquid crystal copolyester, specifically, a prepolymer after melt polymerization is subjected to solid-state polymerization for tens of hours to prepare high molecular weight liquid crystal polyester. But the method obviously has the problem of overlong production period and is not suitable for industrial large-scale continuous production. U.S. Pat. No. 4,169,933 describes a process for preparing polymers containing repeat units derived from hydroquinone, terephthalic acid, 2, 6-naphthalenedicarboxylic acid and 4-hydroxybenzoic acid. U.S. Pat. Nos. 5,079,289, 5,097,001 and 5,221,730 describe the preparation of polymers containing repeat units derived from the conversion of hydroquinone, terephthalic acid, isophthalic acid and 4-hydroxybenzoic acid. U.S. Pat. No. 5,492,946 relates to LCP and U.S. Pat. No. 4,851,497 relates to aromatic polyesters.
Disclosure of Invention
The invention aims to solve the problems of high preparation difficulty and unsatisfactory mechanical properties of liquid crystal polyarylate and provides a preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole.
The preparation method of the thermotropic liquid crystal polyarylate is realized by the following steps:
adding p-hydroxybenzoic acid, 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, acetic anhydride, 3-propylaminopyridine and tin chloride with the molar ratio of the polymerization monomers of (0.4-3.0) 1 into a titanium alloy polymerization kettle, keeping the temperature for 3-7 h at 120-150 ℃, then heating to 320 ℃, keeping the temperature for 3h, filling nitrogen into the titanium alloy polymerization kettle, discharging the nitrogen from the titanium alloy polymerization kettle, crushing and drying to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step under the protection of nitrogen, and carrying out solid-phase polycondensation reaction in a rotary kiln at 190-215 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305-330 ℃ through a double-screw extruder, exhausting, passing through a metering pump and a component, cooling by circular blowing, drafting, and pelletizing to obtain nascent polyarylate;
and fourthly, under the protection of nitrogen, carrying out heat treatment on the nascent polyarylate to obtain the thermotropic liquid crystal polyarylate.
The preparation method of the thermotropic liquid crystal polyarylate has simple operation and easily controlled reaction condition, and the weight average molecular weight of the polymer powder prepared in the step two is 1.0 multiplied by 104～1.9×104And the molecular weight is high. The preparation process can be implemented in a polymerization kettle and a double-screw extruder, continuous production is facilitated, the tensile strength can reach 45-95 MPa, and the tensile strength of the thermotropic liquid crystal polyarylate finally obtained after heat treatment can reach 105-165 MPa. The defects of complex preparation process, difficult control of conditions, unstable quality and lower mechanical property of finished products of the prior thermotropic liquid crystal polyarylate are overcome.
Detailed Description
The first embodiment is as follows: the preparation method of the thermotropic liquid crystalline polyarylate of the present embodiment is carried out by the following steps:
adding p-hydroxybenzoic acid, 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, acetic anhydride, 3-propylaminopyridine and tin chloride with the molar ratio of the polymerization monomers of (0.4-3.0) 1 into a titanium alloy polymerization kettle, keeping the temperature for 3-7 h at 120-150 ℃, then heating to 320 ℃, keeping the temperature for 3h, filling nitrogen into the titanium alloy polymerization kettle, discharging the nitrogen from the titanium alloy polymerization kettle, crushing and drying to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step under the protection of nitrogen, and carrying out solid-phase polycondensation reaction in a rotary kiln at 190-215 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305-330 ℃ through a double-screw extruder, exhausting, passing through a metering pump and a component, cooling by circular blowing, drafting, and pelletizing to obtain nascent polyarylate;
and fourthly, under the protection of nitrogen, carrying out heat treatment on the nascent polyarylate to obtain the thermotropic liquid crystal polyarylate.
The prepolymer obtained in the first step of the present embodiment has an intrinsic viscosity of 0.9 to 3.0dl/g, and [ pentafluorophenol as a solvent, a 0.1mol/l solution is prepared, and the solution is measured with an Ubbelohde viscometer ], and the high molecular weight polymer powder obtained in the second step has an intrinsic viscosity of 4.5 to 9.0dl/g, and a weight average molecular weight of 1.0 × 104～1.9×104。
The preparation method of the thermotropic liquid crystal high-performance polyarylate can be realized by combining a polymerization kettle with a double-screw extruder, a drafting roller and a granulator, fully utilizes the advantages of the double-screw extruder such as large shearing acting force and sufficient material contact, can obviously shorten the production period while preparing the thermotropic liquid crystal polyarylate with high molecular weight, overcomes the defect of unstable product quality, and provides a simple and feasible new method for industrially and continuously producing the liquid crystal polyarylate in a large scale.
The second embodiment is as follows: this embodiment differs from the first embodiment in that the purity of the p-hydroxybenzoic acid and 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole in step one is greater than 99.5%. Other steps and parameters are the same as those in the first embodiment.
The third concrete implementation mode: the embodiment is different from the first or second embodiment in that the molar amount of acetic anhydride in the first step is 1.2 to 3.2 times of the total molar amount of hydroxyl groups in the polymerized monomers of p-hydroxybenzoic acid and 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the embodiment is different from the first to the third embodiments in that the mole number of the 3-propylaminopyridine in the first step is 0.011 to 0.036 times of the total mole number of the polymerized monomers of p-hydroxybenzoic acid and 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole. Other steps and parameters are the same as those in one of the first to third embodiments.
The existing melt polycondensation reaction catalyst is one or more of zinc acetate, manganese acetate, sodium acetate, potassium acetate, cobalt acetate, lithium acetate, titanate, dibutyltin laurate, dibutyltin oxide, antimony trioxide or ethylene glycol antimony, the conversion rate is low, and a high-molecular-weight polymer cannot be formed, so that the high-performance thermotropic liquid crystal polyarylate cannot be prepared. The catalyst used in the invention does not belong to any of the catalysts, so that the conversion rate of the polycondensation reaction is improved.
The fifth concrete implementation mode: the difference between the first embodiment and the fourth embodiment is that the temperature is raised to 320 ℃ at the speed of 0.5 ℃/min, and nitrogen is filled into the titanium alloy polymerization kettle after the temperature is kept for 3 hours. Other steps and parameters are the same as in one of the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is that the prepolymer is obtained by discharging through a 10-hole discharge valve with a diameter of 3mm in a titanium alloy polymerizer, pulverizing, and drying at 145 ℃. Other steps and parameters are the same as those in one of the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and the first to the sixth embodiment is that the speed of the third drawing step is 5 to 30 m/min. Other steps and parameters are the same as those in one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from the first to seventh embodiments in that the heat treatment of the nascent polyarylate at a temperature of 260 to 285 ℃ for 65 hours is performed in the fourth step. Other steps and parameters are the same as those in one of the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the antioxidant added in the preheating stage is tin chloride. Other steps and parameters are the same as those in one to eight of the embodiments.
Commonly used antioxidants in current polyesters are: the color of the polymer can be darkened by one or a combination of several of the following antioxidants 1010, 1076, 1024, 618, 626, 1024 and 1098, which are not expected to be ideal in the present invention, and which can be close to white by tin chloride.
Example (b):
adding 100g of amine aqueous solution into a 250ml three-necked bottle, cooling to 0 ℃, then adding 17.8g of 4-ethyl chloropyridine, heating and refluxing for 1 hour, cooling, adding 50g of toluene, extracting for 2 times, combining extract liquor, adding 10g of anhydrous magnesium sulfate, drying for 24 hours, filtering, carrying out rotary evaporation to obtain a crude product, adding into 50g of xylene, and recrystallizing to obtain 9g of near-colorless flaky crystal 4-propylaminopyridine for later use.
Adding 100g of polyphosphoric acid into a 250ml three-neck flask, vacuumizing to below 20mmHg, heating to 100 ℃, keeping the temperature for 3h, cooling to room temperature, adding 12g of 5-hydroxy-2, 3-diaminopyridine and 17.7g of 3-methoxy-terephthalic acid, heating to 90 ℃, adding 43g of phosphorus pentoxide, heating to 150 ℃ at the speed of 0.5 ℃/min, cooling to room temperature, adding into 1l of water, filtering, adding the obtained crude product into a 15% NaOH solution, refluxing for 2h, adjusting the pH to 3 with a 10% HCl aqueous solution, filtering, recrystallizing the obtained product with a 50g of DMF methanol solution (DMF: methanol: 9:1), and obtaining 10g of pure 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole for later use.
The first embodiment is as follows: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
adding 53g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 315g of acetic anhydride, 2.2g of 3-propylaminopyridine and 0.2g of tin chloride into a titanium alloy polymerization kettle, keeping the temperature at 120 ℃ for 3 hours, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3 hours, then filling 0.2MPa of nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, passing through a 20-mesh sieve, and drying at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Under the protection condition of/h, carrying out solid-phase polycondensation reaction in a rotary kiln for 48h at 190 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
The intrinsic viscosity of the prepolymer prepared in step one of this example was 0.9dl/g, and the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 4.5dl/g, and the weight average molecular weight was 10800. The tensile strength of the nascent polyarylate obtained in the third step is 45MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 105 MPa.
Example two: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
adding 117g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 378g of acetic anhydride, 3.1g of 3-propylaminopyridine and 0.4g of tin chloride into a titanium alloy polymerization kettle, keeping the temperature at 120 ℃ for 5 hours, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3 hours, then filling 0.2MPa of nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, passing through a 20-mesh sieve, and drying at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 190 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
The intrinsic viscosity of the prepolymer prepared in step one of this example was 1.4dl/g, and the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 5.2dl/g, and the weight average molecular weight was 13500. The tensile strength of the nascent polyarylate obtained in the third step is 64MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 130 MPa.
Example three: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
firstly, adding 225g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 617g of acetic anhydride, 4.5g of 3-propylaminopyridine and 0.9g of tin chloride into a titanium alloy polymerization kettle, keeping the temperature at 130 ℃ for 6h, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3h, then filling 0.2MPa nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, passing through a 20-mesh sieve, and drying at 145 ℃ for 2.5h to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 190 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
The intrinsic viscosity of the prepolymer prepared in step one of this example was 2.8dl/g, the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 7.8dl/g, and the weight average molecular weight was 15600. The tensile strength of the nascent polyarylate obtained in the third step is 80MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 155 MPa.
Example four: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
firstly, 288g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 757g of acetic anhydride, 5.4g of 3-propylaminopyridine and 1.0g of tin chloride are added into a titanium alloy polymerization kettle, the mixture is kept at 145 ℃ for 7 hours, then the temperature is increased to 320 ℃ at the speed of 0.5 ℃/min, 0.2MPa of nitrogen is filled into the titanium alloy polymerization kettle after the mixture is kept at the temperature for 3 hours, the mixture is discharged through a 10-hole discharge valve with the diameter of 3mm, crushed, filtered through a 20-mesh sieve, and dried at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 210 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
The intrinsic viscosity of the prepolymer prepared in step one of this example was 3.0dl/g, the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 9.0dl/g, and the weight average molecular weight was 19000. The tensile strength of the nascent polyarylate obtained in the third step is 95MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 165 MPa.
Claims (4)
1. A process for the preparation of polyarylate based on 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole characterized in that it is carried out by the following steps:
adding 53g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 315g of acetic anhydride, 2.2g of 3-propylaminopyridine and 0.2g of tin chloride into a titanium alloy polymerization kettle, keeping the temperature at 120 ℃ for 3 hours, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3 hours, then filling 0.2MPa of nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, passing through a 20-mesh sieve, and drying at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Under the protection condition of/h, carrying out solid-phase polycondensation reaction in a rotary kiln for 48h at 190 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
2. A process for the preparation of polyarylate based on 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole characterized in that it is carried out by the following steps:
adding 117g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 378g of acetic anhydride, 3.1g of 3-propylaminopyridine and 0.4g of stannic chloride into a titanium alloy polymerization kettle, keeping the temperature at 120 ℃ for 5 hours, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3 hours, then filling 0.2MPa of nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, sieving through a 20-mesh sieve, and drying at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 190 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
3. A process for the preparation of polyarylate based on 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole characterized in that it is carried out by the following steps:
firstly, adding 225g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 617g of acetic anhydride, 4.5g of 3-propylaminopyridine and 0.9g of stannic chloride into a titanium alloy polymerization kettle, keeping the temperature at 130 ℃ for 6h, then heating to 320 ℃ at the speed of 0.5 ℃/min, keeping the temperature for 3h, then filling 0.2MPa nitrogen into the titanium alloy polymerization kettle, discharging through a 10-hole discharging valve with the diameter of 3mm, crushing, sieving through a 20-mesh sieve, and drying at 145 ℃ for 2.5h to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 190 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
4. A process for the preparation of polyarylate based on 2- (4-carboxy-3-methoxyphenyl) -5-hydroxypyridoimidazole characterized in that it is carried out by the following steps:
firstly, 288g of p-hydroxybenzoic acid, 248g of 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole, 757g of acetic anhydride, 5.4g of 3-propylaminopyridine and 1.0g of tin chloride are added into a titanium alloy polymerization kettle, the mixture is kept at 145 ℃ for 7 hours, then the temperature is increased to 320 ℃ at the speed of 0.5 ℃/min, 0.2MPa of nitrogen is filled into the titanium alloy polymerization kettle after the mixture is kept at the temperature for 3 hours, the mixture is discharged through a 10-hole discharge valve with the diameter of 3mm, crushed, sieved by a 20-mesh sieve and dried at 145 ℃ for 2.5 hours to obtain a prepolymer;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Performing solid phase polycondensation reaction in a rotary kiln for 48 hours at 210 ℃ under the condition of/h to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and cutting into granules to obtain primary polyarylester;
fourthly, the nitrogen flow is 0.3m3And (2) carrying out heat treatment on the nascent polyarylate at the temperature of 260 ℃ for 65 hours under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
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| US6541535B1 (en) * | 1998-08-07 | 2003-04-01 | Basf Coatings Ag | High powered radiation and/or thermal hardening coating powder with a functionalized based structure |
| CN102186643A (en) * | 2008-08-21 | 2011-09-14 | 因诺瓦动力学股份有限公司 | Enhanced surfaces, coatings, and related methods |
| CN104389045A (en) * | 2014-11-04 | 2015-03-04 | 黑龙江聚翔科技开发有限公司 | Preparation method of thermotropic liquid crystal polyarylester fiber |
| JP2015196802A (en) * | 2014-04-02 | 2015-11-09 | 株式会社ダイセル | Thermosetting aromatic ester, composition thereof, cured product thereof and method for producing the cured product |
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| US6541535B1 (en) * | 1998-08-07 | 2003-04-01 | Basf Coatings Ag | High powered radiation and/or thermal hardening coating powder with a functionalized based structure |
| CN102186643A (en) * | 2008-08-21 | 2011-09-14 | 因诺瓦动力学股份有限公司 | Enhanced surfaces, coatings, and related methods |
| JP2015196802A (en) * | 2014-04-02 | 2015-11-09 | 株式会社ダイセル | Thermosetting aromatic ester, composition thereof, cured product thereof and method for producing the cured product |
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