CN110317324B - Preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole - Google Patents
Preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole Download PDFInfo
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Abstract
The invention discloses a preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, and relates to a preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 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-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, acetic anhydride, 3-aminopyridine and an antioxidant into a titanium alloy 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 final stretching strength of the obtained polymer can reach 80-150 MPa.
Description
Technical Field
The invention relates to a preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole.
Background
TLCP has incomparably excellent properties and an extremely wide range of applications to conventional polymers, and has attracted extensive attention from many researchers. TLCP is a high-performance engineering plastic which is industrialized only in the middle of the 80 s. As the molecular chain of the TLCP is a unique structure of a rod-shaped rigid chain or a semi-rigid chain, the macromolecules of the rigid chain have longer relaxation time, the rigid macromolecules can be fully and highly oriented and arranged along the flow direction in the melt processing process, and the rigid reinforcing phase is maintained after cooling and solidification, so that the TLCP has the self-reinforcing characteristic, presents high strength and high modulus, and has higher mechanical properties than common engineering plastics. Therefore, LCP is called super engineering plastics abroad. However, in the industrial practice of TLCP, many technical problems are encountered, such as the difficulty in controlling the thermotropic liquid crystal polymer polymerization reaction, the narrow processing temperature window of the synthesized TLCP material, etc., and the solution of these problems requires a lot of basic research for application.
At present, only a few companies such as the united states and japan have mastered key production technologies for preparing liquid crystalline polyarylate high performance fibers, TLCP research and development have been carried out for many years in China, and industrialization research has been started in recent years. 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, large difference between the tensile strength and a theoretical value and the like of liquid crystal polyarylate and provide a preparation method of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole.
The preparation method of the thermotropic liquid crystal polyarylate is realized by the following steps:
adding p-hydroxybenzoic acid, 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, acetic anhydride, 3-aminopyridine and tin powder with the molar ratio of the polymerization monomers of (0.6-2.6): 1 into a titanium alloy polymerization kettle, keeping the temperature for 2-6 h at 140-165 ℃, then heating to 330 ℃, keeping the temperature for 2h, then filling nitrogen into the titanium alloy polymerization kettle, discharging the nitrogen through 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 190-240 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305-335 ℃ through a double-screw extruder, exhausting, passing through a metering pump and a component, cooling by circular air 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 the advantages of simple operation, easily controlled reaction conditions and stepsThe weight-average molecular weight of the polymer powder prepared was 2.5X 104～8.0×104And the molecular weight is high. The preparation process can be implemented in a polymerization kettle and a single-screw extruder, continuous production is facilitated, the tensile strength can reach 40-80 MPa, and the tensile strength of the thermotropic liquid crystal polyarylate finally obtained after heat treatment can reach 90-150 MPa. The defects that the preparation process conditions of the prior thermotropic liquid crystal polyarylate are not easy to control, the quality is unstable and the tensile strength of the finished product is low 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-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, acetic anhydride, 3-aminopyridine and tin powder with the molar ratio of the polymerization monomers of (0.6-2.6): 1 into a titanium alloy polymerization kettle, keeping the temperature for 2-6 h at 140-165 ℃, then heating to 330 ℃, keeping the temperature for 2h, then filling nitrogen into the titanium alloy polymerization kettle, discharging the nitrogen through 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 190-240 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 305-335 ℃ through a double-screw extruder, exhausting, passing through a metering pump and a component, cooling by circular air 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 0.6 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 2.5 × 104～8.0×104。
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-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole in step one is greater than 99.8%. 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 1.7 to 2.9 times of the total molar amount of the hydroxyl groups in the polymerized monomers of p-hydroxybenzoic acid and 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole. Other steps and parameters are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between the present embodiment and one of the first to third embodiments is that the mole number of the 3-aminopyridine in the first step is 0.020 to 0.040 times the total mole number of the polymerized monomers of p-hydroxybenzoic acid and 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole. 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 330 ℃ at the speed of 1.5 ℃/min, and nitrogen is filled into the titanium alloy polymerization kettle after the temperature is kept for 2 h. 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 a prepolymer is obtained by discharging through a 10-hole discharge valve having a diameter of 3mm in a titanium alloy polymerizer, pulverizing, and drying at 160 ℃. 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 6 to 45 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 difference between the fourth embodiment and the first to seventh embodiments is that the heat treatment is performed on the nascent polyarylate at 235 to 275 ℃ for 70 hours in the fourth embodiment. 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 powder. 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 stannous chloride.
Example (b):
adding 100g of 40% diethylamine aqueous solution into a 250ml three-necked bottle, cooling to 0 ℃, then adding 16.4g of 4-methylchloropyridine, 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 7g of near-colorless flaky crystal 4-methylaminopyridine 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 15.2g of 5-carboxyl-2, 3-diaminopyridine and 16.8g of 3-methoxy-4-hydroxybenzoic 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: 8:2) to obtain 13.8g of pure 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole 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 104g of p-hydroxybenzoic acid, 381g of 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 465g of acetic anhydride, 4.2g of 3-aminopyridine and 0.45g of tin powder into a titanium alloy polymerization kettle, keeping the temperature at 155 ℃ for 4 hours, then heating to 330 ℃ at the speed of 1.5 ℃/min, keeping the temperature for 2 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 160 ℃ for 3 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, carrying out solid-phase polycondensation reaction in a rotary kiln for 48 hours at 200 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 310 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and pelletizing 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 70h 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 31800. The tensile strength of the nascent polyarylate obtained in the third step is 41MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 90 MPa.
Example two: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
firstly, adding 207g of p-hydroxybenzoic acid, 381g of 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 615g of acetic anhydride, 7.1g of 3-aminopyridine and 0.6g of tin powder into a titanium alloy polymerization kettle, keeping the temperature at 160 ℃ for 4 hours, then heating to 330 ℃ at the speed of 1.5 ℃/min, keeping the temperature for 2 hours, 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 by a 20-mesh sieve, and drying at 160 ℃ for 3 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, carrying out solid-phase polycondensation reaction in a rotary kiln for 48 hours at 200 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 310 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and pelletizing 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 70h 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 2.0dl/g, the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 5.7dl/g, and the weight average molecular weight was 44200. The tensile strength of the nascent polyarylate obtained in the third step is 53MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 112 MPa.
Example three: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
adding 414g of p-hydroxybenzoic acid, 635g of 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 918g of acetic anhydride, 14.0g of 3-aminopyridine and 1.2g of tin powder into a titanium alloy polymerization kettle, keeping the temperature at 165 ℃ for 5 hours, then heating to 330 ℃ at the speed of 1.5 ℃/min, keeping the temperature for 2 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 160 ℃ for 3 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, carrying out solid-phase polycondensation reaction in a rotary kiln for 48 hours at 200 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 310 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and pelletizing 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 70h 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 3.3dl/g, the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 7.6dl/g, and the weight average molecular weight was 51100. The tensile strength of the nascent polyarylate obtained in the third step is 69MPa, and the tensile strength of the thermotropic liquid crystal polyarylate obtained in the fourth step can reach 135 MPa.
Example four: the preparation method of the thermotropic liquid crystalline polyarylate of the present example was carried out by the following steps:
firstly, 443g of p-hydroxybenzoic acid, 381g of 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 1230g of acetic anhydride, 11.4g of 3-aminopyridine and 1.5g of tin powder are added into a titanium alloy polymerization kettle, the temperature is kept for 6 hours at 165 ℃, then the temperature is raised to 330 ℃ at the speed of 1.5 ℃/min, 0.2MPa of nitrogen is filled into the titanium alloy polymerization kettle after the temperature is kept for 2 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 for 3 hours at 160 ℃ 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, carrying out solid-phase polycondensation reaction in a rotary kiln for 48 hours at 200 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 310 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and pelletizing 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 70h 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, and the intrinsic viscosity of the high molecular weight polymer powder prepared in step two was 8.9dl/g, and the weight average molecular weight was 79000. 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 150 MPa.
Claims (1)
1. A process for the preparation of polyarylate based on 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, characterized in that it is carried out by the following steps:
firstly, 443g of p-hydroxybenzoic acid, 381g of 2- (4-hydroxy-3-methoxyphenyl) -5-carboxypyridoimidazole, 1230g of acetic anhydride, 11.4g of 3-aminopyridine and 1.5g of tin powder are added into a titanium alloy polymerization kettle, the mixture is kept at 165 ℃ for 6 hours, then the temperature is raised to 330 ℃ at the speed of 1.5 ℃/min, 0.2MPa of nitrogen is filled into the titanium alloy polymerization kettle after the temperature is kept for 2 hours, the mixture is discharged through a 10-hole discharge valve with the diameter of 3mm, crushed and sieved by 20 meshes, and a prepolymer is obtained after the mixture is dried at 160 ℃ for 3 hours;
secondly, placing the prepolymer obtained in the first step in nitrogen with the flow rate of 0.3m3Under the protection condition, carrying out solid-phase polycondensation reaction in a rotary kiln for 48 hours at 200 ℃ to obtain high molecular weight polymer powder;
thirdly, mixing the high molecular weight polymer powder obtained in the second step at 310 ℃ through a double-screw extruder, exhausting, then passing through a metering pump and a component, blowing and cooling at 25 ℃, and pelletizing 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 70h under the condition of/h to obtain the thermotropic liquid crystal polyarylate.
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