CN110317329A - The preparation method of polyarylate of the one kind based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles - Google Patents
The preparation method of polyarylate of the one kind based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles Download PDFInfo
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- CN110317329A CN110317329A CN201810278563.5A CN201810278563A CN110317329A CN 110317329 A CN110317329 A CN 110317329A CN 201810278563 A CN201810278563 A CN 201810278563A CN 110317329 A CN110317329 A CN 110317329A
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Abstract
The preparation method of polyarylate of the one kind based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles, the present invention relates to a kind of preparation method of polyarylate based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles, it is in order to solve the problems, such as that the existing mechanical property for preparing Thermotropic Liquid Crystalline Copolyesters is undesirable, polyarylate complex manufacturing process.Preparation method: one, by P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles, acetic anhydride and 4- ethylamino pyridine and antioxidant are added to the prepolymer for preparing Thermotropic Liquid Crystalline Copolyesters in polymeric kettle by melt polycondensation；Two, prepolymer is placed under the conditions of nitrogen protection carries out solid state polycondensation in rotary kiln, obtains heavy polymer powder；Three, heavy polymer powder is cooling after being kneaded, and drawing-off prepares nascent polyarylate；Four, nascent polyarylate is heat-treated.The preparation method of Thermotropic Liquid Crystalline Copolyesters of the present invention is easy to operate, and the drawing of finally obtained polyarylate stretches intensity up to 100~160MPa.
Description
Technical field
The present invention relates to a kind of polyarylates based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles
Preparation method.
Background technique
Thermotropic Liquid Crystalline Copolyesters (TLCP) be it is thermoplastic, it can be used existing mechanical technique and is squeezed out or be injected into
Shape makees the materials such as fiber, film, plate, it is follow-on engineering plastics.Now, in world wide not only university, research
It is widely studied in institute, and existing more than 30 company's input researchs exploitation.Thermotropic Liquid Crystalline Copolyesters have excellent resistance to purple
Outside line shielding, impact resistance, surface hardness and creep resistance.It has the incomparable outstanding performance of conventional polymer and
Extremely wide application range makes numerous researchers expand large-scale research to thermotropic liquid crystal polyarylate.
Only have several companies such as the U.S. and Japan to grasp production currently, preparing liquid crystal polyarylate high-performance fiber
Key technology, the country have carried out the TLCP research and development of many years, have also started the exploration of industrialization in recent years.Domestic patent
200410054025.6 report a kind of solid-state preparation method of liquid crystal copolyester, specifically by the performed polymer after melt polymerization into
Ten hours solid-state polymerizations of line number prepare the liquid crystal polyester of high molecular weight.But it is too long that this method is clearly present the production cycle
Problem is not suitable for industrialization large-scale continuous production.United States Patent (USP) 4,169,933 describes a kind of contain from quinhydrones, to benzene two
The method for producing polymer for the repetitive unit that formic acid, 2,6 naphthalene dicarboxylic acid and 4-HBA are transformed.United States Patent (USP) 5,
079,289,5,097,001 and 5,221,730 describe containing from quinhydrones, terephthalic acid (TPA), M-phthalic acid and 4- hydroxyl
The method for producing polymer for the repetitive unit that benzoic acid is transformed.United States Patent (USP) 5,492,946 is related to LCP, United States Patent (USP) 4,
851,497 are related to aromatic polyester.
Summary of the invention
It is undesirable, polyarylate that the purpose of the present invention is to solve the existing mechanical properties for preparing Thermotropic Liquid Crystalline Copolyesters
The problems such as complex manufacturing process, and provide it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester.
The preparation method of Thermotropic Liquid Crystalline Copolyesters of the present invention follows these steps to realize:
It one, is (0.4~3.2): 1 P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxybenzene by polymerized monomer molar ratio
Base) -5- pyridone and imidazoles, acetic anhydride and 4- ethylamino pyridine and glass putty be added in titanium alloy polymeric kettle, 125~
4~9h is kept between 170 DEG C, then heats to 330 DEG C, nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 2h, through titanium alloy
Polymeric kettle discharge crushes, obtains prepolymer after drying；
Two, under the conditions of the prepolymer for obtaining step 1 is placed in nitrogen protection, with 210~240 DEG C in being carried out in rotary kiln
Solid state polycondensation obtains heavy polymer powder；
Three, the heavy polymer powder for obtaining step 2 mixes at 295~325 DEG C by double screw extruder
Refining, again through metering pump and component after exhaust, after ring wind quenching, drawing-off obtains nascent polyarylate after pelletizing；
Four, under the conditions of nitrogen protection, nascent polyarylate is heat-treated, Thermotropic Liquid Crystalline Copolyesters are obtained.
The preparation method of Thermotropic Liquid Crystalline Copolyesters of the present invention is easy to operate, and reaction condition is easily controllable, step 2 preparation
The weight average molecular weight of polymer powder is 8.2 × 103~1.8 × 104, molecular weight height.Preparation process can be in polymeric kettle and double spiral shells
Implement in bar extruder, be convenient for continuous production, tensile strength can reach 50~90MPa, using final after heat treatment
The drawing of obtained Thermotropic Liquid Crystalline Copolyesters stretches intensity up to 100~160MPa.Solves previous Thermotropic Liquid Crystalline Copolyesters preparation step
Rapid cumbersome, condition is not easy to control, unstable quality, the lower disadvantage of product intensity.
Specific embodiment
Specific embodiment 1: the preparation method of present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to implement:
It one, is (0.4~3.2): 1 P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxybenzene by polymerized monomer molar ratio
Base) -5- pyridone and imidazoles, acetic anhydride and 4- ethylamino pyridine and glass putty be added in titanium alloy polymeric kettle, 125~
4~9h is kept between 170 DEG C, then heats to 330 DEG C, nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 2h, through titanium alloy
Polymeric kettle discharge crushes, obtains prepolymer after drying；
Two, under the conditions of the prepolymer for obtaining step 1 is placed in nitrogen protection, with 210~240 DEG C in being carried out in rotary kiln
Solid state polycondensation obtains heavy polymer powder；
Three, the heavy polymer powder for obtaining step 2 mixes at 295~325 DEG C by double screw extruder
Refining, again through metering pump and component after exhaust, after ring wind quenching, drawing-off, pelletizing obtains nascent polyarylate；
Four, under the conditions of nitrogen protection, nascent polyarylate is heat-treated, Thermotropic Liquid Crystalline Copolyesters are obtained.
The inherent viscosity for the prepolymer that present embodiment step 1 obtains is 1.5~3.5dl/g, [is molten with Pentafluorophenol
Agent is made into the solution of 0.1mol/l, with determination of ubbelohde viscometer], the characteristic for the heavy polymer powder that step 2 obtains
For viscosity in 5.5~10.5dl/g, weight average molecular weight is 8.2 × 103~1.8 × 104。
The preparation method of thermotropic liquid crystal high-performance polyarylate described in present embodiment can be squeezed by polymeric kettle and twin-screw
Machine and comprising circular blow wind out, draw roll, the combination of pelleter realize, has made full use of what double screw extruder had to cut
It is big to cut active force, material contacts the advantages that abundant, can also be obvious while the Thermotropic Liquid Crystalline Copolyesters of high molecular weight are made
The shortcomings that shortening the production cycle, and overcoming unstable product quality is industrial large-scale continuous production liquid crystal polyarylate
Provide a simple and easy new method.
Specific embodiment 2: the present embodiment is different from the first embodiment in that P-hydroxybenzoic acid in step 1
It is greater than 99.4% with the purity of 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles.Other steps and parameter and tool
Body embodiment one is identical.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that acetic anhydride in step 1
Mole is hydroxyl in polymerized monomer P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles
1.0~2.5 times of total mole number.Other steps and parameter are the same as one or two specific embodiments.
Specific embodiment 4: 4- second in step 1 unlike one of present embodiment and specific embodiment one to three
- 5- pyridone is simultaneously with 2- (3- carboxyl -4- methoxyphenyl) for polymerized monomer P-hydroxybenzoic acid for the molal quantity of aminopyridine
0.015~0.040 times of imidazoles total mole number.Other steps and parameter are identical as one of specific embodiment one to three.
Existing melt polycondensation reaction catalyst is zinc acetate, manganese acetate, sodium acetate, potassium acetate, cobalt acetate, lithium acetate, titanium
One or more of acid esters, dibutyl tin laurate, dibutyltin oxide, antimony oxide or antimony glycol, conversion ratio compared with
It is low, the polymer of high molecular weight cannot be formed, therefore high performance Thermotropic Liquid Crystalline Copolyesters can not be prepared.And the present invention is made
Catalyst is not belonging to any one of above-mentioned catalyst, improves the conversion ratio of polycondensation reaction.
Specific embodiment 5: step 1 unlike one of present embodiment and specific embodiment one to four then with
The speed of 0.5 DEG C/min is warming up to 330 DEG C, is filled with nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h.Other steps and parameter with
One of specific embodiment one to four is identical.
Specific embodiment 6: step is closed once titanium unlike one of present embodiment and specific embodiment one to five
Golden polymeric kettle diameter be 3mm 10 hole dispensing valves be discharged, crush, 160 DEG C be dried to obtain prepolymer.Other steps and parameter with
One of specific embodiment one to five is identical.
Specific embodiment 7: step 3 drawing-off unlike one of present embodiment and specific embodiment one to six
Speed is 8~45m/min.Other steps and parameter are identical as one of specific embodiment one to six.
Specific embodiment 8: step 4 is unlike one of present embodiment and specific embodiment one to seven with 245
~295 DEG C of temperature carries out heat treatment 70h to nascent polyarylate.Other steps and one of parameter and specific embodiment one to seven
It is identical.
Specific embodiment 9: preheating rank described unlike one of present embodiment and specific embodiment one to eight
The antioxidant that section is added is glass putty.Other steps and parameter are identical as one of specific embodiment one to eight.
Common antioxidant in existing polyester are as follows: antioxidant 1010, antioxidant 1024, resists antioxidant 1076
The combination of one or more of oxidant 618, antioxidant 626, antioxidant 1024, antioxidant 1098, it is common anti-
Oxidant cannot play expected ideal effect in the present invention and polymer color can be made to deepen, and can then make institute using glass putty
The close white of the polymer color obtained.
Embodiment:
100g amine aqueous solution is added in 250ml there-necked flask, is cooled to 0 DEG C, 4- chloropyridine 15g is then added, heats up back
Stream 1 hour after cooling, is added 50g toluene, extracts 2 times, combining extraction liquid, and addition anhydrous magnesium sulfate 10g is dry for 24 hours, filtering,
Revolving, obtains crude product, adds in 50g dimethylbenzene, recrystallizes, obtains nearly colorless plate crystal 4-aminopyridine 8g, spare.
Polyphosphoric acids 100g is added in the there-necked flask of 250ml, is evacuated to 20mmHg hereinafter, being heated to 100 DEG C of heat preservations
3h is down to room temperature, and 15g 3,4- diaminobenzene methanol and 17.7g4- methoxyl group -1,3- M-phthalic acid is added, is warming up to 90
DEG C, phosphorus pentoxide 43g is added, is warming up to 150 DEG C with the speed of 0.5 DEG C/min and is down to room temperature, add in 1L water, filters, institute
Crude product adds in 15% NaOH solution, flow back 2h, with 10% HCL aqueous solution tune pH=3, filtering, products obtained therefrom 50g
The methanol solution (DMF: methanol=9:1) of DMF recrystallizes, and obtaining sterling 2- (3- carboxyl -4- methoxyphenyl), -5- pyridone is simultaneously
Imidazoles 8g, it is spare.
Embodiment one: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 57g P-hydroxybenzoic acid and 265g 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles,
253g acetic anhydride and 2.3g 4- ethylamino pyridine and 0.3g glass putty are added in titanium alloy polymeric kettle, in 125 DEG C of holding 4h,
Then 330 DEG C are warming up to the speed of 0.5 DEG C/min, are filled with 0.2MPa nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h, passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 160 DEG C of dry 2h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 210 DEG C in rotation
Solid state polycondensation 50h is carried out in kiln, obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 295 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of ring wind quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 245 DEG C of temperature
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 1.5dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 5.5dl/g, weight average molecular weight 8200.The tensile strength for the nascent polyarylate that step 3 obtains
Drawing for the obtained Thermotropic Liquid Crystalline Copolyesters of 50MPa, step 4 stretches intensity up to 100MPa.
Embodiment two: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 114g P-hydroxybenzoic acid and 265g 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles,
339g acetic anhydride and 3.5g 4- ethylamino pyridine and 0.5g glass putty are added in titanium alloy polymeric kettle, in 125 DEG C of holding 6h,
Then 330 DEG C are warming up to the speed of 0.5 DEG C/min, are filled with 0.2MPa nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h, passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 160 DEG C of dry 2h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h condition, with 210 DEG C in rotary kiln
Solid state polycondensation 50h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 295 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of ring wind quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 245 DEG C of temperature
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 2.1dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 6.3dl/g, weight average molecular weight 9800.The tensile strength for the nascent polyarylate that step 3 obtains
Drawing for the obtained Thermotropic Liquid Crystalline Copolyesters of 65MPa, step 4 stretches intensity up to 116MPa.
Embodiment three: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 228g P-hydroxybenzoic acid and 265g 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles,
505g acetic anhydride and 4.7g 4- ethylamino pyridine and 0.8g glass putty are added in titanium alloy polymeric kettle, in 125 DEG C of holding 8h,
Then 330 DEG C are warming up to the speed of 0.5 DEG C/min, are filled with 0.2MPa nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h, passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 160 DEG C of dry 2h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h condition, with 210 DEG C in rotary kiln
Solid state polycondensation 50h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 295 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of ring wind quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 245 DEG C of temperature
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 3.0dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 7.8dl/g, weight average molecular weight 15200.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 79MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 135MPa.
Example IV: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 343g P-hydroxybenzoic acid and 265g 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles,
675g acetic anhydride and 6.2g 4- ethylamino pyridine and 1.1g glass putty are added in titanium alloy polymeric kettle, in 125 DEG C of holding 9h,
Then 330 DEG C are warming up to the speed of 0.5 DEG C/min, are filled with 0.2MPa nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h, passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 160 DEG C of dry 2h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h condition, with 210 DEG C in rotary kiln
Solid state polycondensation 50h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 295 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of ring wind quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 245 DEG C of temperature
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 3.5dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 10.5dl/g, weight average molecular weight 18000.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 90MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 160MPa.
Claims (9)
1. the preparation method of polyarylate of the one kind based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles, special
Sign, which is that, to be followed these steps to realize:
It one, is (0.4~3.2): 1 P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxyphenyl)-by polymerized monomer molar ratio
5- pyridone and imidazoles, acetic anhydride and 4- ethylamino pyridine and antioxidant are added in titanium alloy polymeric kettle, 125~
4~9h is kept between 170 DEG C, then heats to 330 DEG C, nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 2h, through titanium alloy
Polymeric kettle discharge crushes, obtains prepolymer after drying；
Two, under the conditions of the prepolymer for obtaining step 1 is placed in nitrogen protection, with 210~240 DEG C in carrying out solid phase in rotary kiln
Polycondensation reaction obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 295~325 DEG C by double screw extruder, is arranged
Again through metering pump and component after gas, after ring wind quenching, drawing-off, pelletizing obtains nascent polyarylate；
Four, under the conditions of nitrogen protection, nascent polyarylate is heat-treated, Thermotropic Liquid Crystalline Copolyesters are obtained.
2. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that P-hydroxybenzoic acid and 2- (3- carboxyl -4- methoxyphenyl) -5- hydroxyl in step 1
The purity of pyridine-imidazole is greater than 99.4%.
3. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that the mole of acetic anhydride is polymerized monomer P-hydroxybenzoic acid and 2- (3- in step 1
Carboxyl -4- methoxyphenyl) 1.0~2.5 times of total hydroxyl moles in -5- pyridone and imidazoles.
4. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that in step 1 the molal quantity of 4- ethylamino pyridine be polymerized monomer P-hydroxybenzoic acid with
0.015~0.040 times of 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles total mole number.
5. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that then step 1 is warming up to 330 DEG C with the speed of 0.5 DEG C/min, keep the temperature after 2h to titanium
Nitrogen is filled in alloy polymeric kettle.
6. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that step is discharged once the 10 hole dispensing valves that titanium alloy polymeric kettle diameter is 3mm, powder
It is broken, be dried to obtain prepolymer at 160 DEG C.
7. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that the speed of step 3 drawing-off is 8~45m/min.
8. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that step 4 carries out heat treatment 70h to nascent polyarylate with 245~295 DEG C of temperature.
9. it is according to claim 1 it is a kind of based on 2- (3- carboxyl -4- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that antioxidant described in step 1 is glass putty.
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| 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 |
| CN106435807A (en) * | 2016-10-14 | 2017-02-22 | 黑龙江大学 | Method for preparing wholly-aromatic polyester fibers based on 4,4'-diaminodiphenyl ether |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100292356A1 (en) * | 2009-05-15 | 2010-11-18 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Preparation method of polybenzimidazole |
| 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 |
| CN106435807A (en) * | 2016-10-14 | 2017-02-22 | 黑龙江大学 | Method for preparing wholly-aromatic polyester fibers based on 4,4'-diaminodiphenyl ether |
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