CN110317330A - The preparation method of polyarylate of the one kind based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles - Google Patents
The preparation method of polyarylate of the one kind based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles Download PDFInfo
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Abstract
The preparation method of polyarylate of the one kind based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles, the present invention relates to a kind of preparation methods of polyarylate based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles, it is in order to which the preparation process for solving the problems, such as liquid crystal polyarylate is complicated, intensity is low.Preparation method: one, P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles, acetic anhydride and 2-aminopyridine and antioxidant are added to the prepolymer for preparing Thermotropic Liquid Crystalline Copolyesters in titanium alloy 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 polymer stretches intensity up to 105~150MPa.
Description
Technical field
The present invention relates to a kind of systems of polyarylate based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles
Preparation Method.
Background technique
TLCP causes numerous grind because it is with the incomparable outstanding performance of conventional polymer and extremely wide application range
The extensive concern for the person of studying carefully.TLCP is referred to as liquid crystal polymer at home, is a kind of novel high molecular material, adds in certain
The form that generally will become liquid crystal under Warm status, so therefore gaining the name.TLCP plastic material has high intensity, high rigidity, resistance to
The very excellent performance such as high temperature, electrical insulating property is used for the fields such as electronics, electrical, optical fiber, automobile and aerospace.Since
The 1970s Jackson report first thermotropic liquid crystalline polyester after, people expand thermotropic liquid crystal polyarylate
Large-scale research.The preparation method of Thermotropic Liquid Crystalline Copolyesters is roughly divided into two classes, and one kind is chloride method, i.e., by binary acyl chlorides and
Dihydric phenol and corresponding catalyst, which are added in organic solvent, to carry out reaction and prepares thermotropic liquid crystal polyarylate.Second class is melting
Binary acid or dihydric phenol are first reacted with the unary alcohol of small molecule or acid compounds and generate ester, then urged by ester condensation methods
Carried out at high temperature with corresponding dihydric phenol or binary acid again under the conditions of agent is existing melt polycondensation reaction prepare it is thermotropic
Liquid crystal polyarylate.But many technical problems are encountered in the industrialization of TLCP practice, as thermotropic liquid crystalline polymer polymerization is anti-
It should be difficult to control, TLCP materials processing temperature window narrows of synthesis etc., the solution of these problems needs to carry out largely to apply base
Plinth research.
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
Complicated, tensile strength that the purpose of the present invention is to solve the preparation processes of liquid crystal polyarylate differed with theoretical value compared with
The problems such as big, and a kind of preparation side of polyarylate based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles is provided
Method.
The preparation method of Thermotropic Liquid Crystalline Copolyesters of the present invention follows these steps to realize:
It one, is (0.3~2.8): 1 P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl benzene by polymerized monomer molar ratio
Base) -6- carboxyl pyridine and imidazoles, acetic anhydride and 2-aminopyridine and stannic chloride be added in titanium alloy polymeric kettle, 145~
2~5h is kept between 160 DEG C, then heats to 325 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 180~230 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 300~330 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 2.5 × 104~7.0 × 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 65~95MPa, using final after heat treatment
The drawing of obtained Thermotropic Liquid Crystalline Copolyesters stretches intensity up to 105~150MPa.Solves previous Thermotropic Liquid Crystalline Copolyesters preparation work
Skill is complicated, unstable quality, the lower disadvantage of finished product tensile strength.
Specific embodiment
Specific embodiment 1: the preparation method of present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to implement:
It one, is (0.3~2.8): 1 P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl benzene by polymerized monomer molar ratio
Base) -6- carboxyl pyridine and imidazoles, acetic anhydride and 2-aminopyridine and stannic chloride be added in titanium alloy polymeric kettle, 145~
2~5h is kept between 160 DEG C, then heats to 325 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 180~230 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 300~330 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 0.5~3.2dl/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 4.3~9.2dl/g, weight average molecular weight is 2.5 × 104~7.0 × 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 out, draw roll, the combination of pelleter realize that the shear force for having made full use of double screw extruder to have is big, object
The advantages that material contact is abundant can also be obviously shortened the production cycle while Thermotropic Liquid Crystalline Copolyesters of high molecular weight are made,
And the shortcomings that overcoming unstable product quality provides one simply for industrial large-scale continuous production liquid crystal polyarylate
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 99.6% with the purity of 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles.Other steps and parameter and specific
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 that polymerized monomer P-hydroxybenzoic acid and hydroxyl in 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles are total
1.6~2.5 times of molal quantity.Other steps and parameter are the same as one or two specific embodiments.
Specific embodiment 4: 2- ammonia in step 1 unlike one of present embodiment and specific embodiment one to three
The molal quantity of yl pyridines is polymerized monomer P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles
0.015~0.035 times of 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 1.0 DEG C/min is warming up to 325 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, 155 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 8~42m/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
~275 DEG C of temperature carries out heat treatment 65h 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 stannic chloride.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 then can using stannous chloride
Make resulting polymer color close to white.
Embodiment:
100g amine aqueous solution is added in 250ml there-necked flask, is cooled to 0 DEG C, 4- chloropyridine 12g is then added, heats up back
Stream 1 hour after cooling, is added 40g toluene, extracts 2 times, combining extraction liquid, and addition anhydrous magnesium sulfate 8g is dry for 24 hours, filters, rotation
It steams, obtains crude product, add in 40g dimethylbenzene, recrystallize, obtain nearly colorless plate crystal 4-aminopyridine 7g, it is 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 15.2g 6- carboxyl -2,3- diamino-pyridine and 15.2g3- hydroxy-4-methyl benzoic 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,
Gained crude product adds in 15% NaOH solution, and flow back 2h, and with 10% HCL aqueous solution tune pH=3, filtering, products obtained therefrom is used
The methanol solution (DMF: methanol=9:1) of 50g DMF recrystallizes, and obtains sterling 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine
And imidazoles 15g, it is spare.
Embodiment one: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 66g P-hydroxybenzoic acid and 305g 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles,
291g acetic anhydride and 2.7g 2-aminopyridine and 0.4g stannic chloride are added in titanium alloy polymeric kettle, in 150 DEG C of holding 3h,
Then 325 DEG C are warming up to the speed of 1 DEG C/min, 0.2MPa nitrogen are filled with into titanium alloy polymeric kettle after keeping the temperature 2h, by straight
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 155 DEG C of dry 3h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 200 DEG C in rotation
Solid state polycondensation 48h is carried out in kiln, obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 310 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 260 DEG C of temperature
65h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 0.72dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 5.4dl/g, weight average molecular weight 31800.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 65MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 95MPa.
Embodiment two: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 166g P-hydroxybenzoic acid and 305g 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles,
492g acetic anhydride and 5.6g 2-aminopyridine and 0.5g stannic chloride are added in titanium alloy polymeric kettle, in 155 DEG C of holding 4h,
Then 325 DEG C are warming up to the speed of 1 DEG C/min, 0.2MPa nitrogen are filled with into titanium alloy polymeric kettle after keeping the temperature 2h, by straight
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 155 DEG C of dry 3h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 200 DEG C in rotation
Solid state polycondensation 48h is carried out in kiln, obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 310 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 260 DEG C of temperature
65h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 1.6dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 7.0dl/g, weight average molecular weight 44200.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 74MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 126MPa.
Embodiment three: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 55.2g P-hydroxybenzoic acid and 305g 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles,
316g acetic anhydride and 2.6g 2-aminopyridine and 0.7g stannic chloride are added in titanium alloy polymeric kettle, in 160 DEG C of holding 4h,
Then 325 DEG C are warming up to the speed of 1 DEG C/min, 0.2MPa nitrogen are filled with into titanium alloy polymeric kettle after keeping the temperature 2h, by straight
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 155 DEG C of dry 3h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 200 DEG C in rotation
Solid state polycondensation 48h is carried out in kiln, obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 310 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 260 DEG C of temperature
65h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 2.6dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 8.3dl/g, weight average molecular weight 51100.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 82MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 126MPa.
Example IV: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 328g P-hydroxybenzoic acid and 305g 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles,
680g acetic anhydride and 6.2g 2-aminopyridine and 1.2g stannic chloride are added in titanium alloy polymeric kettle, in 160 DEG C of holding 5h,
Then 325 DEG C are warming up to the speed of 1 DEG C/min, 0.2MPa nitrogen are filled with into titanium alloy polymeric kettle after keeping the temperature 2h, by straight
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 155 DEG C of dry 3h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 200 DEG C in rotation
Solid state polycondensation 48h is carried out in kiln, obtains heavy polymer powder；
Three, the heavy polymer powder that step 2 obtains is kneaded at 310 DEG C by double screw extruder, is vented
Afterwards again through metering pump and component, after 25 DEG C of quenchings, pelletizing obtains nascent polyarylate；
It four, is 0.3m in nitrogen flow3Under conditions of/h, nascent polyarylate is heat-treated with 260 DEG C of temperature
65h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 3.2dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 9.2dl/g, weight average molecular weight 80000.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 95MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 150MPa.
Claims (9)
1. the preparation method of polyarylate of the one kind based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles, feature
It is that and follows these steps to realize:
It one, is (0.3~2.8): 1 P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl phenyl) -6- by polymerized monomer molar ratio
Carboxyl pyridine and imidazoles, acetic anhydride and 2-aminopyridine and antioxidant are added in titanium alloy polymeric kettle, 145~160
2~5h is kept between DEG C, then heats to 325 DEG C, is filled with nitrogen into titanium alloy polymeric kettle after keeping the temperature 2h, is polymerize through titanium alloy
Kettle discharge crushes, obtains prepolymer after drying；
Two, under the conditions of the prepolymer for obtaining step 1 is placed in nitrogen protection, with 180~230 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 300~330 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. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that P-hydroxybenzoic acid and 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine in step 1
And the purity of imidazoles is greater than 99.6%.
3. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that the mole of acetic anhydride is polymerized monomer P-hydroxybenzoic acid and 2- (3- hydroxyl in step 1
Base -4- aminomethyl phenyl) 1.6~2.5 times of total hydroxyl moles in -6- carboxyl pyridine and imidazoles.
4. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that the molal quantity of 2-aminopyridine is polymerized monomer P-hydroxybenzoic acid and 2- in step 1
0.015~0.035 times of (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles total mole number.
5. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that then step 1 is warming up to 325 DEG C with the speed of 1.0 DEG C/min, close after keeping the temperature 2h to titanium
Nitrogen is filled in golden polymeric kettle.
6. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that step is discharged once the 10 hole dispensing valves that titanium alloy polymeric kettle diameter is 3mm, crush,
Prepolymer is dried to obtain at 155 DEG C.
7. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that the speed of step 3 drawing-off is 8~42m/min.
8. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that step 4 carries out heat treatment 65h to nascent polyarylate with 245~275 DEG C of temperature.
9. a kind of poly- virtue based on 2- (3- hydroxy-4-methyl phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
The preparation method of ester, it is characterised in that antioxidant described in step 1 is stannic chloride.
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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 |
| CN104748886A (en) * | 2015-03-23 | 2015-07-01 | 哈尔滨工业大学 | Method for monitoring phased work temperature peak values of drill during lunar soil drilling and sampling process in real time |
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