CN110317328A - The preparation method of polyarylate of the one kind based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles - Google Patents
The preparation method of polyarylate of the one kind based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles Download PDFInfo
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- CN110317328A CN110317328A CN201810278299.5A CN201810278299A CN110317328A CN 110317328 A CN110317328 A CN 110317328A CN 201810278299 A CN201810278299 A CN 201810278299A CN 110317328 A CN110317328 A CN 110317328A
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Abstract
The preparation method of polyarylate of the one kind based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles, the present invention relates to a kind of preparation methods of polyarylate based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles, it is in order to which the preparation difficulty for solving the problems, such as liquid crystal polyarylate is big, mechanical property is undesirable.Preparation method: one, by P-hydroxybenzoic acid and 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone, simultaneously imidazoles, acetic anhydride and the third aminopyridine of 3- 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 105~165MPa.
Description
Technical field
The present invention relates to a kind of polyarylates based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles
Preparation method.
Background technique
Polyarylate is non-crystalline polymer compound, and molecule amylose regularity is very high, during melt-processed, gathers virtue
Ester molecule chain is in liquid crystal phase always, and easily regular arrangement, forms multilayer oriented structure under external force.It can use thermoplastic
Property plastics method molding, but melt fluidity is poor.Polyarylate is acidproof, oil resistant, but alkaline-resisting, stress cracking resistance, resistance to aromatic hydrocarbons
It is not ideal enough with the performance of ketone.In addition, it also has excellent UV resistant shielding, impact resistance, surface hardness and resistance to
Croop property shows higher tensile strength within the scope of very wide temperature.
TLCP causes numerous researchs because having the incomparable outstanding performance of conventional polymer and extremely wide application range
The extensive concern of person.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.Domestic patent 200410054025.6 reports a kind of solid-state preparation method of liquid crystal copolyester, specifically will melting
Performed polymer after polymerization carries out tens of hours solid-state polymerizations to prepare the liquid crystal polyester of high molecular weight.But this method is clearly present
Production cycle too long problem, be not suitable for industrialization large-scale continuous production.United States Patent (USP) 4,169,933 describes one kind and contains
There is the polymer for the repetitive unit being transformed from quinhydrones, terephthalic acid (TPA), 2,6 naphthalene dicarboxylic acid and 4-HBA to prepare
Method.United States Patent (USP) 5,079,289,5,097,001 and 5,221,730 is described containing from quinhydrones, terephthalic acid (TPA), isophthalic
The method for producing polymer for the repetitive unit that dioctyl phthalate and 4-HBA are 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
The problem that the purpose of the present invention is to solve the preparation difficulty of liquid crystal polyarylate is big, mechanical property is undesirable, and
A kind of preparation method of polyarylate based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles is provided.
The preparation method of Thermotropic Liquid Crystalline Copolyesters of the present invention follows these steps to realize:
It one, is (0.4~3.0): 1 P-hydroxybenzoic acid and 2- (4- carboxyl -3- methoxybenzene by polymerized monomer molar ratio
Base) simultaneously imidazoles, acetic anhydride and the third aminopyridine of 3- and stannic chloride are added in titanium alloy polymeric kettle -5- pyridone, 120
3~7h is kept between~150 DEG C, then heats to 320 DEG C, is filled with nitrogen into titanium alloy polymeric kettle after keeping the temperature 3h, is closed through titanium
Golden 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 190~215 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 305~330 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 1.0 × 104~1.9 × 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 45~95MPa, using final after heat treatment
The drawing of obtained Thermotropic Liquid Crystalline Copolyesters stretches intensity up to 105~165MPa.Solves previous Thermotropic Liquid Crystalline Copolyesters preparation work
Skill is complicated, and condition is not easy to control, unstable quality, the lower disadvantage of finished product mechanical property.
Specific embodiment
Specific embodiment 1: the preparation method of present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to implement:
It one, is (0.4~3.0): 1 P-hydroxybenzoic acid and 2- (4- carboxyl -3- methoxybenzene by polymerized monomer molar ratio
Base) simultaneously imidazoles, acetic anhydride and the third aminopyridine of 3- and stannic chloride are added in titanium alloy polymeric kettle -5- pyridone, 120
3~7h is kept between~150 DEG C, then heats to 320 DEG C, is filled with nitrogen into titanium alloy polymeric kettle after keeping the temperature 3h, is closed through titanium
Golden 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 190~215 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 305~330 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 0.9~3.0dl/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 4.5~9.0dl/g, weight average molecular weight is 1.0 × 104~1.9 × 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 99.5% with the purity of 2- (4- carboxyl -3- 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- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles
1.2~3.2 times of total mole number.Other steps and parameter are the same as one or two specific embodiments.
Specific embodiment 4: 3- third in step 1 unlike one of present embodiment and specific embodiment one to three
- 5- pyridone is simultaneously with 2- (4- carboxyl -3- methoxyphenyl) for polymerized monomer P-hydroxybenzoic acid for the molal quantity of aminopyridine
0.011~0.036 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 320 DEG C, is filled with nitrogen into titanium alloy polymeric kettle after keeping the temperature 3h.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, 145 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 5~30m/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 260
~285 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 can then be made using stannic chloride
The close white of resulting polymer color.
Embodiment:
100g amine aqueous solution is added in 250ml there-necked flask, is cooled to 0 DEG C, 4- ethyl chloropyridine 17.8g is then added,
Temperature rising reflux 1 hour, after cooling, 50g toluene is added, extracts 2 times, combining extraction liquid, anhydrous magnesium sulfate 10g drying is added for 24 hours,
Filtering, revolving, obtains crude product, adds in 50g dimethylbenzene, recrystallizes, obtains the third aminopyridine of nearly colorless plate crystal 4- 9g, standby
With.
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 12g 5- hydroxyl -2,3- diamino-pyridine and 17.7g3- methoxyl group-terephthalic acid (TPA) 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- (4- carboxyl -3- methoxyphenyl), -5- pyridone is simultaneously
Imidazoles 10g, it is spare.
Embodiment one: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 53g P-hydroxybenzoic acid and 248g 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles,
315g acetic anhydride and the third aminopyridine of 2.2g 3- and 0.2g stannic chloride are added in titanium alloy polymeric kettle, are kept at 120 DEG C
Then 3h is warming up to 320 DEG C with the speed of 0.5 DEG C/min, 0.2MPa nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 3h, passes through
After crossing the 10 hole dispensing valves releasing of diameter 3mm, crushes, 20 meshes are crossed, to obtain prepolymer after 145 DEG C of dry 2.5h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h protective condition, with 190 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 305 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 0.9dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 4.5dl/g, weight average molecular weight 10800.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 45MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 105MPa.
Embodiment two: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 117g P-hydroxybenzoic acid and 248g 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles,
378g acetic anhydride and the third aminopyridine of 3.1g 3- and 0.4g stannic chloride are added in titanium alloy polymeric kettle, are kept at 120 DEG C
Then 5h is warming up to 320 DEG C with the speed of 0.5 DEG C/min, 0.2MPa nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 3h, passes through
After crossing the 10 hole dispensing valves releasing of diameter 3mm, crushes, 20 meshes are crossed, to obtain prepolymer after 145 DEG C of dry 2.5h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h condition, with 190 DEG C in rotary kiln
Solid state polycondensation 48h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 305 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 1.4dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 5.2dl/g, weight average molecular weight 13500.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 64MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 130MPa.
Embodiment three: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 225g P-hydroxybenzoic acid and 248g 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles,
617g acetic anhydride and the third aminopyridine of 4.5g 3- and 0.9g stannic chloride are added in titanium alloy polymeric kettle, are kept at 130 DEG C
Then 6h is warming up to 320 DEG C with the speed of 0.5 DEG C/min, 0.2MPa nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 3h, passes through
After crossing the 10 hole dispensing valves releasing of diameter 3mm, crushes, 20 meshes are crossed, to obtain prepolymer after 145 DEG C of dry 2.5h；
Two, it is 0.3m that the prepolymer for obtaining step 1, which is placed in nitrogen flow,3Under/h condition, with 190 DEG C in rotary kiln
Solid state polycondensation 48h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 305 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 2.8dl/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 15600.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 80MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 155MPa.
Example IV: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 288g P-hydroxybenzoic acid and 248g 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles,
757g acetic anhydride and the third aminopyridine of 5.4g 3- and 1.0g stannic chloride are added in titanium alloy polymeric kettle, are kept at 145 DEG C
Then 7h is warming up to 320 DEG C with the speed of 0.5 DEG C/min, 0.2MPa nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 3h, passes through
After crossing the 10 hole dispensing valves releasing of diameter 3mm, crushes, 20 meshes are crossed, to obtain prepolymer after 145 DEG C of dry 2.5h；
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 48h is carried out, heavy polymer powder is obtained；
Three, the heavy polymer powder that step 2 obtains is kneaded at 305 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 3.0dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 9.0dl/g, weight average molecular weight 19000.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 165MPa.
Claims (9)
1. the preparation method of polyarylate of the one kind based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles, special
Sign, which is that, to be followed these steps to realize:
It one, is (0.4~3.0): 1 P-hydroxybenzoic acid and 2- (4- carboxyl -3- methoxyphenyl)-by polymerized monomer molar ratio
5- pyridone and imidazoles, acetic anhydride and the third aminopyridine of 3- and antioxidant are added in titanium alloy polymeric kettle, 120~
3~7h is kept between 150 DEG C, then heats to 320 DEG C, nitrogen is filled with into titanium alloy polymeric kettle after keeping the temperature 3h, 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 190~215 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 305~330 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. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles it is poly-
The preparation method of aromatic ester, it is characterised in that P-hydroxybenzoic acid and 2- (4- carboxyl -3- methoxyphenyl) -5- hydroxyl in step 1
The purity of pyridine-imidazole is greater than 99.5%.
3. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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- (4- in step 1
Carboxyl -3- methoxyphenyl) 1.2~3.2 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- (4- carboxyl -3- 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 the third aminopyridine of 3- be polymerized monomer P-hydroxybenzoic acid with
0.011~0.036 times of 2- (4- carboxyl -3- methoxyphenyl) -5- pyridone and imidazoles total mole number.
5. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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 320 DEG C with the speed of 0.5 DEG C/min, keep the temperature after 3h to titanium
Nitrogen is filled in alloy polymeric kettle.
6. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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 145 DEG C.
7. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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 5~30m/min.
8. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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 65h to nascent polyarylate with 260~285 DEG C of temperature.
9. it is according to claim 1 it is a kind of based on 2- (4- carboxyl -3- 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 stannic chloride.
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| CN201810278299.5A CN110317328B (en) | 2018-03-31 | 2018-03-31 | Preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole |
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| CN201810278299.5A CN110317328B (en) | 2018-03-31 | 2018-03-31 | Preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole |
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| CN110317328A true CN110317328A (en) | 2019-10-11 |
| CN110317328B CN110317328B (en) | 2021-04-30 |
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| CN201810278299.5A Active CN110317328B (en) | 2018-03-31 | 2018-03-31 | Preparation method of polyarylate based on 2- (4-carboxyl-3-methoxyphenyl) -5-hydroxypyridoimidazole |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| 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 |
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