CN109535406A - The preparation method of polyarylate of the one kind based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles - Google Patents
The preparation method of polyarylate of the one kind based on 2- (3- hydroxy 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 phenyl) -6- carboxyl pyridine and imidazoles, the present invention relates to a kind of preparation methods of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine 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- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, acetic anhydride and 4-aminopyridine 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 fiber of the present invention is easy to operate, and the drawing of finally obtained polyarylate fiber stretches intensity up to 160~200MPa.
Description
Technical field
The present invention relates to a kind of preparation methods of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles.
Background technique
TLCP has the incomparable outstanding performance of conventional polymer and extremely wide application range, causes numerous researchers
Extensive concern.After since the 1970s, Jackson reports first thermotropic liquid crystalline polyester, people are to thermotropic liquid
Brilliant polyarylate expands large-scale research.The preparation method of Thermotropic Liquid Crystalline Copolyesters is roughly divided into two classes, and one kind is chloride method,
Binary acyl chlorides and dihydric phenol and corresponding catalyst are added in organic solvent and carries out reaction and prepares the poly- virtue of thermotropic liquid crystal
Ester.Second class is melting ester condensation methods, and binary acid or dihydric phenol are first reacted with the unary alcohol of small molecule or acid compounds
Generate ester, then existing for the catalyst under the conditions of to carry out melt polycondensation at high temperature with corresponding dihydric phenol or binary acid again anti-
Thermotropic liquid crystal polyarylate should be prepared.But many technical problems are encountered in the industrialization of TLCP practice, such as thermotropic liquid
Polycrystalline macromolecule polymerization reaction is not easy to control, TLCP materials processing temperature window narrows of synthesis etc., the solution of these problems need into
The a large amount of applied basic research of row.
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
Big, tensile strength that the purpose of the present invention is to solve the preparation difficulty of liquid crystal polyarylate differs larger with theoretical value
The problems such as, and a kind of preparation method of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine 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- (3- hydroxy phenyl) -6- carboxylic by polymerized monomer molar ratio
Simultaneously imidazoles, acetic anhydride and 4-aminopyridine and stannous chloride are added in Hastelloy polymeric kettle yl pyridines, 120~160
3~6h is kept between DEG C, then heats to 320 DEG C, nitrogen is filled with into Hastelloy polymeric kettle after keeping the temperature 3h, through Hastelloy
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 200~210 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 310~335 DEG C by single screw extrusion machine
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 3.0 × 104~8.0 × 104, molecular weight height.Preparation process can be in polymeric kettle and single spiral shell
Implement in bar extruder, be convenient for continuous production, tensile strength can reach 75~130MPa, using final after heat treatment
The drawing of obtained Thermotropic Liquid Crystalline Copolyesters stretches intensity up to 160~200MPa.Solves previous Thermotropic Liquid Crystalline Copolyesters preparation work
Skill condition is not easy to control, 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 (0.4~3.0): 1 P-hydroxybenzoic acid and 2- (3- hydroxy phenyl) -6- carboxylic by polymerized monomer molar ratio
Simultaneously imidazoles, acetic anhydride and 4-aminopyridine and stannous chloride are added in Hastelloy polymeric kettle yl pyridines, 120~160
3~6h is kept between DEG C, then heats to 320 DEG C, nitrogen is filled with into Hastelloy polymeric kettle after keeping the temperature 3h, through Hastelloy
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 200~210 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 310~335 DEG C by single screw extrusion machine
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 0.6~3.0dl/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 3.0 × 104~8.0 × 104。
The preparation method of thermotropic liquid crystal high-performance polyarylate described in present embodiment can be squeezed by polymeric kettle and single screw rod
Machine out, draw roll, the combination of pelleter realize that the shear force for having made full use of single screw extrusion machine 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- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles.Other steps and parameter and specific embodiment party
Formula 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 total hydroxyl moles in polymerized monomer P-hydroxybenzoic acid and 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles
1.8~2.8 times.Other steps and parameter are the same as one or two specific embodiments.
Specific embodiment 4: 4- 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 phenyl) -6- carboxyl pyridine and imidazoles total mole number
0.020~0.035 times.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 Hastelloy polymeric kettle after keeping the temperature 3h.Other steps and parameter
It is identical as one of specific embodiment one to four.
Specific embodiment 6: step is once Kazakhstan unlike one of present embodiment and specific embodiment one to five
Alloy polymeric kettle diameter be 3mm 10 hole dispensing valves be discharged, crush, 150 DEG C be dried to obtain prepolymer.Other steps and parameter
It is identical as one of specific embodiment one to five.
Specific embodiment 7: step 3 drawing-off unlike one of present embodiment and specific embodiment one to six
Speed is 10~40m/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 240
~270 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 stannous 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 13.8g m-hydroxybenzoic acid is added, is warming up to 90 DEG C, adds
Enter phosphorus pentoxide 43g, be warming up to 150 DEG C with the speed of 0.5 DEG C/min and be down to room temperature, add in 1l water, filters, gained crude product
It adds in 15% NaOH solution, flow back 2h, and with 10% HCL aqueous solution tune pH=3, filtering, products obtained therefrom is with 50g DMF's
Methanol solution (DMF: methanol=9:1) recrystallization obtains sterling 2- (3- hydroxy phenyl) -6- carboxyl pyridine simultaneously imidazoles 15g, spare.
Embodiment one: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 69g P-hydroxybenzoic acid and 254g 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, 310g acetic anhydride
It is added in 2l Hastelloy polymeric kettle with 2.8g 4-aminopyridine and 0.3g stannous chloride, in 120 DEG C of holding 3h, then
320 DEG C are warming up to the speed of 0.5 DEG C/min, 0.2MPa nitrogen is filled with into Hastelloy polymeric kettle after keeping the temperature 3h, by straight
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 150 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 single screw extrusion machine, 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
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 0.6dl/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 31800.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 75MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 160MPa.
Embodiment two: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 138g P-hydroxybenzoic acid and 254g 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, 410g acetic acid
Acid anhydride and 4.7g 4-aminopyridine and 0.4g stannous chloride are added in 2l Hastelloy polymeric kettle, in 130 DEG C of holding 4h, so
320 DEG C are warming up to the speed of 0.5 DEG C/min afterwards, is filled with 0.2MPa nitrogen into Hastelloy polymeric kettle after keeping the temperature 3h, is passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 150 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 single screw extrusion machine, 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
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 1.3dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 5.8dl/g, weight average molecular weight 44200.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 179MPa.
Embodiment three: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 276g P-hydroxybenzoic acid and 254g 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, 612g acetic acid
Acid anhydride and 6.1g 4-aminopyridine and 0.8g stannous chloride are added in 2l Hastelloy polymeric kettle, in 140 DEG C of holding 5h, so
320 DEG C are warming up to the speed of 0.5 DEG C/min afterwards, is filled with 0.2MPa nitrogen into Hastelloy polymeric kettle after keeping the temperature 3h, is passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 150 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 single screw extrusion machine, 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
70h obtains Thermotropic Liquid Crystalline Copolyesters.
The inherent viscosity of the prepolymer of the present embodiment step 1 preparation is 2.2dl/g, the high-molecular-weight poly of step 2 preparation
The inherent viscosity for closing object powder is 7.6dl/g, weight average molecular weight 51100.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 117MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 168MPa.
Example IV: the preparation method of the present embodiment Thermotropic Liquid Crystalline Copolyesters follows these steps to realize:
One, by 413g P-hydroxybenzoic acid and 254g 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, 820g acetic acid
Acid anhydride and 7.6g 4-aminopyridine and 1.0g stannous chloride are added in 2l Hastelloy polymeric kettle, in 160 DEG C of holding 6h, so
320 DEG C are warming up to the speed of 0.5 DEG C/min afterwards, is filled with 0.2MPa nitrogen into Hastelloy polymeric kettle after keeping the temperature 3h, is passed through
It after the 10 hole dispensing valves of diameter 3mm are released, crushes, 20 meshes is crossed, to obtain prepolymer after 150 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 single screw extrusion machine, 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
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 9.0dl/g, weight average molecular weight 80000.The stretching for the nascent polyarylate that step 3 obtains is strong
Degree is 130MPa, and the drawing for the Thermotropic Liquid Crystalline Copolyesters that step 4 obtains stretches intensity up to 200MPa.
Claims (9)
1. the preparation method of polyarylate of the one kind based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles, it is characterised in that be
It follows these steps to realize:
It one, is (0.4~3.0): 1 P-hydroxybenzoic acid and 2- (3- hydroxy phenyl) -6- carboxyl pyrrole by polymerized monomer molar ratio
Pyridine and imidazoles, acetic anhydride and 4-aminopyridine and antioxidant are added in Hastelloy polymeric kettle, 120~160 DEG C it
Between keep 3~6h, then heat to 320 DEG C, be filled with nitrogen into Hastelloy polymeric kettle after keeping the temperature 3h, polymerize through Hastelloy
Kettle discharge crushes, obtains prepolymer after drying；
Two, under the conditions of the prepolymer for obtaining step 1 is placed in nitrogen protection, with 200~210 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 310~335 DEG C by single screw extrusion machine, 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 system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that the purity of P-hydroxybenzoic acid and 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles in step 1
Greater than 99.5%.
3. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that the mole of acetic anhydride is polymerized monomer P-hydroxybenzoic acid and 2- (3- hydroxy benzenes in step 1
Base) 1.8~2.8 times of total hydroxyl moles in -6- carboxyl pyridine and imidazoles.
4. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that the molal quantity of 4-aminopyridine is polymerized monomer P-hydroxybenzoic acid and 2- (3- hydroxyl in step 1
Phenyl) 0.020~0.035 times of -6- carboxyl pyridine and imidazoles total mole number.
5. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that then step 1 is warming up to 320 DEG C with the speed of 0.5 DEG C/min, gather after keeping the temperature 3h to Hastelloy
It closes in kettle and is filled with nitrogen.
6. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that step is discharged once the 10 hole dispensing valves that Hastelloy polymeric kettle diameter is 3mm, crushes, 150
DEG C it is dried to obtain prepolymer.
7. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that the speed of step 3 drawing-off is 10~40m/min.
8. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that step 4 carries out heat treatment 70h to nascent polyarylate with 240~270 DEG C of temperature.
9. a kind of system of polyarylate based on 2- (3- hydroxy phenyl) -6- carboxyl pyridine and imidazoles according to claim 1
Preparation Method, it is characterised in that antioxidant described in step 1 is stannous chloride.
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