CN109666141B - Polyamide acid stock solution and preparation method and application thereof - Google Patents
Polyamide acid stock solution and preparation method and application thereof Download PDFInfo
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- CN109666141B CN109666141B CN201710961382.8A CN201710961382A CN109666141B CN 109666141 B CN109666141 B CN 109666141B CN 201710961382 A CN201710961382 A CN 201710961382A CN 109666141 B CN109666141 B CN 109666141B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/74—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polycondensates of cyclic compounds, e.g. polyimides, polybenzimidazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention provides a polyamic acid stock solution and a preparation method and application thereof, and mainly solves the problem that the quality of a product is not easy to control in a process caused by uneven polyamic acid stock solution and more gel particles in the prior art. The invention provides a polyamic acid solution which has the following characteristics: (a) the polyamic acid has a molecular weight distribution of 1.2 to 1.5 as determined by gel permeation chromatography; (b) the solution is filtered through a 2-micron glass fiber filter screen, and the filter screen is irradiated by an ultraviolet fluorescent lamp without generating foreign matters, so that the technical scheme better solves the problem and can be used in the industrial production of polyimide materials.
Description
Technical Field
The invention relates to a polyamic acid solution with narrow and homogenized molecular weight distribution, a preparation method and application thereof.
Background
Polyimide is a polymer with excellent comprehensive performance, and has the characteristics of excellent heat resistance, low temperature resistance, self-lubricating property, radiation resistance, flame retardance and the like, and also has excellent mechanical property and dielectric property.
The common polyimide main chain contains a large number of imide ring structures, and strong acting force exists among polyimide molecular chains due to electronic polarization and crystallinity, so that the polyimide molecular chains are tightly stacked, and are difficult to dissolve and infusible and difficult to process and mold, thereby seriously influencing the application value of the polyimide. In order to solve the problem of solubility, a polyamic acid solution, which is a precursor of polyimide, is generally synthesized, and is first processed into a polyamic acid material by coating, spinning, or the like, and then converted into a final polyimide material by thermal imidization, chemical imidization, or the like. The processing and molding properties of polyimide materials are directly related to the quality of the polyamic acid solution.
Generally, polyamic acids are typically prepared by reacting a dianhydride and a diamine in an aprotic polar solvent at low temperatures. The common polymerization method is to dissolve diamine monomer in aprotic polar solvent, then add dianhydride monomer by one-time feeding or batch feeding, and adjust the relative molecular mass by adding more or less dianhydride monomer or hydrolyzing a part of dianhydride by aqueous solvent. The polyamic acid solution prepared by the polymerization method has the advantages that the apparent viscosity of the solution is rapidly increased in a short time, the local molecular weight of the system is very large before dianhydride is dissolved, the mass transfer is difficult to react sufficiently, a large amount of gel particles are formed, and the processing performance is seriously influenced due to the wide molecular weight distribution of the obtained polyamic acid.
Disclosure of Invention
One of the technical problems to be solved by the invention is to solve the problem that the quality of a product is not easy to control in a process caused by uneven polyamic acid stock solution and more gel particles in the prior art, and provide a polyamic acid stock solution which has narrow molecular weight distribution and low gel particle content, is easy to control stably in a subsequent processing process, is not easy to generate defects in a product, and can obtain a high-performance polyimide product.
The second technical problem to be solved by the present invention is to provide a method for preparing a polyamic acid solution corresponding to the first technical problem.
The present invention is also directed to a method for preparing a polyamic acid solution corresponding to one of the technical problems.
The fourth technical problem to be solved by the present invention is to provide a method for applying polyamic acid solution corresponding to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a polyamic acid solution having the following characteristics:
(1) the polyamic acid has a molecular weight distribution of 1.2 to 1.5 as determined by gel permeation chromatography;
(2) after passing through a 2 μm glass fiber filter membrane, the filter membrane was free from foreign matter under irradiation of an ultraviolet fluorescent lamp.
In the above technical solution, the polyamic acid is selected from the structures represented by the general formula (1):
wherein Ar is1Is a tetravalent aromatic residue having at least one carbon six-membered ring, and is more preferably an aromatic residue represented by the following formula (1)
Ar2Preferably a tetravalent aromatic residue comprising at least one carbon six-membered ring, more preferably an aromatic residue represented by the following structural formula (2):
in the above structural formula (2), R2H-, CH-, is preferably selected3-、Cl-、Br-、F-、CH3O-, etc.
In the above technical solution, the organic solvent in the polyamic acid solution may be any organic solvent known in the art, and is preferably at least one of strong polar aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and sulfolane.
In the technical scheme, the solid content of the polyamic acid solution is 5-30%, and more preferably 10-20%.
In the technical scheme, the total molar ratio of dianhydride monomer to diamine monomer in the polyamic acid solution is 0.95-1.05: 1.
in order to solve the second technical problem, the invention adopts the technical scheme that: a method for producing a polyamic acid solution according to any one of the technical solutions to solve one of the technical problems, comprising the steps of:
(a) dissolving a diamine monomer in an organic solvent to obtain a diamine monomer solution;
(b) and (b) adding a dianhydride monomer into the diamine monomer solution obtained in the step (a), and reacting to obtain the polyamic acid solution.
In the above technical solution, the step (a) is preferably performed under the protection of an inert gas.
In the technical scheme, the reaction time in the step (b) is preferably 6-12 h.
In the technical scheme, the reaction temperature in the step (b) is-10-40 ℃, and preferably 0-30 ℃.
In the technical scheme, the molar ratio of the dianhydride monomer to the diamine monomer is 0.95-1.05: 1.
in the above technical solution, the water content in the organic solvent is preferably less than 800ppmw, and more preferably 100ppmw to 300 ppmw.
In the above technical solution, the inert gas is preferably at least one of nitrogen, argon or helium.
In the above technical scheme, the reaction stirring speed in the step (b) is usually 50 to 600 rpm, preferably 100 to 400 rpm.
In the above technical solution, the dianhydride monomer is added at a rate satisfying the following formula in the step (b):
in order to solve the third technical problem, the invention adopts the technical scheme that: a second method for preparing a polyamic acid solution according to any one of the above technical solutions, comprising the steps of:
(a) dissolving diamine in X mol in an organic solvent, and then adding dianhydride in Y mol to react to obtain a prepolymer solution 1;
(b) dissolving diamine in Z mol in an organic solvent, and then adding dianhydride in K mol to react to obtain a prepolymer solution 2;
(c) adding the prepolymer solution 2 in the step (b) into the prepolymer solution 1 in the step (a), and uniformly mixing to obtain the polyamic acid solution;
wherein X, Y, Z, K satisfies the conditions that Y/X is more than or equal to 0.8 and less than or equal to 0.98 and K/Z is more than or equal to 1.02 and less than or equal to 2.
In the above technical solution, the step (a) and the step (b) are preferably performed under the protection of inert gas; the organic solvent may be any one of the organic solvents known in the art, and is preferably at least one of strong polar aprotic solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and sulfolane.
In the above technical solution, the water content in the organic solvent is preferably less than 800ppmw, and more preferably 100ppmw to 300 ppmw.
In the technical scheme, the reaction temperature in the step (a) and the step (b) is preferably-10-40 ℃ independently, and is further preferably 0-30 ℃ independently; the solid content of the obtained polyamic acid solution is preferably 5-30%, and more preferably 10-20%.
In the above technical solution, the inert gas is preferably at least one of nitrogen, argon or helium.
In the above technical scheme, the reaction stirring speed in the step (a) and the step (b) is usually 50 to 600 rpm, and preferably 100 to 400 rpm.
In the above technical solution, the adding speed of the prepolymer solution 2 in the step (c) preferably satisfies the following formula:
in order to solve the fourth technical problem, the invention adopts the technical scheme that: a method for using the polyamic acid solution according to any one of the above technical means.
In the above technical solutions, the application may be various uses of the polyamic acid solution known to those skilled in the art, such as applications in processing polyimide materials, such as processing the polyamic acid solution into a film, spinning, and the like, which are preferable but not limited.
The test equipment and test conditions used in the present invention are:
molecular weight and molecular weight distribution: a DMF solution sample of PAA at 1mg/ml was prepared using Agilent PL-GPC 200 high temperature GPC with DMF as the mobile phase, and the molecular weight and distribution of PAA were measured at a constant temperature of 35 ℃.
Apparent viscosity: BROOKFIELD DV-III ULTRA PROGRAMMABLE RHEOMETER, USA, and LV-4 trochanter is adopted for testing at 25 ℃;
mechanical properties of the fiber: the monofilament strength test is carried out on a full-automatic single fiber universal tester FAVIMAT +, monofilaments with the length of more than 20mm are separated, and the test is carried out when the initial stress is 0.3cN and the drawing speed is 10 mm/min.
And (3) mechanical tensile test of the film: the films were formed into dumbbell-shaped test bars with a test width of 5mm, and tensile testing was carried out at a constant tensile rate of 100mm/min until the bars broke, using a universal material tester 3344 from Instron, USA, and the tensile strength, elongation at break and tensile modulus of the samples were recorded.
By adopting the technical scheme of the invention, the obtained polyamic acid solution has narrow component distribution, less gel particles and difficult generation of defects in the processing and forming process, so that the quality of the manufactured polyimide products is greatly improved, the irregularity of the PI fiber products is reduced by about 2.3-4.5, the defects and the bad points of the obtained PI film are obviously reduced, and better technical effects are obtained.
The invention is further illustrated by the following examples:
Detailed Description
[ example 1 ]
24.03g (120mmol) of diphenyletherdiamine (ODA) were dissolved in 283.62g N, N-dimethylacetamide (water content 180ppmw), at 25 ℃ N2Stirring under protection, dissolving completely, adding 26.02g (119.28mmol) pyromellitic dianhydride (PMDA) at 0.5g/min, and continuing to add N at 25 deg.C2Stirring for 1h under protection, and stirring at the speed of 250rpm to obtain uniform transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 290 Pa.s, a number average molecular weight of 202000 and a molecular weight distribution of 1.38 at 25 ℃, and after passing through a 2-micron glass fiber filter membrane, no foreign matter is generated on the filter membrane under the irradiation of an ultraviolet fluorescent lamp.
[ example 2 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 238.28g of N, N-dimethylacetamide (water content 350ppmw) at 0 ℃ N2Stirring under protection, dissolving completely, adding 22.03g (101mmol) pyromellitic dianhydride (PMDA) at 0.1g/min, and continuing to add N at 0 deg.C2Stirring for 1h under protection, and stirring at the speed of 200rpm to obtain uniform transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 210 Pa.s, a number average molecular weight of 223000 and a molecular weight distribution of 1.41 at 25 ℃, and no foreign matter is generated on a filter screen under the irradiation of an ultraviolet fluorescent lamp after the solution passes through a 2-micron glass fiber filter screen.
[ example 3 ]
24.03g (120mmol) of diphenyletherdiamine (ODA) were dissolved in 283.62g N, N-dimethylformamide (water content 460ppmw) and the solution was heated at 20 ℃ under reduced pressure2Stirring under protection, dissolving completely, adding 26.02g (119.28mmol) pyromellitic dianhydride (PMDA) at 0.85g/min, and continuing to add N at 20 deg.C2Stirring for 1h under protection, and stirring at the speed of 400rpm to obtain uniform transparent viscous polyamic acid solution. The polyamide acid solution has the apparent viscosity of 70 Pa.s, the number average molecular weight of 181000 and the molecular weight distribution of 1.20 at 25 ℃ and is tested to pass through a 2-micron glass fiber filter screen, and the filter screen generates no foreign matters under the irradiation of an ultraviolet fluorescent lamp.
[ example 4 ]
24.03g (120mmol) of diphenyletherdiamine (ODA) were dissolved in 283.62g N-methylpyrrolidone (water content 740)ppmw), at-10 ℃ N2Stirring under protection, dissolving completely, adding 26.02g (119.28mmol) pyromellitic dianhydride (PMDA) at 0.3g/min, and continuing to add N at-10 deg.C2Stirring for 1h under protection, and stirring at the speed of 200rpm to obtain uniform transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 68 Pa.s at 25 ℃, a number average molecular weight of 179000 and a molecular weight distribution of 1.28, and after passing through a 2-micron glass fiber filter membrane, no foreign matter is generated on the filter membrane under the irradiation of an ultraviolet fluorescent lamp.
[ example 5 ]
2.00kg (10mol) of diphenyletherdiamine (ODA) were dissolved in 30.36kg of N, N-dimethylacetamide (water content 510ppmw) at 40 ℃ N2Stirring under protection, dissolving completely, adding 2.14kg (9.8mol) pyromellitic dianhydride (PMDA) at 5.95g/min, and continuing to add N at 40 deg.C2Stirring for 1h under protection, and stirring at 50rpm to obtain uniform transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has the apparent viscosity of 8 Pa.s, the number average molecular weight of 207000 and the molecular weight distribution of 1.31 at 25 ℃, and after the solution passes through a 2-micron glass fiber filter membrane, no foreign matter is generated on the filter membrane under the irradiation of an ultraviolet fluorescent lamp.
[ example 6 ]
12.01g (60mmol) of diphenyletherdiamine (ODA) and 6.49g (60mmol) of p-phenylenediamine (p-PDA) were dissolved in 156.12g of dimethyl sulfoxide (water content 260ppmw) and N was added at 20 ℃2Stirring under protection, dissolving completely, adding 33.54g (114mmol) of biphenyl dianhydride (BPDA) at a speed of 0.25g/min, and continuing to add at 20 deg.C N2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a uniform polyamic acid solution. The test shows that the polyamic acid solution has the apparent viscosity of 16.1 Pa.s, the number average molecular weight of 101000 and the molecular weight distribution of 1.36 at 25 ℃, and after the solution passes through a 2-micron glass fiber filter membrane, the filter membrane generates no foreign matters under the irradiation of an ultraviolet fluorescent lamp.
[ example 7 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 470.16g N, N-dimethylacetamide (water content 400ppmw) at 10 ℃ N2Stirring under protection, dissolving completely, adding 32.22g (100mmol) benzophenone dianhydride (BTDA) at 0.5g/min, and continuing to add at 10 deg.C N2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a uniform transparent polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 2.4 Pa.s, a number average molecular weight of 87000 and a molecular weight distribution of 1.48 at 25 ℃, and after passing through a 2-micron glass fiber filter, no foreign matter is generated on the filter under the irradiation of an ultraviolet fluorescent lamp.
[ example 8 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 228.20g of N, N-dimethylacetamide (water content 100ppmw) at 0 ℃ N2Stirring under protection, dissolving completely, adding 20.25g (102mmol) pyromellitic dianhydride (PMDA) at 0.1g/min, and continuing to add at 0 deg.C N2Stirring for 1h under protection, and stirring at the speed of 200rpm to obtain uniform transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 110 Pa.s at 25 ℃, a number average molecular weight of 21600 and a molecular weight distribution of 1.40, and the solution passes through a 2-micron glass fiber filter membrane, and the filter membrane generates no foreign matters under the irradiation of an ultraviolet fluorescent lamp.
[ example 9 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 289.23g N, N-dimethylacetamide (water content 630ppmw) at 0 ℃ N2Stirring under protection, dissolving completely, adding 31.02g (100mmol) diphenyl ether dianhydride (ODPA) at 0.5g/min, and continuing to add at 0 deg.C N2Stirring for 1h under protection at the stirring speed of 200rpm to obtain a uniform light yellow transparent viscous polyamic acid solution. The test shows that the polyamic acid solution has an apparent viscosity of 115 Pa.s at 25 ℃, a number average molecular weight of 183000 and a molecular weight distribution of 1.33, and after passing through a 2-micron glass fiber filter screen, no foreign matter is generated on the filter screen under the irradiation of an ultraviolet fluorescent lamp.
[ example 10 ]
24.03g (120mmol) of diphenyletherdiamine (ODA) were dissolved in 281.52g of N, N-dimethylacetamide (water content 180ppmw) at 25 ℃ N2Stirring under protection, dissolving completely, and stirring at 0.5g/min25.65g (117.6mmol) of pyromellitic dianhydride (PMDA) were added, and after the addition was completed, N was continued at 25 ℃2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a prepolymer solution 1. 20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 298.86g of N, N-dimethylacetamide (water content 180ppmw) at 25 ℃ N2Stirring under protection, dissolving completely, adding 32.72g (150mmol) pyromellitic dianhydride (PMDA), and continuing to add N at 25 deg.C2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a prepolymer solution 2. 11.81g of the prepolymer solution 2 is added into the prepolymer solution 1 at the speed of 0.5g/min, and stirring is continued for 1h, so that a uniform transparent viscous polyamic acid solution is obtained. The test shows that the polyamic acid solution has an apparent viscosity of 213 Pa.s, a number average molecular weight of 211000 and a molecular weight distribution of 1.23 at 25 ℃, and after passing through a 2-micron glass fiber filter, no foreign matter is generated on the filter under the irradiation of an ultraviolet fluorescent lamp.
[ example 11 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 224.68g N, N-dimethylacetamide (water content 350ppmw) at 0 ℃ N2Stirring under protection, dissolving completely, adding 19.63g (90mmol) pyromellitic dianhydride (PMDA) at 0.1g/min, and continuing to add at 0 deg.C N2Stirring for 1h under protection at a stirring speed of 200rpm to obtain a prepolymer solution 1. 20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 267.98g of N, N-dimethylacetamide (water content 180ppmw) at 25 ℃ N2Stirring under protection, dissolving completely, adding 27.27g (125mmol) pyromellitic dianhydride (PMDA), and continuing to add N at 25 deg.C2Stirring for 1h under protection at a stirring speed of 250rpm to obtain a prepolymer solution 2. 34.77g of prepolymer solution 2 is added into the prepolymer solution 1 at the speed of 1g/min, and stirring is continued for 1h, so that uniform transparent viscous polyamic acid solution is obtained. The test shows that the polyamic acid solution has the apparent viscosity of 198Pa · s, the number average molecular weight of 219000 and the molecular weight distribution of 1.32 at 25 ℃, and after the solution passes through a 2-micron glass fiber filter membrane, no foreign matter is generated on the filter membrane under the irradiation of an ultraviolet fluorescent lamp.
[ example 12 ]
2.40kg of (12mol) of 4, 4' -diphenyletherdiamine and 28.33kg of N, N-dimethylacetamide (water content 380ppmw) were placed in a four-necked flask, stirred at room temperature and kept under N2Under protection, after complete dissolution, cooling to 0 ℃ in an ice water bath, adding 2.60kg (11.93mol) of pyromellitic dianhydride powder at a speed of 50g/min, stirring at a temperature of 10 ℃ at a stirring speed of 250 r/min, and after complete dissolution, maintaining the reaction for 2 hours to obtain a light yellow transparent viscous solution. The test shows that the apparent viscosity is 168 Pa.S at 25 ℃, the number average molecular weight is 217000, the molecular weight distribution is 1.42, after the solution passes through a 2 mu m glass fiber filter membrane, the filter membrane generates no foreign matters under the irradiation of an ultraviolet fluorescent lamp.
Filtering and defoaming the polyamide acid solution obtained by polymerization to obtain polyamide acid spinning solution, carrying out spinning through a spinneret orifice with the diameter of 0.12mm by using a dry-jet wet spinning process, washing, oiling, drying and collecting filaments, and carrying out thermal imidization and thermal drafting at the temperature of 100-600 ℃ to obtain the final polyimide fiber. The mechanical properties of the obtained fiber are as follows: the breaking strength T is 6.02cN/dtex, the CV value is 3.0; the modulus of rupture M is 86.52 cN/dtex; elongation at break E9.52%.
[ example 13 ]
20.02g (100mmol) of diphenyletherdiamine (ODA) were dissolved in 224.68g N, N-dimethylacetamide (DMAc) at 0 ℃ N2Stirring under protection, dissolving completely, adding 19.63g (90mmol) pyromellitic dianhydride (PMDA) at 0.3g/min, and adding N at 0 deg.C2Stirring for 1h under protection at a stirring speed of 30rpm to obtain a uniform pale yellow transparent viscous polyamic acid solution. The polyamide acid solution has the apparent viscosity of 4.3 Pa.s, the number average molecular weight of 162000 and the molecular weight distribution of 1.22 at 25 ℃ through testing, and after the solution passes through a 2-micron glass fiber filter screen, the filter screen generates no foreign matters under the irradiation of an ultraviolet fluorescent lamp.
Filtering and defoaming the polyamic acid solution obtained by polymerization, directly extruding and casting the polyamic acid solution on a stainless steel belt through a flat-slit die orifice, removing a solvent at the temperature of 100-250 ℃, drying the polyamic acid solution, peeling the polyamic acid solution from the stainless steel belt, performing biaxial stretching and imidization at the temperature of 100-450 ℃ to finally obtain a polyimide film with the thickness of 20 mu m, and detecting whether the PI film is damaged or has defects by adopting AOI scanning. The mechanical properties of the obtained film were: the tensile strength was 220MPa, the modulus of elasticity was 3.5GPa, and the elongation at break was 21%.
[ COMPARATIVE EXAMPLE 1 ]
24.03g (120mmol) of diphenyl ether diamine (ODA) is dissolved in 283.62g N, N-dimethylacetamide (DMAc), stirred under the protection of N2 at 25 ℃, after complete dissolution, 26.02g (119.28mmol) of pyromellitic dianhydride (PMDA) is added at one time, and after the addition is finished, stirring is continued for 1h under the protection of N2 at 25 ℃, the stirring speed is 250rpm, and the mass transfer effect of the solution is not ideal, so that the obtained polyamic acid solution is not uniform. The test shows that the polyamic acid solution has an apparent viscosity of 183 Pa.s, a number average molecular weight of 193000 and a molecular weight distribution of 2.87 at 25 ℃, and the solution passes through a 2-micron glass fiber filter screen which has a large amount of white foreign matters under the irradiation of an ultraviolet fluorescent lamp.
Filtering and defoaming the polyamide acid solution obtained by polymerization to obtain polyamide acid spinning solution, carrying out spinning through a spinneret orifice with the diameter of 0.12mm by using a dry-jet wet spinning process, washing, oiling, drying and collecting filaments, and carrying out thermal imidization and thermal drafting at the temperature of 100-600 ℃ to obtain the final polyimide fiber. The mechanical properties of the obtained fiber are as follows: the breaking strength T is 4.66cN/dtex, the CV value is 12.1; the modulus of rupture M is 65.33 cN/dtex; elongation at break E11.25%.
[ COMPARATIVE EXAMPLE 2 ]
20.02g (100mmol) of diphenyl ether diamine (ODA) is dissolved in 237.04g N, N-dimethylacetamide (DMAc), stirred under the protection of N2 at 0 ℃, after complete dissolution, 21.81g (100mmol) of pyromellitic dianhydride (PMDA) is added at one time, and after the addition is finished, the stirring is continued for 2 hours under the protection of N2 at 0 ℃, the stirring speed is 200rpm, the solution has uncontrolled exothermic violent viscosity, the mass transfer effect is not ideal, and the obtained polyamic acid solution is in uneven gel. The solution is in a gel state, the apparent viscosity is difficult to measure, the intrinsic viscosity is 3.12dL/g, and the subsequent processing and molding are difficult to perform due to the excessive viscosity.
[ COMPARATIVE EXAMPLE 3 ]
30.04kg (150mol) of diphenyletherdiamine (ODA) were dissolved in 328.00kg of N, N-dimethylacetamide (DMAc) at 30 ℃ under reduced pressure2Stirring under protection, after complete dissolution, adding 31.74kg (145.5mol) of pyromellitic dianhydride (PMDA), and stirring for 3h to obtain a polyamic acid prepolymer solution. 0.98kg (4.5mol) of pyromellitic dianhydride was dissolved in 27.00kg of dimethyl sulfoxide (DMSO) to prepare a dianhydride solution. Adding the polyamic acid prepolymer solution and the dianhydride solution into a kettle at a certain speed, mixing and stirring to obtain the final polyamic acid solution which is an opaque viscous solution. The polyamic acid solution was tested to have an apparent viscosity of 289 Pa.s, a number average molecular weight of 186000, and a molecular weight distribution of 1.79 at 25 deg.C, and after passing through a 2 μm glass fiber filter, the filter was exposed to ultraviolet fluorescent light to provide white foreign matter.
Filtering and defoaming the polyamic acid solution obtained by polymerization, directly extruding and casting the polyamic acid solution on a stainless steel belt through a flat-slit die orifice, removing a solvent at the temperature of 100-250 ℃, drying the polyamic acid solution, peeling the polyamic acid solution from the stainless steel belt, performing biaxial stretching and imidization at the temperature of 100-450 ℃, and finally obtaining a polyimide film with the thickness of 20 mu m, wherein the PI film obtained by AOI scanning detection is very uneven and has a plurality of defects. The mechanical properties of the obtained film were: the tensile strength was 186MPa, the modulus of elasticity was 2.8GPa, and the elongation at break was 19%.
Claims (6)
1. A polyamic acid solution characterized by:
(1) the polyamic acid has a molecular weight distribution of 1.2 to 1.5 as determined by gel permeation chromatography;
(2) after the polyamic acid solution passes through a 2-micron glass fiber filter membrane, no foreign matter is generated on the filter membrane under the irradiation of an ultraviolet fluorescent lamp;
the polyamic acid solution is prepared by the following steps:
(a) dissolving diamine in X mol in an organic solvent, and then adding dianhydride in Y mol to react to obtain a prepolymer solution 1;
(b) dissolving diamine in Z mol in an organic solvent, and then adding dianhydride in K mol to react to obtain a prepolymer solution 2;
(c) adding the prepolymer solution 2 in the step (b) into the prepolymer solution 1 in the step (a), and uniformly mixing to obtain the polyamic acid solution;
wherein X, Y, Z, K satisfies the conditions that Y/X is more than or equal to 0.8 and less than or equal to 0.98 and K/Z is more than or equal to 1.02 and less than or equal to 2.
2. The polyamic acid solution according to claim 1, wherein said polyamic acid is selected from the group consisting of structures represented by the general formula (1):
wherein Ar is1Is a tetravalent aromatic radical having at least one carbon-six membered ring, Ar2Is a divalent aromatic residue containing at least one carbon six-membered ring.
3. The polyamic acid solution according to claim 1, wherein said organic solvent in said polyamic acid solution is at least one selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, and dimethylsulfoxide.
4. The polyamic acid solution according to claim 1, wherein said polyamic acid solution has a solid content of 5 to 30%.
5. The method for producing a polyamic acid solution according to claim 1 to 4,
(a) dissolving diamine in X mol in an organic solvent, and then adding dianhydride in Y mol to react to obtain a prepolymer solution 1;
(b) dissolving diamine in Z mol in an organic solvent, and then adding dianhydride in K mol to react to obtain a prepolymer solution 2;
(c) adding the prepolymer solution 2 in the step (b) into the prepolymer solution 1 in the step (a), and uniformly mixing to obtain the polyamic acid solution;
wherein X, Y, Z, K satisfies the conditions that Y/X is more than or equal to 0.8 and less than or equal to 0.98 and K/Z is more than or equal to 1.02 and less than or equal to 2.
6. Use of the polyamic acid solution according to any one of claims 1 to 4 in the processing of polyimide materials.
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| US4954609A (en) * | 1989-02-28 | 1990-09-04 | Hoechst Celanese Corp. | Intermediate molecular weight fluorine containing polymide and method for preparation |
| JP2005105079A (en) * | 2003-09-29 | 2005-04-21 | Sumitomo Bakelite Co Ltd | Manufacturing method of polyimide precursor and polyimide resin |
| CN105175722A (en) * | 2015-09-02 | 2015-12-23 | 宜兴市高拓高分子材料有限公司 | Preparation method of aromatic polyamic acid with characteristics of high relative molecular mass and narrow molecular weight distribution |
| CN106589371A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamide acid composition and preparation method and application thereof |
| CN106589368A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamic acid composition and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4954609A (en) * | 1989-02-28 | 1990-09-04 | Hoechst Celanese Corp. | Intermediate molecular weight fluorine containing polymide and method for preparation |
| JP2005105079A (en) * | 2003-09-29 | 2005-04-21 | Sumitomo Bakelite Co Ltd | Manufacturing method of polyimide precursor and polyimide resin |
| CN105175722A (en) * | 2015-09-02 | 2015-12-23 | 宜兴市高拓高分子材料有限公司 | Preparation method of aromatic polyamic acid with characteristics of high relative molecular mass and narrow molecular weight distribution |
| CN106589371A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamide acid composition and preparation method and application thereof |
| CN106589368A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Polyamic acid composition and preparation method and application thereof |
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