CN117624595A - Method for preparing polyamide acid slurry with high solid content and low viscosity - Google Patents
Method for preparing polyamide acid slurry with high solid content and low viscosity Download PDFInfo
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- 239000007787 solid Substances 0.000 title claims abstract description 65
- 239000002002 slurry Substances 0.000 title claims abstract description 53
- 239000002253 acid Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000004952 Polyamide Substances 0.000 title claims abstract description 16
- 229920002647 polyamide Polymers 0.000 title claims abstract description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 83
- 238000003756 stirring Methods 0.000 claims abstract description 43
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 102
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 32
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 28
- 239000003960 organic solvent Substances 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000006267 biphenyl group Chemical group 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 28
- 229920001721 polyimide Polymers 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 17
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 16
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- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
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- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a method for preparing polyamide acid slurry with high solid content and low viscosity, which comprises the following raw materials: an aromatic tetracarboxylic dianhydride monomer, an aromatic diamine monomer and a polycarboxylic acid compound, wherein the sum of the molar amount of the aromatic tetracarboxylic dianhydride monomer and the molar amount of the polycarboxylic acid compound is equal to the molar amount of the aromatic diamine monomer, and the molar ratio of the aromatic tetracarboxylic dianhydride monomer to the polycarboxylic acid compound is (90:10) - (98:2); the method comprises the following steps: preparing an aromatic diamine solution or an aromatic diamine suspension with the solid content of 7.5-17.5%; adding aromatic tetracarboxylic dianhydride monomer into the prepared aromatic diamine solution or aromatic diamine suspension, and stirring to react to obtain polyamic acid solution; and then adding a polycarboxylic acid organic solution with the mass concentration of 2-10% into the obtained polyamic acid solution, and stirring to obtain polyamic acid slurry. The invention can obtain polyamide acid slurry with remarkable high solid content and low viscosity characteristics.
Description
Technical Field
The invention relates to a method for preparing polyamide acid slurry with high solid content and low viscosity, belonging to the technical field of functional material preparation.
Background
Because the aromatic Polyimide (PI) film has the advantages of high temperature resistance, low temperature resistance, corrosion resistance, high insulation, low dielectric constant, low dielectric loss, excellent mechanical property and the like, the aromatic Polyimide (PI) film has been widely applied to the high-tech fields such as flexible printed circuits, flexible photoelectric display, aerospace, semiconductor manufacturing and packaging and the like.
However, most of polyimide having high heat resistance is insoluble in an organic solvent, and molding processing of polyimide itself is not usually easy. Accordingly, polyimide films have been produced industrially at present by molding a film or the like from a polyamic acid solution of a precursor, and then performing a dehydration and ring closure (imidization) by heating at a high temperature of 250 to 350 ℃.
In addition, with the rapid development of smart display terminals in the directions of light weight, high definition, bending, curling and folding, flexible display has gradually become an important mainstream display technology of smart display terminals, and has been widely applied to the display fields of smart phones, wearable devices, large-size televisions and the like. In the flexible display device, the flexible substrate is a key material for realizing flexible display, and polyimide has the characteristics of good heat resistance, lower linear thermal expansion coefficient, excellent mechanical property and the like, so that in the production of the display substrate, the coating line has high requirements on the viscosity and the solid content of polyamide acid slurry. Because the solid content of the polyamic acid solution is too low, polyimide film with uniform thickness is difficult to obtain due to too fast solvent volatilization of the polyamic acid slurry in the curing and film forming process; if the solid content is high but the viscosity is high, the problem that the film thickness is difficult to adjust exists when coating is performed, but if the polyamide acid slurry can realize the characteristics of high solid content and low viscosity, the use amount of the organic solvent can be reduced under the condition that the process requirement of a tape casting coating line is met, so that the environmental protection pressure of a production enterprise on exhaust emission can be reduced, the production cost can be reduced, and the environmental protection requirement can be met easily. Accordingly, there is an urgent need in the art to develop a method for preparing a high solids low viscosity polyamic acid slurry.
In chinese patent application No. CN201911425337.6, a polyamic acid solution is disclosed, which is obtained by mixing an aromatic diamine monomer and a solvent, stirring once, adding an aromatic tetracarboxylic dianhydride monomer, stirring twice, adding a polycarboxylic acid solid compound, stirring three times, and reacting. Although this patent application can achieve a solid content of 20% and a viscosity of 9880cP at 25 ℃, the solid content is lifted only from 15% to 20% in the prior art; the key is that a hydrogen bond intermediate is formed between the polyamic acid and the polar solvent, and the solubility of the polycarboxylic acid compound in the polyamic acid solution is reduced due to the intermediate, so that the solid polycarboxylic acid compound added after secondary stirring is difficult to dissolve in the reaction solution, a uniform polyamic acid solution is not obtained, and the stability of the quality of the polyamide film is further affected, so that the solid content of the polyamic acid solution cannot be further improved.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a method for preparing a polyamide acid slurry with high solid content and low viscosity, which can make the solid content of the obtained polyamide acid slurry up to 35%, and at the same time, the viscosity at 25 ℃ is only 2 to 20pa.s, and has remarkable characteristics of high solid content and low viscosity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing high solids low viscosity polyamic acid slurry, the preparation raw materials comprising: an aromatic tetracarboxylic dianhydride monomer, an aromatic diamine monomer and a polycarboxylic acid compound, wherein the sum of the molar amount of the aromatic tetracarboxylic dianhydride monomer and the molar amount of the polycarboxylic acid compound is equal to the molar amount of the aromatic diamine monomer, and the molar ratio of the aromatic tetracarboxylic dianhydride monomer to the polycarboxylic acid compound is (90:10) - (98:2); the method comprises the following steps:
a) Adding the formula amount of aromatic diamine into the organic solvent A to prepare an aromatic diamine solution or an aromatic diamine suspension with 7.5-17.5% of solid content at 25-40 ℃;
b) Adding the formula amount of aromatic tetracarboxylic dianhydride monomer into the aromatic diamine solution or aromatic diamine suspension prepared in the step a), and stirring for 12-24 hours at 25-40 ℃ to obtain a polyamic acid solution;
c) Adding a polycarboxylic acid compound into an organic solvent B at 25-40 ℃ to prepare a polycarboxylic acid organic solution with the mass concentration of 2-10%, then adding the polycarboxylic acid organic solution with the mass concentration of 2-10% into the polyamic acid solution obtained in the step B), and continuously stirring for 12-36 hours at 25-40 ℃ to obtain polyamic acid slurry; wherein the addition amount of the polycarboxylic acid organic solution is required to satisfy the following conditions:
(1) the molar amount of polycarboxylic acid compound contained in the polycarboxylic acid organic solution added is the molar amount of aromatic diamine used in step a) minus the molar amount of aromatic tetracarboxylic dianhydride monomer used in step b);
(2) the sum of the mass of the organic solvent B contained in the added polycarboxylic acid organic solution and the mass of the organic solvent A used in the step a) can lead the solid content of the prepared polyamide acid slurry to reach 20-35 percent.
In a preferred embodiment, the aromatic tetracarboxylic dianhydride monomer is diphenyl tetracarboxylic dianhydride.
In a preferred embodiment, the aromatic diamine monomer is p-phenylenediamine.
In a preferred embodiment, the polycarboxylic acid compound is selected from one or more of 3,3',4' -biphenyltetracarboxylic acid, 2', 3' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid and pyromellitic acid.
In a preferred embodiment, the organic solvent a and the organic solvent B are the same or different polar aprotic solvents.
In a further preferred embodiment, the organic solvent a and the organic solvent B are independently selected from any one or more of N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide and dimethylsulfoxide.
Compared with the prior art, the invention has the following beneficial effects:
experiments prove that the polyamide acid slurry with the solid content up to 35 percent and the viscosity at 25 ℃ of only 2-20 Pa.s and obvious high-solid content and low-viscosity characteristics can be obtained by adopting the method, the process requirements of a subsequent tape casting coating line can be well met, a uniform coating film can be easily obtained, the use amount of an organic solvent can be greatly reduced, and the production cost and the environmental protection pressure of production enterprises can be obviously reduced; in particular, the polyimide film prepared from the polyamide acid slurry according to the prior art can lead the thermal decomposition temperature to be higher than 545 ℃, the thermal expansion coefficient to be 4-11 ppm/K and the tensile strength to be higher than 445MPa, and the prepared polyimide film has excellent heat resistance, dimensional stability and mechanical property and has obvious application value for industrially preparing high-quality polyimide films.
Detailed Description
The technical scheme of the invention is further and fully described in the following by combining examples and comparative examples. It should be understood that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
The experimental procedures, which do not address the specific conditions in the examples below, are generally carried out under conventional conditions or under conditions recommended by the manufacturer.
The test methods for each index referred to in the following examples and comparative examples are as follows:
1) Solid content: taking a certain amount of sample solution, wherein the mass of the sample solution is recorded as W1; in a vacuum hot air oven, heating was performed at 120℃for 10 minutes, then at 180℃for 20 minutes, then at 325℃for 30 minutes, and finally the mass of the remaining solid was measured and denoted as W2, the solid content= (W2/W1) ×100%.
2) Viscosity: viscosity measurements were carried out using a rotational viscometer, units: pa.s, test temperature 25 ℃.
3) Film formation quality evaluation: taking a certain amount of sample solution, placing the sample solution in a centrifugal deaerator with the model of TD5A, and deaerating for 3min at the rotating speed of 2000 rpm/min; after removing bubbles, coating the glass plate, and then putting the glass plate into an oven, wherein a step heating mode is adopted, namely: the temperature is kept at 120 ℃ for 60min, then at 180 ℃ for 30min, then at 300 ℃ for 20min and finally at 450 ℃ for 20min. The film obtained was visually observed for the presence or absence of significant defects such as holes, tears and bumps, and if no significant defects such as holes, tears and bumps were present, the film evaluation was rated as v and if significant defects such as holes, tears and bumps were present, the film evaluation was rated as x.
4) Heat resistance test: measuring the thermal decomposition temperature of the prepared polyimide film by using a thermal weightlessness analyzer, respectively weighing 5-10 mg of polyimide film, placing into a dry pot, and starting to flush at room temperature at a speed of 3 ℃/min in N 2 Heating to 800 ℃ under the atmosphere, recording a thermal weight loss curve within the range of 50-800 ℃, and calculating the thermal decomposition temperature Td (1%) of 1% of the material;
5) Thermal expansion performance test: test conditions are performed with reference to the A-method related specifications in ISO 11359-1:2014: cutting a polyimide film sample into blocks with the size of 5mm multiplied by 15 mm; adopting a film stretching mode, setting the load to 98mN, heating and cooling at a speed of 5 ℃/min under an N2 atmosphere, measuring the coefficient of thermal expansion (CTE/(ppm/K)) of the polyimide film within the range of 50-200 ℃ under the nitrogen flow of 200 mL/min; the laboratory environmental conditions were: the temperature is 23+/-2 ℃ and the humidity is 50+/-5%;
6) Mechanical property test: test conditions are performed with reference to ASTM D882-2012 related specifications: the width of the polyimide film sample is 10mm; the test speed is 50mm/min; the initial distance between the clamps is 100mm; the number of the sample bars is 5; the laboratory environmental conditions were: the temperature is 23+/-2 ℃ and the humidity is 50+/-10%; and taking the average value as a mechanical property test result of the polyimide film.
In addition, the following examples and comparative examples each use a three-necked flask as a reaction vessel, and a matched tetrafluoroethylene stirring paddle was installed in the reaction vessel as a stirring device; meanwhile, in order to prevent water from mixing in the reaction system, nitrogen is injected into the reaction vessel to form a nitrogen protective atmosphere.
Example 1
179.7g of N-methyl pyrrolidone (NMP) and 16.08g (0.1489 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 25 ℃ to obtain a p-phenylenediamine solution with the solid content of about 8.2%;
42.69g (0.1452 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 97.5% of PDA molar amount) was continuously added to the p-phenylenediamine solution, followed by stirring at 25℃for 12 hours to obtain a polyamic acid solution;
meanwhile, 2g of 3,3',4' -biphenyl tetracarboxylic acid is added into 98g of NMP solvent at 25 ℃, and the mixture is stirred until the mixture is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 2% is prepared; next, 61.5g of a 2% by mass tetracarboxylic acid solution (containing 1.23g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0037mol, and a molar amount of about 2.5% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 25℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 15.5pa.s, a solid content of 19.8%, and a film formation quality evaluation of ∈.
Example 2
179.7g of N-methyl pyrrolidone (NMP) and 16.08g (0.1489 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 25 ℃ to obtain a p-phenylenediamine solution with the solid content of about 8.2%;
42.69g (0.1452 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 97.5% of PDA molar amount) was continuously added to the p-phenylenediamine solution, followed by stirring at 25℃for 12 hours to obtain a polyamic acid solution;
meanwhile, 2g of 2,2', 3' -biphenyl tetracarboxylic acid is added into 98g of NMP solvent at 25 ℃, and the mixture is stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 2% is prepared; next, 61.5g of a 2% by mass tetracarboxylic acid solution (containing 1.23g of 2,2', 3' -biphenyltetracarboxylic acid, about 0.0037mol, and a molar amount of about 2.5% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 25℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 14.2pa.s, a solid content of 19.9%, and a film formation quality evaluation of-.
Example 3
193.5g of N-methyl pyrrolidone (NMP) and 16.16g (0.1496 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and the mixture is stirred under the constant temperature oil bath condition at 25 ℃ to obtain a p-phenylenediamine solution with the solid content of about 7.7 percent;
42.89g (0.1459 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 97.5% of PDA molar amount) was continuously added to the p-phenylenediamine solution, followed by stirring at 25℃for 12 hours to obtain a polyamic acid solution;
simultaneously, 1g of 1,2,3, 4-benzene tetracarboxylic acid was added to 49g of NMP solvent at 25℃and stirred until it was completely dissolved, to prepare a tetracarboxylic acid solution having a mass concentration of 2%; next, 47.5g of a 2% by mass tetracarboxylic acid solution (containing 0.95g of 1,2,3, 4-benzene tetracarboxylic acid, about 0.0037mol, and a molar amount of about 2.5% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 25℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 9.6pa.s, a solid content of 20.1%, and a film formation quality evaluation of-.
Example 4
166.2g of N-methyl pyrrolidone (NMP) and 20.08g (0.1859 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 30 ℃ to obtain a p-phenylenediamine solution with the solid content of about 10.8%;
52.47g (0.1785 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, molar amount: 96.0% of PDA) was continuously added to the above-mentioned p-phenylenediamine solution, followed by stirring at 30℃for 15 hours to obtain a polyamic acid solution;
meanwhile, 4g of 3,3',4' -biphenyl tetracarboxylic acid was added to 96g of NMP solvent at 30℃and stirred until it was completely dissolved, to prepare a tetracarboxylic acid solution having a mass concentration of 4%; next, 61.25g of a 4% by mass tetracarboxylic acid solution (containing 2.45g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0074mol, about 4% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 30℃for 24 hours to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 5.2pa.s, a solid content of 24.9%, and a film formation quality evaluation of-.
Example 5
140.9g of N-methylpyrrolidone (NMP) and 24.05g (0.2227 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition of 35 ℃ to obtain a p-phenylenediamine suspension with the solid content of about 14.6 percent (wherein the p-phenylenediamine is supersaturated and cannot be completely dissolved);
61.54g (0.2093 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 94.0% of PDA molar mass) was continuously added to the above-mentioned p-phenylenediamine suspension, followed by stirring at 35℃for 18 hours to obtain a polyamic acid solution;
meanwhile, 6g of 3,3',4' -biphenyl tetracarboxylic acid was added to 94g of NMP solvent at 35℃and stirred until it was completely dissolved, to prepare a tetracarboxylic acid solution having a mass concentration of 6%; next, 73.5g of a 6% by mass tetracarboxylic acid solution (containing 4.41g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0134mol, about 6% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 35℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 4.2pa.s, a solid content of 30.3%, and a film formation quality evaluation of-.
Example 6
Firstly, 133.4g of N-methyl pyrrolidone (NMP) and 28.01g (0.2594 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition of 40 ℃ to obtain a p-phenylenediamine suspension with the solid content of about 17.4 percent (wherein the p-phenylenediamine is supersaturated and cannot be completely dissolved);
70.14g (0.2386 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 92.0% molar amount of PDA) was continuously added to the above-mentioned p-phenylenediamine suspension, followed by stirring at 40℃for 24 hours to obtain a polyamic acid solution;
meanwhile, 10g of 3,3',4' -biphenyl tetracarboxylic acid is added into 90g of NMP solvent at 40 ℃, and the mixture is stirred until the mixture is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 10% is prepared; next, 68.5g of a tetracarboxylic acid solution having a mass concentration of 10% (containing 6.85g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0208mol, and a molar amount of about 8% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant-temperature oil bath at 40℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 3.6pa.s, a solid content of 35.4%, and a film formation quality evaluation of-.
Example 7
140.9g of N-methylpyrrolidone (NMP) and 24.05g (0.2227 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition of 35 ℃ to obtain a p-phenylenediamine suspension with the solid content of about 14.6 percent (wherein the p-phenylenediamine is supersaturated and cannot be completely dissolved);
61.54g (0.2093 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 94.0% of PDA molar mass) was continuously added to the above-mentioned p-phenylenediamine suspension, followed by stirring at 35℃for 18 hours to obtain a polyamic acid solution;
meanwhile, 6g of 3,3',4' -biphenyl tetracarboxylic acid is added into 94g of dimethyl sulfoxide (DMSO) solvent at 35 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 6% is prepared; next, 73.5g of a 6% by mass tetracarboxylic acid solution (containing 4.41g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0134mol, about 6% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 35℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 2.5pa.s, a solid content of 29.6%, and a film formation quality evaluation of ∈.
Example 8
Firstly, 133.4g of N-methyl pyrrolidone (NMP) and 28.01g (0.2594 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition of 40 ℃ to obtain a p-phenylenediamine suspension with the solid content of about 17.4 percent (wherein the p-phenylenediamine is supersaturated and cannot be completely dissolved);
70.14g (0.2386 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 92.0% molar amount of PDA) was continuously added to the p-phenylenediamine suspension, followed by stirring at 40℃for 24 hours to obtain a polyamic acid solution;
simultaneously, 10g of 3,3',4' -biphenyl tetracarboxylic acid is added into 90g of dimethyl sulfoxide (DMSO) solvent at 40 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 10% is prepared; next, 68.5g of a tetracarboxylic acid solution having a mass concentration of 10% (containing 6.85g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0208mol, and a molar amount of about 8% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant-temperature oil bath at 40℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 3.1pa.s, a solid content of 35.1%, and a film formation quality evaluation of-.
Example 9
140.9g of dimethyl sulfoxide (DMSO) and 24.05g (0.2227 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 35 ℃ to obtain a p-phenylenediamine solution with the solid content of about 14.6%;
61.54g (0.2093 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 94.0% of PDA molar mass) was continuously added to the p-phenylenediamine solution, followed by stirring at 35℃for 18 hours to obtain a polyamic acid solution;
meanwhile, 6g of 3,3',4' -biphenyl tetracarboxylic acid is added into 94g of dimethyl sulfoxide (DMSO) solvent at 35 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 6% is prepared; next, 73.5g of a 6% by mass tetracarboxylic acid solution (containing 4.41g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0134mol, about 6% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 35℃for 24 hours, to obtain a polyamic acid slurry.
The resulting polyamic acid slurry was tested to have a viscosity of 2.3pa.s, a solids content of 29.6%, and a film formation quality evaluation of-.
Example 10
Firstly, 133.4g of dimethyl sulfoxide (DMSO) and 28.01g (0.2594 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 40 ℃ to obtain a p-phenylenediamine solution with the solid content of about 17.4%;
70.14g (0.2386 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 92.0% of PDA molar weight) was continuously added to the p-phenylenediamine solution, followed by stirring at 40℃for 24 hours to obtain a polyamic acid solution;
simultaneously, 10g of 3,3',4' -biphenyl tetracarboxylic acid is added into 90g of dimethyl sulfoxide (DMSO) solvent at 40 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 10% is prepared; next, 68.5g of a tetracarboxylic acid solution having a mass concentration of 10% (containing 6.85g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0208mol, and a molar amount of about 8% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant-temperature oil bath at 40℃for 24 hours, to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 2.0pa.s, a solid content of 35.0%, and a film formation quality evaluation of-.
Example 11
Firstly, 179.7g of N, N-dimethylacetamide (DMAc) and 16.08g (0.1489 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 25 ℃ to obtain a p-phenylenediamine solution with the solid content of about 8.2%;
42.69g (0.1452 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 97.5% of PDA molar amount) was continuously added to the p-phenylenediamine solution, followed by stirring at 25℃for 12 hours to obtain a polyamic acid solution;
meanwhile, 2g of 3,3',4' -biphenyl tetracarboxylic acid is added into 98g of N, N-dimethylacetamide (DMAc) solvent at 25 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 2% is prepared; next, 61.5g of a 2% by mass tetracarboxylic acid solution (containing 1.23g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0037mol, and a molar amount of about 2.5% of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 25℃for 24 hours, to obtain a polyamic acid slurry.
The resulting polyamic acid slurry was tested to have a viscosity of 18.0pa.s, a solids content of 19.7%, and a film formation quality evaluation of-.
Example 12
166.2g of N, N-dimethylacetamide (DMAc) and 20.08g (0.1859 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 30 ℃ to obtain a p-phenylenediamine solution with the solid content of about 10.8%;
52.47g (0.1785 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, molar amount: 96.0% of PDA) was continuously added to the above-mentioned p-phenylenediamine solution, followed by stirring at 30℃for 15 hours to obtain a polyamic acid solution;
meanwhile, 4g of 3,3',4' -biphenyl tetracarboxylic acid is added into 96g of N, N-Dimethylformamide (DMF) solvent at 30 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 4% is prepared; next, 61.25g of a 4% by mass tetracarboxylic acid solution (containing 2.45g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0074mol, about 4% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 30℃for 24 hours to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 6.0pa.s, a solid content of 25.2%, and a film formation quality evaluation of-.
Example 13
166.2g of N, N-Dimethylformamide (DMF) and 20.08g (0.1859 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the condition of constant temperature oil bath at 30 ℃ to obtain a p-phenylenediamine solution with the solid content of about 10.8%;
52.47g (0.1785 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, molar amount: 96.0% of PDA) was continuously added to the above-mentioned p-phenylenediamine solution, followed by stirring at 30℃for 15 hours to obtain a polyamic acid solution;
meanwhile, 4g of 3,3',4' -biphenyl tetracarboxylic acid is added into 96g of N, N-Dimethylformamide (DMF) solvent at 30 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 4% is prepared; next, 61.25g of a 4% by mass tetracarboxylic acid solution (containing 2.45g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0074mol, about 4% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 30℃for 24 hours to obtain a polyamic acid slurry.
The obtained polyamic acid slurry was tested to have a viscosity of 4.2pa.s, a solid content of 25.0%, and a film formation quality evaluation of-.
Example 14
140.9g of N, N-Dimethylformamide (DMF) and 24.05g (0.2227 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 35 ℃ to obtain a p-phenylenediamine solution with the solid content of about 14.6%;
61.54g (0.2093 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 94.0% of PDA molar mass) was continuously added to the p-phenylenediamine solution, followed by stirring at 35℃for 18 hours to obtain a polyamic acid solution;
meanwhile, 6g of 3,3',4' -biphenyl tetracarboxylic acid is added into 94g of dimethyl sulfoxide (DMSO) solvent at 35 ℃ and stirred until the biphenyl tetracarboxylic acid is completely dissolved, so that a tetracarboxylic acid solution with the mass concentration of 6% is prepared; next, 73.5g of a 6% by mass tetracarboxylic acid solution (containing 4.41g of 3,3',4' -biphenyltetracarboxylic acid, about 0.0134mol, about 6% by mole of PDA) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 35℃for 24 hours, to obtain a polyamic acid slurry.
The resulting polyamic acid slurry was tested to have a viscosity of 2.6pa.s, a solids content of 29.4%, and a film formation quality evaluation of-.
Comparative example 1
240g of N-methyl pyrrolidone (NMP) and 16.11g (0.1493 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and the mixture is stirred under the constant temperature oil bath condition at 30 ℃ to obtain a p-phenylenediamine solution with the solid content of about 6.29%;
43.88g (0.1493 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, molar amount: 100% of PDA) was continuously added to the above-mentioned p-phenylenediamine solution, followed by stirring at 30℃for 12 hours to obtain a polyamic acid solution.
Through testing, the viscosity of the obtained polyamic acid solution is 193Pa.s, and the solid content is 20.6%; the film formation quality was evaluated as x because the viscosity was so high that coating was not easy and a uniform coating film could not be obtained.
Comparative example 2
240g of N-methyl pyrrolidone (NMP) and 16.08g (0.1489 mol) of p-Phenylenediamine (PDA) are added into a reaction vessel, and stirred under the constant temperature oil bath condition at 30 ℃ to obtain a p-phenylenediamine solution with the solid content of about 6.28%;
42.69g (0.1452 mol) of 3,3',4' -biphenyltetracarboxylic dianhydride (BPDA, 97.5% of PDA molar amount) was continuously added to the above-mentioned p-phenylenediamine solution, followed by stirring at 30℃for 12 hours to obtain a polyamic acid solution;
1.23g of 3,3',4' -biphenyltetracarboxylic acid (about 0.0037mol, about 2.5% of PDA molar amount) was added to the above polyamic acid solution, followed by stirring again in a constant temperature oil bath at 30℃for 24 hours to obtain a polyamic acid slurry, but the 3,3',4' -biphenyltetracarboxylic acid was not completely dissolved therein and could not be uniformly dispersed in the polyamic acid slurry.
Through testing, the viscosity of the obtained polyamide acid slurry is 11Pa.s, and the solid content is 20.3%; the film formation quality was evaluated as being so high that the coating was not easy and a uniform coating film could not be obtained.
Table 1 shows the performance test data of polyimide films prepared by the conventional preparation process using the polyamic acid slurries of examples 1 to 14 and comparative example 2, respectively.
TABLE 1 Performance test data for polyimide films
| Test sample | Td(1％)/℃ | CTE/ppm/K | Tensile Strength/MPa |
| Example 1 | 558 | 7 | 451 |
| Example 2 | 555 | 5 | 448 |
| Example 3 | 564 | 6 | 446 |
| Example 4 | 568 | 5 | 453 |
| Example 5 | 569 | 4 | 461 |
| Example 6 | 576 | 8 | 450 |
| Example 7 | 557 | 6 | 463 |
| Example 8 | 569 | 5 | 451 |
| Example 9 | 567 | 5 | 468 |
| Example 10 | 575 | 5 | 466 |
| Example 11 | 546 | 11 | 445 |
| Example 12 | 556 | 9 | 448 |
| Example 13 | 558 | 6 | 452 |
| Example 14 | 561 | 8 | 456 |
| Comparative example 2 | 530 | 18 | 380 |
The results shown in Table 1 can be seen: the polyamide acid slurry with obvious high solid content and low viscosity can be obtained by the method, the process requirement of a subsequent tape casting coating line can be well met, a uniform coating film can be easily obtained, and the polyimide film prepared by the method has excellent heat resistance, dimensional stability and mechanical property. Compared with the prior art (the solid content of the solution of the p-phenylenediamine is lower, and the added polycarboxylic acid compound is directly added as solid powder) under the same condition, the invention (see the example and the comparative example 2) can not only improve the thermal decomposition temperature of the prepared polyimide film from 530 ℃ to 558 ℃, improve 5.28 percent, reduce the thermal expansion coefficient from 18ppm/K to 7ppm/K, reduce 61.11 percent, improve the tensile strength from 380MPa to 451MPa and improve 18.68 percent, thus showing that the invention has obvious application value for industrially preparing the polyimide film with high quality.
Finally, it is pointed out here that: the above is only a part of the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adaptations of the present invention based on the foregoing are within the scope of the present invention.
Claims (6)
1. A method for preparing high solids low viscosity polyamic acid slurry, the preparation raw materials comprising: an aromatic tetracarboxylic dianhydride monomer, an aromatic diamine monomer and a polycarboxylic acid compound, wherein the sum of the molar amount of the aromatic tetracarboxylic dianhydride monomer and the molar amount of the polycarboxylic acid compound is equal to the molar amount of the aromatic diamine monomer, and the molar ratio of the aromatic tetracarboxylic dianhydride monomer to the polycarboxylic acid compound is (90:10) - (98:2); characterized in that the method comprises the following steps:
a) Adding the formula amount of aromatic diamine into the organic solvent A to prepare an aromatic diamine solution or an aromatic diamine suspension with 7.5-17.5% of solid content at 25-40 ℃;
b) Adding the formula amount of aromatic tetracarboxylic dianhydride monomer into the aromatic diamine solution or aromatic diamine suspension prepared in the step a), and stirring for 12-24 hours at 25-40 ℃ to obtain a polyamic acid solution;
c) Adding a polycarboxylic acid compound into an organic solvent B at 25-40 ℃ to prepare a polycarboxylic acid organic solution with the mass concentration of 2-10%, then adding the polycarboxylic acid organic solution with the mass concentration of 2-10% into the polyamic acid solution obtained in the step B), and continuously stirring for 12-36 hours at 25-40 ℃ to obtain polyamic acid slurry; wherein the addition amount of the polycarboxylic acid organic solution is required to satisfy the following conditions:
(1) the molar amount of polycarboxylic acid compound contained in the polycarboxylic acid organic solution added is the molar amount of aromatic diamine used in step a) minus the molar amount of aromatic tetracarboxylic dianhydride monomer used in step b);
(2) the sum of the mass of the organic solvent B contained in the added polycarboxylic acid organic solution and the mass of the organic solvent A used in the step a) can lead the solid content of the prepared polyamide acid slurry to reach 20-35 percent.
2. The method according to claim 1, characterized in that: the aromatic tetracarboxylic dianhydride monomer is diphenyl tetracarboxylic dianhydride.
3. The method according to claim 1, characterized in that: the aromatic diamine monomer is p-phenylenediamine.
4. The method according to claim 1, characterized in that: the polycarboxylic acid compound is selected from one or more of 3,3',4' -biphenyltetracarboxylic acid, 2', 3' -biphenyltetracarboxylic acid, 2, 3',4' -biphenyltetracarboxylic acid and pyromellitic acid.
5. The method according to claim 1, characterized in that: the organic solvent A and the organic solvent B are the same or different polar aprotic solvents.
6. The method according to claim 1 or 5, characterized in that: the organic solvent A and the organic solvent B are independently selected from any one or more of N-methyl pyrrolidone, N-dimethylformamide, N-dimethylacetamide or dimethyl sulfoxide.
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