CN113292726B - Polyimide molding powder and preparation method and application thereof - Google Patents
Polyimide molding powder and preparation method and application thereof Download PDFInfo
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- CN113292726B CN113292726B CN202110385724.2A CN202110385724A CN113292726B CN 113292726 B CN113292726 B CN 113292726B CN 202110385724 A CN202110385724 A CN 202110385724A CN 113292726 B CN113292726 B CN 113292726B
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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
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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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Abstract
The invention discloses polyimide molding powder and a preparation method and application thereof, wherein the preparation method of the polyimide molding powder comprises the steps of reacting a diamine monomer and a dianhydride monomer in a polar aprotic solvent to obtain a polyamic acid solution, adding an azeotropic dehydrating agent into the polyamic acid solution, heating to reflux reaction, cooling and crystallizing a reacted system, filtering, washing, drying, grinding and sieving, then drying and aging at high temperature, and finally sieving and grading by a rotary sieve to obtain the polyimide molding powder; wherein: the diamine monomer is terephthalic acid di-p-aminophenyl ester and/or p-aminobenzoic acid p-aminophenyl ester; the dianhydride monomer is one or more than two of PMDA, ODPA, BTDA, BPDA and DSDA. The polyimide molding powder has the glass transition temperature of more than 500 ℃, the water absorption of less than 0.5 percent, and lower linear thermal expansion coefficient and friction coefficient, and can be used for preparing aerospace precise parts.
Description
Technical Field
The invention belongs to the technical field of polyimide molding powder, and particularly relates to polyimide molding powder for preparing aerospace precision parts, and a preparation method and application thereof.
Background
Polyimide has been fully recognized as a structural material or a functional material due to its outstanding characteristics in terms of performance and synthesis, and is called "problem-solving". In recent years, the research, development and utilization of polyimide are one of the most promising engineering plastics in 21 st century in various countries.
At present, the glass transition temperature of the existing polyimide molding powder is mostly below 400 ℃, and the adopted diamine monomers are mostly diamino diphenyl ethers and/or phenylenediamines and/or benzimidazoles; for example, the glass transition temperature of VESPEL-SP1 molding powder (PMDA-ODA type) from DuPont is about 380 ℃; also, for example, chinese patent documents CN101392057A, CN103497335A, CN104710789A, CN105175721A, and the like; for the occasions with higher requirement on temperature resistance grade, the polyimide molding powder is difficult to meet the use requirement.
At present, there are also a few publications disclosing polyimide molding powders having a glass transition temperature of 400 ℃ or higher, such as chinese patent documents CN102604091A, CN104231269A, and the like; however, for the occasions with higher requirements on temperature resistance grade, such as aerospace precision parts, the polyimide molding powder is still difficult to meet the use requirements.
In addition, for aerospace precision parts, low hygroscopicity, low coefficient of linear thermal expansion and low coefficient of friction are required in addition to high temperature resistance, and the conventional polyimide molding powder has a water absorption rate of more than 1% and is difficult to meet the use requirements.
Disclosure of Invention
The invention aims to solve the problems and provides polyimide molding powder with low hygroscopicity, low linear thermal expansion coefficient, low friction coefficient and high temperature resistance, and a preparation method and application thereof.
The technical scheme for realizing the purpose of the invention is as follows: a polyimide molding powder is prepared from diamine monomers and dianhydride monomers; the diamine monomer is di-p-aminophenyl terephthalate (hereinafter abbreviated as BPTP) and/or p-aminobenzoic acid p-aminophenyl ester (hereinafter abbreviated as APAB).
The structure of the BPTP is as follows:
the structure of the APAB is as follows:
the dianhydride monomers are pyromellitic dianhydride (hereinafter abbreviated as PMDA), 3', 4' -diphenyl ether tetracarboxylic dianhydride (hereinafter abbreviated as ODPA), 3', 4' -benzophenone tetracarboxylic dianhydride (hereinafter abbreviated as BTDA), and 3,3', one or more (including two) of 4,4' -biphenyltetracarboxylic dianhydride [ hereinafter abbreviated as BPDA ] and 3,3', 4' -diphenylsulfone tetracarboxylic dianhydride [ hereinafter abbreviated as DSDA ], preferably PMDA.
The molar ratio of the diamine monomer to the dianhydride monomer is 1: 0.95-1: 1.05, preferably 1: 1.
The preparation method of the polyimide molding powder comprises the following steps:
(1) reacting a diamine monomer and a dianhydride monomer in a polar aprotic solvent to obtain a polyamic acid solution;
(2) adding an azeotropic dehydrating agent into the polyamic acid solution obtained in the step (1), and heating until reflux reaction;
(3) and (3) cooling and crystallizing the system reacted in the step (2), filtering, washing, drying, grinding and sieving, drying and aging at high temperature, and finally sieving and grading by a rotary sieve to obtain the polyimide molding powder.
In the step (1), the molar ratio of the diamine monomer to the dianhydride monomer is 1: 0.95-1: 1.05, preferably 1: 1.
The mass fraction of the polyamic acid solution in the step (1) is 5 to 45%.
In the step (1), the polar aprotic solvent is one or more (including two) of N-methylpyrrolidone (NMP), N-Cyclohexylpyrrolidone (CHP), and dimethyl sulfoxide (DMSO).
The reaction temperature in the step (1) is room temperature (15 to 25 ℃ C., the same applies hereinafter).
In the step (2), the azeotropic dehydrating agent is one or more than two (including two) of toluene, xylene, cyclopentanone and cyclohexanone.
The dosage of the azeotropic dehydrating agent is 15 to 30 percent of the dosage of the polar aprotic solvent.
In the step (3), one or more than two (including two) of methanol, ethanol, acetone and butanone are adopted for washing.
The drying temperature in the step (3) is 90-110 ℃, and the drying time is 1-2 h.
The high-temperature drying and aging in the step (3) is to dry the mixture at 170-190 ℃ for 1-2 h and then at 240-260 ℃ for 2-3 h.
The polyimide molding powder is applied to the preparation of aerospace precision parts.
The invention has the following positive effects: the polyimide molding powder has the glass transition temperature of more than 500 ℃, the water absorption of less than 0.5 percent, and lower linear thermal expansion coefficient and friction coefficient, and can be used for preparing aerospace precise parts.
Detailed Description
(example 1)
The preparation method of the polyimide molding powder of the present example had the following steps:
(1) 348.35g (1.0 mol) of BPTP and 2.18L of N-methylpyrrolidone were added to a 5L three-necked round-bottomed flask equipped with a mechanical stirrer, a thermometer and a nitrogen gas guard, and after stirring to form a homogeneous solution, 218.12g (1.0 mol) of PMDA was added in portions, and then the residual material was rinsed with 100mL of N-methylpyrrolidone, and the reaction was stirred at room temperature for 3 hours to obtain a polyamic acid solution (20% by mass).
(2) 456mL of toluene was added to the polyamic acid solution obtained in step (1), and the mixture was heated to reflux for 5 hours.
(3) And (3) cooling the system reacted in the step (2) for crystallization, filtering, washing a filter cake with acetone, drying at 100 ℃ for 1h, grinding and sieving, drying at 180 ℃ for 1h, drying at 250 ℃ for 2h, and finally sieving and grading by a rotary sieve to obtain the polyimide molding powder.
(examples 2 to 5)
The polyimide molding powders of the respective examples were prepared in substantially the same manner as in example 1, except that diamine monomers and dianhydride monomers were used, as specified in Table 1.
Comparative example 1
The polyimide molding powder of this comparative example was prepared in substantially the same manner as in example 1, except that the diamine monomer and the dianhydride monomer were used, as specified in Table 1.
TABLE 1
| Diamine monomer | Dianhydride monomer | |
| Example 1 | 348.35g（1.0mol）BPTP | 218.12g（1.0mol）PMDA |
| Example 2 | 228.25g（1.0mol）APAB | 294.22g（1.0mol）BPDA |
| Example 3 | 114.13g（0.5mol）BPTP+174.18g（0.5mol）APAB | 218.12g（1.0mol）PMDA |
| Example 4 | 228.25g（1.0mol）APAB | 109.06g（0.5mol）PMDA +155.11g（0.5mol）ODPA |
| Example 5 | 348.35g（1.0mol）BPTP | 294.22g（1.0mol）BPDA |
| Comparative example 1 | 200.24g (1.0 mol) of 4,4' -diaminodiphenyl ether [ ODA ] | 218.12g（1.0mol）PMDA |
(test example)
The polyimide molding powders obtained in the examples and comparative examples were tested for their relevant properties and the results are shown in Table 2. Wherein:
D 50 the testing method of the granularity is as follows: the particle size distribution of the sample was measured by using a BT-9300ST laser particle size analyzer (Dandong Baite instruments Co., ltd.) according to the national standard GB/T19077-2016 particle size distribution laser diffraction method.
Intrinsic viscosity test method: part 5 of the viscosity of the dilute polymer solution was determined according to the national standard GB/T1632.5-2008 for plastics using a capillary viscometer: thermoplastic homo-and copolyester (TP) tests; the test conditions were: NMP as solvent, 0.5% concentration and 30 deg.C test temperature.
Method for testing Water absorption: adopting an HR-83 moisture rapid tester according to the national standard GB/T12006.2-2009 plastic polyamide part 2: method A test in Water content determination.
TABLE 2
| D 50 Particle size | Intrinsic viscosity | Water absorption rate | |
| Example 1 | 14.85μm | 0.9dl/g | 0.36% |
| Example 2 | 11.92μm | 1.2dl/g | 0.27% |
| Example 3 | 15.18μm | 1.1dl/g | 0.39% |
| Example 4 | 11.37μm | 1.2dl/g | 0.25% |
| Example 5 | 12.25μm | 1.0dl/g | 0.23% |
| Comparative example 1 | 22.55μm | 0.8dl/g | 1.00% |
(application example 1)
The polyimide molding powder prepared in the example 1 is added into a QLB/D-500T flat plate vulcanizing machine, the temperature and the pressure are raised to 250 ℃ and 10MPa for 30min, then the gas is discharged, the temperature and the pressure are raised to 400 ℃ and 100MPa for 2h, then the gas is discharged, the temperature and the pressure are reduced to 200 ℃, and finally the demolding is carried out, thus obtaining the polyimide molded product.
The polyimide molded articles were tested for their relevant properties and the results are shown in Table 3. Wherein:
the method for testing the linear expansion coefficient comprises the following steps: a thermo-mechanical analysis (TMA) instrument Q400 (TA, USA) is adopted, the temperature range is 100-600 ℃, the heating rate is 5 ℃/min, and the atmosphere is nitrogen.
Glass transition temperature test method: a Q800 dynamic thermal mechanical analyzer (DMA) instrument manufactured by TA of America is adopted, the temperature range is 100-600 ℃, the heating rate is 5 ℃/min, and the atmosphere is nitrogen.
The friction coefficient test method comprises the following steps: the test is carried out by adopting an M-200 friction wear testing machine (Beijing crown test electro-rectification equipment Co., ltd.) according to the national standard GB/T3960-2016 plastic sliding friction wear test method.
(application examples 2 to 5)
Polyimide molded articles obtained by the polyimide molding powders obtained in examples 2 to 5 were each prepared by the method of application example 1, and the relevant properties were measured, and the results are shown in Table 3.
(comparative application example)
The polyimide molding powder obtained in comparative example 1 was used to prepare a polyimide molded article by the method of application example 1, and the results of the tests for the relevant properties are shown in Table 3.
TABLE 3
| Coefficient of linear thermal expansion | Glass transition temperature | Coefficient of friction | |
| Example 1 | -1ppm/K | 559℃ | 0.10 |
| Example 2 | 38ppm/K | 547℃ | 0.13 |
| Example 3 | 2ppm/K | 550℃ | 0.12 |
| Example 4 | 25ppm/K | 538℃ | 0.15 |
| Example 5 | 12ppm/K | 537℃ | 0.12 |
| Comparative example 1 | 41ppm/K | 380℃ | 0.20 |
As can be seen from table 3: the polyimide molded product adopting PMDA as dianhydride monomer has higher glass transition temperature and lower linear thermal expansion coefficient.
Claims (10)
1. A polyimide molding powder is prepared from diamine monomers and dianhydride monomers; the method is characterized in that: the diamine monomer is terephthalic acid di-p-aminophenyl ester and/or p-aminobenzoic acid p-aminophenyl ester.
2. The polyimide molding powder according to claim 1, characterized in that: the dianhydride monomers are pyromellitic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, and 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride.
3. The polyimide molding powder according to claim 1 or 2, characterized in that: the molar ratio of the diamine monomer to the dianhydride monomer is 1: 0.95-1: 1.05.
4. A method for preparing polyimide molding powder comprises the following steps: (1) diamine monomer and dianhydride monomer react in polar aprotic solvent to obtain polyamic acid solution; the diamine monomer is di-p-aminophenyl terephthalate and/or p-aminobenzoic acid p-aminophenyl ester; (2) adding an azeotropic dehydrating agent into the polyamic acid solution obtained in the step (1), and heating to reflux reaction; (3) and (3) cooling and crystallizing the system reacted in the step (2), filtering, washing, drying, grinding and sieving, drying and aging at high temperature, and finally sieving and grading by a rotary sieve to obtain the polyimide molding powder.
5. The method of producing a polyimide molding powder according to claim 4, characterized in that: the dianhydride monomers are pyromellitic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, and 3,3', 4' -diphenyl sulfone tetracarboxylic dianhydride.
6. The method of producing a polyimide molding powder according to claim 4 or 5, characterized in that: in the step (1), the molar ratio of the diamine monomer to the dianhydride monomer is 1: 0.95-1: 1.05; the mass fraction of the polyamic acid solution is 5-45%; the polar aprotic solvent is one or more than two of N-methyl pyrrolidone, N-cyclohexyl pyrrolidone and dimethyl sulfoxide.
7. The method of producing a polyimide molding powder according to claim 4 or 5, characterized in that: the azeotropic dehydrating agent in the step (2) is one or more than two of toluene, xylene, cyclopentanone and cyclohexanone; the dosage of the azeotropic dehydrating agent is 15 to 30 percent of the dosage of the polar aprotic solvent in the step (1).
8. The method of producing a polyimide molding powder according to claim 4 or 5, characterized in that: in the step (3), one or more than two of methanol, ethanol, acetone and butanone are adopted for washing; the drying temperature is 90-110 ℃, and the drying time is 1-2 h; the high-temperature drying and aging is to dry the mixture for 1 to 2 hours at the temperature of between 170 and 190 ℃ and then dry the mixture for 2 to 3 hours at the temperature of between 240 and 260 ℃.
9. Use of the polyimide molding powder according to claim 1 or 2 for the production of aerospace precision parts.
10. Use of the polyimide molding powder of claim 3 for the production of aerospace precision parts.
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| CN112940253A (en) * | 2015-09-24 | 2021-06-11 | 旭化成株式会社 | Polyimide precursor, resin composition, and method for producing resin film |
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