CN113817188A - Polyimide film and preparation method thereof - Google Patents
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Abstract
The application discloses a polyimide film and a preparation method thereof, and introduces an asymmetric structure and a flexible group into a polyimide structure through molecular design. On one hand, the rigid benzene ring of the polymer main chain can keep the heat resistance and the mechanical property of the polymer, so that the thermal decomposition temperature of the polymer exceeds 400 ℃, and the tensile strength of the polymer reaches about 100 MPa. On the other hand, the asymmetric structure and the flexible group destroy the close packing of polyimide molecular chains, reduce the acting force among the molecular chains, reduce the glass transition temperature of the polymer, improve the solubility, and ensure that the glass transition temperature Tg is lower than 250 ℃, and the polymer can be dissolved in organic solvents such as DMF, DMAc and the like at normal temperature.
Description
Technical Field
The application relates to the technical field of polymers, in particular to a polyimide film and a preparation method thereof.
Background
The aromatic polyimide is a polyimide material taking aromatic heterocycles as a main polymer chain, has excellent performance, and is the only commercialized aromatic heterocycle polymer material. Aromatic polyimides have excellent heat resistance because of a large number of aromatic heterocycles in the molecular main chain, and the heat resistance of general varieties exceeds 500 ℃ and some varieties can exceed 600 ℃. Meanwhile, certain mechanical strength can be still maintained in liquid nitrogen. The aromatic polyimide has good mechanical property, and the tensile strength of the unfilled polyimide plastic is more than 100 MPa. As engineering plastics, the elastic modulus is usually 3-4 GPa, and the fiber can reach 200 GPa; according to theory, the fiber synthesized by the pyromellitic dianhydride and the p-phenylenediamine can reach 500GPa, and is second to the carbon fiber. And can be used for aerospace materials due to low volatile content under vacuum condition. The aromatic polyimide has good heat resistance, and also has excellent dimensional stability, oxidation stability, chemical corrosion resistance, irradiation resistance, good mechanical properties and dielectric properties. It also has good biocompatibility, can be used to make medical instruments and tableware, and can be sterilized thousands of times. Blood compatibility experiments show that the polyimide has nonhemolytic property and in vitro cytotoxicity experiments prove that the polyimide is non-toxic. However, the aromatic heterocyclic ring in the aromatic polyimide structure also causes the polyimide to be difficult to dissolve, and is difficult to dissolve in most organic solvents; at the same time, the polymer is difficult to melt, and the glass transition temperature of the polymer is generally more than 250 ℃. Some varieties have glass transition temperatures in excess of 400 ℃. The defect of difficult dissolution of refractory materials brings great difficulty to the processing of the materials.
Content of application
The application provides a polyimide film and a preparation method thereof, which can enable the polyimide film to have better processing performance and wider application prospect.
The following technical scheme is adopted in the application:
the application provides a polyimide film, which comprises a polymer with a chemical structural formula shown in a formula 1:
in formula 1, n is the number of degrees of polymerization;
ar is any one of the following structures:
the chemical structural formula of R is shown as formula 2,
in formula 2, Ar' is any one of the following structures:
the polyimide film is specifically a soluble polyimide film containing an asymmetric structure, and the polyimide film is prepared by introducing the asymmetric structure and a flexible group into a polyimide main chain through polymerization. That is, compared with the conventional polyimide film, the polymer main chain of the polyimide film with an asymmetric structure is chemically bonded with a flexible group, and the symmetric structure and regularity of the molecular chain are destroyed. The flexible group can improve the fluidity of a polyimide molecular chain, thereby improving the solubility and the melting property of the polyimide and reducing the glass transition temperature of the polymer. The asymmetric structure enables the polyimide molecular chain segment to be distorted, reduces or destroys a conjugated system of the polyimide molecular main chain, and can effectively reduce the close degree of the molecular chain segment accumulation, thereby reducing the intermolecular force.
Further, the polyimide film is prepared from aromatic dianhydride and diamine monomer containing a symmetrical structure and a flexible group.
The application also provides a preparation method of the polyimide film, which comprises the following steps: step 1) completely dissolving diamine containing a symmetrical structure and a flexible group in an organic solvent in an inert gas atmosphere, and then adding aromatic dianhydride to obtain a polyamic acid solution. And 2) coating the polyamic acid solution on a substrate, curing, completely cyclizing, stripping and drying to obtain the polyimide film.
The polyimide film prepared by the preparation method is good in dissolving performance, and in addition, the preparation method is simple and mature and can realize mass production.
Further, the aromatic dianhydride is one or a combination of several of pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 4,4' - (hexafluoroisopropyl) diphthalic anhydride and 2, 6-bis [4- (3 ", 4" -dicarboxyphenoxy) benzoyl ] pyridine dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride and 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride.
Further, the diamine monomer is 3-amino-4 ' -aminobenzoylbenzene, 4' -diamino-3, 4' -diamido-benzoylbenzene, 2-trifluoromethyl-diaminodiphenyl ether, 5-amino-2- (4-aminophenoxy) -pyridine, 4-amino-4 ' (4-amino-2-fluoromethylphenoxy) -benzophenone, 3-amino-4 ' (4-amino-2-fluoromethylphenoxy) -benzophenone, 1,4- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene, 1,3- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene, or a mixture thereof, 1,4- (2 ', 4' -diamino-diphenoxy) benzene and 1,4- (2 ', 3' -diamino-diphenoxy) benzene.
Further, the organic solvent is one or a combination of several of N-methyl-2-pyrrolidone, N-dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
Further, the molar ratio of the diamine monomer to the aromatic dianhydride is 0.96-1.04: 1.
Further, the addition temperature of the aromatic dianhydride is 10-15 ℃. In the polycondensation reaction of the aromatic diamine and the aromatic dianhydride in the step 1, the reaction is exothermic. To allow the reaction to proceed in the forward direction, the aromatic dianhydride is chosen to be added at a low temperature, and the experimental addition temperature is chosen to be between 10 ℃ and 15 ℃.
Further, the curing conditions were: drying at 80-100 deg.C for 12-24 hr.
Further, the conditions for complete cyclization were: sequentially drying at 110-130 ℃ for 0.5-1.5h, at 140-160 ℃ for 0.5-1.5h, at 170-190 ℃ for 0.5-1.5h, at 200-220 ℃ for 0.5-1.5h, and at 240-260 ℃ for 0.5-1.0 h. Complete cyclization is a temperature-programmed process.
Further, the substrate is any one of a glass plate, a resin plate, a silicon wafer, and a stainless steel plate.
Further, the solid content of the polyamic acid solution is 10 wt% to 30 wt%. The film forming property is influenced by too low solid content, the film is brittle and even does not form, the solution with too high solid content is viscous, and the performance is influenced by the uneven film thickness.
Compared with the prior art, the method has the following beneficial effects:
according to the preparation method, an asymmetric structure and a flexible group are introduced into a polyimide structure through molecular design, so that on one hand, a rigid benzene ring of a polymer main chain can keep the heat resistance and the mechanical property of a polymer, the thermal decomposition temperature of the polymer exceeds 400 ℃, and the tensile strength of the polymer reaches about 100 MPa; on the other hand, the asymmetric structure and the flexible group destroy the close packing of polyimide molecular chains, reduce the acting force among the molecular chains, reduce the glass transition temperature of the polymer, improve the solubility, and ensure that the glass transition temperature Tg is lower than 250 ℃, and the polymer can be dissolved in organic solvents such as DMF, DMAc and the like at normal temperature. The obtained polyimide film has better processing performance and wider application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a thermogravimetric plot of a polyimide film in the examples of the present application;
FIG. 2 is a DSC chart of a polyimide film in the examples of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
Example 1
(1) Under inert gas, 3.6g (0.01mol) of 1,4- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene and 53g of NMP were added to a 50mL three-necked flask equipped with mechanical stirring and completely dissolved at room temperature with stirring. Then 3.1g (0.01mol) of 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 15 wt%.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 24 hours at the temperature of 80 ℃. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 550 ℃, a glass transition temperature of 230 ℃ and a tensile strength of 121 MPa. Thermogravimetry and DSC spectra referring to figures 1, 2, the solubility data is shown in the following table:
(ii) a ++: soluble at room temperature; +: heating to 80 deg.C to dissolve; + -: heating to 80 deg.C to make it partially soluble; - -: insoluble at 80 ℃.
Example 2
(1) 2.91g (0.00995mol) of 1,4- (2, 4' -diamino-diphenoxy) benzene and 30g of DMAc were added to a three-necked flask with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. 4.51g (0.0101mol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were then added portionwise at 12 ℃ and reacted at room temperature for 24h to give a polyamic acid solution having a solid content of 20% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 12 hours at the temperature of 100 ℃. Then, thermal amidation was carried out in a muffle furnace to complete cyclization, which is a stepwise temperature rise process, and the specific steps were 110 ℃ for 1.5h, 140 ℃ for 1.5h, 170 ℃ for 1.5h, 200 ℃ for 1.5h, and 240 ℃ for 1.0 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 548 ℃, a glass transition temperature of 245 ℃ and a tensile strength of 109 MPa.
Example 3
(1) Under inert gas, 4.32g (0.012mol) of 1,3- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene and 46g of DMF were added to a three-necked flask equipped with mechanical stirring and completely dissolved by stirring at room temperature. Then 3.79g (0.0117mol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride was added in portions at 15 ℃ and reacted at room temperature for 16 hours to obtain a polyamic acid solution having a solid content of 15 wt%.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 18 hours at the temperature of 90 ℃. Then, thermal amidation was carried out in a muffle furnace to complete cyclization, which is a stepwise temperature rise process, and the specific steps were 0.5h at 130 ℃, 0.5h at 160 ℃, 0.5h at 190 ℃, 0.5h at 220 ℃ and 0.5h at 260 ℃. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 545 ℃, a glass transition temperature of 217 ℃ and a tensile strength of 110 MPa.
Example 4
(1) 2.12g (0.01mol) of 3-amino-4' -aminobenzoylbenzene and 40g of NMP were added to a three-necked flask equipped with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. Then 3.25g (0.0101mol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 18% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 24 hours at the temperature of 80 ℃. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film has the thermal decomposition temperature of 420 ℃, the glass transition temperature of 219 ℃ and the tensile strength of 99 MPa.
Example 5
(1) Under the protection of inert gas, 0.01mol of 3-amino-4 '-aminobenzoylbenzene or 1,4- (2, 4' -diamino-diphenoxy) benzene and 45g of NMP or 35g of DMAc were added into a three-necked flask equipped with mechanical stirring and stirred at room temperature to be completely dissolved. Then 0.0103mol of 3,3',4,4' -benzophenonetetracarboxylic dianhydride or 4,4' - (hexafluoroisopropyl) diphthalic anhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 10 wt%.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 24 hours at the temperature of 80 ℃. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 435 ℃, a glass transition temperature of 230 ℃ and a tensile strength of 100 MPa.
Example 6
(1) Under the protection of inert gas, 0.01mol of 3-amino-4 '-aminobenzoylbenzene or 1,4- (2, 4' -diamino-diphenoxy) benzene and 30g of NMP or 20g of DMAc are added into a three-necked flask with mechanical stirring and stirred to be completely dissolved at room temperature. Then, 0.0101mol of 3,3',4,4' -benzophenonetetracarboxylic dianhydride or 4,4' - (hexafluoroisopropyl) diphthalic anhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 30% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 24 hours at the temperature of 80 ℃. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 450 ℃, a glass transition temperature of 245 ℃ and a tensile strength of 115 MPa.
Some embodiments of the present application are different from the above embodiments in that the diamine monomer, the aromatic dianhydride and the organic solvent are other optional diamine monomers, aromatic dianhydrides and organic solvents, which are not described in detail herein.
Comparative example 1
(1) 2.12g (0.01mol) of 3-amino-4' -aminobenzoylbenzene and 40g of NMP were added to a three-necked flask equipped with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. Then 3.25g (0.0101mol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 18% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 24 hours at the temperature of 70 ℃. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film has the thermal decomposition temperature of 400 ℃, the glass transition temperature of 200 ℃ and the tensile strength of 75 MPa.
Comparative example 2
(1) 2.12g (0.01mol) of 3-amino-4' -aminobenzoylbenzene and 40g of NMP were added to a three-necked flask equipped with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. Then 3.25g (0.0101mol) of 3,3',4,4' -benzophenonetetracarboxylic dianhydride was added in portions at 10 ℃ and reacted at room temperature for 24 hours to obtain a polyamic acid solution having a solid content of 18% by weight.
(2) The polyamic acid obtained in (1) was defoamed in vacuum, spread on a glass plate, and cured in an oven to volatilize the solvent under 105 ℃ for 24 hours. Then carrying out thermal amidation in a muffle furnace to complete cyclization, wherein the complete cyclization is a step heating process and comprises the specific steps of maintaining at 120 ℃ for 1h, maintaining at 150 ℃ for 1h, maintaining at 180 ℃ for 1h, maintaining at 210 ℃ for 1h and maintaining at 250 ℃ for 1 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film had a thermal decomposition temperature of 390 ℃, a glass transition temperature of 200 ℃ and a tensile strength of 70 MPa.
Comparative example 3
(1) 2.91g (0.00995mol) of 1,4- (2, 4' -diamino-diphenoxy) benzene and 30g of DMAc were added to a three-necked flask with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. 4.51g (0.0101mol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were then added portionwise at 12 ℃ and reacted at room temperature for 24h to give a polyamic acid solution having a solid content of 20% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 10 hours at the temperature of 90 ℃. Then, thermal amidation was carried out in a muffle furnace to complete cyclization, which is a stepwise temperature rise process, and the specific steps were 110 ℃ for 1.5h, 140 ℃ for 1.5h, 170 ℃ for 1.5h, 200 ℃ for 1.5h, and 240 ℃ for 1.0 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film has the thermal decomposition temperature of 400 ℃, the glass transition temperature of 200 ℃ and the tensile strength of 80 MPa.
Comparative example 4
(1) 2.91g (0.00995mol) of 1,4- (2, 4' -diamino-diphenoxy) benzene and 30g of DMAc were added to a three-necked flask with mechanical stirring under inert gas and stirred at room temperature to dissolve completely. 4.51g (0.0101mol) of 4,4' - (hexafluoroisopropyl) diphthalic anhydride were then added portionwise at 12 ℃ and reacted at room temperature for 24h to give a polyamic acid solution having a solid content of 20% by weight.
(2) And (2) defoaming the polyamic acid obtained in the step (1) in vacuum, spreading the polyamic acid on a glass plate, and curing and volatilizing the solvent in an oven for 30 hours at the temperature of 90 ℃. Then, thermal amidation was carried out in a muffle furnace to complete cyclization, which is a stepwise temperature rise process, and the specific steps were 110 ℃ for 1.5h, 140 ℃ for 1.5h, 170 ℃ for 1.5h, 200 ℃ for 1.5h, and 240 ℃ for 1.0 h. After the polyimide film is obtained, the glass plate is soaked in deionized water, and then the film falls off and is dried.
The obtained imide film was subjected to infrared spectroscopic analysis, thermogravimetric analysis, DSC analysis, mechanical property analysis and solubility test. Wherein, the infrared spectrum analysis adopts a Fourier infrared spectrometer for measurement, the sample preparation method adopts a KBr tablet pressing method or a thin film (with the thickness of 10-20 μm), and the measuring range is 4000-500cm < -1 >. Thermogravimetric analysis was carried out using a TGA analyzer with a temperature rise rate of 20 ℃/min and a sample size of about 5 mg. DSC analysis is measured by a calorimetric differential scanning analyzer, and the heating rate in nitrogen protection is 20 ℃/min. The mechanical property analysis is carried out by adopting a universal tester, and the drawing speed is 100 mm/min. Solubility test method: under stirring, 10mg of the polymer was placed in 1mL of an organic solvent, and the polymer was first observed for dissolution at room temperature, and if insoluble, the polymer was observed for dissolution by heating. The results are as follows:
the obtained polyimide film has the thermal decomposition temperature of 450 ℃, the glass transition temperature of 280 ℃ and the tensile strength of 120 MPa.
By comparing comparative examples 1 to 4, it is understood that the polyimide film obtained under the curing conditions of the present application is better in thermal decomposition temperature, glass transition temperature and tensile strength.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A polyimide film comprising a polymer having a chemical formula as shown in formula 1:
in formula 1, n is the number of degrees of polymerization;
ar is any one of the following structures:
the chemical structural formula of R is shown as formula 2,
in formula 2, Ar' is any one of the following structures:
2. the polyimide film according to claim 1,
the polyimide film is prepared from aromatic dianhydride and diamine monomer containing symmetric structure and flexible group.
3. A preparation method of a polyimide film is characterized by comprising the following steps:
step 1) completely dissolving diamine containing a symmetrical structure and a flexible group in an organic solvent in an inert gas atmosphere, and then adding aromatic dianhydride to obtain a polyamic acid solution;
and 2) coating the polyamic acid solution on a substrate, curing, completely cyclizing, stripping and drying to obtain the polyimide film.
4. The method according to claim 3,
the aromatic dianhydride is one or a combination of more of pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 4,4' - (hexafluoroisopropyl) diphthalic anhydride and 2, 6-bis [4- (3 ', 4' -dicarboxyphenoxy) benzoyl ] pyridine dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride and 3,3',4,4' -diphenyl sulfone tetracarboxylic dianhydride.
5. The method according to claim 3,
the diamine monomer is 3-amido-4 ' -aminobenzoyl benzene, 4' -diamino-3, 4' -diamido-benzoyl benzene, 2-trifluoromethyl-diaminodiphenyl ether, 5-amino-2- (4-aminophenoxy) -pyridine, 4-amino-4 ' (4-amino-2-fluoromethylphenoxy) -benzophenone, 3-amino-4 ' (4-amino-2-fluoromethylphenoxy) -benzophenone, 1,4- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene, 1,3- (2 ' -trifluoromethyl-4 ', 4' -diaminophenoxy) benzene, or a mixture thereof, 1,4- (2 ', 4' -diamino-diphenoxy) benzene and 1,4- (2 ', 3' -diamino-diphenoxy) benzene.
6. The method according to claim 3,
the organic solvent is one or a combination of several of N-methyl-2-pyrrolidone, N-dimethylformamide, dimethylacetamide and dimethyl sulfoxide.
7. The method according to claim 3,
the molar ratio of the diamine monomer to the aromatic dianhydride is 0.96-1.04: 1.
8. The method according to claim 3,
the adding temperature of the aromatic dianhydride is 10-15 ℃.
9. The method according to claim 3,
the curing conditions are as follows: drying at 80-100 deg.C for 12-24 hr.
10. The method according to claim 3,
the conditions for complete cyclization are as follows: sequentially drying at 110-130 ℃ for 0.5-1.5h, at 140-160 ℃ for 0.5-1.5h, at 170-190 ℃ for 0.5-1.5h, at 200-220 ℃ for 0.5-1.5h, and at 240-260 ℃ for 0.5-1.0 h.
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| CN114230791B (en) * | 2021-12-29 | 2023-10-24 | 山东华夏神舟新材料有限公司 | Intrinsic low-dielectric fluorine-containing polyimide film and preparation method thereof |
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