CN113667304B - Light-colored transparent bending-resistant semi-aromatic polyimide film and preparation method thereof - Google Patents
Light-colored transparent bending-resistant semi-aromatic polyimide film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a light-colored transparent bending-resistant semi-aromatic polyimide film and a preparation method thereof; uniformly coating the nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a base material, eliminating bubbles, heating to 300 +/-2 ℃, and cooling and stripping to obtain the nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution; the nano silicon dioxide/crown ether-semi-aromatic polyamide acid compound solution is obtained by adding nano silicon dioxide dispersion liquid into the crown ether-semi-aromatic polyamide acid compound solution; the crown ether-semi-aromatic polyamic acid compound solution is prepared by dissolving alicyclic diamine and crown ether containing heterocyclic ring or aromatic ring substituent in polar organic solvent, stirring and adding 3,3', 4' -biphenyl tetracarboxylic anhydride for reaction. The semi-aromatic polyimide obtained by the invention has high thermal stability, high strength, low thermal expansion coefficient, light color, transparency and enough bending resistance, and can well meet the manufacturing requirements of flexible electronic devices.
Description
Technical Field
The invention relates to a semi-aromatic polyimide film, in particular to a light-colored, transparent and bending-resistant semi-aromatic polyimide film and a preparation method thereof, belonging to the technical field of modification of organic polymer film materials.
Background
The Polyimide (PI) is generally a wholly aromatic polyimide obtained by condensation polymerization of aromatic dianhydride and aromatic diamine, and the molecular chain of the polyimide comprises a very stable five-membered imide heterocycle and a high-density aromatic ring, and has a regular structure, excellent heat resistance, a low thermal expansion coefficient, high strength and the like, and is widely applied to the microelectronic industry. However, since a charge transfer complex is formed in and among molecules, the film has strong absorption in a visible light region, and the prepared film is yellow to dark brown, so that the application requirements of a cover plate, a substrate and the like in a flexible electronic device on light color or even colorless transparency are difficult to meet. The semi-aromatic polyimide obtained by condensation polymerization of an alicyclic structure in one of dianhydride and diamine monomers has a lighter color and higher transparency because the charge transfer effect between molecular chains is weakened because pi electrons do not exist in the alicyclic structure.
Chinese patent application CN112194791A discloses a transparent polyimide film, which is polymerized from diamine compound and dianhydride compound containing both imide structure and alicyclic structure, and utilizes the planar characteristics of the bisimide structure in the dianhydride compound to improve the packing density of molecular chains and reduce the thermal expansion coefficient; however, the dianhydride compound used for preparing the polyimide has a complex structure, and the preparation and purification processes are complex, so that the practical application is difficult to obtain. Alicyclic diamines such as 1, 4-diaminocyclohexane and 4,4' -diaminodicyclohexylmethane are common diamine compounds, but due to strong alkalinity, the alicyclic diamines and aromatic dianhydride 3,3', 4' -biphenyl tetracarboxylic anhydride have serious salt forming effect, which prevents the reaction of the alicyclic diamines and aromatic dianhydride 3,3', 4' -biphenyl tetracarboxylic anhydride and the like to obtain high molecular weight semi-aromatic polyimide, and the five-membered imide of the semi-aromatic polyimide has high distribution density on a molecular chain, so that the obtained semi-aromatic polyimide film is very brittle and cannot be bent. The method is used for preparing the semi-aromatic polyimide film which has light color, transparency, bending resistance, high thermal stability, high strength and low thermal expansion coefficient by using the conventional semi-aromatic polyimide polymerization and film forming conditions and methods and using commercial raw materials such as 1, 4-diaminocyclohexane or 4,4' -diaminodicyclohexylmethane and the like, and has very important significance for the application in the fields of flexible electronic devices and the like. The polyimide film has better effects of increasing thermal stability, strengthening and toughening by introducing the nano silicon dioxide particles, but the light transmittance of the polyimide film is generally influenced by the adding mode and the using amount of the nano silicon dioxide, so that the film with good transparency is difficult to obtain.
The invention patent application CN201410612335.9 in China is a crown ether modified polyimide hybrid membrane and a preparation method thereof, the method is characterized in that crown ether and aromatic diamine are dissolved in a polar organic solvent under the conditions that the humidity is lower than 50%, the room temperature and mechanical stirring are carried out, and the crown ether/diamine inclusion compound solution is obtained by continuously stirring after the crown ether and the aromatic diamine are completely dissolved; adding aromatic dianhydride into the crown ether/diamine inclusion compound solution, and continuously stirring after the aromatic dianhydride is added to obtain crown ether modified polyamic acid solution; uniformly coating the crown ether modified polyamide acid solution on a clean glass sheet to eliminate bubbles; heating according to a set program, cooling to room temperature after treatment, demoulding and drying to obtain the crown ether modified polyimide hybrid membrane. The crown ether molecules are sleeved on the polyamide acid chains to form a neck ring type supramolecular structure, polyimide molecular chains are expanded from two dimensions to three dimensions, the flexibility of the molecular chains is reduced, the rigidity is improved, the tensile strength and the elongation at break of the film are improved, but the thermal expansion coefficient is increased and the thermal stability is deteriorated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a semi-aromatic polyimide film which has high thermal stability, high strength, low thermal expansion coefficient, light color, transparency and bending resistance, can well meet the manufacturing requirement of a flexible electronic device, resists bending and has light color and transparency, and a preparation method thereof.
According to the invention, the nano silicon dioxide and crown ether are used for modifying the semi-aromatic polyimide, and on the premise of basically keeping the light color and transparency of the semi-aromatic polyimide film, the semi-aromatic polyimide film is subjected to reinforcing, toughening and flexibility increasing modification, the tensile strength and elongation at break are simultaneously and obviously improved, and the low thermal expansion coefficient and the high T are maintained 5％ And (4) horizontal. The obtained semi-aromatic polyimide has high thermal stability, high strength, low thermal expansion coefficient, light color, transparency and enough bending resistance, and can well meet the manufacturing requirements of flexible electronic devices.
The purpose of the invention is realized by the following technical scheme:
a light-colored transparent bending-resistant semi-aromatic polyimide film is prepared by uniformly coating a nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a substrate, eliminating bubbles, heating to 300 +/-2 ℃, and then cooling and stripping; the nano-silica/crown ether-semi-aromatic polyamic acid compound solution is obtained by adding nano-silica dispersion liquid into the crown ether-semi-aromatic polyamic acid compound solution, wherein the median particle size of nano-silica particles is 15-30 nm; the crown ether-semi-aromatic polyamic acid compound solution is prepared by dissolving alicyclic diamine and crown ether containing heterocyclic or aromatic ring substituent in a polar organic solvent, stirring, and adding 3,3', 4' -biphenyl tetracarboxylic anhydride for reaction; the molar ratio of crown ether containing heterocyclic or aromatic ring substituent to alicyclic diamine is 0.1-0.2: 1.
in order to further achieve the purpose of the invention, preferably, the light-color transparent bending-resistant semi-aromatic polyimide film has a light transmittance of more than 70% at 500nm and a thermal expansion coefficient of less than 20ppm/K; the tensile strength is 178MPa-189MPa; the 5% thermal weight loss temperature is 473-492 ℃, and the glass transition temperature is 331-347 ℃.
Preferably, the cycloaliphatic diamine is trans-1, 4-diaminocyclohexane, cis-trans mixed-1, 4-diaminocyclohexane or 4,4' -diaminodicyclohexylmethane.
Preferably, the crown ether containing heterocyclic or aromatic substituents is dibenzo-18-crown-6, dibenzo-24-crown-8 or bicyclohexane-18-crown-6.
Preferably, the polar organic solvent is one or more of N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide, and the amount of the polar organic solvent is 15-25 times of the mass of the alicyclic diamine.
Preferably, the nano-silica dispersion is a dispersion of nano-silica particles in propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether or propylene glycol monobutyl ether (wherein the median particle size of the silica particles is 15 nm-30 nm).
The preparation method of the light-color transparent bending-resistant semi-aromatic polyimide film comprises the following steps:
1) In ice bath and nitrogen atmosphere, alicyclic diamine and crown ether are dissolved in a polar organic solvent, 3', 4' -biphenyl tetracarboxylic anhydride is added after stirring for 2-3 hours, and the reaction is continued for 6-10 hours after the generated insoluble salt is completely dissolved, so as to obtain crown ether-semi-aromatic polyamic acid compound solution;
2) Adding the nano-silica dispersion liquid into the obtained crown ether-semi-aromatic polyamic acid compound solution, and continuously stirring for 8-12 hours to obtain a nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
3) Uniformly coating the nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a base material, eliminating bubbles, heating to 300 +/-2 ℃, cooling to room temperature, stripping the film, and drying the film in vacuum to obtain the light-colored transparent bending-resistant semi-aromatic polyimide film.
Preferably, the mass of the nano silicon dioxide is 0.1 to 0.5 percent of the sum of the mass of 3,3', 4' -biphenyl tetracarboxylic anhydride and the mass of alicyclic diamine; the molar ratio of 3,3', 4' -biphenyltetracarboxylic anhydride to alicyclic diamine is 1.02 to 1.05:1.0; the substrate is a clean glass sheet.
Preferably, the bubble elimination is carried out in a vacuum drying oven under vacuum for 3 to 5 hours; the temperature is increased to 300 +/-2 ℃ and is kept for 5-8 hours at 75 +/-2 ℃, 1.2-1.5 hours at 100 +/-2 ℃, 1.5-1.8 hours at 150 +/-2 ℃, 1.2-1.5 hours at 200 +/-2 ℃, 1.2-1.5 hours at 250 +/-2 ℃ and 1.0-1.2 hours at 300 +/-2 ℃.
Preferably, the 3,3', 4' -biphenyl tetracarboxylic anhydride is added in three equal parts, and each part is added at intervals of 35-45 minutes; after the 3,3', 4' -biphenyl tetracarboxylic anhydride is added, quickly transferring the reaction system to an oil bath at 110-120 ℃ for heating, and transferring to an ice bath after the generated insoluble salt is completely heated and dissolved;
the stirring speed in the steps (1) and (2) is 200 r/min-400 r/min;
the film is peeled off by soaking in distilled water at the temperature of 60-80 ℃; the vacuum drying of the film is to dry the film for 4 to 6 hours in a vacuum oven at a temperature of between 50 and 80 ℃.
The invention relates to crown ethers containing heterocyclic or aromatic substituents, e.g. bisBenzo-18-crown-6, dibenzo-24-crown-8 or bicyclohexane-18-crown-6 have higher boiling point, and react with alicyclic diamine through hydrogen bond and inclusion to obtain a crown ether/alicyclic diamine inclusion compound, and the inclusion compound reacts with aromatic dianhydride to generate a crown ether-semi-aromatic polyamic acid compound; the tensile strength and the elongation at break of the film prepared by imidization are improved. However, in the case of a large amount of crown ether, the 5% thermogravimetric temperature (T) of the formed composite film was high 5％ ) The reduction is obvious, the thermal expansion coefficient is greatly increased, and the bending resistance is not obviously improved. The nano silicon dioxide (SiO 2) is a kind of inorganic particles with nano scale, which has excellent performances of high thermal stability and low thermal expansion coefficient, and the nano silicon dioxide particles with the median diameter of 15 nm-30 nm are dispersed in propylene glycol methyl ether acetate, ethylene glycol monobutyl ether or propylene glycol monobutyl ether, etc., and can be fully mixed with crown ether-semi-aromatic polyamide acid compound solution in the invention, and the silicon dioxide can still keep the nano particle state in the film matrix.
Compared with the prior art, the invention has the following effects:
1. the invention uses crown ether containing heterocyclic or aromatic ring substituent to perform inclusion on semi-aromatic polyamic acid; and then, the nano-silica particles are introduced by using a solution blending method, so that the semi-aromatic polyimide is simultaneously reinforced, toughened and softened, the problems of brittleness and bending intolerance of the semi-aromatic polyimide film in the prior art are well solved, and the semi-aromatic polyimide film with light color, transparency, bending resistance, high thermal stability, high strength and low thermal expansion coefficient is obtained.
2. The invention adopts commercial raw materials, and prepares the light-color, transparent and bending-resistant semi-aromatic polyimide film by the conventional polymerization and film-forming method and conditions, and is easy to implement.
3. The crown ether/alicyclic diamine inclusion compound is obtained by hydrogen bond and inclusion between crown ether containing heterocyclic or aromatic ring substituent such as dibenzo-18-crown ether-6, dibenzo-24-crown ether-8 or dicyclohexyl-18-crown ether-6 and alicyclic diamine monomer, and can reduce the salt forming action of alicyclic diamine and aromatic dianhydride to some extent, so that semi-aromatic polyamic acid with high molecular weight can be obtained more easily, and the imidized crown ether and semi-aromatic polyimide form a stable compound with high rigidity and toughness.
4. The preparation method adopts a solution blending method, fully mixes a silica dispersion solution with a crown ether-semi-aromatic polyamide acid compound solution, and performs thermal imidization to obtain a nano silica/crown ether-semi-aromatic polyimide compound film, so that the nano silica/crown ether-semi-aromatic polyimide compound film is uniformly dispersed in a semi-aromatic polyimide matrix, and the maximum diameter of an agglomerate is smaller than the wavelength of visible light, thus the transparency of the semi-aromatic polyimide film is not influenced, and the addition amount of the nano silica is preferably controlled to be 0.1-0.5 wt%; the median particle diameter of the particles of the silicon dioxide dispersion liquid is preferably 15 nm-30 nm, and the nano-sized silicon dioxide inorganic particles in the preferable range are uniformly dispersed in the semi-aromatic polyimide matrix, so that when an external force is applied, on one hand, the larger rigidity of the particles plays a role in stress concentration and has a reinforcing effect; on the other hand, the semi-aromatic polyimide film can be used as a stress concentration point to effectively prevent the expansion of cracks generated by stress of the film, and a small amount of cavities of particles can absorb part of energy, so that the toughness of the semi-aromatic polyimide film is improved, and the problems of reduction of thermal stability and increase of thermal expansion caused by introduction of crown ether can be compensated.
Drawings
FIG. 1 is a photograph of a light colored transparent bend resistant semi-aromatic polyimide film made in accordance with an embodiment of the present invention; wherein (a) is a photograph of the light colored transparent bending resistant semi-aromatic polyimide film prepared in example 1; (b) A photograph of a light colored transparent bend resistant semi-aromatic polyimide film prepared for example 2; (c) A photograph of a light colored transparent bend resistant semi-aromatic polyimide film prepared for example 4; (d) A photograph of a light colored transparent bend resistant semi-aromatic polyimide film prepared for example 6.
FIG. 2 is a scanning electron microscope photograph of a cross section of a light-colored transparent bending-resistant semi-aromatic polyimide film prepared in an example of the present invention after tensile strength test; wherein a is a scanning electron microscope photograph of a section of the light-colored transparent bending-resistant semi-aromatic polyimide film prepared in the embodiment 1 after tensile strength test; b is a scanning electron microscope photograph of a cross section of the light-colored transparent bending-resistant semi-aromatic polyimide film prepared in example 2 after tensile strength test.
Detailed Description
In order that the invention may be better understood, the invention will now be further described with reference to the following specific examples. The invention is not to be limited in scope by the examples.
The trans-1, 4-diaminocyclohexane (t-CHDA), cis-trans mixed-1, 4-diaminocyclohexane (CHDA), 4' -diaminodicyclohexylmethane (MBCHA) used in the following examples are all products of Chiese chemical Co., ltd. (TCI); 3,3',4,4' -biphenyltetracarboxylic anhydride (BPDA), dibenzo-24-crown-8, dibenzo-18-crown-6 and dicyclohexyl-18-crown-6 are products of Aladdin chemical Agents of Aradin; n-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) or N, N-dimethylacetamide (DMAc) is a product of Shanghai Runjie chemical company; calcium hydride (CaH) 2 ) Products of mclin chemicals, inc.
The N, N-dimethylacetamide is subjected to water removal treatment before use, and the specific method comprises the following steps: adding proper amount of CaH 2 After 24 hours at room temperature, taking supernatant liquor, distilling and purifying the supernatant liquor under reduced pressure for use; drying diamine monomers t-CHDA, CHDA and MBCHA in a vacuum oven at 80 ℃ for 24 hours; drying the dianhydride monomer BPDA in a vacuum oven at 140 ℃ for 24 hours; all glassware was dried in an oven at 100 ℃ to remove water before use during the experiment.
The nano silicon dioxide dispersion liquid adopts three varieties purchased in the market: (1) The German Digananopol-C764 brand product has the dispersant of propylene glycol monomethyl ether acetate, the content of nano silicon dioxide particles is about 50wt%, and the median particle diameter is 20nm; (2) The dispersion agent is ethylene glycol monobutyl ether, the content of nano silicon dioxide particles is 20wt%, and the median particle diameter is 15nm; (3) The Hangzhou Zhi titanium purification science and technology limited company VK-SP30E brand product is characterized in that the dispersant is propylene glycol monobutyl ether, the content of nano silicon dioxide particles is 20wt%, and the median particle size is 30nm.
Example 1
(1) Placing a 50mL three-neck flask in an ice bath, introducing nitrogen, adding 0.4568g of t-CHDA, 0.2163g of dibenzo-18-crown-6 and 9.136g of N, N-dimethylacetamide, and stirring at the rotating speed of 250r/min for 2 hours; dividing 1.2000g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 40 minutes; adding the last part, stirring for 30 minutes, quickly transferring the three-neck flask to a 110 ℃ oil bath pot, heating until insoluble salts are dissolved, transferring the three-neck flask to an ice bath, and continuously reacting for 10 hours to obtain a dibenzo-18-crown ether-6 and t-CHDA-BPDA type polyamic acid compound solution; 0.0035g of nano-silica dispersion (DBS-C764, digao NANOPOL), was added dropwise to the solution and stirred continuously for 12 hours to obtain a nano-silica/crown ether-semi-aromatic polyamic acid composite solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamide acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to remove bubbles for 3 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 8 hr, 100 + -2 deg.C for 1.2 hr, 150 + -2 deg.C for 1.8 hr, 200 + -2 deg.C for 1.2 hr, 250 + -2 deg.C for 1.5 hr, and 300 + -2 deg.C for 1.0 hr; then cooling to room temperature, putting the glass plate into distilled water at 60 ℃ for soaking and demoulding, putting the obtained film into a vacuum oven, and drying the film for 6 hours in vacuum at 50 ℃ and taking out the film, wherein the film is a light-colored, transparent and bending-resistant semi-aromatic polyimide film, the theoretical content of nano silicon dioxide is 0.1wt%, and the mass of the nano silicon dioxide is only half of that of dibenzo-18-crown ether-6; the photo of the real object is shown as (a) in the attached figure 1, and the film is light in color and transparent; the scanning electron micrograph of the cross section of the film after tensile strength test is shown as a in figure 2, and it can be seen from the figure that nano silica particles are uniformly dispersed in the semi-aromatic polyimide matrix. The photographs of the semi-aromatic polyimide films obtained in examples 3 and 5 were substantially the same as those of example 1, and the films were light in color and transparent; scanning electron micrographs of cross sections of the light-colored transparent bending-resistant semi-aromatic polyimide films obtained in examples 3 to 6 after tensile strength testing were also substantially the same as in a of fig. 2, and the nano-silica particles were uniformly dispersed in the semi-aromatic polyimide matrix.
Example 2
(1) Placing a 50mL three-neck flask in an ice bath, introducing nitrogen, adding 0.4568g of t-CHDA, 0.1794g of dibenzo-24-crown-8 and 11.42g of N, N-dimethylformamide, and stirring at the rotating speed of 200r/min for 3 hours; dividing 1.2239g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 35 minutes; adding the last part of the mixture, stirring for 30 minutes, quickly transferring the three-neck flask to an oil bath pan at 120 ℃ for heating until insoluble salts are dissolved, transferring the three-neck flask to an ice bath for continuing to react for 6 hours to obtain a dibenzo-24-crown ether-8 and t-CHDA-BPDA type polyamic acid compound solution; 0.0106g of nano-silica dispersion (DBP-C764 trademark of Digao Nanopol Germany) is added into the solution drop by drop, and the solution is continuously stirred for 8 hours to obtain nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamide acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to remove bubbles for 4 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 5 hr, 100 + -2 deg.C for 1.5 hr, 150 + -2 deg.C for 1.5 hr, 200 + -2 deg.C for 1.5 hr, 250 + -2 deg.C for 1.2 hr, and 300 + -2 deg.C for 1.2 hr; then cooling to room temperature, and putting the glass plate into distilled water at 70 ℃ for soaking and demoulding; the obtained film is placed in a vacuum oven for vacuum drying for 4 hours at the temperature of 80 ℃, and then taken out to be a light-color, transparent and bending-resistant semi-aromatic polyimide film, wherein the theoretical content of nano silicon dioxide is 0.3wt%, and the mass of dibenzo-24-crown ether-8 is only half calculated in calculation; the photo of the real object is shown as (b) in the attached figure 1, and the film is light in color and transparent; after the tensile strength test is carried out on the film, as shown in a scanning electron micrograph of a section in a figure 2 b, compared with example 1, the appearance of the section is rougher, the matrix is subjected to sufficient tensile deformation to generate more tearing bands and cavities, and the film is dispersed in the semi-aromatic polyimide matrix uniformly without agglomeration despite the increase of the content of the nano silicon dioxide.
Example 3
(1) A50 mL three-necked flask was placed in an ice bath, nitrogen was introduced, 0.8414g of 4,4' -diaminodicyclohexylmethane (MBCHA), 0.2980g of dicyclohexyl-18-crown-6 and 12.62g of N-methylpyrrolidone were added, and stirring was carried out at 300r/min for 2.5 hours; dividing 1.2256g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 45 minutes; adding the last part, stirring for 30 minutes, quickly transferring the three-neck flask to a 120 ℃ oil bath pot, heating until insoluble salts are dissolved, transferring the three-neck flask to an ice bath, and continuously reacting for 8 hours to obtain a dicyclohexyl-18-crown ether-6 and MBCHA-BPDA type polyamic acid compound solution; adding 0.0558g of nano-silica dispersion (VK-SP 15E brand of Hangzhou Zhi titanium purification technology Co., ltd.) dropwise into the solution, and continuously stirring for 10 hours to obtain a nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamide acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to remove bubbles for 5 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 6 hr, 100 + -2 deg.C for 1.3 hr, 150 + -2 deg.C for 1.6 hr, 200 + -2 deg.C for 1.4 hr, 250 + -2 deg.C for 1.3 hr, and 300 + -2 deg.C for 1.1 hr; then cooling to room temperature, putting the glass plate into distilled water at the temperature of 80 ℃ for soaking and demoulding; and (3) placing the obtained film in a vacuum oven for vacuum drying at 70 ℃ for 3 hours, and taking out the film to obtain the light-color, transparent and bending-resistant semi-aromatic polyimide film, wherein the theoretical content of nano silicon dioxide is 0.5wt%, and the calculated mass is only half of that of the dicyclohexyl-18-crown ether-6.
Example 4
(1) A50 mL three-necked flask was placed in an ice bath, nitrogen was introduced, 0.8414g of 4,4' -diaminodicyclohexylmethane (MBCHA), 0.2883g of dibenzo-18-crown-6 and 12.62g of N-methylpyrrolidone were added, and stirring was carried out at a rate of 400r/min for 2 hours; dividing 1.2239g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 40 minutes; adding the last part, stirring for 30 minutes, quickly transferring the three-neck flask to a 110 ℃ oil bath pot, heating until insoluble salt is dissolved, transferring the three-neck flask to an ice bath, and continuously reacting for 9 hours to obtain a dibenzo-18-crown ether-6 and MBCHA-BPDA type polyamic acid compound solution; adding 0.0177g of nano-silica dispersion liquid (DBM) dropwise into the solution, and continuously stirring for 11 hours to obtain nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to eliminate bubbles for 5 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 6 hr, 100 + -2 deg.C for 1.3 hr, 150 + -2 deg.C for 1.6 hr, 200 + -2 deg.C for 1.4 hr, 250 + -2 deg.C for 1.3 hr, and 300 + -2 deg.C for 1.1 hr; then cooling to room temperature, putting the glass plate into distilled water at the temperature of 80 ℃ for soaking and demoulding; the obtained film is placed in a vacuum oven for vacuum drying at 70 ℃ for 3 hours and then taken out to be a light-color, transparent and bending-resistant semi-aromatic polyimide film, wherein the theoretical content of nano silicon dioxide is 0.4wt%, and the mass of dibenzo-18-crown ether-6 is only half calculated in calculation; the photo of the real object is shown in (c) of the attached figure 1, and the film can be seen to be light and transparent.
Example 5
(1) Placing a 50mL three-neck flask in an ice bath, introducing nitrogen, adding 0.4568g of CHDA, 0.1794g of dibenzo-24-crown-8 and 11.42g of N, N-dimethylformamide, and stirring at the rotating speed of 200r/min for 3 hours; dividing 1.2239g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 35 minutes; adding the last part, stirring for 30 minutes, quickly transferring the three-neck flask to an oil bath kettle at 115 ℃, heating until insoluble salts are dissolved, transferring the three-neck flask to an ice bath, and continuously reacting for 6 hours to obtain a dibenzo-24-crown ether-8 and CHDA-BPDA type polyamic acid compound solution; adding 0.0265g nanometer silica dispersion (VK-SP 30E brand of Hangzhou Zhi titanium purification technology Co., ltd.) dropwise into the solution, and continuously stirring for 8 hours to obtain nanometer silica/crown ether-semi-aromatic polyamic acid compound solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to eliminate bubbles for 4 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 5 hr, 100 + -2 deg.C for 1.5 hr, 150 + -2 deg.C for 1.5 hr, 200 + -2 deg.C for 1.5 hr, 250 + -2 deg.C for 1.2 hr, and 300 + -2 deg.C for 1.2 hr; then cooling to room temperature, and putting the glass plate into distilled water at 70 ℃ for soaking and demoulding; the obtained film is placed in a vacuum oven to be dried for 4 hours under vacuum at the temperature of 80 ℃ and then taken out, the film is a light-colored, transparent and bending-resistant semi-aromatic polyimide film, the theoretical content of the nano silicon dioxide is 0.3wt%, and the calculated mass of dibenzo-24-crown ether-8 is only half of the mass of the nano silicon dioxide.
Example 6
(1) Placing a 50mL three-neck flask in an ice bath, introducing nitrogen, adding 0.4568g t-CHDA, 0.2163g dibenzo-18-crown-6 and 9.136g N-methylpyrrolidone, and stirring at the rotating speed of 400r/min for 2 hours; dividing 1.2000g of BPDA into three equal parts, and sequentially adding the three equal parts into a three-neck flask, wherein the time interval of each addition is 40 minutes; stirring the last part for 30 minutes after adding, quickly transferring the three-neck flask to an oil bath pan at 120 ℃ for heating until insoluble salts are dissolved, transferring the three-neck flask to an ice bath for continuously reacting for 10 hours to obtain a dibenzo-18-crown ether-6 and t-CHDA-BPDA type polyamic acid compound solution; adding 0.0175g of nano-silica dispersion (Dugao NanOPOL-C764 Germany) dropwise into the solution, and continuously stirring for 12 hours to obtain a nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
(2) Uniformly spreading the prepared nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a clean glass sheet, and placing the clean glass sheet in a vacuum drying oven to eliminate bubbles for 3 hours under vacuum; then heating and preserving heat according to a set program: keeping at 75 + -2 deg.C for 8 hr, 100 + -2 deg.C for 1.2 hr, 150 + -2 deg.C for 1.8 hr, 200 + -2 deg.C for 1.2 hr, 250 + -2 deg.C for 1.5 hr, and 300 + -2 deg.C for 1.0 hr; then cooling to room temperature, and putting the glass plate into distilled water at 60 ℃ for soaking and demoulding; the obtained film is placed in a vacuum oven for vacuum drying for 6 hours at the temperature of 50 ℃, and then taken out to be a light-color, transparent and bending-resistant semi-aromatic polyimide film, wherein the theoretical content of nano silicon dioxide is 0.5wt%, and the mass of dibenzo-18-crown ether-6 is only half calculated in calculation; the photo of the real object is shown in (d) of the attached figure 1, and the film is light in color and transparent.
Comparative example 1
In example 6, the t-CHDA-BPDA type polyamic acid solution was directly subjected to thermal imidization treatment under the same conditions without adding dibenzo-18-crown-6 and nano-silica dispersion, and the obtained semi-aromatic polyimide film was light-colored and transparent; but the film was so brittle that tensile testing could not be performed.
Comparative example 2
In example 6, dibenzo-18-crown-6 was used in an amount of 0.4326g, and the molar ratio thereof to t-CHDA was 0.3, and a crown ether-semi-aromatic polyimide film was obtained without adding the nano-silica dispersion under the same conditions.
Comparative example 3
In example 6, in step (1), 0.021g of nano silica dispersion (trade name of digan NANOPOL-C764, germany) was added dropwise to the polyamic acid solution without adding dibenzo-18-crown-6, and the other was not changed, and the obtained nano silica/semi-aromatic polyimide film was found to have a theoretical content of nano silica of 0.6wt%.
The tensile modulus, tensile strength and elongation at break of the film were measured according to GB/T1040.3-2006 standards, the coefficient of thermal expansion of the film was measured with a static thermomechanical analyzer (TMA, NETZSCH 402F3, germany), and the temperature of 5% thermal weight loss (T.sub.weight loss) was measured with a thermogravimetric analyzer (NETZSCH TG-209F1, germany) 5％ ) Dynamic thermomechanical analyzer (TA DMA-Q800, USA) for measuring glass transition temperature (T) g ) An ultraviolet-visible spectrophotometer (Hitachi, japan, UV-3010) measured the transmittance of the film at 500 nm. And selecting a film with the thickness of about 50 mu m, carrying out 180-degree bending test, controlling the same bending strength every time, and observing whether the film is broken or has cracks after pressing for 3 seconds. The results of the mechanical properties, the thermal expansion coefficient, the transmittance at 500nm, and the 180 ° bending test of the semi-aromatic polyimide films prepared in examples 1 to 6 and comparative examples 1 to 3 are shown in table 1.
As can be seen from table 1, it is,the pure semi-aromatic polyimide film (comparative example 1) was very brittle and could not be even tested for tensile strength, while the semi-aromatic polyimide film modified with crown ether alone (comparative example 2) was high in both tensile strength and elongation at break, but T 5％ The reduction is obvious, the increase amplitude of the thermal expansion coefficient is large, the test of 180-degree bending cannot be passed, and the bending resistance is not improved enough; the semi-aromatic polyimide film (comparative example 3) obtained by modifying nano-silica alone can resist bending, and compared with the pure semi-aromatic polyimide film, the thermal expansion coefficient is reduced, and T is 5％ However, when the content is 0.6%, the transmittance at 500nm is reduced to 70% or less. The invention adopts commercial raw materials and conventional polymerization and film-forming methods and conditions of semi-aromatic polyimide, the content of nano silicon dioxide is controlled to be 0.1-0.5%, the light transmittance of the obtained semi-aromatic polyimide film at 500nm is more than 70%, and the thermal expansion coefficient is less than 20ppm/K; the tensile strength is 178MPa-189MPa; the 5% thermal weight loss temperature is 473-492 ℃, the glass transition temperature is 331-347 ℃, and the crack is not generated in a 180-degree bending test.
TABLE 1 Properties of semi-aromatic polyimide films prepared in examples 1 to 6 and comparative examples 1 to 3
According to the invention, the semi-aromatic polyimide is modified by the nano silicon dioxide and crown ether complex pair, so that the semi-aromatic polyimide film is simultaneously enhanced, toughened and softened under the premise of basically keeping light color and transparency, the tensile strength and elongation at break are simultaneously and obviously improved, and a lower thermal expansion coefficient, a higher light transmittance and T are maintained 5％ The flexible display device can better meet the application requirements in the field of flexible display, is easy to implement and has wide market application prospect.
Claims (7)
1. A light-colored transparent bending-resistant semi-aromatic polyimide film is characterized in that a nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution is uniformly coated on a base material, bubbles are eliminated, the temperature is raised to 300 +/-2 ℃, and then the temperature is reduced and the film is peeled off to obtain the light-colored transparent bending-resistant semi-aromatic polyimide film; the nano-silica/crown ether-semi-aromatic polyamic acid compound solution is obtained by adding a nano-silica dispersion solution into a crown ether-semi-aromatic polyamic acid compound solution, wherein the median particle size of nano-silica particles is 15-30 nm; the crown ether-semi-aromatic polyamic acid compound solution is prepared by dissolving alicyclic diamine and crown ether in a polar organic solvent, stirring, and adding 3,3', 4' -biphenyl tetracarboxylic anhydride for reaction; the molar ratio of the crown ether to the alicyclic diamine is 0.1-0.2: 1; the nano silicon dioxide dispersion liquid is the dispersion liquid of nano silicon dioxide particles in propylene glycol methyl ether acetate, ethylene glycol monobutyl ether or propylene glycol monobutyl ether; the alicyclic diamine is trans-1, 4-diaminocyclohexane, cis-trans mixed-1, 4-diaminocyclohexane or 4,4' -diaminodicyclohexylmethane; the mass of the nano silicon dioxide is 0.1% -0.5% of the mass sum of 3,3', 4' -biphenyltetracarboxylic anhydride and alicyclic diamine; the crown ether is dibenzo-18-crown ether-6, dibenzo-24-crown ether-8 or dicyclohexyl-18-crown ether-6.
2. The light colored transparent bend resistant semi-aromatic polyimide film of claim 1 wherein the light colored transparent bend resistant semi-aromatic polyimide film has a light transmittance at 500nm of greater than 70% and a coefficient of thermal expansion of less than 20ppm/K; the tensile strength is 178MPa-189MPa; the 5% thermal weight loss temperature is 473-492 ℃, and the glass transition temperature is 331-347 ℃.
3. The light-colored transparent bending-resistant semi-aromatic polyimide film according to claim 1, wherein the polar organic solvent is one or more of N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide, and the amount of the polar organic solvent is 15 to 25 times of the mass of the alicyclic diamine.
4. The method for preparing the light-colored transparent bending-resistant semi-aromatic polyimide film as claimed in any one of claims 1 to 3, which is characterized by comprising the following steps:
1) In an ice bath and a nitrogen atmosphere, dissolving alicyclic diamine and crown ether in a polar organic solvent, stirring for 2 to 3 hours, adding 3,3', 4' -biphenyltetracarboxylic anhydride, and continuing to react for 6 to 10 hours after the generated insoluble salt is completely dissolved to obtain a crown ether-semi-aromatic polyamic acid compound solution;
2) Adding the nano-silica dispersion liquid into the obtained crown ether-semi-aromatic polyamic acid compound solution, and continuously stirring for 8 to 12 hours to obtain a nano-silica/crown ether-semi-aromatic polyamic acid compound solution;
3) Uniformly coating the nano silicon dioxide/crown ether-semi-aromatic polyamic acid compound solution on a base material, eliminating bubbles, heating to 300 +/-2 ℃, cooling to room temperature, stripping the film, and drying the film in vacuum to obtain the light-colored transparent bending-resistant semi-aromatic polyimide film.
5. The method for producing a light-colored transparent bending-resistant semi-aromatic polyimide film according to claim 4, wherein the molar ratio of 3,3', 4' -biphenyltetracarboxylic anhydride to alicyclic diamine is from 1.02 to 1.05:1.0; the substrate is a clean glass sheet.
6. The method for preparing the light-colored transparent bending-resistant semi-aromatic polyimide film as claimed in claim 4, wherein the air bubble elimination is carried out in a vacuum drying oven under vacuum for 3 to 5 hours; the temperature is raised to 300 +/-2 ℃ and is kept for 5 to 8 hours at 75 +/-2 ℃, 1.2 to 1.5 hours at 100 +/-2 ℃, 1.5 to 1.8 hours at 150 +/-2 ℃, 1.2 to 1.5 hours at 200 +/-2 ℃, 1.2 to 1.5 hours at 250 +/-2 ℃ and 1.0 to 1.2 hours at 300 +/-2 ℃.
7. The method for preparing the light-colored transparent bending-resistant semi-aromatic polyimide film as claimed in claim 4, wherein the 3,3', 4' -biphenyl tetracarboxylic anhydride is added in three equal parts at intervals of 35 to 45 minutes; after the 3,3', 4' -biphenyl tetracarboxylic anhydride is added, quickly transferring the reaction system to an oil bath at 110-120 ℃ for heating, and transferring to an ice bath after the generated insoluble salt is completely heated and dissolved;
the stirring speed in the steps (1) and (2) is 200 r/min-400 r/min;
the film is peeled off by soaking in distilled water at the temperature of 60-80 ℃; the vacuum drying of the film is to dry the film in a vacuum oven at 50 to 80 ℃ for 4 to 6 hours.
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