CN112980014B - Blended polyimide film, preparation method thereof and application thereof in flexible display substrate - Google Patents
Blended polyimide film, preparation method thereof and application thereof in flexible display substrate Download PDFInfo
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Abstract
The invention belongs to the field of high polymer materials, and particularly relates to a blended polyimide film, a preparation method thereof and application thereof in a flexible display substrate. The preparation method of the blended polyimide precursor comprises the steps of reacting an aromatic dianhydride with rigidity and an aromatic diamine in a polar aprotic solvent to obtain the component A, reacting the aromatic dianhydride with flexibility and the aromatic diamine in the polar aprotic solvent to obtain the component B, heating and blending the component B, and blocking the component B after chain exchange to obtain the blended polyimide precursor. Compared with the prior art, the blended polyimide film provided by the invention has the advantages of high temperature resistance, high dimensional stability and good mechanical strength, and can be applied to a backboard for flexible display.
Description
Technical Field
The invention relates to the field of polymer films, in particular to a preparation method of a blending type polyimide film and application of the blending type polyimide film in a flexible display substrate.
Background
Aromatic polyimide is a rigid material containing imide five-membered ring in molecular main chain, has excellent high temperature resistance, mechanical property, chemical resistance, dimensional stability, insulating property, irradiation resistance, flame retardant property and the like, and is widely used in the fields of aerospace, engineering machinery, weaponry and microelectronic semiconductors. Among them, in the field of electronic display, polyimide substrates having the characteristics of flexibility and light weight are becoming one of the main development directions of display technologies.
However, compared with inorganic materials, polyimide has poor thermal stability, and is mainly characterized by a large Coefficient of Thermal Expansion (CTE), which can warp, crack or delaminate from the inorganic substrate during the process of the display substrate, and in addition, the flexibility display has high requirements on the flexibility of the back plate, and the polyimide film needs to have good bending resistance. Therefore, how to realize the combination of low thermal expansion coefficient and high flexibility of polyimide films is the best focus of research. In the prior art, the CTE and mechanical properties of polyimide films are regulated by blending inorganic nanoparticles with PI or copolymerizing rigid and flexible monomers, as mentioned in the patent CN 108530628A, and the CTE of the size-stable polyimide film prepared by compounding silica or aluminum oxide nanoparticles with polyimide can reach 1.47 ppm/. Degree.C (50-300 ℃). However, the introduction of inorganic nanoparticles tends to result in a decrease in the mechanical properties of the film. In addition, the copolymerization method has the difference of the sequence structures of the high polymer chains due to the different activities of the monomers, the difficult control of the polymerization process and the like, and the instability of polyimide performance is easily caused. Therefore, the preparation of polyimide films with stable performance, low expansion coefficient and high mechanical property is of great significance.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a blended polyimide film with stable performance, low expansion coefficient and high mechanical property, a preparation method thereof and application thereof in a flexible display substrate.
The aim of the invention can be achieved by the following technical scheme: a preparation method of a blended polyimide film is characterized in that a PI molecular main chain is provided with a rigid chain segment and a flexible chain segment simultaneously by a method of exchanging and re-blocking a blending chain. Adjusting the content of the rigid segment and the soft segment achieves the combination of low CTE and high elongation of the PI film. And polyimide precursors can be prepared simply and stably by a homopolymerization method. The method is characterized by comprising the following steps of:
1) Adding an aromatic diamine and an aromatic dianhydride into a polar aprotic solvent protected by nitrogen or other inert gases, stirring at the temperature of-20-60 ℃ to react for 2-24 hours, and controlling the molar ratio of the aromatic diamine to the aromatic dianhydride to be 1:0.95-1:1.05 to obtain a polyamic acid solution A with the apparent viscosity of 1000-50000 cps;
2) Controlling the molar ratio of the aromatic diamine to the aromatic dianhydride to be 1:0.95-1:1.05 by using another aromatic diamine and another aromatic dianhydride according to the method of the step 1) to obtain a polyamic acid solution B with the apparent viscosity of 1000-50000 cps;
3) Mixing the polyamic acid solution A in the step 1) and the polyamic acid solution B in the step 2), controlling the temperature to be 20-80 ℃, stirring for 4-12 hours, and then adding a blocking agent to prepare a blending type polyamic acid solution;
4) Removing impurities with the particle size of more than 1 mu m in the blended polyamide acid solution obtained in the step 3) through positive pressure filtration, uniformly coating the mixture on a clean substrate with a preset thickness after vacuum defoamation, heating to 60-120 ℃ at the speed of 0-10 ℃/min, drying for 20-60min, then placing the mixture in an oven for step programming heating to remove residual solvent and carrying out thermal imidization, taking out the mixture after the temperature of the oven is cooled to the ambient temperature, soaking and demolding the mixture in deionized water with the temperature of 25-80 ℃, and drying the mixture to obtain the blended polyimide film.
The aromatic diamine in the step 1) and the step 2) is the same diamine or different diamines, and comprises the following monomers: one of phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4' -diaminodiphenyl sulfone (DDS), biphenyldiamine (BDE), 4' -Diaminobenzidine (DABA), 3' -dimethyl-4, 4' -diaminobiphenyl (o-TLD), 4' -diaminodiphenyl ether, 2- (4-aminophenyl) -5-aminobenzoxazole (p-BOA), 2- (3-aminophenyl) -5-aminobenzoxazole (m-BOA), 2- (3-aminophenyl) -5-aminobenzimidazole (m-BIA), 2- (4-aminophenyl) -5-aminobenzimidazole (p-BIA).
The aromatic dianhydrides described in step 1) and step 2) are the same dianhydride or are different dianhydrides, comprising the following monomers: one of 1,2,4, 5-pyromellitic dianhydride (PMDA), 3'4,4' -biphenyl tetracarboxylic dianhydride (s-BPDA), 2,3'3,4' -biphenyl tetracarboxylic dianhydride (a-BPDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 4-p-phenylene-bis-trimellitate dianhydride (TAHQ).
The end-capping agent of step 3) comprises one of the following monomers: 4-phenylethynyl aniline, 4-phenylethynyl phthalic anhydride, 4-dimethylaminophenyl isocyanate, trimellitic anhydride, 4-ethynyl aniline, 4-ethynyl phthalic anhydride, 4-aminopropynylphenyl ether, phthalic anhydride or norbornene dianhydride.
The usage amount of the end capping agent in the step 3) is determined according to the proportion of the whole dianhydride and the diamine in the mixed system, and is 0.5-5% of the mole number of the polyimide precursor in order to ensure high mechanical property.
The mass ratio of the polyamic acid solution A to the polyamic acid solution B in the step 3) is 50:50-99:1, preferably 70:30-95:5.
Step-programmed heating to 300-500 c, preferably 350-450 c, is performed in the oven described in step 4).
The substrate in the step 4) comprises a glass, stainless steel or plastic substrate.
The invention also provides the blended polyimide film prepared by the method.
The invention also provides an application of the blended polyimide film, which is characterized in that the blended polyimide film is used in a flexible display substrate.
Compared with the prior art, the invention has the beneficial effects that:
the blended polyimide precursor consists of a component A with a rigid chain segment and a component B with a flexible chain segment, the preparation method is a multi-step polycondensation method, firstly, the component A is obtained by using rigid aromatic dianhydride and aromatic diamine to react in a polar aprotic solvent, then the component B is obtained by using flexible aromatic dianhydride and aromatic diamine to react in the polar aprotic solvent,
1. the method adopts a homopolymerization method, has simple process and low cost, is more stable in reaction than a copolymerization method, and respectively prepares the component A with the rigid chain segment and the component B with the flexible chain segment by adjusting the proportion of dianhydride and diamine. Firstly, an aromatic dianhydride and an aromatic diamine with a specific molar ratio are reacted in a polar aprotic solvent to obtain a component A, wherein the aromatic dianhydride and the aromatic diamine can both have a rigid structure or one of the aromatic dianhydride and the aromatic diamine has a rigid structure, and the number of rigid repeating units in the component A is ensured to be larger than that of flexible repeating units. And then the aromatic dianhydride and the aromatic diamine are reacted in a polar aprotic solvent to obtain a component B, wherein the aromatic dianhydride and the aromatic diamine can both have flexible structures or one of the aromatic dianhydride and the aromatic diamine has flexible structures, and the number of flexible repeating units in the component A is ensured to be larger than that of rigid repeating units. The component A and the component B are blended at high temperature, and a chain exchange and capping method is carried out, so that a PI molecular main chain is provided with a rigid chain segment and a flexible chain segment at the same time, and the thermal expansion coefficient and the mechanical property of the film are regulated and controlled by regulating the content of the rigid chain segment and the flexible chain segment, so that the requirements of the flexible display field on the polyimide film with low thermal expansion coefficient and high mechanical property are met;
2. the invention uses the same kind of solution blending mode, has better affinity than the blending with other organic matters or inorganic matters, is easy to stably prepare the polyimide film with excellent comprehensive performance, and does not sacrifice the heat resistance of polyimide due to weak bonding force between two phases.
3. The preparation method of the invention can be widely applied to industrial production.
Drawings
FIG. 1 is a graph showing the tensile at break of the blended polyimide film prepared in example 1;
FIG. 2 is a graph showing the tensile at break of the blended polyimide film prepared in comparative example 17;
FIG. 3 is a TMA spectrum of the blended polyimide films prepared in example 1 and comparative example 17.
Detailed Description
The invention is described in further detail below in connection with specific embodiments, which are given for illustration only and are not intended to limit the scope of the invention.
Example 1
The present example enables the preparation of a blended polyimide film by:
1. 19.47g of PDA and 50.84g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred and reacted for 8 hours at 25 ℃, and the molar ratio of PDA to s-BPDA is controlled to be 1:0.96, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride is controlled to be 1:1 according to the method of the step 1) by using 36.04g of p-BOA and 34.90g of PMDA, and the mixture is stirred and reacted for 24 hours at 35 ℃ to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 95:5, stirring at 65 ℃ for 8 hours, and then adding 2.77g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 80 ℃ at the speed of 10 ℃/min, predrying for 30min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 447 ℃, the 5% thermal decomposition temperature of 556 ℃ and the coefficient of thermal expansion CTE of 5ppm/K (50 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 453MPa, the tensile modulus was 8GPa, and the elongation at break was 60%, as shown in FIG. 1. It can be seen that the blended polyimide film obtained by the method of the invention has excellent mechanical properties.
Example 2
1. 19.47g of PDA and 51.90g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred at 25 ℃ for 8 hours, and the molar ratio of PDA to s-BPDA is controlled to be 1:0.98, thus obtaining polyamic acid solution A;
2. using 35.88g p-BIA and 34.90g PMDA, controlling the molar ratio of diamine to anhydride to be 1:1 according to the method of step 1), stirring and reacting at 40 ℃ for 20 hours to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 90:10, stirring at 60 ℃ for 10 hours, and then adding 1.38g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 80 ℃ at the speed of 10 ℃/min, predrying for 40min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 425 ℃, the 5% thermal decomposition temperature of 549 ℃, the coefficient of thermal expansion CTE of 9ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 416MPa, the tensile modulus was 8GPa, and the elongation at break was 45%. Excellent mechanical properties.
Example 3
1. 21.63g of PDA and 41.88g of PMDA are added into nitrogen or other polar aprotic solvents protected by inert gases, and the mixture is stirred at 25 ℃ for 6 hours to react, and the molar ratio of PDA to PMDA is controlled to be 1:0.96, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 30.04g of ODA and 48.33g of BTDA, and the mixture was stirred at 25℃for 15 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 80:20, stirring at 60 ℃ for 8 hours, and then adding 3.97g of 4-phenylacetylene phthalic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 100 ℃ at a speed of 5 ℃/min for predrying for 35min, then placing the polyamide acid solution in an oven for step programming heating to 450 ℃ to remove the solvent and carrying out thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 385 ℃,5% thermal decomposition temperature of 526 ℃, and coefficient of thermal expansion CTE of 12ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 260MPa, the tensile modulus was 9GPa, and the elongation at break was 15%. The mechanical properties are better.
Example 4
1. 38.21g of o-TLD and 51.90g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred and reacted for 24 hours at 35 ℃, and the molar ratio of the o-TLD to the s-BPDA is controlled to be 1:0.98, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1.005 according to the method of step 1) using 21.63g PDA and 43.84g PMDA, and the mixture was stirred at 35℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 90:10, stirring at 75 ℃ for 9 hours, and then adding 1.38g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at the speed of 5 ℃/min, predrying for 30min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 412 ℃, the 5% thermal decomposition temperature is 549 ℃, the coefficient of thermal expansion CTE is 14ppm/K (100 ℃ -200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 326MPa, the tensile modulus was 9GPa, and the elongation at break was 25%. Excellent mechanical properties.
Example 5
1. Adding 16.22g of PDA and 45.50g of s-BPDA into nitrogen or other polar aprotic solvents protected by inert gases, stirring at 25 ℃ to react for 8 hours, and controlling the molar ratio of the PDA to the s-BPDA to be 0.97:1 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 34.09g of DABA and 68.75g of TAHQ, and the mixture was stirred at 25℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 95:5, stirring at 65 ℃ for 8 hours, and then adding 1.79g of 4-phenylacetylene aniline to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at the speed of 10 ℃/min, predrying for 50min, then placing the polyamide acid solution in an oven, heating to 460 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 70 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 383 ℃, the 5% thermal decomposition temperature of 540 ℃, and the coefficient of thermal expansion CTE of 5ppm/K (100 ℃ -200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 465MPa, the tensile modulus was 9GPa, and the elongation at break was 43%. Excellent mechanical properties.
Example 6
1. 33.64g of p-BIA and 45.50g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred for 24 hours at 35 ℃ to react, and the molar ratio of the p-BIA to the s-BPDA is controlled to be 1:0.97 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 36.04g PDA and 34.90g PMDA, and the mixture was stirred at 35℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 85:15, stirring at 75 ℃ for 5 hours, and then adding 1.48g of norbornene dianhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 100 ℃ at the speed of 10 ℃/min, predrying for 60min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 383 ℃, the 5% thermal decomposition temperature of 545 ℃, and the coefficient of thermal expansion CTE of 14ppm/K (100-200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 324MPa, the tensile modulus was 10GPa, and the elongation at break was 35%. Excellent mechanical properties.
Example 7
1. Adding 16.22g of PDA and 42.37g of s-BPDA into nitrogen or other polar aprotic solvents protected by inert gases, stirring at 35 ℃ to react for 9 hours, and controlling the molar ratio of the PDA to the s-BPDA to be 1:0.96 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1.002 according to the method of step 1) using 34.09g of DABA and 44.22g of s-BPDA, and the mixture was stirred at 25℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 95:5, stirring at 60 ℃ for 9 hours, and then adding 1.78g of phthalic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at a speed of 5 ℃/min, predrying for 30min, then placing the polyamide acid solution in an oven, heating to 460 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 70 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 369 ℃, the 5% thermal decomposition temperature of 584 ℃, and the coefficient of thermal expansion CTE of 5ppm/K (100 ℃ -200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 416MPa, the tensile modulus was 8GPa, and the elongation at break was 33%. Excellent mechanical properties.
Example 8
1. 16.22g of PDA and 45.97g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred for 9 hours at 25 ℃, and the molar ratio of the PDA to the s-BPDA is controlled to be 0.96:1, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride is controlled to be 1:1 according to the method of the step 1) by using 36.04g of p-BOA and 34.90g of PMDA, and the mixture is stirred and reacted for 24 hours at 35 ℃ to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 95:5, stirring at 85 ℃ for 8 hours, and then adding 2.03g of 4-dimethylaminobenzene isocyanate to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 80 ℃ at the speed of 10 ℃/min, predrying for 30min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 375 ℃, the 5% thermal decomposition temperature is 561 ℃, the coefficient of thermal expansion CTE is 11ppm/K (100 ℃ -200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 358MPa, the tensile modulus was 9GPa, and the elongation at break was 41%. Excellent mechanical properties.
Example 9
1. 33.64g of p-BIA and 45.50g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred for 24 hours at 35 ℃ to react, and the molar ratio of the p-BIA to the s-BPDA is controlled to be 1:0.97 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 16.22g PDA and 44.13g a-BPDA, and the mixture was stirred at 25℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 85:15, stirring at 75 ℃ for 5 hours, and then adding 1.48g of norbornene dianhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 100 ℃ at a speed of 5 ℃/min for predrying for 30min, then placing the polyamide acid solution in an oven for step programming heating to 450 ℃ to remove the solvent and carrying out thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 363 ℃, the 5% thermal decomposition temperature is 535 ℃, the coefficient of thermal expansion CTE is 34ppm/K (100 ℃ -200 ℃), and the film has the characteristic of thermal stability. Mechanical properties test results of the films: the tensile strength was 294MPa, the tensile modulus was 7GPa, and the elongation at break was 25%. Excellent mechanical properties.
Example 10
1. Adding 16.22g of PDA and 45.50g of s-BPDA into nitrogen or other polar aprotic solvents protected by inert gases, stirring at 25 ℃ to react for 8 hours, and controlling the molar ratio of the PDA to the s-BPDA to be 0.97:1 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 31.84g of o-TLD and 48.33g of TAHQ, and the mixture was stirred at 25℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 90:10, stirring at 75 ℃ for 12 hours, and then adding 1.79g of 4-phenylacetylene aniline to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at the speed of 10 ℃/min, predrying for 50min, then placing the polyamide acid solution in an oven, heating to 460 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 70 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 373 ℃, the 5% thermal decomposition temperature is 554 ℃, the coefficient of thermal expansion CTE is 5ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 348MPa, the tensile modulus was 9GPa, and the elongation at break was 34%. Excellent mechanical properties.
Example 11
1. 19.47g of PDA and 50.84g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred and reacted for 8 hours at 25 ℃, and the molar ratio of PDA to s-BPDA is controlled to be 1:0.96, so as to obtain polyamic acid solution A;
2. using 39.73g DDS and 34.90g PMDA, controlling the molar ratio of diamine to anhydride to be 1:1 according to the method of step 1), stirring and reacting for 24 hours at 35 ℃ to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 92:8, stirring at 80 ℃ for 4 hours, and then adding 2.77g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at a speed of 5 ℃/min, predrying for 50min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 353 ℃, the 5% thermal decomposition temperature is 530 ℃, the coefficient of thermal expansion CTE is 17ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 160MPa, the tensile modulus was 5GPa, and the elongation at break was 45%. Excellent mechanical properties.
Example 12
1. 19.47g of PDA and 50.84g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred and reacted for 8 hours at 25 ℃, and the molar ratio of PDA to s-BPDA is controlled to be 1:0.96, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride is controlled to be 1:1 according to the method of the step 1) by using 36.04g of p-BOA and 34.90g of PMDA, and the mixture is stirred and reacted for 24 hours at 35 ℃ to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 91:9, stirring at 65 ℃ for 8 hours, and then adding 2.77g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 80 ℃ at the speed of 10 ℃/min, predrying for 30min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 383 ℃, the 5% thermal decomposition temperature is 530 ℃, the coefficient of thermal expansion CTE is 17ppm/K (100-200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 297MPa, the tensile modulus was 9GPa, and the elongation at break was 17%. Excellent mechanical properties.
Example 13
1. 17.30g of PDA and 45.66g of s-BPDA are added into nitrogen or other polar aprotic solvents protected by inert gases, stirred and reacted for 16 hours at 25 ℃, and the molar ratio of PDA to s-BPDA is controlled to be 1:0.97, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 42.46g of ODA and 43.62g of PMDA, and the mixture was stirred at 25℃for 6 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to the mass ratio of 95:5, stirring at 65 ℃ for 8 hours, and then adding 2.77g of trimellitic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 100 ℃ at the speed of 10 ℃/min, predrying for 20min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 365 ℃, the 5% thermal decomposition temperature is 560 ℃, the coefficient of thermal expansion CTE is 10ppm/K (100 ℃ -200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 426MPa, the tensile modulus was 9GPa, and the elongation at break was 51%. Excellent mechanical properties.
Example 14
1. Adding 16.22g of PDA and 45.50g of s-BPDA into nitrogen or other polar aprotic solvents protected by inert gases, stirring at 25 ℃ to react for 8 hours, and controlling the molar ratio of the PDA to the s-BPDA to be 0.97:1 to obtain polyamic acid solution A;
2. according to the method of step 1), 38.21g of o-TLD and 51.90g of s-BPDA are used, the molar ratio of diamine to anhydride is controlled to be 1:1, and the mixture is stirred and reacted for 24 hours at 35 ℃ to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 84:16, stirring at 65 ℃ for 12 hours, and then adding 1.79g of 4-phenylacetylene aniline to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 100 ℃ at the speed of 8 ℃/min, predrying for 10min, then placing the polyamide acid solution in an oven, heating to 470 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 80 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 363 ℃, the 5% thermal decomposition temperature is 559 ℃, the coefficient of thermal expansion CTE is 9ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 438MPa, the tensile modulus was 9GPa, and the elongation at break was 35%. Excellent mechanical properties.
Example 15
1. Adding 16.22g of PDA and 42.37g of s-BPDA into nitrogen or other polar aprotic solvents protected by inert gases, stirring at 35 ℃ to react for 9 hours, and controlling the molar ratio of the PDA to the s-BPDA to be 1:0.96 to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1.005 according to the method of step 1) using 31.84g of ODA and 44.35g of s-BPDA, and the mixture was stirred at 25℃for 14 hours to obtain polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 96:4, stirring at 60 ℃ for 9 hours, and then adding 1.78g of phthalic anhydride to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 80 ℃ at a speed of 5 ℃/min, predrying for 20min, then placing the polyamide acid solution in an oven, heating to 450 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 70 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested to obtain the glass transition temperature of 349 ℃, the 5% thermal decomposition temperature of 564 ℃, and the coefficient of thermal expansion CTE of 14ppm/K (100-200 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 364MPa, the tensile modulus was 8GPa, and the elongation at break was 29%. Excellent mechanical properties.
Example 16
1. 21.63g of PDA and 44.97g of PMDA are added into nitrogen or other polar aprotic solvents protected by inert gases, and the mixture is stirred at 25 ℃ for 9 hours to react, and the molar ratio of PDA to PMDA is controlled to be 0.97:1, so as to obtain polyamic acid solution A;
2. the molar ratio of diamine to anhydride was controlled to be 1:1 according to the method of step 1) using 31.84g of o-TLD and 48.33g of TAHQ, and the mixture was stirred at 25℃for 24 hours to obtain a polyamic acid solution B;
3. mixing the polyamic acid solution A in the step 1 and the polyamic acid solution B in the step 2 according to a mass ratio of 60:40, stirring at 75 ℃ for 12 hours, and then adding 1.79g of 4-phenylacetylene aniline to prepare a blended polyamic acid solution;
4. and (3) filtering the polyamide acid solution obtained in the step (3) by using a filter membrane with the aperture of 0.3 mu m through positive pressure, uniformly coating the polyamide acid solution on a clean substrate with a preset thickness after vacuum defoamation, heating to 90 ℃ at the speed of 10 ℃/min, predrying for 50min, then placing the polyamide acid solution in an oven, heating to 460 ℃ through a step program, removing the solvent, performing thermal imidization, taking out the polyamide acid solution after the temperature of the oven is cooled to the ambient temperature, soaking the polyamide acid solution in deionized water at 70 ℃, demolding, and drying to obtain the blending type polyimide film.
The thermal performance of the film is tested, the glass transition temperature is 458 ℃, the 5% thermal decomposition temperature is 561 ℃, the coefficient of thermal expansion CTE is 27ppm/K (100 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 294MPa, the tensile modulus was 11GPa, and the elongation at break was 14%. The mechanical properties are better.
Comparative example 17
Example 1 was repeated except that 21.63g of PDA, 1.88g of p-BOA, 2.09g of PMDA and 53.67g of s-BPDA were added to a polar aprotic solvent protected by nitrogen or other inert gas in a mass ratio of 95:5, and stirred at 35℃for 24 hours, and then stirred at 65℃for 8 hours, followed by addition of 3.07g of trimellitic anhydride to obtain a resin. The subsequent steps are the same as in the examples.
The thermal performance of the film is tested, the glass transition temperature is 443 ℃, the 5% thermal decomposition temperature is 546 ℃, the coefficient of thermal expansion CTE is 6ppm/K (50 ℃ -400 ℃), and the film has the characteristics of thermal stability and low coefficient of expansion. Mechanical properties test results of the films: the tensile strength was 402MPa, the tensile modulus was 9GPa, and the elongation at break was 37%, as shown in FIG. 2. It can be seen that the mechanical properties of the film prepared by the copolymerization method are inferior to those of the film obtained by the invention. As shown in fig. 3, for the TMA spectra of the blended polyimide films prepared in example 1 and comparative example 17, it can be seen that the thermal stability of the blend film and the copolymer film is similar, but the thermal expansion coefficient of the blend film is slightly low and the glass transition temperature is slightly high.
The embodiments have been described so as to facilitate a person of ordinary skill in the art in view of the description and with the application it will be readily apparent to those of ordinary skill in the art that various modifications may be made to these embodiments and that the general principles described herein may be applied to other embodiments without undue burden. Accordingly, the present application is not limited to the embodiments herein, and those skilled in the art, based on the present disclosure, may make improvements and modifications without departing from the scope and spirit of the present application.
Claims (9)
1. The preparation method of the blended polyimide film is characterized by comprising the following steps of:
1) Adding an aromatic diamine and an aromatic dianhydride into a polar aprotic solvent protected by nitrogen or other inert gases, stirring at the temperature of-20-60 ℃ to react for 2-24 hours, and controlling the molar ratio of the aromatic diamine to the aromatic dianhydride to be 1:0.95-1:1.05 to obtain a polyamic acid solution A with the apparent viscosity of 1000-50000 cps;
2) Controlling the molar ratio of the aromatic diamine to the aromatic dianhydride to be 1:0.95-1:1.05 by using another aromatic diamine and another aromatic dianhydride according to the method of the step 1) to obtain a polyamic acid solution B with the apparent viscosity of 1000-50000 cps;
3) Mixing the polyamic acid solution A in the step 1) and the polyamic acid solution B in the step 2), controlling the temperature to be 20-80 ℃, stirring for 4-12 hours, and then adding a blocking agent to prepare a blending type polyamic acid solution;
4) Removing impurities with the particle size of more than 1 mu m in the blended polyamide acid solution obtained in the step 3) through positive pressure filtration, uniformly coating the mixture on a clean substrate after vacuum defoamation, heating to 60-120 ℃ at the speed of 0-10 ℃/min, drying for 20-60min, then placing the mixture in an oven for step programming heating to remove residual solvent and carrying out thermal imidization, taking out the mixture after the temperature of the oven is cooled to the ambient temperature, soaking the mixture in deionized water at the temperature of 25-80 ℃, demolding and drying the mixture to obtain the blended polyimide film;
the aromatic diamine in step 1) and step 2) comprises the following monomers: one of p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 4' -diaminodiphenyl sulfone (DDS), biphenyldiamine (BDE), 4' -diaminobenzil-idine (DABA), 3' -dimethyl-4, 4' -diaminobiphenyl (o-TLD), 4' -diaminodiphenyl ether, 2- (4-aminophenyl) -5-aminobenzoxazole (p-BOA), 2- (3-aminophenyl) -5-aminobenzoxazole (m-BOA), 2- (3-aminophenyl) -5-aminobenzimidazole (m-BIA), 2- (4-aminophenyl) -5-aminobenzimidazole (p-BIA);
the aromatic dianhydride in step 1) and step 2) comprises the following monomers: one of 1,2,4, 5-pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (s-BPDA), 2,3',3,4' -biphenyl tetracarboxylic dianhydride (a-BPDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 4-p-phenylene-bis-trimellitate dianhydride (TAHQ);
the end-capping agent of step 3) comprises one of the following monomers: 4-phenylethynyl aniline, 4-phenylethynyl phthalic anhydride, 4-dimethylaminophenyl isocyanate, trimellitic anhydride, 4-ethynyl aniline, 4-ethynyl phthalic anhydride, 4-aminopropynylphenyl ether, phthalic anhydride or norbornene dianhydride.
2. The method for preparing a blended polyimide film according to claim 1, wherein the amount of the end capping agent in the step 3) is determined according to the ratio of the total dianhydride to diamine in the mixed system, and is 0.5-5% of the mole number of the polyimide precursor in order to ensure high mechanical properties.
3. The method for preparing a blended polyimide film according to claim 1, wherein the mass ratio of the polyamic acid solution A to the polyamic acid solution B in the step 3) is 50:50-99:1.
4. The method for producing a blended polyimide film according to claim 3, wherein the mass ratio of the polyamic acid solution A to the polyamic acid solution B in the step 3) is 70:30 to 95:5.
5. The method for preparing a blended polyimide film according to claim 1, wherein the step programming is performed in the oven of step 4) to 300-500 ℃.
6. The method for preparing a blended polyimide film according to claim 5, wherein the step programming is performed in the oven of step 4) to 350-450 ℃.
7. The method of claim 1, wherein the substrate in step 4) comprises a glass, stainless steel or plastic substrate.
8. A blended polyimide film made by the method of any one of claims 1-7.
9. Use of the blended polyimide film of claim 8 in a flexible display substrate.
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Effective date of registration: 20230904 Address after: No. 1251, Zhulu West Road, Xujing Town, Qingpu District, Shanghai, 201702 Patentee after: SHANGHAI PLASTICS RESEARCH INSTITUTE CO.,LTD. Address before: 200235 No. 36, Xuhui District, Shanghai, Caobao Road Patentee before: SHANGHAI RESEARCH INSTITUTE OF SYNTHETIC RESINS Co.,Ltd. |