CN110229609B - Polyimide coating with functional material and method for preparing functional polyimide material by adopting coating - Google Patents
Polyimide coating with functional material and method for preparing functional polyimide material by adopting coating Download PDFInfo
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Abstract
The invention discloses a polyimide coating with functional materials, which is prepared by mixing a polyamic acid solution and a functional inorganic filler; the polyamic acid solution is prepared by reacting and polymerizing dianhydride and diamine in an organic solvent. The invention also discloses a method for preparing the functional polyimide material by coating the polyimide coating with the functional material on a polyimide film. Compared with the traditional adhesive, when the polyimide coating is used for preparing a coating or a bonding functional material on the surface of polyimide, the coating and the polyimide film have better bonding strength, and the coating can resist higher temperature which is over 400 ℃; when the adhesive force of the coating is tested by using a 3M600 adhesive tape, the falling area of the coating is not more than 10%; and after the coating is subjected to a bending test, no obvious wrinkles and cracks are observed in most areas.
Description
Technical Field
The invention relates to a polyimide coating with a functional material, and also relates to a method for preparing the functional polyimide material by adopting the polyimide coating, belonging to the technical field of polymer films.
Background
Polyimide (PI) is an organic polymer material with excellent heat resistance, mechanical property, low temperature resistance, dielectric property and radiation resistance, and is widely applied to the fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membrane, laser and the like due to the excellent performance of PI. The main application forms of polyimide have the following aspects: 1. a film; 2. coating; 3. advanced composite materials; 4. engineering plastics; 5. a foamed plastic; 6. an adhesive; 7. a separation membrane; 8. photoresist; 9. application in microelectronic devices.
The film product is one of the earliest commodities in polyimide application, can meet the basic physical property requirements of various products, has various properties such as high strength, high toughness, wear resistance, high temperature resistance and the like, can meet various design requirements in the processing process, and is a high-temperature-resistant insulating material with competitive advantages. The composite material is widely applied to the electronic fields of soft boards, semiconductor packaging, photovoltaic (solar) energy sources, liquid crystal displays and the like, and is applied to various industries such as aerospace military industry, machinery, automobiles and the like in the field of motors. However, the PI film has a smooth surface and low surface chemical activity, which leads to poor surface adhesion, and thus greatly limits the application range of polyimide. The traditional polyimide surface modification methods comprise acid-base treatment, plasma treatment, ion beam and surface grafting methods, however, the methods generally have various problems, the acid-base treatment damages the chemical structure of the polyimide film, and thus the performance of the polyimide film is affected, and the plasma treatment, the ion beam and the surface grafting methods are high in cost and not suitable for large-scale production treatment. When coating or bonding other materials on the surface of polyimide by using an adhesive, the required bonding strength is often difficult to meet, and some additional problems are caused. Polyurethane glue and silicon rubber adhesives in traditional adhesives generally have good adhesive strength to polyimide films, but the cured adhesives have large difference with the mechanical properties of polyimide base materials, the adhesives generally do not resist high temperature (above 200 ℃), and the polyimide materials are limited by the adhesives when applied in a high-temperature environment, so that the application range of the adhesives is influenced.
Polyimide materials often require additional properties for their use in certain applications. When the material is applied to the military field, the material is required to have good electromagnetic wave shielding effect and military camouflage effect, common polyimide has no good shielding effect on electromagnetic waves, and when the material is operated in different landforms, various military tents, clothes and the like prepared from the polyimide material need to adapt to the colors of the environment so as to achieve the purpose of military camouflage, so that exogenous electromagnetic shielding materials are required to be coated on the polyimide and the polyimide is required to be dyed, and therefore, when the polyimide is coated on the polyimide in an adhesion manner, the polyimide is required to basically keep the original excellent performances such as high and low temperature resistance, dielectric property, mechanical property and the like. At present, the electromagnetic shielding material is generally metal alloy powder, ferromagnetic material conductive polymer and carbon material, when the electromagnetic shielding material is applied to a polyimide film as a coating, different adhesives are generally required to be combined to coat and solidify the electromagnetic shielding material on a required material, and when the adhesive is applied to the polyimide film, the adhesive strength is often weak and the polyimide film is not high in temperature resistance, so that the application of the electromagnetic shielding material is affected.
Disclosure of Invention
The purpose of the invention is as follows: the technical problem to be solved by the invention is to provide a polyimide coating with a functional material, when the coating is coated on the surface of a polyimide film, because the base material of the coating is polyimide and has no mechanical property difference with the polyimide film base body, the structure of the polyimide film is not changed, the problem that the polyimide film is not high-temperature resistant after coating is not existed, and the functional material is attached to the polyimide film when the coating is coated, so that the operation step of removing the adhesive coating of the functional material coating is saved.
The invention also aims to provide a method for coating the polyimide coating with the functional material on the surface of the polyimide film.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a polyimide coating with functional material is prepared by mixing a polyamic acid solution and a functional inorganic filler; wherein, the polyamic acid solution is obtained by reacting dianhydride and diamine in an organic solvent.
The polyimide coating is prepared from the following components in percentage by mass:
dianhydride: 5-15%;
diamine (b): 5-15%;
organic solvent: 40-60%;
functional inorganic filler: 10 to 30 percent.
Wherein the structural general formula of the dianhydride is as follows:
wherein, the structure of R in the dianhydride is as follows:
wherein, the structural general formula of the diamine is as follows:
wherein, M in the diamine has a structure as follows:
wherein the organic solvent is any one or a combination of any several of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) or N-methylpyrrolidone (NMP).
The functional inorganic filler is an inorganic filler capable of improving the high temperature resistance, the strength, the electromagnetic shielding performance and the coloring of the polyimide, and comprises an inorganic filler with high temperature resistance, an inorganic filler for improving the electromagnetic shielding effect of the polyimide, an inorganic filler for improving the strength of the polyimide and an inorganic pigment for coloring the polyimide; wherein, the inorganic filler with high temperature resistance is one or the combination of more than two of titanium dioxide, silicon dioxide, calcium oxide, boron nitride or carbon nano tube; the inorganic filler for improving the strength of the polyimide is titanium dioxide and/or silicon dioxide; the inorganic filler for improving the electromagnetic shielding effect of the polyimide is copper powder and/or silver powder; the inorganic pigment for coloring polyimide is one of iron oxide, titanium dioxide or carbon black.
The polyimide coating has a solid content (solute mass fraction) of 10-20%, and polyimide coatings with different solid contents are selected according to the characteristics of the functional inorganic filler.
Wherein the functional inorganic filler is solid particles or powder, and the average particle size of the functional inorganic filler is 0.01-10 mu m.
The method for preparing the functional polyimide material by adopting the functional polyimide coating comprises the steps of uniformly coating a proper amount of coating (mixed solution) on a polyimide film, and curing by a heating program to obtain the polyimide film with the functional material coating on the surface;
the method specifically comprises the following steps:
selecting polyimide coating with corresponding types and solid contents by combining different functional inorganic fillers and the mechanical strength of the required coating; firstly, mixing functional inorganic filler and polyamic acid solution according to a proper proportion to obtain polyimide paint, then coating the polyimide paint on a polyimide substrate by adopting one of a brushing method, a spin-coating method or a dip-coating method, and carrying out temperature programming and curing, wherein the temperature raising process comprises the following steps: preserving heat for 2-5 h at 70-90 ℃; preserving the heat for 0.5-2 h at the temperature of 120-160 ℃; preserving the heat for 0.5 to 3 hours at the temperature of 200 to 240 ℃; keeping the temperature at 260-300 ℃ for 0.5-1.5 h; and obtaining a polyimide product (polyimide film) with a functional material coating carried on the surface.
Compared with the traditional adhesive, the coating prepared based on the coating has better adhesive strength on polyimide, and meanwhile, the introduction of the functional material in the coating endows the polyimide product with the functions of high temperature resistance, high strength, electromagnetic shielding and coloring.
The polyimide has poor adhesive property due to low surface chemical activity, when some exogenous functional materials need to be coated on the polyimide, the functional materials need to be coated on the surface of the polyimide by using an adhesive, and the application of the polyimide is greatly influenced because the adhesive has low adhesive strength and is not high in temperature resistance; the polyimide coating provided by the invention can provide good bonding strength, can work for a long time at high temperature, and can introduce functional materials into a polyimide film, so that the polyimide film has various excellent properties.
The polyimide coating is prepared from different types of polyamic acid solutions and different functional inorganic fillers, wherein coatings prepared by mixing and coating the different polyamic acid solutions and the functional inorganic fillers on the polyimide have different bonding strengths and mechanical strengths. Different functional inorganic fillers are added into the polyamic acid solution, so that the high temperature resistance, the strength and the electromagnetic shielding performance of polyimide (polyimide product with a coating) can be respectively improved, and polyimide products with different colors can be obtained. In practical application, different functional inorganic fillers are selected according to the required requirements to meet different performance requirements. After titanium dioxide, silicon dioxide, calcium oxide and boron nitride are added into the polyamic acid solution, the high temperature resistance of the finally prepared polyimide product is improved by 50-120 ℃, and the tensile strength of the finally prepared polyimide product can be improved by 5-15 MPa. The iron oxide, titanium dioxide and carbon black are added into the polyamic acid solution to respectively obtain brownish red, beige yellow and black coatings.
Has the advantages that: the invention is a method for coating exogenous functional material on polyimide product by bulk polymerization, the method can not generate structural influence on polyimide, and the bonding strength of the coating and polyimide film is better, compared with the traditional adhesive, when the polyimide coating is used for preparing the coating or the bonding functional material on the polyimide surface, the coating and polyimide film have better bonding strength, and the coating can resist higher temperature which is more than 400 ℃; when the adhesive force of the coating is tested by using a 3M600 adhesive tape, the falling area of the coating is not more than 10%; and after the coating is subjected to a bending test, no obvious wrinkles and cracks are observed in most areas.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 4.00g of 4, 4-diaminodiphenyl ether (ODA) in a three-neck flask, adding 80mLN, N-Dimethylacetamide (DMAC) in the three-neck flask, stirring under the protection of nitrogen and ice-water bath until the 4, 4-diaminodiphenyl ether (ODA) is completely dissolved, adding 8.88g of hexafluoro dianhydride (6FDA) in a reaction system at one time, continuing to react for 12 hours under the ice-water bath, and obtaining a yellowish viscous polyamide acid solution (PAA1) after the reaction is finished; 10.00g of a polyamic acid solution (PAA1) was mixed with 2.40g of titanium dioxide powder having a particle size of 60nm to obtain a polyimide coating 1.
In the process of mixing and stirring, a proper amount of polyimide coating 1 is uniformly coated on a polyimide film and a ceramic sheet, and then the polyimide film and the ceramic sheet are placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ multiplied by 5h, 120 ℃ multiplied by 1h, 160 ℃ multiplied by 1h, 200 ℃ multiplied by 1h, 240 ℃ multiplied by 1h and 290 ℃ multiplied by 1 h; the polyimide film 1 having a functional material coating on the surface thereof is obtained.
The polyimide film 1 obtained in example 1 was compared with a polyimide film not coated with the polyimide paint 1, the polyimide film not coated with the polyimide paint 1 had a tensile strength of 150Mpa, and the polyimide film 1 had a tensile strength of 158 Mpa; and (3) carrying out temperature resistance test on the coating on the surface of the polyimide film 1, and compared with a polyimide coating without a filler, the high temperature resistance of the polyimide coating is improved by 50-80 ℃.
Example 2
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 8.00g of 4, 4 ' -diaminodiphenyl ether (ODA) in a three-neck flask, adding 120mLN, N-Dimethylformamide (DMF) in the three-neck flask, stirring under the protection of nitrogen and in an ice-water bath until the DMF is completely dissolved, adding 11.76g of 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride (BPDA) in a reaction system at a time, continuing to react for 8 hours in the ice-water bath, and obtaining a viscous polyamide acid solution (PAA2) with an egg white color after the reaction is finished; 12.00g of a polyamic acid solution (PAA2) was mixed with 3.00g of silica having a particle size of 16nm to obtain a polyimide coating 2.
In the process of mixing and stirring, a proper amount of polyimide coating 2 is uniformly coated on a polyimide film and a ceramic sheet, and then the polyimide film and the ceramic sheet are placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 290 ℃ X1 h. The polyimide film 2 with the functional material coating on the surface is obtained.
The polyimide film 2 obtained in example 2 was compared with a polyimide film not coated with the polyimide paint 2, and the polyimide film not coated with the polyimide paint 2 had a tensile strength of 160Mpa and the polyimide film 2 had a tensile strength of 172 Mpa. And (3) carrying out temperature resistance test on the coating on the surface of the polyimide film 2, and compared with a polyimide coating without a filler, improving the high temperature resistance by 50-100 ℃.
Example 3
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 4.97g of 4, 4 ' -diaminodiphenyl sulfone in a three-necked flask, adding 60mL of N, N-Dimethylacetamide (DMAC) into the three-necked flask, stirring under the protection of nitrogen and in an ice-water bath until the N, N-Dimethylacetamide (DMAC) is completely dissolved, adding 5.88g of 3, 3 ', 4, 4 ' -biphenyl tetracarboxylic dianhydride (BPDA) into a reaction system at one time, continuing to react for 10 hours in the ice-water bath, and obtaining a yellowish viscous polyamide acid solution (PAA3) after the reaction is finished; 11.00g of a polyamic acid solution (PAA3) was mixed with 3.00g of calcium oxide having a particle size of 160nm to obtain a polyimide coating 3.
In the process of mixing and stirring, a proper amount of polyimide coating 3 is uniformly coated on a polyimide film and a ceramic sheet, and then the polyimide film and the ceramic sheet are placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 290 ℃ X1 h. To obtain the polyimide film 3 with the functional material coating on the surface.
After the calcium oxide is added to the polyimide coating in the embodiment, the temperature resistance test is performed on the coating on the surface of the polyimide film 3, and compared with a polyimide coating without a filler, the high temperature resistance of the polyimide coating is improved by 70-100 ℃.
Example 4
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 5.20g of bisphenol A type diether dianhydride (BPADA) into a three-neck flask, adding 70mL of N, N-Dimethylacetamide (DMAC) into the three-neck flask, stirring the mixture under the protection of nitrogen at room temperature until the mixture is completely dissolved, adding 2.00g of 4, 4' -diaminodiphenyl ether (ODA) into the reaction system at one time, continuing the reaction for 16 hours at room temperature, and obtaining a nearly colorless transparent viscous polyamide acid solution (PAA4) after the reaction is finished; a polyimide dope 4 was obtained by mixing 9.00g of a polyamic acid solution (PAA4) with 2.00g of boron nitride having a particle size of 1 μm.
In the process of mixing and stirring, a proper amount of polyimide coating 4 is uniformly coated on a polyimide film and a ceramic sheet, and then the polyimide film and the ceramic sheet are placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 280 ℃ X1 h. The polyimide film 4 with the functional material coating on the surface is obtained.
After the polyimide coating in this embodiment is added with boron nitride, the temperature resistance of the coating is tested, and compared with a polyimide coating without a filler, the high temperature resistance of the coating is improved by 100-120 ℃.
After the four embodiments are added with the high-temperature-resistant nano material, the high-temperature-resistant performance of the polyimide coating is respectively improved to different degrees, and the strength of the polyimide coating is also improved after the reinforcing filler is added.
Example 5
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 5.20g of bisphenol A type diether dianhydride (BPADA) into a three-neck flask, adding 50mL of N, N-Dimethylacetamide (DMAC) into the three-neck flask, stirring the mixture under the protection of nitrogen at room temperature until the mixture is completely dissolved, adding 2.92g of 1, 4-bis (4-aminophenoxy) benzene into the reaction system at one time, continuing the reaction for 12 hours at room temperature, and obtaining a yellowish viscous polyamide acid solution (PAA5) after the reaction is finished; 6.00g of a polyamic acid solution (PAA5) was mixed with 2.00g of copper powder to obtain a polyimide coating 5.
During the mixing and stirring process, a proper amount of polyimide coating 5 is uniformly coated on the polyimide film, and then the polyimide film is placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 280 ℃ X1 h. A polyimide film 5 having an electromagnetic shielding coating is obtained.
The polyimide film 5 obtained in example 5 has an electromagnetic shielding effect.
Example 6
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 5.20g of bisphenol A type diether dianhydride (BPADA) into a three-neck flask, adding 56mL of N, N-Dimethylacetamide (DMAC) into the three-neck flask, stirring the mixture under the protection of nitrogen at room temperature until the mixture is completely dissolved, adding 4.11g of 2, 2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP) into the reaction system at one time, continuing the reaction at room temperature for 10 hours, and obtaining a light brown viscous polyamide acid solution (PAA6) after the reaction is finished; 7.00g of a polyamic acid solution (PAA6) was mixed with 2.20g of iron oxide having a particle size of 60nm to obtain a polyimide coating 6.
During the mixing and stirring process, a proper amount of polyimide coating 6 is uniformly coated on the polyimide film, and then the polyimide film is placed in an oven for curing, wherein the curing procedure is as follows: obtaining a brownish red polyimide film 6 by multiplying by 5h at 80 ℃, multiplying by 1h at 120 ℃, multiplying by 1h at 160 ℃, multiplying by 1h at 200 ℃, multiplying by 1h at 240 ℃ and multiplying by 1h at 280 ℃, wherein the polyimide film 6 is provided with a brownish red coating which can dye the polyimide film into brownish red.
Example 7
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 2.94g of 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride (BPDA) and 5.20g of bisphenol A diether dianhydride (BPADA) in a three-neck flask, adding 60mL of N, N-Dimethylacetamide (DMAC) into the three-neck flask, and stirring under the protection of nitrogen at room temperature until the N, N-Dimethylacetamide (DMAC) is completely dissolved to obtain a mixed solution A; weighing 4.00g of 4, 4' -diaminodiphenyl ether (ODA) and dissolving in 30mL of N, N-Dimethylacetamide (DMAC) to obtain a mixed solution B, slowly dropwise adding the mixed solution B into the obtained mixed solution A by using a constant-pressure dropping funnel, reacting for 12 hours at room temperature, and obtaining a light brown viscous polyamide acid solution (PAA7) after the reaction is finished; 4.00g of a polyamic acid solution (PAA7) was mixed with 1.20g of titanium dioxide powder having a particle size of 60nm to obtain a polyimide coating 7.
During the mixing and stirring process, a proper amount of polyimide coating 7 is uniformly coated on the polyimide film, and then the polyimide film is placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 280 ℃ X1 h. The beige polyimide film 7 is obtained, and the beige polyimide film 7 is provided with a beige coating which can dye the polyimide film to beige.
Example 8
The preparation method of the polyimide coating with the functional material comprises the following steps: weighing 2.22g of hexafluorodianhydride (6FDA) and 2.06g of 2, 2' -bis [4- (4-aminophenoxyphenyl) ] propane (BAPP) in a three-neck flask, adding 25mL of N, N-Dimethylacetamide (DMAC) into the three-neck flask, and stirring the mixture under the protection of nitrogen at room temperature until the N, N-Dimethylacetamide (DMAC) is completely dissolved to obtain a mixed solution A; weighing 5.20g of bisphenol A diether dianhydride (BPADA) and dissolving in 25mL of N, N-Dimethylacetamide (DMAC) to obtain a mixed solution B; slowly dripping the mixed solution B into the mixed solution A by using a constant-pressure dropping funnel, reacting for 12 hours at room temperature to obtain light brown viscous polyamic acid solution (PAA8) after the reaction is finished; 6.00g of a polyamic acid solution (PAA8) was mixed with 1.60g of carbon black to obtain a polyimide paint 8.
During the mixing and stirring process, a proper amount of polyimide coating 8 is uniformly coated on the polyimide film, and then the polyimide film is placed in an oven for curing, wherein the curing procedure is as follows: 80 ℃ X5 h, 120 ℃ X1 h, 160 ℃ X1 h, 200 ℃ X1 h, 240 ℃ X1 h, 280 ℃ X1 h. A polyimide film 8 having a black coating was obtained. The nano carbon black is an inorganic pigment and can dye polyimide into black.
The contrast sample is a coating prepared by mixing two-component epoxy resin glue with nano iron oxide, and the coating has the advantages of higher rigidity, yellow color and poorer bonding strength after being cured. The coating begins to melt and char above 250 c and the coating begins to detach from the polyimide film.
In the above examples, the polyimide-based base film was a pyromellitic polyimide film (Kapton) available from dupont, U.S. and had a thickness of 0.2 mm. The functional materials respectively have the characteristics of improving the high temperature resistance, the strength, the electromagnetic shielding and the coloring of the polyimide, and have good dispersibility in the polyimide coating. Adhesive strength and high temperature resistance of coating material and polyimide film
Coating quality testing
And (3) testing the adhesion of the coating: the coating adhesion test adopts a 3M600 adhesive tape test, and is a test adhesive tape of international universal standard. The polyimide films were respectively adhered to the coatings of polyimide samples 1, 2, 3, 4, 5, 6, 7 and 8 with 3M600 tape, pressed tightly, and the tape was torn off after 5 minutes. Adopting a Baige test method to respectively detect the falling area percentage of each coating, wherein the calculation formula is as follows:
area of peel off (%). area of coating peeled off after test ÷ area of tape application × 100%
The test results are shown in table 1.
Coating thickness test: the coating thickness was measured using a digital coating thickness gauge, and the measurement results are shown in table 1.
Coating bending test: polyimide samples 1, 2, 3, 4, 5, 6, 7, and 8 were each wrapped around a cylindrical shaft having a diameter of 2mm as a bending axis, and the coating surface was observed. The coating was rated "good" if the coating surface was free of any wrinkles and cracks, "good" if few areas of the coating surface had no significant wrinkles, medium "if few wrinkles or cracks had occurred on the coating surface, and" poor "if most areas of the coating surface had significant wrinkles and cracks. The analysis results are shown in table 1.
TABLE 1 test results
As can be seen from Table 1, the adhesion strength of the polyimide coating of the present invention on the polyimide film is better than that of the conventional epoxy resin adhesive. From the view of the polyimide coating, the coating prepared by curing the coating prepared by using the monomer with the non-coplanar and large polarity and the flexible structure has high bonding strength, good flexibility and better bending and breaking resistance.
The coating prepared on the surface of the polyimide by the polyimide coating has better high temperature resistance which is over 400 ℃; the adhesive strength between the coating and the polyimide film is good, and when the adhesive force of the coating is tested by using a 3M600 adhesive tape, the falling area of the coating is not more than 10%; meanwhile, different functional inorganic fillers can be added into the coating according to requirements, so that the polyimide film product has different functions and different applications are realized.
Claims (6)
1. The utility model provides a take polyimide coating of functional material which characterized in that: the polyimide coating is prepared by mixing a polyamic acid solution and a functional inorganic filler; wherein, the polyamic acid solution is formed by the reaction and polymerization of dianhydride and diamine in an organic solvent; the functional inorganic filler comprises an inorganic filler with high temperature resistance, an inorganic filler for improving the electromagnetic shielding effect of polyimide, an inorganic filler for improving the strength of the polyimide and an inorganic pigment for coloring the polyimide; wherein, the inorganic filler with high temperature resistance is one or the combination of more than two of titanium dioxide, silicon dioxide, calcium oxide, boron nitride or carbon nano tube; the inorganic filler for improving the strength of the polyimide is titanium dioxide and/or silicon dioxide; the inorganic filler for improving the electromagnetic shielding effect of the polyimide is copper powder and/or silver powder; the inorganic pigment for coloring the polyimide is one of ferric oxide, titanium dioxide or carbon black; the functional inorganic filler is solid particles or powder, and the average particle size of the functional inorganic filler is 0.01-10 mu m;
the method for preparing the functional polyimide material by adopting the polyimide coating with the functional material comprises the following steps of coating the polyimide coating on a polyimide base material by adopting one of a brushing method, a spin-coating method or a dip-coating method, and carrying out temperature programming and curing, wherein the temperature raising process comprises the following steps: preserving heat for 2-5 h at 70-90 ℃; preserving the heat for 0.5-2 h at the temperature of 120-160 ℃; preserving the heat for 0.5 to 3 hours at the temperature of 200 to 240 ℃; keeping the temperature at 260-300 ℃ for 0.5-1.5 h; and obtaining the polyimide with the functional material coating loaded on the surface.
2. The polyimide coating with functional material according to claim 1, characterized in that: the polyimide coating is prepared from the following components in percentage by mass:
dianhydride: 5-15%;
diamine (b): 5-15%;
organic solvent: 40-60%;
functional inorganic filler: 10 to 30 percent.
3. The polyimide coating with functional material according to claim 2, characterized in that: the structural general formula of the dianhydride is as follows:
wherein, the structure of R in the dianhydride is as follows:
4. the polyimide coating with functional material according to claim 2, characterized in that: the structural general formula of the diamine is as follows:
wherein, M in the diamine has a structure as follows:
5. the polyimide coating with functional material according to claim 2, characterized in that: the organic solvent is any one or combination of any several of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
6. The polyimide coating with functional material according to claim 2, characterized in that: the solid content of the polyimide coating is 10-20%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1732230A (en) * | 2002-12-27 | 2006-02-08 | 株式会社I.S.T | Polyimide precursor liquid composition and polyimide coating film |
| TW201343722A (en) * | 2012-03-14 | 2013-11-01 | Mitsui Chemicals Inc | Polyimide precursor varnish, polyimide resin, electrical component, heat resistant tape, heat resistant coating and adhesive for aerospace |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1732230A (en) * | 2002-12-27 | 2006-02-08 | 株式会社I.S.T | Polyimide precursor liquid composition and polyimide coating film |
| CN1718658A (en) * | 2005-01-21 | 2006-01-11 | 桂林工学院 | Polyimide/inorganic nano-composite insulating varnish and its preparation method |
| TW201343722A (en) * | 2012-03-14 | 2013-11-01 | Mitsui Chemicals Inc | Polyimide precursor varnish, polyimide resin, electrical component, heat resistant tape, heat resistant coating and adhesive for aerospace |
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