CN109081939B - Polyimide composite film with both conductivity and magnetism and preparation method thereof - Google Patents
Polyimide composite film with both conductivity and magnetism and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of polyimide films, and provides a polyimide composite film with both conductivity and magnetism and a preparation method thereof. The method comprises the steps of firstly synthesizing 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, then synthesizing porous polyimide containing a triptycene structure with hexafluoro-dianhydride, and simultaneously generating Fe in situ2O3Coating the polyimide film in a porous structure of polyimide, performing tape casting to form a film, and forming silver conductive layers on the upper and lower surfaces of the film by magnetron sputtering to obtain the polyimide composite film with both conductivity and magnetism. Compared with the traditional method, the polyimide composite film prepared by the invention has the advantages of good ductility, high modulus, good superparamagnetism and conductivity, and can be used as an electromagnetic shielding material.
Description
Technical Field
The invention belongs to the technical field of polyimide films, and provides a polyimide composite film with both conductivity and magnetism and a preparation method thereof.
Background
The polyimide film has excellent comprehensive performance, and has outstanding heat resistance, electric performance, radiation resistance and fire resistance. In the development of high and new technologies, particularly in the development of aerospace industry, electrical and electronic industry, and information industry, polyimide films play a very important role. In recent years, not only a few new functional polyimide film products have been developed abroad, but also new advances have been made in the application technology.
On the other hand, in recent decades, with the popularization of various electric appliances, the electromagnetic radiation pollution caused by the wide application of electronic computers, communication satellites, high-voltage power transmission networks, some medical devices and the like is more and more serious, so that electromagnetic shielding is necessary, and in the electromagnetic shielding material, a surface conductive shielding material, especially a conductive coating, still occupies the main market at present due to the low cost and the medium shielding effect, and a filling composite shielding material (namely conductive composite plastic) is convenient for mass production due to the one-time completion of the molding processing and shielding, can be used once and for all, and therefore becomes an important development direction of the electromagnetic shielding material.
The filling composite type shielding material is composed of synthetic resin with good electrical insulation property, conductive filler with excellent conductive performance and other additives, wherein the common synthetic resin comprises polyphenyl ether, polycarbonate, ABS, nylon, thermoplastic polyester and the like; the conductive filler is generally selected from large-sized fibrous and flaky materials, and at present, the most commonly used conductive fillers include metal fibers, metal sheets, carbon fibers, superconducting carbon black, metal alloy fillers and the like. In recent years, polyimide films have been attracting attention in the field of electromagnetic shielding because of their excellent overall properties.
The Chinese patent application No. 201410033581.9 discloses a flexible conductive polyimide film and a preparation method thereof, wherein the film is composed of the following substances in parts by weight: 30-80 parts of polyimide, 1-10 parts of a sedge extract, 2-10 parts of a coupling agent, 5-20 parts of metal powder and 5-20 parts of carbon powder. The polyimide film disclosed by the invention has better conductivity and is soft, but because the filler is dispersed unevenly and agglomerated, the conductivity still needs to be enhanced, and the ductility and the modulus are poorer.
Chinese patent application No. 201210587222.9 discloses a method for preparing a fluorine-containing magnetic coating polyimide composite film, which is obtained by coating magnetic powder-doped fluorine-containing emulsion on the surface of a polyimide film and then drying and sintering the polyimide film in a drying and sintering furnace with an electromagnet, overcomes the defects of complex process, high cost and reduced performance in the conventional method for producing the magnetic polyimide film by mixing or other chemical and physical methods, simplifies the production process and improves the comprehensive performance of the film. The magnetic coating of the composite film has the problems of easy falling, non-ideal magnetism and poor use durability, and the coating affects the mechanical property of the composite film.
In conclusion, when the polyimide film is compounded with a conductive or magnetic filler or is prepared by coating, the problems of nonuniform dispersion, serious agglomeration and easy falling of the filler generally exist, so that the conductivity and magnetism of the composite film are poor, the mechanical property of the composite film is influenced, the further development and application of the composite film in the electronic field are limited, and particularly, the research application in the electronic shielding field is rarely reported at home and abroad.
Disclosure of Invention
Therefore, when the polyimide film in the prior art is compounded with conductive and magnetic fillers or coated with the conductive and magnetic fillers, the defects of uneven dispersion, easy agglomeration and easy shedding of the fillers exist, so that the conductivity and magnetism of the composite film are poor, the mechanical property of the film is influenced, and further development and application are limited. Aiming at the situation, the polyimide composite film with both conductivity and magnetism and the preparation method are provided, the dispersibility of the filler in the film matrix can be effectively improved, and the obtained film has better conductivity and superparamagnetism and can be widely used in the fields of electronic shielding materials and the like.
In order to achieve the purpose, the invention relates to the following specific technical scheme:
a preparation method of a polyimide composite film with both conductivity and magnetism comprises the following specific steps:
(1) adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 16-20 h at room temperature, stirring for 4-6 h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2-3 h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to obtain porous polyimide with triptycene structure, and reactingCarrying out pyrolysis on the iron acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in a porous structure of polyimide, filtering and drying to prepare porous polyimide/Fe2O3A composite material;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism.
Preferably, the reducing agent in step (1) is at least one of hydrazine hydrate or phenylhydrazine.
Preferably, the raw materials in the step (1) comprise, by weight, 15-20 parts of 1,2,3, 4-tetrachlorotriptycene, 20-25 parts of acetic anhydride, 2-4 parts of nitric acid, 49-62 parts of acetone and 1-2 parts of a reducing agent.
Preferably, the catalyst in step (2) is at least one of palladium/carbon catalyst, nickel/carbon catalyst, cobalt/carbon catalyst and iron/carbon catalyst.
Preferably, the raw materials in the step (2) comprise 18-22 parts by weight of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 22-25 parts by weight of hexafluoro dianhydride, 5-8 parts by weight of ferric acetylacetonate, 1-2 parts by weight of a catalyst and 43-54 parts by weight of p-chlorophenol.
Preferably, the reaction temperature in the step (2) is 160-200 ℃, and the reaction time is 16-20 h.
Preferably, the raw materials in the step (3) are porous polyimide/Fe in parts by weight2O325-30 parts of composite material, 8-12 parts of waterborne polyurethane and 58-67 parts of deionized water.
Preferably, the strong alkali solution in the step (4) is one of a potassium hydroxide solution and a sodium hydroxide solution, and the soaking time is 10-20 min.
Preferably, the vacuum degree of the back bottom of the magnetron sputtering in the step (4) is 4-5 kPa, the working pressure is 1.5-1.8 mm, the target base distance is 100-120 mm, and the deposition time is 5-10 min.
Triptycenes have a unique D in organic compounds3hThe polymer has a large specific surface area when a unique three-dimensional rigid structure of the three-dimensional structure is introduced into the polymer, so that the porous material is prepared. The invention utilizes the principle to prepare the polyimide containing the triptycene structure, and utilizes the micropore pair thereof to generate Fe in situ2O3Carrying out loading, wherein the micropores of the polyimide structure are Fe2O3Provide space and promote Fe2O3Uniform dispersion in the film. Furthermore, due to the fact that the polyimide contains a triptycene structure, polymer chains are separated from chains, strong interaction among the chains does not exist, the film has good ductility, the triptycenes are close to each other under the action of tension, loads are transmitted among the chains, and the film has high modulus.
The invention adopts ferric acetylacetonate to generate Fe in situ at high temperature2O3And the composite film is uniformly coated in a porous structure of triptycene polyimide, and after the tape casting film forming, a silver conducting layer is formed on the upper surface and the lower surface through magnetron sputtering, so that the composite film with superparamagnetism and conductivity is prepared. The whole preparation process is simple, easy to control and low in energy consumption, and can be widely used in industrial production.
The invention also provides a polyimide composite film with both conductivity and magnetism prepared by the preparation method. The polyimide composite film is prepared by firstly synthesizing 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, then synthesizing porous polyimide containing a triptycene structure with hexafluoro-dianhydride, and simultaneously generating Fe in situ2O3Coating in a porous structure of polyimide, performing tape casting to form a film, and forming silver conductive layers on the upper and lower surfaces of the film by magnetron sputtering.
Compared with the prior art, the invention provides the polyimide composite film with both conductivity and magnetism and the preparation method thereof, and the outstanding characteristics and excellent effects are as follows:
1. the polyimide composite film prepared by the invention has good superparamagnetism and conductivity, and can be used as an electromagnetic shielding material.
2. The polyimide composite film prepared by the invention has good ductility and higher modulus.
3. The polyimide composite film prepared by the invention has higher specific surface area and porosity, and Fe2O3Is generated in situ and is coated in the porous structure of the polyimide, so the dispersibility is good.
4. According to the preparation method, the silver conducting layer is formed through magnetron sputtering, the process is simple, and the control is easy.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 19h at room temperature, stirring for 5h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2.5h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is hydrazine hydrate; the weight parts of the raw materials are 17 parts of 1,2,3, 4-tetrachlorotriptycene, 23 parts of acetic anhydride, 3 parts of nitric acid, 56 parts of acetone and 1 part of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, and pyrolyzing ferric acetylacetonateIron oxide is generated, and is evenly coated in the porous structure of the polyimide, and then the porous polyimide/Fe is obtained after filtration and drying2O3A composite material; the catalyst is a palladium/carbon catalyst; the reaction temperature is 190 ℃, and the reaction time is 17 h; the weight parts of the raw materials are 21 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 23 parts of hexafluoro dianhydride, 7 parts of ferric acetylacetonate, 1 part of catalyst and 48 parts of parachlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O327 parts of composite material, 9 parts of waterborne polyurethane and 64 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the alkali solution is potassium hydroxide solution, and the soaking time is 16 min; the vacuum degree of the back bottom of the magnetron sputtering is 4.5kPa, the working pressure is 1.7mm, the target base distance is 110mm, and the deposition time is 7 min.
The test method comprises the following steps:
(1) superparamagnetism (saturation magnetization, coercivity, remanence): testing by adopting a magnetometer of a vibration sample of American LDJ Electronics VSM-4HF, taking the composite film prepared by the invention in any shape, and obtaining a hysteresis loop by controlling the test environment temperature to be 23 +/-2 ℃ and the relative humidity to be 55 +/-5%, thereby obtaining the coercive magnetism, the residual magnetism and the saturation magnetization intensity of the magnetic composite film;
(2) conductivity (resistivity): testing by adopting a Gishili 4200 series four-probe tester, taking the composite film prepared by the invention in any shape, and obtaining the resistivity of the conductive composite film, wherein the test environment temperature is 23 +/-2 ℃, and the relative humidity is 55 +/-5%;
(3) ductility, modulus (tensile strength, tensile modulus): the method comprises the following steps of (1) adopting a Japanese Shimadzu AGS-X5KN tensile testing machine to test, wherein the test environment temperature is 23 +/-2 ℃, the relative humidity is 55 +/-5%, preparing the polyimide composite film prepared by the method into a standard sample, accurately measuring the thickness of the standard sample, and testing and calculating the tensile modulus and the tensile strength of the composite film, wherein the tensile rate is 5 mm/min;
(4) specific surface area: testing by adopting a Behcet BET specific surface area tester, taking the composite film prepared by the invention in any shape, and measuring the specific surface area of the composite film;
(5) porosity: testing by using a PoreMaster series film porosity tester, and measuring the porosity of the composite film in any shape by using the composite film prepared by the invention;
the data obtained are shown in Table 1.
Example 2
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 160h at room temperature, stirring for 4h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is phenylhydrazine; the weight parts of the raw materials are 15 parts of 1,2,3, 4-tetrachlorotriptycene, 20 parts of acetic anhydride, 2 parts of nitric acid, 62 parts of acetone and 1 part of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, carrying out pyrolysis on ferric acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in the porous structure of the polyimide, filtering and drying to obtain the porous polyimide/Fe2O3A composite material; the catalyst is a nickel/carbon catalyst; the reaction temperature is 160 ℃, and the reaction time is 20 hours; the weight portions of the raw materials are 18 portions of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 22 portions of hexafluoro dianhydride, 5 portions of ferric acetylacetonate and catalyst1 part by weight, 54 parts by weight of p-chlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O325 parts of composite material, 8 parts of waterborne polyurethane and 67 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the strong alkali solution is sodium hydroxide solution, and the soaking time is 10 min; the vacuum degree of the back bottom of the magnetron sputtering is 4kPa, the working pressure is 1.5mm, the target base distance is 100mm, and the deposition time is 10 min.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 3
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 20h at room temperature, stirring for 6h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 3h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is hydrazine hydrate; the weight parts of the raw materials are 20 parts of 1,2,3, 4-tetrachlorotriptycene, 25 parts of acetic anhydride, 4 parts of nitric acid, 49 parts of acetone and 2 parts of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, carrying out pyrolysis on ferric acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in the porous structure of the polyimide, filtering and drying to obtain the porous polyimide/Fe2O3A composite material;the catalyst is cobalt/carbon catalyst; the reaction temperature is 200 ℃, and the reaction time is 16 h; the weight parts of the raw materials are 22 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 25 parts of hexafluoro dianhydride, 8 parts of ferric acetylacetonate, 2 parts of catalyst and 43 parts of parachlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O330 parts of composite material, 12 parts of waterborne polyurethane and 58 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the alkali solution is potassium hydroxide solution, and the soaking time is 20 min; the vacuum degree of the back bottom of the magnetron sputtering is 5kPa, the working pressure is 1.8mm, the target base distance is 120mm, and the deposition time is 5 min.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 4
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 17 hours at room temperature, stirring for 5.5 hours in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2 hours, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is phenylhydrazine; the weight parts of the raw materials are 16 parts of 1,2,3, 4-tetrachlorotriptycene, 22 parts of acetic anhydride, 2 parts of nitric acid, 59 parts of acetone and 1 part of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and catalyst into p-chlorophenol, heating for reaction, and reacting dianhydride and diamine to generate porous triptycene structurePolyimide and ferric acetylacetonate are pyrolyzed to generate iron oxide in situ, and then the iron oxide is uniformly coated in the porous structure of the polyimide, and then the porous polyimide/Fe is obtained by filtering and drying2O3A composite material; the catalyst is an iron/carbon catalyst; the reaction temperature is 170 ℃, and the reaction time is 19 hours; the weight parts of the raw materials are 19 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 23 parts of hexafluoro dianhydride, 6 parts of ferric acetylacetonate, 1 part of catalyst and 51 parts of parachlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O326 parts of composite material, 9 parts of waterborne polyurethane and 65 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the strong alkali solution is sodium hydroxide solution, and the soaking time is 12 min; the vacuum degree of the back bottom of the magnetron sputtering is 4kPa, the working pressure is 1.6mm, the target base distance is 105mm, and the deposition time is 8 min.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 5
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 19h at room temperature, stirring for 5.5h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 3h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is hydrazine hydrate or phenylhydrazine; the weight parts of the raw materials are 19 parts of 1,2,3, 4-tetrachlorotriptycene, 24 parts of acetic anhydride, 4 parts of nitric acid, 51 parts of acetone and 2 parts of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, carrying out pyrolysis on ferric acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in the porous structure of the polyimide, filtering and drying to obtain the porous polyimide/Fe2O3A composite material; the catalyst is a palladium/carbon catalyst; the reaction temperature is 190 ℃, and the reaction time is 17 h; the weight parts of the raw materials are 21 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 24 parts of hexafluoro dianhydride, 7 parts of ferric acetylacetonate, 2 parts of catalyst and 46 parts of parachlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O329 parts of composite material, 11 parts of waterborne polyurethane and 60 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the alkali solution is potassium hydroxide solution, and the soaking time is 18 min; the vacuum degree of the back bottom of the magnetron sputtering is 5kPa, the working pressure is 1.7mm, the target base distance is 115mm, and the deposition time is 7 min.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Example 6
(1) Adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 18h at room temperature, stirring for 5h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2.5h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene; the reducing agent is phenylhydrazine; the weight parts of the raw materials are 18 parts of 1,2,3, 4-tetrachlorotriptycene, 22 parts of acetic anhydride, 3 parts of nitric acid, 55 parts of acetone and 2 parts of reducing agent;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, carrying out pyrolysis on ferric acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in the porous structure of the polyimide, filtering and drying to obtain the porous polyimide/Fe2O3A composite material; the catalyst is a nickel/carbon catalyst; the reaction temperature is 180 ℃ and the reaction time is 18 h; the weight parts of the raw materials are 20 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 24 parts of hexafluoro dianhydride, 6 parts of ferric acetylacetonate, 2 parts of catalyst and 48 parts of parachlorophenol;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film; the weight portion of each raw material is porous polyimide/Fe2O328 parts of composite material, 10 parts of waterborne polyurethane and 62 parts of deionized water;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in a strong alkaline solution for surface etching to open the polyimide on the surface layer to form polyamic acid, and then respectively plating silver conductive layers on the upper surface and the lower surface by adopting magnetron sputtering to prepare the polyimide composite film with both conductivity and magnetism; the alkali solution is sodium hydroxide solution, and the soaking time is 15 min; the vacuum degree of the back bottom of the magnetron sputtering is 4.5kPa, the working pressure is 1.6mm, the target base distance is 110mm, and the deposition time is 8 min.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Comparative example 1
The preparation method is characterized in that a triptycene structure is not introduced into the polyimide, the polyimide is prepared by taking 4,4' -diaminodiphenyl ether and hexafluorodianhydride as raw materials, and other preparation conditions are consistent with those of example 6.
The test method was in accordance with example 1, and the data obtained are shown in Table 1.
Table 1:
Claims (10)
1. a preparation method of a polyimide composite film with both conductivity and magnetism is characterized by comprising the following specific steps:
(1) adding 1,2,3, 4-tetrachlorotriptycene into acetic anhydride, dropwise adding a nitric acid solution, reacting for 16-20 h at room temperature, stirring for 4-6 h in an ice bath, performing suction filtration, adding the obtained solid into acetone, adding a reducing agent, performing heating reflux reaction for 2-3 h, performing suction filtration, and performing rotary evaporation on the filtrate to obtain 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene;
(2) adding 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, hexafluoro dianhydride, ferric acetylacetonate and a catalyst into p-chlorophenol, heating for reaction, reacting dianhydride and diamine to generate porous polyimide with a triptycene structure, carrying out pyrolysis on ferric acetylacetonate to generate iron oxide in situ, uniformly coating the iron oxide in the porous structure of the polyimide, filtering and drying to obtain the porous polyimide/Fe2O3A composite material;
(3) mixing porous polyimide/Fe2O3Dispersing the composite material and the waterborne polyurethane resin in deionized water, casting to form a film, and drying by infrared rays to obtain the porous polyimide/Fe2O3A polyurethane composite film;
(4) mixing porous polyimide/Fe2O3Soaking the polyurethane composite film in strong alkaline solution for surface etching to open the polyimide ring on the surface layer to form polyamic acid, and plating silver conductive layers on the upper and lower surfaces by magnetron sputtering to obtain the conductive and magnetic filmA polyimide composite film.
2. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the reducing agent in the step (1) is at least one of hydrazine hydrate or phenylhydrazine.
3. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the raw materials in the step (1) comprise, by weight, 15-20 parts of 1,2,3, 4-tetrachlorotriptycene, 20-25 parts of acetic anhydride, 2-4 parts of nitric acid, 49-62 parts of acetone and 1-2 parts of a reducing agent.
4. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the catalyst in the step (2) is at least one of palladium/carbon catalyst, nickel/carbon catalyst, cobalt/carbon catalyst and iron/carbon catalyst.
5. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the raw materials in the step (2) comprise, by weight, 18-22 parts of 2, 6-diamino-13, 14,15, 16-tetrachlorotriptycene, 22-25 parts of hexafluoro dianhydride, 5-8 parts of ferric acetylacetonate, 1-2 parts of a catalyst and 43-54 parts of parachlorophenol.
6. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the reaction temperature in the step (2) is 160-200 ℃, and the reaction time is 16-20 h.
7. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the raw materials in the step (3) comprise porous polyimide/Fe in parts by weight2O325-30 parts by weight of composite material and water-based polymer8-12 parts of polyurethane and 58-67 parts of deionized water.
8. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: and (4) the strong alkali solution in the step (4) is one of a potassium hydroxide solution and a sodium hydroxide solution, and the soaking time is 10-20 min.
9. The method for preparing the polyimide composite film with both conductivity and magnetism according to claim 1, wherein: the vacuum degree of the back bottom of the magnetron sputtering in the step (4) is 4-5 kPa, the working pressure is 1.5-1.8 mm, the target base distance is 100-120 mm, and the deposition time is 5-10 min.
10. A polyimide composite film having both conductivity and magnetism, which is obtained by the preparation method according to any one of claims 1 to 9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949212A (en) * | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| CN105244484A (en) * | 2015-09-24 | 2016-01-13 | 复旦大学 | Iron oxide nano-particle/graphene-polyimide-based carbon aerogel composite material and preparation method thereof |
| WO2018062422A1 (en) * | 2016-09-28 | 2018-04-05 | 日産化学工業株式会社 | Diamine and use thereof |
| CN108291028A (en) * | 2015-10-08 | 2018-07-17 | 阿卜杜拉国王科技大学 | The diamines based on triptycene, monomer and the polymer of ortho position substitution, preparation method and the usage |
-
2018
- 2018-07-28 CN CN201810849031.2A patent/CN109081939B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103949212A (en) * | 2014-04-11 | 2014-07-30 | 上海交通大学 | Preparation method of biomass-based magnetic biochar |
| CN105244484A (en) * | 2015-09-24 | 2016-01-13 | 复旦大学 | Iron oxide nano-particle/graphene-polyimide-based carbon aerogel composite material and preparation method thereof |
| CN108291028A (en) * | 2015-10-08 | 2018-07-17 | 阿卜杜拉国王科技大学 | The diamines based on triptycene, monomer and the polymer of ortho position substitution, preparation method and the usage |
| WO2018062422A1 (en) * | 2016-09-28 | 2018-04-05 | 日産化学工業株式会社 | Diamine and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| One-pot preparation of polyimide-Fe3O4 magnetic nanofibers with solvent resistant properties;Chao Luo;《Composites Science and Technology》;20160725;第133卷;第2.1-2.4节 * |
| 基于三蝶烯结构新型聚酰亚胺的合成及性能研究;郑学建;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20150215;第3.2.3-3.2.6节 * |
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