CN112898587A - Graphene grafted modified hyperbranched polyimide dielectric material and preparation method thereof - Google Patents
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Abstract
The invention relates to the technical field of polyimide materials, and discloses a graphene grafted modified hyperbranched polyimide dielectric material, which takes 1,3, 5-tri (4-aminophenyl) benzene as a hypercrosslinking center to perform a polymerization reaction with a dianhydride monomer to generate an amino-terminated polyamic acid precursor, the active amino-terminated group of the amino-terminated polyamic acid precursor and the epoxy group of graphene perform a ring-opening addition reaction, and the graphene grafted modified hyperbranched polyimide is obtained by thermal imide treatment, the graphene and the polyimide are organically combined, the compatibility and the interfacial adhesion between the graphene and the polyimide are enhanced, the graphene is uniformly dispersed in the matrix of the polyimide, the problems of agglomeration and aggregation are overcome, the graphene nanoparticles and the polyimide form an interfacial polarization phenomenon, the polarization strength in the system is improved, a stable percolation system is constructed, and the dielectric constant of the polyimide is improved, improves the dielectric loss and shows excellent dielectric properties.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to a graphene grafted modified hyperbranched polyimide dielectric material and a preparation method thereof.
Background
Engineering plastics such as polyamide, polyimide, polyphenyl ester, polyphenylene sulfide, polycarbonate and the like have high rigidity, high strength, good heat resistance and excellent electrical insulation, can be used as engineering structure materials and replace metals to manufacture machine parts, wherein the polyimide is one of the engineering plastics with the best comprehensive performance, is widely applied to the fields of aerospace, microelectronic industry, liquid crystal materials, separation film materials and the like, and has excellent processing performance, good thermal stability, wide use temperature and electrochemical properties of monomers, so that the polyimide material has wide application prospects in the aspects of capacitor dielectric materials, dielectric materials and the like.
At present, the high dielectric composite material is prepared by taking an organic polymer as a substrate, adding an inorganic dielectric substance, processing through a miniaturized integrated circuit, using the high dielectric composite material as a material such as an embedded electronic element and the like, applying the high dielectric composite material to an energy storage and conversion technology and a device, at present, improving the dielectric constant and the dielectric property of materials such as polyimide and the like, usually adding the inorganic dielectric substance such as ferroferric oxide, barium titanate and the like, but adding a large amount of the inorganic dielectric substance to effectively improve the dielectric property, in recent years, the research on a seepage theory and an interface polarization theory is mature, adding a trace amount of high conductive substance such as nano particles such as graphene, carbon nano tubes and the like into materials such as polyimide and the like can obviously improve the dielectric property of the materials, but because the compatibility and the interface bonding force of the graphene nano particles and organic polymers such as polyimide and the like are poor, and the agglomeration, resulting in excessive dielectric loss of the material, which can seriously affect the dielectric properties and thermal stability of the material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the graphene grafted modified hyperbranched polyimide dielectric material and the preparation method thereof, so that the polyimide material has excellent dielectric property and thermal stability.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of the graphene grafted modified hyperbranched polyimide dielectric material is as follows:
(1) and introducing nitrogen into the three-necked bottle to exhaust air, adding an N, N-dimethylformamide solution and graphene oxide, performing ultrasonic dispersion, adding an N-butyllithium solution, and performing ultrasonic activation reaction for 1-2 hours.
(2) And adding epoxy chloropropane into the activated graphene oxide solution, performing nucleophilic substitution reaction, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) And introducing nitrogen into the three-necked bottle to exhaust air, adding an N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and a dianhydride monomer, performing hyperbranched polymerization, cooling the three-necked bottle in an ice-water bath, adding a methanol solvent, precipitating, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) And adding an N, N-dimethylacetamide solvent, an amino-terminated polyamic acid precursor and epoxidized graphene into a three-necked bottle, performing addition reaction, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And placing the graphene grafted polyamide acid precursor in an oven, and performing thermal imidization treatment to obtain the graphene grafted modified hyperbranched polyimide dielectric material.
Preferably, the mass ratio of the graphene oxide to the n-butyl lithium in the step (1) is 100: 15-40.
Preferably, the mass ratio of the activated graphene oxide to the epichlorohydrin in the step (2) is 100: 80-160.
Preferably, the nucleophilic substitution reaction in the step (2) is carried out for 6-12h at 20-40 ℃.
Preferably, the dianhydride monomer in step (3) is one of pyromellitic anhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride or 4,4' -biphenyl ether dianhydride.
Preferably, the mass ratio of the 1,3, 5-tri (4-aminophenyl) benzene and the dianhydride monomer in the step (3) is 100: 55-75.
Preferably, the hyperbranched polymerization reaction in the step (3) is carried out at 40-55 ℃ for 10-18 h.
Preferably, the mass ratio of the amino-terminated polyamic acid precursor to the epoxidized graphene in the step (4) is 100: 0.8-2.
Preferably, the addition reaction in the step (4) is carried out at 40-80 ℃ for 6-12 h.
Preferably, the thermal imidization treatment in the step (5) is performed by pre-treating at 100-120 ℃ for 40-60min, then performing heat treatment at 160-200 ℃ for 2-3h, then performing heat treatment at 240-260 ℃ for 1-1.5h, and finally performing heat treatment at 320-340 ℃ for 1-1.5 h.
(III) advantageous technical effects
Compared with the prior art, the invention has the following chemical mechanism and beneficial technical effects:
according to the graphene grafted modified hyperbranched polyimide dielectric material, surface hydroxyl of graphene oxide is activated through n-butyl lithium to form activated oxygen anions, and then the oxygen anions and chlorine atoms of epoxy chloropropane undergo nucleophilic substitution reaction to obtain epoxidized graphene, so that epoxy groups are introduced to the surface of the graphene to realize functional modification of the graphene.
The graphene grafted modified hyperbranched polyimide dielectric material takes 1,3, 5-tris (4-aminophenyl) benzene as a hypercrosslinked center, performs polymerization reaction with dianhydride monomer, generates an amino-terminated polyamic acid precursor by controlling the dosage of the 1,3, 5-tris (4-aminophenyl) benzene, further generates an open loop addition reaction between active amino-terminated groups of the polyamic acid precursor and epoxy groups of graphene, and obtains graphene grafted modified hyperbranched polyimide by thermal imine treatment, so that the graphene and the polyimide are covalently grafted, the graphene and the polyimide are organically combined by chemical bond connection, the compatibility and the interface bonding force between graphene nanoparticles and the polyimide are obviously enhanced, the graphene is uniformly dispersed in the polyimide matrix, and the problems of agglomeration and aggregation are overcome, the interface polarization phenomenon is formed between the graphene nano particles and the polyimide, the polarization strength in the system is improved, and when the content of the graphene nano particles is close to a critical threshold value, a stable seepage system is constructed, so that the dielectric constant of the polyimide is improved, the dielectric loss is improved, and excellent dielectric properties are shown.
According to the graphene grafted modified hyperbranched polyimide dielectric material, polyimide has a unique hyperbranched three-dimensional structure, the crystallinity is good, the space between molecular chains is smaller, and meanwhile, the graphene is used as a chemical crosslinking site to further limit the movement of the molecular chains of the polyimide and fix the molecular chains, so that the thermal decomposition temperature and the thermal stability of the polyimide are obviously improved.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the graphene grafted modified hyperbranched polyimide dielectric material is as follows:
(1) introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:15-40, and carrying out ultrasonic activation reaction for 1-2 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:80-160, carrying out nucleophilic substitution reaction for 6-12h at 20-40 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to discharge air, adding N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and dianhydride monomer with the mass ratio of 100:55-75, wherein the dianhydride monomer is one of pyromellitic dianhydride, 3',4,4' -biphenyltetracarboxylic dianhydride or 4,4' -biphenylether dianhydride, performing hyperbranched polymerization reaction for 10-18h at 40-55 ℃, placing the three-necked bottle in an ice-water bath for cooling, adding methanol solvent for precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:0.8-2 into a three-necked bottle, performing addition reaction at 40-80 ℃ for 6-12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) Placing the graphene grafted polyamic acid precursor in an oven, performing thermal imidization treatment, pretreating for 40-60min at 100-120 ℃, then performing thermal treatment for 2-3h at 160-200 ℃, then performing thermal treatment for 1-1.5h at 240-260 ℃, and finally performing thermal treatment for 1-1.5h at 320-340 ℃, wherein the graphene grafted and modified hyperbranched polyimide dielectric material is prepared.
Example 1
(1) Introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:15, and carrying out ultrasonic activation reaction for 1 h.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:80, carrying out nucleophilic substitution reaction for 6h at 20 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to exhaust air, adding N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and pyromellitic dianhydride in a mass ratio of 100:55, performing hyperbranched polymerization reaction for 10h at 40 ℃, placing the three-necked bottle in an ice-water bath for cooling, adding methanol solvent for precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:0.8 into a three-necked bottle, performing addition reaction for 6 hours at 40 ℃, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And (2) placing the graphene grafted polyamide acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is carried out on the graphene grafted polyamide acid precursor for pretreatment for 40min at 100 ℃, then for heat treatment for 2h at 160 ℃, then for heat treatment for 1h at 240 ℃, and finally for heat treatment for 1h at 320 ℃, so that the graphene grafted modified hyperbranched polyimide dielectric material is obtained.
Example 2
(1) Introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:22, and carrying out ultrasonic activation reaction for 2 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:100, carrying out nucleophilic substitution reaction for 8h at 40 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to discharge air, adding N, N-dimethylacetamide solvent, 1,3, 5-tri (4-aminophenyl) benzene and 3,3',4,4' -biphenyltetracarboxylic dianhydride in a mass ratio of 100:72, performing hyperbranched polymerization reaction at 55 ℃ for 18h, cooling the three-necked bottle in an ice-water bath, adding methanol solvent for precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:1.2 into a three-necked bottle, performing addition reaction at 60 ℃ for 12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And placing the graphene grafted polyamic acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is firstly carried out for 40min at 120 ℃, then is carried out for 2.5h at 180 ℃, then is carried out for 1h at 250 ℃, and finally is carried out for 1.5h at 320 ℃, so that the graphene grafted and modified hyperbranched polyimide dielectric material is obtained.
Example 3
(1) And introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:32, and performing ultrasonic activation reaction for 1.5 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:130, carrying out nucleophilic substitution reaction for 8h at 30 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to discharge air, adding N, N-dimethylacetamide solvent, 1,3, 5-tri (4-aminophenyl) benzene and 3,3',4,4' -biphenyltetracarboxylic dianhydride in a mass ratio of 100:75, performing hyperbranched polymerization reaction for 15h at 50 ℃, cooling the three-necked bottle in ice-water bath, adding methanol solvent to perform precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:1.6 into a three-necked bottle, performing addition reaction at 60 ℃ for 12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And (2) placing the graphene grafted polyamide acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is firstly carried out for 50min at 110 ℃, then is carried out for 2.53h at 180 ℃, then is carried out for 1.5h at 250 ℃, and finally is carried out for 1.5h at 330 ℃, so that the graphene grafted modified hyperbranched polyimide dielectric material is obtained.
Example 4
(1) Introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:40, and carrying out ultrasonic activation reaction for 2 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:160, carrying out nucleophilic substitution reaction for 12h at 40 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to exhaust air, adding N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and 4,4' -diphenyl ether dianhydride in a mass ratio of 100:75, performing hyperbranched polymerization at 55 ℃ for 18h, cooling the three-necked bottle in an ice-water bath, adding methanol solvent to perform precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:2 into a three-necked bottle, performing addition reaction at 80 ℃ for 12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And (2) placing the graphene grafted polyamic acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is carried out on the precursor for 60min at 120 ℃, then carrying out thermal treatment for 3h at 200 ℃, then carrying out thermal treatment for 1.5h at 260 ℃, and finally carrying out thermal treatment for 1.5h at 340 ℃, thus obtaining the graphene grafted modified hyperbranched polyimide dielectric material.
Comparative example 1
(1) Introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:8, and carrying out ultrasonic activation reaction for 2 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:50, carrying out nucleophilic substitution reaction for 12h at 30 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to exhaust air, adding N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and pyromellitic dianhydride in a mass ratio of 100:45, performing hyperbranched polymerization reaction for 15h at 55 ℃, placing the three-necked bottle in an ice-water bath for cooling, adding methanol solvent for precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:0.3 into a three-necked bottle, performing addition reaction at 80 ℃ for 12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And placing the graphene grafted polyamic acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is firstly carried out for 50min at 110 ℃, then is carried out for 2h at 200 ℃, then is carried out for 1.5h at 250 ℃, and finally is carried out for 1.5h at 330 ℃, so that the graphene grafted and modified hyperbranched polyimide dielectric material is obtained.
Comparative example 2
(1) Introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, controlling the mass ratio of the graphene oxide to the N-butyllithium to be 100:50, and carrying out ultrasonic activation reaction for 2 hours.
(2) Adding epichlorohydrin into the activated graphene oxide solution, controlling the mass ratio of the activated graphene oxide to the epichlorohydrin to be 100:180, carrying out nucleophilic substitution reaction for 12h at 30 ℃, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene.
(3) Introducing nitrogen into a three-necked bottle to discharge air, adding N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and 4,4' -diphenyl ether dianhydride in a mass ratio of 100:82, performing hyperbranched polymerization reaction at 45 ℃ for 15h, cooling the three-necked bottle in an ice-water bath, adding methanol solvent to perform precipitation, filtering the solvent, washing the product with methanol, and preparing the amino-terminated polyamic acid precursor.
(4) Adding N, N-dimethylacetamide solvent, amino-terminated polyamic acid precursor and epoxidized graphene in a mass ratio of 100:2.5 into a three-necked bottle, performing addition reaction at 60 ℃ for 12h, cooling the solution, precipitating with methanol, filtering and washing to obtain the graphene grafted polyamic acid precursor.
(5) And (2) placing the graphene grafted polyamide acid precursor in an oven, and carrying out thermal imidization treatment, wherein the thermal imidization treatment is firstly carried out for 60min at 100 ℃, then is carried out for 3h at 180 ℃, then is carried out for 1.5h at 260 ℃, and finally is carried out for 1.5h at 330 ℃, so that the graphene grafted modified hyperbranched polyimide dielectric material is obtained.
And testing the dielectric constant and the dielectric loss of the graphene grafted modified hyperbranched polyimide dielectric material by using a GDAT-A high-frequency dielectric constant tester.
The initial decomposition temperature of the graphene grafted modified hyperbranched polyimide dielectric material was tested using a TGA1350D thermogravimetric analyzer.
Claims (10)
1. A graphene grafted modified hyperbranched polyimide dielectric material is characterized in that: the preparation method of the graphene grafted modified hyperbranched polyimide dielectric material is as follows:
(1) introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylformamide solution and graphene oxide, adding an N-butyllithium solution after ultrasonic dispersion, and performing ultrasonic activation reaction for 1-2 hours;
(2) adding epoxy chloropropane into the activated graphene oxide solution, carrying out nucleophilic substitution reaction, centrifugally separating to remove the solvent, washing the solid product with distilled water and acetone, and preparing the epoxidized graphene;
(3) introducing nitrogen into a three-necked bottle to discharge air, adding an N, N-dimethylacetamide solvent, 1,3, 5-tris (4-aminophenyl) benzene and a dianhydride monomer, performing hyperbranched polymerization, cooling the three-necked bottle in an ice-water bath, adding a methanol solvent for precipitation, filtering the solvent, washing the product with methanol, and preparing an amino-terminated polyamic acid precursor;
(4) adding an N, N-dimethylacetamide solvent, an amino-terminated polyamic acid precursor and epoxidized graphene into a three-necked bottle, performing addition reaction, cooling the solution, precipitating with methanol, filtering and washing to obtain a graphene grafted polyamic acid precursor;
(5) and placing the graphene grafted polyamide acid precursor in an oven, and performing thermal imidization treatment to obtain the graphene grafted modified hyperbranched polyimide dielectric material.
2. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the mass ratio of the graphene oxide to the n-butyllithium in the step (1) is 100: 15-40.
3. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the mass ratio of the activated graphene oxide to the epichlorohydrin in the step (2) is 100: 80-160.
4. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: in the step (2), the nucleophilic substitution reaction is carried out for 6-12h at the temperature of 20-40 ℃.
5. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the dianhydride monomer in the step (3) is one of pyromellitic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride or 4,4' -biphenyl ether dianhydride.
6. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the mass ratio of the 1,3, 5-tri (4-aminophenyl) benzene and the dianhydride monomer in the step (3) is 100: 55-75.
7. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the hyperbranched polymerization reaction in the step (3) is carried out for 10-18h at the temperature of 40-55 ℃.
8. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the mass ratio of the amino-terminated polyamic acid precursor to the epoxidized graphene in the step (4) is 100: 0.8-2.
9. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the addition reaction in the step (4) is carried out for 6-12h at the temperature of 40-80 ℃.
10. The graphene grafted modified hyperbranched polyimide dielectric material of claim 1, wherein: the thermal imidization treatment in the step (5) is firstly pretreated at the temperature of 100-120 ℃ for 40-60min, then is thermally treated at the temperature of 160-200 ℃ for 2-3h, then is thermally treated at the temperature of 240-260 ℃ for 1-1.5h, and finally is thermally treated at the temperature of 320-340 ℃ for 1-1.5 h.
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| CN116253319A (en) * | 2023-02-17 | 2023-06-13 | 沈阳富创精密设备股份有限公司 | Uniform treatment method of micro-nano material suspension |
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| CN116875052B (en) * | 2023-07-25 | 2024-02-20 | 北京清大际光科技发展有限公司 | Thermoplastic polyimide antibacterial composite material and preparation method thereof |
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