CN105061763A - Sulfonated graphene-containing high heat conduction and high barrier polyimide film and production method thereof - Google Patents
Sulfonated graphene-containing high heat conduction and high barrier polyimide film and production method thereof Download PDFInfo
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Abstract
The invention discloses a sulfonated graphene-containing high heat conduction and high barrier polyimide film. The polyimide film comprises sulfonated graphene and polyimide according to a mass ratio of 0.5-25:100, the radial dimension of sulfonated graphene is 500nm-50[mu]m, the thickness of sulfonated graphene is 1-20nm, and a molar ratio of C to S in the sulfonated graphene is 12:1-6:1. The invention also discloses a production method of the polyimide film. The method comprises the following steps: dissolving aromatic diamine, aromatic tetracid dihydride and sulfonated graphene in an organic solvent, reacting while stirring at room temperature for 2-48h to form a polyimide organic solution, forming a film, carrying out heating treatment at 60-300DEG C, and naturally cooling. The polyimide film has the characteristics of high heat conduction coefficient, excellent mechanical performances, basically consistent heat conduction performances and mechanical performances of all positions, and excellent barrier to oxygen, helium and other gases, and the production method has the advantages of simplicity, easy operation, high controllability, and suitableness for large scale production.
Description
Technical field
The present invention relates to a kind of polyimide film and preparation method thereof, particularly a kind of high heat conduction high-barrier polyimide film adding sulfonated graphene and preparation method thereof.
Background technology
If Kapton is a kind of novel organic polymer thin film, it can by pyromellitic acid anhydride (PMDA) and diaminodiphenyl oxide (ODA) at extremely strong property solvent N, through polycondensation and casting film-forming in N-N,N-DIMETHYLACETAMIDE (DMAC), then form through imidization.There is excellent mechanical property, electrical property, chemical stability, radioresistance, high temperature resistant and resistance to low temperature.But Kapton comes with some shortcomings, such as its thermal conductivity is only 0.16W/ (MK), limits the application in technical field of electronic materials.Therefore, how modification is carried out to promote the study hotspot that its performance has become industry to polyimide.
Publication No. is the heat conduction film that the application for a patent for invention of CN103738940A discloses a kind of Graphene modification, comprises polyimide emulsion, binding agent, auxiliary agent and solvent, adds Graphene in described heat conduction film.It is high that this patented technology has intensity according to Graphene, and specific surface area is large, high chemical reactivity, high thermal conductivity coefficient, the feature of high fillibility; The thin film strength of heat conduction, mechanical property and thermal conductivity is improve to a certain extent by adding Graphene in heat conduction film, but still there are some problems being difficult to overcome in it, such as, Graphene cannot realize dispersed in heat conduction film, and ubiquity agglomeration, cause the heat conduction of the different zones of film, mechanical property exists larger difference, be difficult to drop into practical application.
Summary of the invention
The object of the present invention is to provide a kind of high heat conduction high-barrier polyimide film adding sulfonated graphene and preparation method thereof, to overcome deficiency of the prior art.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
Add a high heat conduction high-barrier polyimide film for sulfonated graphene, it comprises polyimide and sulfonated graphene, and the mass ratio of described sulfonated graphene and polyimide is 0.5 ~ 25:100.
Further, the radial dimension of described sulfonated graphene is 500nm ~ 50 μm, and thickness is 1nm ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
A kind of method preparing the high heat conduction high-barrier polyimide film of described interpolation sulfonated graphene, it comprises: after aromatic diamine, aromatic tetrahydric dianhydride and sulfonated graphene are dissolved in organic solvent, at stirring at room temperature reaction 2 ~ 48h, form polyimide organic solution, prepare film forming afterwards, again at 60 ~ 300 DEG C of heat treated 2-8 hour, then naturally cooling obtains described polyimide film;
The radial dimension of wherein said sulfonated graphene is 500nm ~ 50 μm, and thickness is 1nm ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
Among a better embodiment, described preparation method specifically comprises: by described polyimide organic solution casting film-forming, afterwards 60 ~ 300 DEG C of heat treated.
Comparatively preferred, the consumption of described sulfonated graphene is 0.5% ~ 25% of polyimide quality in described polyimide film.
Comparatively preferred, the mol ratio of described aromatic diamine and aromatic tetrahydric dianhydride is 1:0.8 ~ 1:1.05.
Further, described organic solvent can preferably from but be not limited to N-Methyl pyrrolidone (NMP), dimethyl formamide (DMF), N,N-DIMETHYLACETAMIDE (DMAc) or dimethyl sulfoxide (DMSO) (DMSO) etc.
Further, described aromatic tetrahydric dianhydride can preferably from but be not limited to the two Tetra hydro Phthalic anhydride (ODPA) or 3,3 ', 4 of 4,4-oxygen, 4 '-benzophenone tetracarboxylic dianhydride (BTDA) etc.
Further, described aromatic diamines can preferably from but be not limited to 4,4'-diaminodiphenyl oxide (ODA), Isosorbide-5-Nitrae-bis-(4-amino-2-4-trifluoromethylphenopendant) benzene (6FAPB) etc.
Comparatively preferred, the polyimide solid content in described polyimide organic solution is 5wt% ~ 30wt%.
Among a better embodiment, the preparation method of described sulfonated graphene comprises: be 50nm ~ 50 μm by radial dimension, thickness is that to add primarily of mass ratio be in the mixed acid solution that forms of the oleum of 1 ~ 4:3 ~ 6 and chlorsulfonic acid for the Graphene of 1nm ~ 20nm or graphene oxide, and 1h ~ 10h is reacted at 60 DEG C ~ 150 DEG C, then distill more than 160 DEG C, residue, after cleaning, obtains described sulfonated graphene.
Compared with prior art, advantage of the present invention comprises:
(1) polyimide film of the present invention there is the heat conductivility at each position of the features, particularly film such as thermal conductivity high (0.5-20W/ (m.K)), good mechanical performance (such as tensile strength is greater than 100Mpa) and mechanical property basically identical;
(2) inventor also finds very unexpectedly, and polyimide film of the present invention also has excellent barrier for the gas such as oxygen, helium;
(3) preparation technology of polyimide film of the present invention is simple to operation, and controllability is high, is suitable for large-scale production.
Embodiment
Below in conjunction with the technical solution of the present invention is further explained the explanation of some embodiments.
Embodiment 1
Be 50nm ~ 50 μm by radial dimension, thickness is that to add by mass ratio be in the mixed acid solution that forms of the oleum of 1:6 and chlorsulfonic acid for the Graphene of 1nm ~ 20nm, and 1h is reacted at 150 DEG C, then 165 DEG C of distillations, residue is after cleaning, obtain sulfonated graphene, find through XRD and Infrared Characterization, wherein there is sulfonic group, separately find through ultimate analysis, in this sulfonated graphene, the mol ratio of C and S is about 12:1, levy in high-resolution TEM following table existing, its radial dimension is about 500nm ~ 50 μm, and thickness is about 1nm ~ 20nm.
6FAPB and aforementioned sulfonated graphene (addition is the 0.5wt% of polyimide in the finished product) are dissolved in DMSO, then the equimolar ODPA with 6FAPB is added, be stirred to and dissolve completely, at stirring at room temperature reaction 24h, obtain polyimide organic solution, by this solution casting film-forming on glass, through each 1 hour of 60 DEG C, 100 DEG C, 150 DEG C, 200 DEG C, 300 DEG C heat treated in High Temperature Furnaces Heating Apparatus, naturally cooling obtains polyimide film.
Embodiment 2
Be 50nm ~ 50 μm by radial dimension, thickness is that to add by mass ratio be in the mixed acid solution that forms of the oleum of 4:3 and chlorsulfonic acid for the Graphene of 1nm ~ 20nm, and 10h is reacted at 60 DEG C, then 160 DEG C of distillations, residue is after cleaning, obtain sulfonated graphene, in this sulfonated graphene, the mol ratio of C and S is about 6:1, and its size is about 500nm ~ 50 μm, and thickness is about 1nm ~ 20nm.
ODA and aforementioned sulfonated graphene (addition is the 25wt% of polyimide in the finished product) are dissolved in DMF, then the equimolar BTDA with ODA is added, be stirred to and dissolve completely, at stirring at room temperature reaction 24h, obtain polyimide organic solution, by this solution casting film-forming on metallic substrates, through 60 DEG C, 100 DEG C, 150 DEG C, 200 DEG C, 300 DEG C heat treated in High Temperature Furnaces Heating Apparatus, naturally cooling obtains polyimide film.
Embodiment 3
Be 50nm ~ 50 μm by radial dimension, thickness is that to add by mass ratio be in the mixed acid solution that forms of the oleum of 2:5 and chlorsulfonic acid for the Graphene of 1nm ~ 20nm, and 5h is reacted at 100 DEG C, then 170 DEG C of distillations, residue is after cleaning, obtain sulfonated graphene, in this sulfonated graphene, the mol ratio of C and S is about 1:6, and its radial dimension is about 500nm ~ 50 μm, and thickness is about 1nm ~ 20nm.
ODA and aforementioned sulfonated graphene (addition is the 2wt% of polyimide in the finished product) are dissolved in DMF, then the equimolar BTDA with ODA is added, be stirred to and dissolve completely, at stirring at room temperature reaction 48h, obtain polyimide organic solution, by this solution casting film-forming on metallic substrates, through 60 DEG C, 100 DEG C, 150 DEG C, 200 DEG C, 300 DEG C heat treated in High Temperature Furnaces Heating Apparatus, naturally cooling obtains polyimide film.
Reference examples 1
ODA and graphene oxide (are consulted CN102225754A preparation, addition is the 5wt% of polyimide in the finished product) be dissolved in DMF, then the equimolar BTDA with ODA is added, be stirred to and dissolve completely, at stirring at room temperature reaction 24h, obtain polyimide organic solution, by this solution casting film-forming on metallic substrates, through 60 DEG C, 100 DEG C, 150 DEG C, 200 DEG C, 300 DEG C heat treated in High Temperature Furnaces Heating Apparatus, naturally cooling obtains polyimide film.
Reference examples 2
ODA and sulfonated graphene (are consulted CN103613097A preparation, addition is the 10wt% of polyimide in the finished product) be dissolved in DMF, then the equimolar BTDA with ODA is added, be stirred to and dissolve completely, at stirring at room temperature reaction 48h, obtain polyimide organic solution, by this solution casting film-forming on metallic substrates, through 60 DEG C, 100 DEG C, 150 DEG C, 200 DEG C, 300 DEG C heat treated in High Temperature Furnaces Heating Apparatus, naturally cooling obtains polyimide film.
Example 1-3, reference examples 1-2 obtain polyimide film product and test respectively, then:
(1) high resolving power tem observation is utilized to find, in embodiment 1-3 product, sulfonated graphene is dispersed in polyimide base material, basic soilless sticking phenomenon, in reference examples 1 product there is obvious agglomeration in graphene oxide, and in reference examples 2 product, sulfonated graphene also has to a certain degree agglomeration.
(2) thermal conductivity of embodiment 1-3 product is in 0.5-20W/ (m.K) scope, tensile strength is greater than 100Mpa, the thermal conductivity of reference examples 1 product is 0.28W/ (m.K), tensile strength is 65Mpa, the thermal conductivity of reference examples 2 product is 0.39W/ (m.K), and tensile strength is 80Mpa.
In addition, the thermal conductivity of each different sites of the big area Kapton prepared according to embodiment 1-3, reference examples 1-2 technique, tensile strength are tested respectively, can find, the diversity factor of the thermal conductivity at each position of embodiment 1-3 product is within 5%, the diversity factor of tensile strength is within 10%, and the diversity factor of the thermal conductivity at each position of reference examples 1 product is 50%, the diversity factor of tensile strength is 100%, the diversity factor of the thermal conductivity at each position of reference examples 2 product is 30%, and the diversity factor of tensile strength is 50%.
(3) embodiment 1-3 product is 1.5 ~ 8 times of reference examples 1 product for the average rejection rate of the gas such as oxygen, helium, 1.2 ~ 5 times of reference examples 2 product.
Should be appreciated that the above is only the preferred embodiment of the present invention, should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. one kind is added the high heat conduction high-barrier polyimide film of sulfonated graphene, it is characterized in that comprising sulfonated graphene and polyimide that mass ratio is 0.5 ~ 25:100, the radial dimension of described sulfonated graphene is 500nm ~ 50 μm, thickness is 1nm ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
2. described in claim 1, add the preparation method of the high heat conduction high-barrier polyimide film of sulfonated graphene, it is characterized in that comprising: after aromatic diamine, aromatic tetrahydric dianhydride and sulfonated graphene are dissolved in organic solvent, at stirring at room temperature reaction 2 ~ 48h, form polyimide organic solution, prepare film forming afterwards, again at 60 DEG C ~ 300 DEG C heat treated 1h ~ 6h, then naturally cooling obtains described polyimide film;
The radial dimension of wherein said sulfonated graphene is 500nm ~ 50 μm, and thickness is 1nm ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
3. preparation method according to claim 2, is characterized in that specifically comprising: by described polyimide organic solution casting film-forming, afterwards 60 ~ 300 DEG C of heat treated.
4. preparation method according to claim 2, is characterized in that the consumption of described sulfonated graphene is 0.5% ~ 25% of polyimide quality in described polyimide film.
5. preparation method according to claim 2, is characterized in that the mol ratio of described aromatic diamine and aromatic tetrahydric dianhydride is 1:0.8 ~ 1:1.05.
6. preparation method according to claim 2, is characterized in that described organic solvent comprises N-Methyl pyrrolidone, dimethyl formamide, N,N-DIMETHYLACETAMIDE or dimethyl sulfoxide (DMSO).
7. preparation method according to claim 2, is characterized in that described aromatic tetrahydric dianhydride comprises the two Tetra hydro Phthalic anhydride or 3 of 4,4-oxygen, 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride.
8. preparation method according to claim 2, is characterized in that described aromatic diamines comprises 4,4'-diaminodiphenyl oxide or Isosorbide-5-Nitrae-bis-(4-amino-2-4-trifluoromethylphenopendant) benzene.
9. the preparation method according to Claims 2 or 3, is characterized in that the polyimide solid content in described polyimide organic solution is 5wt% ~ 30wt%.
10. preparation method according to claim 2, it is characterized in that the preparation method of described sulfonated graphene comprises: be 50nm ~ 50 μm by radial dimension, thickness is that to add primarily of mass ratio be in the mixed acid solution that forms of the oleum of 1 ~ 4:3 ~ 6 and chlorsulfonic acid for the Graphene of 1nm ~ 20nm or graphene oxide, and 1h ~ 10h is reacted at 60 DEG C ~ 150 DEG C, then distill more than 160 DEG C, residue, after cleaning, obtains described sulfonated graphene.
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| CN107324314A (en) * | 2017-05-18 | 2017-11-07 | 潍坊科技学院 | A kind of preparation method for vulcanizing graphene |
| CN110803930A (en) * | 2019-11-12 | 2020-02-18 | 李周芊芊 | High-thermal-conductivity and high-electric-conductivity sulfonated graphene-based composite film and preparation method thereof |
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