CN107828210A - A kind of graphene compound polyimide film and preparation method thereof - Google Patents

A kind of graphene compound polyimide film and preparation method thereof Download PDF

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CN107828210A
CN107828210A CN201711132280.1A CN201711132280A CN107828210A CN 107828210 A CN107828210 A CN 107828210A CN 201711132280 A CN201711132280 A CN 201711132280A CN 107828210 A CN107828210 A CN 107828210A
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graphene
polyimide film
polyimide resin
graphene compound
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CN107828210B (en
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徐伟伟
王勇
祁晓东
姜新
陈晨
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JIANGSU YABAO INSULATION MATERIAL CO Ltd
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    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2003/2241—Titanium dioxide
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Abstract

The invention discloses a kind of graphene compound polyimide film, by following components by weight：150 300 parts of polyimide resin polymer, 12 parts of fullerene, 0.1 0.2 parts of rare earth oxide, 2.5 3.5 parts of modifying agent.The graphene compound polyimide film of the present invention, excellent in mechanical performance, elongation at break are more than 40%, film thickness only has 8 12 μm, and normal temperature tensile strength is more than 200MPa, and modulus of elasticity is more than 2.88GPa and wrinkle resistant, flatness is high, and specific insulation is 4.5 × 101‑3.7×106。

Description

A kind of graphene compound polyimide film and preparation method thereof
Technical field
The present invention relates to a kind of Kapton, more particularly to a kind of graphene compound polyimide film and its preparation Method.
Background technology
At present, the booming demand for high polymer material of Aero-Space cause is more and more urgent, but due to too The influence of Altitude, there is the requirement of harshness for the various aspects of performance of high polymer material.Polyimides is as a kind of high resistance to The material of heat, while high chemical stability, high-mechanical property, high radiation resistance and height machinability are also equipped with, in space flight thing There is very big application space in industry.But the resistivity of polyimides is higher, electronics is not easily moveable in material, the electricity saved bit by bit Lotus is difficult to spread, and will form electrostatic, and electrostatic is extremely hazardous in space industry, is easily destroyed air material, damage electricity Subcomponent.
Graphene is as a kind of new carbon material, and it has special two-dimensional structure, and electronics can be on its surface almost Do not have resistant rapid movement, therefore there is good electric conductivity, in addition, graphene all has in calorifics, electricity, terms of mechanics Extremely outstanding performance, far above other inorganic material, and these to be exactly some high molecular polymers be short of, so stone Black alkene/polymer composite is gradually taken seriously in each research institution.
At present, there has been substantial amounts of report for extraordinary polyimide composite film material, but still suffer from this prepare it is cumbersome, The problems such as pollution is big, and the open and flat degree of final composite is low, and performance is undesirable.
The content of the invention
The present invention is to overcome above-mentioned defect in the prior art, is made poly- by rational component proportion and process modification Acid imide laminated film.The thin film mechanical performance, electric property, which are respectively provided with, to be obviously improved, and top layer uniform ground, yield rate Height, comprehensive quality are good.
A kind of graphene compound polyimide film, by following components by weight：
Polyimide resin polymer 150-300 parts, fullerene 1-2 parts, rare earth oxide 0.1-0.2 parts, modifying agent 2.5-3.5 part；
Polyimide resin polymer includes following weight percentage component：Graphene 0.2-1.5%, titanium dioxide 1- 5%th, Ludox 0.5-6%, fluoro-acrylate copolymer 2-10%, wherein polyimide resin surplus, fluorinated acrylate Copolymer is molecular weight 3000-10000 dissaving polymers.
Preferably, the modifying agent by gaultherolin and liquid paraffin according to weight ratio (3-5)：1 proportional arrangement and Into.
Preferably, the polyimide resin polymer includes following percentage composition component：Graphene 0.5-0.75%, titanium White powder 2-3%, Ludox 2-5%, fluoro-acrylate copolymer 3-6%, polyimide resin surplus.
Preferably, polyimide resin polymer also includes composite filler 1-2%, and the composite filler is mass ratio 1： 0-2 nano magnesia whisker, nano silicon oxide.
Preferably, the preparation process of polyimide resin polymer is as follows：
1) raw material is weighed by weight, and polyimide resin slow heating is warming up to 60-80 DEG C, then added thereto Fluoro-acrylate copolymer, first quick stirring 10-15min, is then incubated and mixes slowly 0.5-1h, then is cooled to 30 ± 5 DEG C, 10-12min is ultrasonically treated, then insulation stands 2-4h, obtains mixture one；
2) graphene is added in mixture one in batches under normal temperature condition, keeps being ultrasonically treated in adding procedure, treat 20-30min is ultrasonically treated every 15min after the completion of addition, interval is ultrasonically treated 4-5 times, obtains mixture two；
3) titanium dioxide is ground to nanoscale, then adds silicon under the conditions of 45 DEG C of isothermal vibrations together with composite filler In colloidal sol, insulation reaction 0.5-1.5h, mixture three is obtained；
4) mixture three is slowly added in mixture two under agitation, first in 45-50 DEG C of insulated and stirred 30min, Then stirring at normal temperature is down into homogeneously.
The preparation method of above-mentioned graphene compound polyimide film, all components are sufficiently mixed, using curtain coating legal system It is standby to obtain film layer, then cool down, draw through double roller, batch it is obtained.
Preferably, the graphene compound polyimide film thickness is 8-12 μm；Specific insulation is 4.5 × 101- 3.7×106。
Compared with prior art, the present invention has the advantages that：What the present invention was prepared by rational component proportion Graphene compound polyimide polymer architecture electric conductivity is strong, microcosmos network Stability Analysis of Structures, is combined between component by chemical modification, Mechanical property, electric property, which are respectively provided with, to be obviously improved, and by each component step-by-step processing, modification is mixed successively, first by polyimides Resin and fluoro-acrylate copolymer blending reaction, the transparency and toughness of film are on the one hand improved, on the other hand super disproportionation Block copolymer significantly improve the spacial framework of resin, and with good amphoteric reaction activity, improve group Between crosslinking it is binding affinity.The lamellar graphite alkene then added, a part of top layer combine, and a part is internal chimeric, can combine space Containment is strong, and dispersiveness significantly improves, and performance boost degree is good.Finally filled nanometer titanium dioxide, composite filler and Ludox, On the one hand mechanical property is improved, reinforcement is strengthened, and on the other hand can further consolidate network structure, such as titanium dioxide and polyimides tree Bonding overlaps between the spatial molecular of " bridge " can be formed between fat, and Ludox promotes space rheological characteristic, and is total to fluorinated acrylate Polymers blending dilution combines, and accelerates the joint efficiency with resin matrix.
The graphene compound polyimide film of the present invention, excellent in mechanical performance, elongation at break are more than 45%, and film is thick Only 8-12 μm of degree, normal temperature tensile strength are more than 180MPa, and modulus of elasticity is more than 2.88GPa and wrinkle resistant, flatness height, volume Resistivity is 4.5 × 101-3.7×106。
Embodiment
The embodiment of the present invention is described in detail below, it is to be understood that protection scope of the present invention is not Limited by embodiment.
Embodiment 1
A kind of graphene compound polyimide film, by following components by weight：Polyimide resin gathers 170 parts of compound, 1.2 parts of fullerene, 0.13 part of rare earth oxide, 2.7 parts of modifying agent；The modifying agent is by gaultherolin and liquid State paraffin is according to weight than 3.5：1 proportional arrangement forms.
Polyimide resin polymer includes following weight percentage component：Graphene 1%, titanium dioxide 2%, Ludox 0.5%th, fluoro-acrylate copolymer 4%, polyimide resin surplus, are carried out in accordance with the following steps：
1) raw material is weighed by weight, and polyimide resin slow heating is warming up to 60 DEG C, then adds and contains thereto Perfluoroalkyl acrylate ester copolymer, 15min is quickly first stirred with 150rpm, then constant temperature mixes slowly 0.5h with 50rpm, then is cooled to 30 ± 5 DEG C, 10-12min is ultrasonically treated with 45KHz, then insulation stands 3h, obtains mixture one；
2) kept under normal temperature condition by 5 addition mixtures one of graphene point in adding procedure at 28KHz ultrasounds Reason, whole adding procedure is no less than 20min, ultrasonic with 35KHz supersound process 30min, interval every 15min after the completion of to be added Processing totally 4 times, obtains mixture two；
3) titanium dioxide is ground to nanoscale, then adds silicon under the conditions of 45 DEG C of isothermal vibrations together with composite filler In colloidal sol, insulation reaction 1h, mixture three is obtained；
4) mixture three is slowly added in mixture two under agitation, first in 50 DEG C of insulated and stirred 30min, then Stirring at normal temperature is down into homogeneously.
By being sufficiently mixed all components of graphene compound polyimide film, film is prepared using the tape casting, Cool down, draw through double roller again, batch it is obtained.
The graphene compound polyimide film thickness of above-mentioned preparation is 15 μm, and normal temperature tensile strength is 190MPa, fracture Elongation is 46%, modulus of elasticity 2.90GPa, and it is wrinkle resistant, flatness is high.
Embodiment 2
A kind of graphene compound polyimide film, by following components by weight：Polyimide resin gathers 200 parts of compound, 1.8 parts of fullerene, 0.2 part of rare earth oxide, 3 parts of modifying agent；The modifying agent is by gaultherolin and liquid Paraffin is according to weight than 4：1 proportional arrangement forms.
Polyimide resin polymer includes following weight percentage component：Graphene 0.2%, titanium dioxide 1%, silicon are molten Glue 4%, fluoro-acrylate copolymer 3%, polyimide resin surplus, in addition to composite filler 1.5%, this is composite filled Expect for mass ratio 1：2 nano magnesia whisker, nano silicon oxide.Polyimide resin polymer is carried out in accordance with the following steps：
1) raw material is weighed by weight, and polyimide resin slow heating is warming up to 80 DEG C, then adds and contains thereto Perfluoroalkyl acrylate ester copolymer, 15min is quickly first stirred with 150rpm, then constant temperature mixes slowly 0.5h with 30rpm, then is cooled to 30 ± 5 DEG C, 10-12min is ultrasonically treated with 48KHz, then insulation stands 4h, obtains mixture one；
2) kept under normal temperature condition by 5 addition mixtures one of graphene point in adding procedure at 28KHz ultrasounds Reason, whole adding procedure is no less than 20min, ultrasonic with 35KHz supersound process 20min, interval every 15min after the completion of to be added Processing totally 5 times, obtains mixture two；
3) titanium dioxide is ground to nanoscale, then adds silicon under the conditions of 45 DEG C of isothermal vibrations together with composite filler In colloidal sol, insulation reaction 1h, mixture three is obtained；
4) mixture three is slowly added in mixture two under agitation, first in 50 DEG C of insulated and stirred 30min, then Stirring at normal temperature is down into homogeneously.
By being sufficiently mixed all components of graphene compound polyimide film, film is prepared using the tape casting, Cool down, draw through double roller again, batch it is obtained.
The graphene compound polyimide film thickness of above-mentioned preparation is 12 μm, and normal temperature tensile strength is 202MPa, fracture Elongation is 50%, modulus of elasticity 2.95GPa, and it is wrinkle resistant, flatness is high.
Embodiment 3
A kind of graphene compound polyimide film, by following components by weight：Polyimide resin gathers 200 parts of compound, 1.8 parts of fullerene, 0.2 part of rare earth oxide, 3 parts of modifying agent；The modifying agent is by gaultherolin and liquid Paraffin is according to weight than 4.5：1 proportional arrangement forms.
Polyimide resin polymer includes following weight percentage component：Graphene 0.75%, titanium dioxide 3%, silicon Colloidal sol 3%, fluoro-acrylate copolymer 6%, polyimide resin surplus, in addition to composite filler 2%, this is composite filled Expect for mass ratio 1：1 nano magnesia whisker, nano silicon oxide.Polyimide resin method for producing polymer is the same as embodiment 2.
By being sufficiently mixed all components of graphene compound polyimide film, film is prepared using the tape casting, Cool down, draw through double roller again, batch it is obtained.
The graphene compound polyimide film thickness of above-mentioned preparation is 10 μm, and normal temperature tensile strength is 208MPa, elasticity Modulus is 3.01GPa, elongation at break 52%, and it is wrinkle resistant, flatness is high.
Disclosed above is only several specific embodiments of the present invention, and still, the present invention is not limited to this, any ability What the technical staff in domain can think change should all fall into protection scope of the present invention.

Claims (7)

1. a kind of graphene compound polyimide film, it is characterised in that by following components by weight：
Polyimide resin polymer 150-300 parts, fullerene 1-2 parts, rare earth oxide 0.1-0.2 parts, modifying agent 2.5-3.5 Part；
Polyimide resin polymer includes following weight percentage component：Graphene 0.2-1.5%, titanium dioxide 1-5%, silicon Colloidal sol 0.5-6%, fluoro-acrylate copolymer 2-10%, wherein polyimide resin surplus, fluoro-acrylate copolymer For molecular weight 3000-10000 dissaving polymers.
2. a kind of graphene compound polyimide film according to claim 1, it is characterised in that the modifying agent is by water Poplar acid methyl esters and liquid paraffin are according to weight ratio (3-5)：1 proportional arrangement forms.
A kind of 3. graphene compound polyimide film according to claim 1, it is characterised in that the polyimides tree Lipopolymer includes following percentage composition component：Graphene 0.5-0.75%, titanium dioxide 2-3%, Ludox 2-5%, fluorine-containing third Olefin(e) acid ester copolymer 3-6%, polyimide resin surplus.
4. a kind of graphene compound polyimide film according to claim 1, it is characterised in that polyimide resin gathers Compound also includes composite filler 1-2%, and the composite filler is mass ratio 1：It is 0-2 nano magnesia whisker, nano oxidized Silicon.
5. a kind of graphene compound polyimide film according to claim 1, it is characterised in that polyimide resin gathers The preparation process of compound is as follows：
1) raw material is weighed by weight, and polyimide resin slow heating is warming up to 60-80 DEG C, then added thereto fluorine-containing Acrylate copolymer, first quick stirring 10-15mi n, are then incubated and mix slowly 0.5-1h, then are cooled to 30 ± 5 DEG C, surpass Sonication 10-12mi n, then insulation stand 2-4h, obtain mixture one；
2) graphene is added in mixture one in batches under normal temperature condition, keeps being ultrasonically treated in adding procedure, it is to be added After the completion of every 15mi n be ultrasonically treated 20-30mi n, interval be ultrasonically treated 4-5 times, obtain mixture two；
3) titanium dioxide is ground to nanoscale, then adds Ludox under the conditions of 45 DEG C of isothermal vibrations together with composite filler In, insulation reaction 0.5-1.5h, obtain mixture three；
4) mixture three is slowly added in mixture two under agitation, first in 45-50 DEG C of insulated and stirred 30mi n, then Stirring at normal temperature is down into homogeneously.
6. the preparation method of the graphene compound polyimide film described in claim 1-5, it is characterised in that by all components Be sufficiently mixed, film be prepared using the tape casting, then cool down, draw through double roller, batch it is obtained.
7. preparation method according to claim 6, it is characterised in that the graphene compound polyimide film thickness is 8-12μm；Specific insulation is 4.5 × 101-3.7×106。
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CN110894292A (en) * 2019-10-31 2020-03-20 安徽国风塑业股份有限公司 Fluorescent polyimide film and preparation method thereof
CN114846052A (en) * 2019-12-26 2022-08-02 三菱瓦斯化学株式会社 Polyimide resin, polyimide resin composition, polyimide varnish, and polyimide film

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WO2019095259A1 (en) * 2017-11-15 2019-05-23 江苏亚宝绝缘材料股份有限公司 Graphene-composited polyimide film and preparation method therefor
CN110894292A (en) * 2019-10-31 2020-03-20 安徽国风塑业股份有限公司 Fluorescent polyimide film and preparation method thereof
CN114846052A (en) * 2019-12-26 2022-08-02 三菱瓦斯化学株式会社 Polyimide resin, polyimide resin composition, polyimide varnish, and polyimide film

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