CN103665866B - The preparation method of graphene-polyimide composite film - Google Patents

The preparation method of graphene-polyimide composite film Download PDF

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CN103665866B
CN103665866B CN201310685647.8A CN201310685647A CN103665866B CN 103665866 B CN103665866 B CN 103665866B CN 201310685647 A CN201310685647 A CN 201310685647A CN 103665866 B CN103665866 B CN 103665866B
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graphene
polyamic acid
acid anhydride
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composite film
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CN103665866A (en
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岑建军
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Ningbo Jinshan New Material Co ltd
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NINGBO JINSHAN ELECTRONIC MATERIALS CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Abstract

The invention discloses a kind of preparation method of graphene-polyimide composite film, comprise and adopt Graphene and by 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride polycondensation and the polyamic acid obtained in a solvent, scattered graphene suspension is joined in the above-mentioned polyamic acid obtained through polycondensation, through circulation dispersion, continue 10 hours ~ 16 hours, again the mol ratio of amine in polyamic acid and acid anhydride is transferred to 1:0.98 ~ 1:0.995, viscosity reaches 60000CP ~ 90000CP, and wherein Graphene ratio in the solid content of polyamic acid is 1% ~ 15%; Then deaeration casting film-forming, last imidization, rolling are cut.The graphene-polyimide composite film that the present invention obtains, its tensile strength >=100Mpa, heat conductivility >=5w/m.k, elongation at break >=15%.

Description

The preparation method of graphene-polyimide composite film
Technical field
The present invention relates to a kind of preparation method of graphene-polyimide composite film.
Background technology
Kapton (PI film) is since the sixties in last century drops into application, and with the thermal characteristics of its excellence, dielectric properties and mechanical property etc. become the preferred material of the industrial circle such as electronics and space flight.Along with the development of high and new technology, common polyimide material can not meet the requirement of manufacture to material property of high-new technology products, therefore the polyimide modified focus just becoming research now.Inorganic component is introduced in polyimide matrix the compound reaching inorganic-organic performance, to become in its modification work comparatively effective means.
There are some researches show, the Graphene only adding trace just can produce larger lifting to the capacity of heat transmission of resin matrix and linear expansivity, greatly strengthens and has widened its Application Areas.But the relevant research and development for graphene/polyimide composite material are little, and its heat conductivility of the material developed at present is poor, is generally less than 0.5w/m.k, cannot be satisfied with the demand on market well.
Summary of the invention
The object of the invention is the preparation method that the better graphene-polyimide composite film of a kind of heat conductivility is provided to solve above-mentioned the deficiencies in the prior art.
To achieve these goals, the preparation method of the graphene-polyimide composite film designed by the present invention, comprises and adopts Graphene and by diamine and binary acid anhydride polycondensation and the polyamic acid that obtains in a solvent, its concrete steps are as follows:
Step one: first by 1 part of Graphene by milling, disperseing, dispersion particle diameter reach below 100nm, be distributed in 9 parts of dimethylacetamide solvents equably, then in above-mentioned suspension, add 1 part of polyamic acid again, continue dispersion, finally obtain graphene suspension;
Step 2: using as 4 of diamine, 4-diaminodiphenyl oxide and being simultaneously dissolved in dimethylacetamide solvent as the pyromellitic acid anhydride of binary acid anhydride, wherein 4, part of 4-diaminodiphenyl oxide and pyromellitic acid anhydride with the mole number of the mole number of amine and acid anhydride for 1:0.80 ~ 1:0.90 proportioning, then above-mentioned scattered graphene suspension is joined in the above-mentioned polyamic acid obtained through polycondensation, through circulation dispersion, continue 10 hours ~ 16 hours, again the mol ratio of amine in polyamic acid and acid anhydride is transferred to 1:0.98 ~ 1:0.995, viscosity reaches 60000CP ~ 90000CP, wherein Graphene ratio in the solid content of polyamic acid is 1% ~ 15%,
Step 3: by above-mentioned polymkeric substance deaeration casting film-forming, last imidization, rolling are cut.
The graphene-polyimide composite film that the present invention obtains, because graphenic surface has the group such as hydroxyl, carboxyl, can form hydrogen bond with the group on polyimide, both consistencies are good, and what make graphene uniform is dispersed in polyimide matrix; In addition, polyimide matrix Stability Analysis of Structures, the good heat conductivility that Graphene has and conductivity, heat conductivility and the specific inductivity of polyimide can be improved, tensile strength >=the 100Mpa of the laminated film obtained, heat conductivility >=5w/m.k, elongation at break >=15%.
Embodiment
Below in conjunction with embodiment, the present invention is further described.
Embodiment 1:
The preparation method of graphene-polyimide composite film provided by the invention, comprise and adopt Graphene and polyamic acid, its concrete steps are as follows:
Step one: first by 1 part of Graphene by being distributed in 9 parts of dimethylacetamide solvents with milling, be uniformly dispersed, then in above-mentioned suspension, add 1 part of polyamic acid again, continue dispersion, finally obtain graphene suspension;
Step 2: by 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride are dissolved in dimethylacetamide solvent simultaneously, wherein 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride with the mole number of the mole number of amine and acid anhydride for 1:0.80 proportioning, then above-mentioned scattered graphene suspension is joined in polyamic acid, through circulation dispersion, continue 10 hours ~ 16 hours, again the mol ratio of amine in polyamic acid and acid anhydride is transferred to 1:0.98, viscosity reaches 60000CP, and wherein Graphene ratio in the solid content of polyamic acid is 7%;
Step 3: by above-mentioned polymkeric substance deaeration casting film-forming, last imidization, rolling are cut.
The tensile strength 118Mpa of the graphene-polyimide composite film of the present embodiment gained, heat conductivility reaches 5.3w/m.k, elongation at break 18%.
Embodiment 2:
In the present embodiment, the concrete steps of the preparation method of graphene-polyimide composite film are as follows:
Step one: first by 1 part of Graphene by being distributed in 9 parts of dimethylacetamide solvents with milling, be uniformly dispersed, then in above-mentioned suspension, add 1 part of polyamic acid again, continue dispersion, finally obtain graphene suspension;
Step 2: by 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride are dissolved in dimethylacetamide solvent simultaneously, wherein 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride with the mole number of the mole number of amine and acid anhydride for 1:0.90 proportioning, then above-mentioned scattered graphene suspension is joined in polyamic acid, through circulation dispersion, continue 10 hours ~ 16 hours, again the mol ratio of amine in polyamic acid and acid anhydride is transferred to 1:0.99, viscosity reaches 90000CP, and wherein Graphene ratio in the solid content of polyamic acid is 10%;
Step 3: by above-mentioned polymkeric substance deaeration casting film-forming, last imidization, rolling are cut.
The tensile strength 110Mpa of the graphene-polyimide composite film of the present embodiment gained, heat conductivility reaches 5.8w/m.k, elongation at break 15.1%.

Claims (1)

1. a preparation method for graphene-polyimide composite film, comprises and adopts Graphene and by 4,4-diaminodiphenyl oxide and pyromellitic acid anhydride polycondensation and the polyamic acid that obtains in a solvent, it is characterized in that in accordance with the following steps:
Step one: first by 1 part of Graphene by milling, disperseing, dispersion particle diameter reach below 100nm, be distributed in 9 parts of dimethylacetamide solvents equably, then in above-mentioned suspension, add 1 part of polyamic acid again, continue dispersion, finally obtain graphene suspension;
Step 2: using as 4 of diamine, 4-diaminodiphenyl oxide and being simultaneously dissolved in dimethylacetamide solvent as the pyromellitic acid anhydride of binary acid anhydride, wherein 4, part of 4-diaminodiphenyl oxide and pyromellitic acid anhydride with the mole number of the mole number of amine and acid anhydride for 1:0.80 ~ 1:0.90 proportioning, then above-mentioned scattered graphene suspension is joined in the above-mentioned polyamic acid obtained through polycondensation, through circulation dispersion, continue 10 hours ~ 16 hours, again the mol ratio of amine in polyamic acid and acid anhydride is transferred to 1:0.98 ~ 1:0.995, viscosity reaches 60000cP ~ 90000cP, wherein Graphene ratio in the solid content of polyamic acid is 7% ~ 10%,
Step 3: by above-mentioned polymkeric substance deaeration casting film-forming, last imidization, rolling are cut.
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CN107265451A (en) * 2017-07-17 2017-10-20 安徽国风塑业股份有限公司 A kind of preparation method of the polyimides graphite film of high conductive high strength

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CN104130576A (en) * 2014-07-03 2014-11-05 苏州世优佳电子科技有限公司 Graphene heat-conduction film
CN105061763B (en) * 2015-07-31 2017-09-26 苏州高通新材料科技有限公司 Add high heat conduction high-barrier polyimide film of sulfonated graphene and preparation method thereof
CN106496611A (en) * 2016-09-26 2017-03-15 安徽国风塑业股份有限公司 A kind of preparation method of high heat conduction Kapton
CN106496615A (en) * 2016-11-08 2017-03-15 贵阳学院 A kind of preparation method of heat-pesistant thin film
CN106867256B (en) * 2017-02-27 2019-10-18 华烁科技股份有限公司 A kind of graphene fabric-modifying anisotropic thermal Kapton, preparation method and application
CN107760028B (en) * 2017-11-16 2020-06-09 中国运载火箭技术研究院 Light-propelled graphene composite material film and preparation method and application thereof
CN109437905B (en) * 2018-11-27 2021-08-17 宁波今山新材料有限公司 Preparation method of tear-resistant graphite film
CN110191571B (en) * 2019-05-27 2020-11-17 维沃移动通信有限公司 Circuit board device and terminal equipment
CN110128654A (en) * 2019-06-11 2019-08-16 慧迈材料科技(广东)有限公司 A kind of Kapton of novel containing graphene
CN110396193A (en) * 2019-09-04 2019-11-01 江苏亚宝绝缘材料股份有限公司 A kind of preparation method and product of in-situ polymerization graphene hybrid modification polyamic acid resin
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