CN105754120A - Preparation method of graphene/polyimide composite film - Google Patents

Preparation method of graphene/polyimide composite film Download PDF

Info

Publication number
CN105754120A
CN105754120A CN201610153106.4A CN201610153106A CN105754120A CN 105754120 A CN105754120 A CN 105754120A CN 201610153106 A CN201610153106 A CN 201610153106A CN 105754120 A CN105754120 A CN 105754120A
Authority
CN
China
Prior art keywords
graphene
composite film
preparation
polar solvent
polyimide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610153106.4A
Other languages
Chinese (zh)
Inventor
王君
孙高辉
韩世辉
刘连河
张超
王文鹏
魏浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Harbin Engineering University
Original Assignee
Harbin Engineering University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Harbin Engineering University filed Critical Harbin Engineering University
Priority to CN201610153106.4A priority Critical patent/CN105754120A/en
Publication of CN105754120A publication Critical patent/CN105754120A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a preparation method of a graphene/polyimide composite film. The preparation method comprises the steps that functionalized graphene is uniformly dispersed into a polar solvent at room temperature; then polyisocyanate is added to the polar solvent containing functionalized graphene, after sufficient reaction of functional groups on functionalized graphene with polyisocyanate, a poly-aromatic anhydride monomer is added for a reaction, and a graphene/polyimide precursor solution is prepared; the graphene/polyimide composite film is obtained finally through gradient heating thermal imidization. The method is based on a one-step preparation technology of polyimide, the preparation time and the preparation process of the graphene/polyimide composite film are shortened greatly on the basis that graphene is uniformly dispersed in polyimide matrix resin, and the reaction temperature is reduced effectively. The preparation process is simple, the preparation cost is low, the reaction conditions are mild, and industrial production is facilitated.

Description

The preparation method of Graphene and polyimide composite film
Technical field
The preparation method that the present invention relates to a kind of multi-function membrane, especially relates to new method prepared by a kind of Graphene/polyimide composite film.
Background technology
Graphene is by monoatomic layer sp2The two-dimensional material that the carbon atom close-packed arrays of hydridization becomes, has unique physicochemical properties such as the electric property of excellence, prominent heat conductivility, extraordinary specific surface area and perfect quantum tunneling effect.
Kapton belongs to high-performance polymer thin-film material, has the electric property of excellence, mechanical property, resistance to elevated temperatures and decay resistance etc., has been widely used as Aero-Space and the High Performance Insulation material in the field such as electric at present.
Graphene/polyimide composite film is a kind of advanced thin films material integrating Graphene, two kinds of high-performance of polyimides, multifunctional material premium properties.Graphene/polyimide composite film shows more excellent electrical insulation properties, heat resistance and mechanical property compared with pure Kapton, widen the application of Kapton further, made Kapton show more wide application prospect.
The method preparing Graphene/polyimide composite film being currently known specifically includes that solution blended process and situ aggregation method.
First graphite oxide is dissolved in organic solvent by solution blended process, graphite oxide is made fully to peel off into graphene oxide then through supersound process, it is subsequently added dianhydride and diamidogen stirring, blending reaction obtain Graphene/polyimide precursor solution, after, obtain Graphene/Kapton through hot imidization.This method be found in the earliest Fudan University Liu Tian west et al. in 2010 " AppliedMaterial&Interfaces " on the article " InSituThermalPreparationofPolyimideNanocompositeFilmsCon tainingFunctionalizedGrapheneSheets " delivered, the patent document such as CN102592749A, CN103613927A discloses surface self-organization graphene/polyimide transparent electric conduction film and the technology of fluorinated graphene/polyimide composite film prepared with the solution blended process of solution blended process and improvement in succession subsequently.
Interface binding power for effectively strengthening Graphene and polyimide matrix improves the mechanical performance of Graphene/polyimide composite film further, Chen-ChiM.Ma et al. proposed a kind of method preparing Graphene/polyimide composite film by situ aggregation method in 2011, and related ends is published on " JournalofMaterialsChemistry ".First graphite oxide and diamidogen are dissolved in organic solvent by the method jointly, then through supersound process, graphite oxide is made fully to peel off into graphene oxide at ultrasonication, make the epoxy radicals in graphite oxide react with the amino in diamidogen simultaneously, obtain the graft of graphene oxide-diamidogen, it is subsequently added that dianhydride is stirred, blending reaction obtains Graphene/polyimide precursor solution, after, obtains Graphene/polyimide composite film through hot imidization.The method can make to form effective chemical bond between Graphene with polyimid-base resin and be connected, thus reaching to be effectively improved the purpose of material mechanical performance.The patent document such as KR20140055332 discloses the technology being prepared Graphene/Kapton by the situ aggregation method improved in succession subsequently.
Although Graphene can be dispersed in polyimid-base resin in by the Graphene/polyimide composite film prepared by above two method, but both approaches is all based on the two-step method technology of preparing of polyimides, there is the shortcomings such as response time length, reaction temperature height, complicated process of preparation.
Summary of the invention
It is an object of the invention to provide that a kind of preparation technology is simple, cheap for manufacturing cost, reaction condition is gentle and is prone to the Graphene of industrialized production and the preparation method of polyimide composite film.
The object of the present invention is achieved like this:
(1) when room temperature, normal pressure, nitrogen protection, functionalization graphene is joined in polar solvent, within ultrasonic 2～6 hours, make its dispersed polar solvent obtaining functionalization graphene in polar solvent；
(2) polyisocyanates is added dropwise in the polar solvent of functionalization graphene; reacting 1～2 hour in room temperature, normal pressure, nitrogen protection when, the active function groups on standby function functionalized graphene and NCO add polynary fragrance anhydride monomer after fully reacting；
(3) mixed system that step (3) obtains is placed in the oil bath pan being previously heated to 90 DEG C when normal pressure, nitrogen protection; stirring reaction 1～2 hour; until polynary acid anhydride solid is completely dissolved; mixed system, without stopped reaction after gas releasing, obtains Graphene and polyimide precursor solution；
(4) by described Graphene and polyimide precursor solution even spread to glass plate, being then placed in resistance furnace control chamber gradient solidifies, and finally gives Graphene and polyimide composite film.
The present invention can also include:
1, the ratio of weight and number of polynary fragrance acid anhydride, polar solvent, polyisocyanates and functionalization graphene is, polynary fragrance acid anhydride 100～200 parts, polar solvent 1000～2000 parts, polyisocyanates 80～200 parts, functionalization graphene 2～20 parts.
2, described gradient solidifies is 100 DEG C, 200 DEG C, 300 DEG C each solidifications 1 hour.
First functionalization graphene is evenly spread in polar solvent by the present invention at ambient temperature；Then in the polar solvent of functionalization graphene, add polyisocyanates, react formation Graphene/polyimide precursor solution when the functional group on functionalization graphene and polyisocyanates add polynary fragrance anhydride monomer after reacting completely；With after finally give Graphene/polyimide composite film through gradient increased temperature hot imidization.The method is based on the one-step method technology of preparing of polyimides, can ensure on the basis that graphene uniform is scattered in polyimid-base resin, substantially reduce preparation time and the preparation technology of Graphene/polyimide composite film, effectively reduce reaction temperature simultaneously.The preparation technology of this method is simple, cheap for manufacturing cost, reaction condition is gentle and is prone to industrialized production, it is provided that new approaches prepared by a kind of Graphene/polyimide composite film, has reached the purpose of invention.
Described polynary fragrance acid anhydride includes: pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-xenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-oxydiphthalic, 3,3 ', 4,4 '-xenyl sulfone tetracarboxylic dianhydride, mellic acid. three acid anhydride, three trimellitic anhydride-1,3,5-benzene three esters, 1,3,5-tri-oxygen-three (4-phthalic anhydride) benzene etc..
Described polar solvent includes: N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide etc..
Described polyisocyanates includes: methyl diphenylene diisocyanate (MDI), toluene di-isocyanate(TDI) (TDI), polyphenyl polymethylene polyisocyanates (PAPI) etc..
Described functionalization graphene includes: graphene oxide, amination Graphene etc..
Compared with prior art, the present invention initially with polyisocyanates grafting functional functionalized graphene, then with polynary fragrance anhydride reactant, prepare Graphene/polyimide precursor, finally obtain Graphene/Kapton through heat cure.This method is based on the one-step method technology of preparing of polyimides, compared to conventional graphite alkene/polyimide composite film technology of preparing, there is the advantages such as technological process is simple and easy to do, reaction condition is gentle, preparation cost is cheap, be conducive to promoting further large-scale industrial production and the extensive use of Graphene/polyimide film material.
Detailed description of the invention
Illustrate below and the present invention is described in more detail.
Embodiment 1
When room temperature nitrogen protection under normal pressure; 100ml there-necked flask is firstly added 30 grams of N; dinethylformamide, 0.3g graphene oxide and magneton; adding 2.5 grams of polyphenyl polymethylene multicyanate esters subsequently, supersound process makes graphite oxide be uniformly dispersed and fully reacts with NCO for 2 hours.It is subsequently adding 3 gram 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), there-necked flask is placed in the oil bath pan being previously heated to 90 DEG C simultaneously and heats 2 hours and connect reflux condensate device, stopped reaction after BTDA is completely dissolved and bubble-free produces.By on obtained composite solution even spread to glass plate, put into gradient increased temperature in resistance furnace control chamber (100 DEG C, 200 DEG C, 300 DEG C each 1 hour) hot imidization, finally prepare Graphene/polyimide composite film.
Embodiment 2
When room temperature nitrogen protection under normal pressure; 100ml there-necked flask is firstly added 30 grams of N-Methyl pyrrolidone, 0.4g graphene oxide and magneton; adding 2.5 grams of polyphenyl polymethylene multicyanate esters subsequently, ultrasonic 2 process hour make graphite oxide be uniformly dispersed and fully react with NCO.It is subsequently adding 3 gram 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), there-necked flask is placed in the oil bath pan being previously heated to 90 DEG C simultaneously and heats 2 hours and connect reflux condensate device, stopped reaction after BTDA is completely dissolved and bubble-free produces.By on obtained composite solution even spread to glass plate, put into gradient increased temperature in resistance furnace control chamber (100 DEG C, 200 DEG C, 300 DEG C each 1 hour) hot imidization, finally prepare Graphene/polyimide composite film.
Embodiment 3
When room temperature nitrogen protection under normal pressure; 100ml there-necked flask is firstly added 30 grams of N-Methyl pyrrolidone, 0.4g amination Graphene and magneton; adding 2.5 grams of polyphenyl polymethylene multicyanate esters subsequently, ultrasonic 2 process hour make graphite oxide be uniformly dispersed and fully react with NCO.It is subsequently adding 2 grams of pyromellitic acid dianhydrides (PMDA), there-necked flask is placed in the oil bath pan being previously heated to 90 DEG C simultaneously and heats 2 hours and connect reflux condensate device, stopped reaction after BTDA is completely dissolved and bubble-free produces.By on obtained composite solution even spread to glass plate, put into gradient increased temperature in resistance furnace control chamber (100 DEG C, 200 DEG C, 300 DEG C each 1 hour) hot imidization, finally prepare Graphene/polyimide composite film.

Claims (3)

1. Graphene and a preparation method for polyimide composite film, is characterized in that:
(1) when room temperature, normal pressure, nitrogen protection, functionalization graphene is joined in polar solvent, within ultrasonic 2～6 hours, make its dispersed polar solvent obtaining functionalization graphene in polar solvent；
(2) polyisocyanates is added dropwise in the polar solvent of functionalization graphene; reacting 1～2 hour in room temperature, normal pressure, nitrogen protection when, the active function groups on standby function functionalized graphene and NCO add polynary fragrance anhydride monomer after fully reacting；
(3) mixed system that step (3) obtains is placed in the oil bath pan being previously heated to 90 DEG C when normal pressure, nitrogen protection; stirring reaction 1～2 hour; until polynary acid anhydride solid is completely dissolved; mixed system, without stopped reaction after gas releasing, obtains Graphene and polyimide precursor solution；
(4) by described Graphene and polyimide precursor solution even spread to glass plate, being then placed in resistance furnace control chamber gradient solidifies, and finally gives Graphene and polyimide composite film.
2. the preparation method of Graphene according to claim 1 and polyimide composite film, it is characterized in that: the ratio of weight and number of polynary fragrance acid anhydride, polar solvent, polyisocyanates and functionalization graphene is, polynary fragrance acid anhydride 100～200 parts, polar solvent 1000～2000 parts, polyisocyanates 80～200 parts, functionalization graphene 2～20 parts.
3. Graphene according to claim 1 and 2 and the preparation method of polyimide composite film, is characterized in that: it is 100 DEG C, 200 DEG C, 300 DEG C each solidifications 1 hour that described gradient solidifies.
CN201610153106.4A 2016-03-17 2016-03-17 Preparation method of graphene/polyimide composite film Pending CN105754120A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610153106.4A CN105754120A (en) 2016-03-17 2016-03-17 Preparation method of graphene/polyimide composite film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610153106.4A CN105754120A (en) 2016-03-17 2016-03-17 Preparation method of graphene/polyimide composite film

Publications (1)

Publication Number Publication Date
CN105754120A true CN105754120A (en) 2016-07-13

Family

ID=56332121

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610153106.4A Pending CN105754120A (en) 2016-03-17 2016-03-17 Preparation method of graphene/polyimide composite film

Country Status (1)

Country Link
CN (1) CN105754120A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106750295A (en) * 2017-02-13 2017-05-31 常州大学 One class oh type polyimide/graphene nanocomposite material and preparation method thereof
CN106832363A (en) * 2016-12-31 2017-06-13 南京新月材料科技有限公司 The preparation method and flexible PCB of Graphene modified polyimide based coextruded film
CN107033591A (en) * 2016-10-11 2017-08-11 陕西科技大学 A kind of high temperature resistance polyester imine nanometer ultrathin membrane and preparation method thereof
CN112795036A (en) * 2020-12-31 2021-05-14 南京航空航天大学 Preparation method of graphene modified polyimide composite film
CN113248717A (en) * 2021-06-11 2021-08-13 江苏传艺科技股份有限公司 Polyimide film with high thermal stability and production process thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268134A (en) * 2011-04-21 2011-12-07 扬中市华鑫氟塑电器设备有限公司 Preparation method for polyimide/graphene nanocomposite material
CN104861651A (en) * 2015-03-27 2015-08-26 华东理工大学 Preparation method of modified graphene oxide and polyimide in-situ grafting composite material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102268134A (en) * 2011-04-21 2011-12-07 扬中市华鑫氟塑电器设备有限公司 Preparation method for polyimide/graphene nanocomposite material
CN104861651A (en) * 2015-03-27 2015-08-26 华东理工大学 Preparation method of modified graphene oxide and polyimide in-situ grafting composite material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JEN-YU WANG ET.AL: ""Preparation and properties of graphene oxide/polyimide composite films with low dielectric constant and ultrahigh strength via in situ polymerization"", 《JOURNAL OF MATERIALS CHEMISTRY》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107033591A (en) * 2016-10-11 2017-08-11 陕西科技大学 A kind of high temperature resistance polyester imine nanometer ultrathin membrane and preparation method thereof
CN106832363A (en) * 2016-12-31 2017-06-13 南京新月材料科技有限公司 The preparation method and flexible PCB of Graphene modified polyimide based coextruded film
CN106750295A (en) * 2017-02-13 2017-05-31 常州大学 One class oh type polyimide/graphene nanocomposite material and preparation method thereof
CN112795036A (en) * 2020-12-31 2021-05-14 南京航空航天大学 Preparation method of graphene modified polyimide composite film
CN113248717A (en) * 2021-06-11 2021-08-13 江苏传艺科技股份有限公司 Polyimide film with high thermal stability and production process thereof

Similar Documents

Publication Publication Date Title
CN105754120A (en) Preparation method of graphene/polyimide composite film
CN109762166B (en) Polyimide precursor and preparation method of polyimide film
CN111470876B (en) High-graphitization polyimide-based graphite thick film and preparation method thereof
CN106928481A (en) The optimization preparation method of Kapton
CN104672477A (en) Preparation method and product of low-roughness polyimide film and application of product
CN107104242B (en) Polysiloxane polyphosphonic acid doped SPEEK high and low temperature universal proton exchange membrane and preparation method thereof
CN104710617B (en) Polyamide-imide polymer, graphite film and preparation method thereof
CN114437349B (en) Polyimide film, method for producing the same, and graphite film
CN105237785A (en) Preparation method for polyimide thin film
CN108148201A (en) Method for producing polyimide film and method for producing graphite film using same
CN112266260B (en) Preparation method of polyimide graphite film
CN101487190B (en) Polyimide carbon fiber sizing agent and method for producing the same
CN105542335A (en) High temperature-resistant imide-polyvinyl chloride alloy structure foam and preparation method thereof
CN112430379A (en) High-thermal-conductivity modified hexagonal boron nitride/epoxy resin nano insulating composite material and preparation method thereof
CN114181529A (en) High-thermal-conductivity modified hexagonal boron nitride/water-based polyimide composite material
Wang et al. Shape memory polyimides and composites with tunable chain stiffness and ultrahigh transition temperature range
CN104478788A (en) Transparent polyimide material and preparation method thereof
CN113184842A (en) High-graphitization graphite thick film and preparation method thereof
CN105820366A (en) Surface modified nano polyimide film and preparation method thereof
CN110387041B (en) Polyimide composite film and preparation method thereof
CN110563988B (en) High-temperature-resistant polyimide/polytetrafluoroethylene anti-bonding composite film and preparation method thereof
CN110358121B (en) Method for preparing polyimide film at low temperature through microwave radiation
CN107722272B (en) Preparation method of polyimide film
CN108727587B (en) Heat-resistant polyimide containing imidazolyl aromatic ring structure and preparation method thereof
CN114516959B (en) Polyamide film, method for producing same, and graphite film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20160713

RJ01 Rejection of invention patent application after publication