CN109081939A - A kind of polyimide composite film and preparation method having both electric conductivity and magnetism - Google Patents
A kind of polyimide composite film and preparation method having both electric conductivity and magnetism Download PDFInfo
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- CN109081939A CN109081939A CN201810849031.2A CN201810849031A CN109081939A CN 109081939 A CN109081939 A CN 109081939A CN 201810849031 A CN201810849031 A CN 201810849031A CN 109081939 A CN109081939 A CN 109081939A
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- C—CHEMISTRY; METALLURGY
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- 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
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- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
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- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- 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
- C08K2201/01—Magnetic additives
Abstract
The invention belongs to the technical fields of Kapton, provide a kind of polyimide composite film and preparation method for having both electric conductivity and magnetism.This method first synthesizes 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene, and the porous polyimide of the structure containing triptycene, while in-situ preparation Fe are then synthesized with hexafluorodianhydride (6FDA)2O3It is coated in the porous structure of polyimides, then carries out casting film-forming, and the upper and lower surface using magnetron sputtering in film forms silver conductive layer, is made and has both electric conductivity and magnetic polyimide composite film.It is compared with the traditional method, polyimide composite film prepared by the present invention, ductility is preferable, and modulus is higher, has both good superparamagnetism and electric conductivity, can be used as electromagnetic shielding material.
Description
Technical field
The invention belongs to the technical fields of Kapton, provide a kind of polyimides for having both electric conductivity and magnetism
Laminated film and preparation method.
Background technique
Kapton has excellent comprehensive performance, heat resistance, electric property, radiation resistance and fire resistance
It can be very prominent.In the development of new and high technology, the especially hair of aerospace industry, electronic and electrical industry and information industry
Exhibition, Kapton have played very important effect.It is sub- that Abroad in Recent Years not only develops many new functional polyamides
Amine film product, and also constantly have new progress in terms of application technology.
On the other hand, in recent decades, with universal, electronic computer, communications satellite, the grid of various electric appliances
With the extensive use of some medical equipments etc., thus bring electromagnetic radiation pollution is also increasingly severe, it is therefore necessary to carry out electricity
Magnetic screen, in electromagnetic shielding material, surface layer conductivity type shielding material, especially conductive coating, with its low cost and medium shielding
Effect still occupies staple market at present, and filled composite type shielding material (i.e. conductive composite plastic) is due to its processing and forming and screen
The primary completion covered can put things right once and for all convenient for producing in enormous quantities, therefore be the important development side as electromagnetic shielding material
To.
Filled composite type shielding material is by the preferable synthetic resin of electrical insulating property and with the conduction of excellent conductive capability
Filler and other additives are formed, wherein common synthetic resin has polyphenylene oxide, polycarbonate, ABS, nylon and thermoplastic poly
Ester etc.；Conductive filler generally select it is large-sized threadiness and flaky material, it is most common have metallic fiber, sheet metal,
Carbon fiber, superconducting carbon black, metal alloy filler etc..And in recent years, Kapton is with its excellent comprehensive performance in electromagnetism
Shielding field attracts attention.
Chinese invention patent application number 201410033581.9 discloses a kind of Flexible conductive polyimide film and its system
Preparation Method, the film by following parts by weight material composition: 30 ~ 80 parts of polyimides, 1 ~ 10 part of nutgrass flatsedge extract, coupling agent
2 ~ 10 parts, 5 ~ 20 parts of metal powders and 5 ~ 20 parts of carbon dusts.The Kapton electric conductivity of the invention is preferable, soft, but because filling out
Material dispersion is uneven, there is reunion, causes electric conductivity still and have to be reinforced, and ductility and modulus are poor.
Chinese invention patent application number 201210587222.9 discloses that a kind of to prepare fluorine-containing magnetisable coating polyimides multiple
Method for manufacturing thin film is closed, by then having electromagnetism in the fluorine-containing latex that Kapton surface coats doped magnetic powder
Drying and sintering obtains in the drying and sintering furnace of iron, and it is magnetic by mixing or the production of other Chemical Physics methods to overcome existing method
Complex process in the method for Kapton, it is at high cost, the shortcomings that reduced performance, production technology is simplified, film is improved
Comprehensive performance.There are caducous problems for the magnetisable coating of the laminated film, and magnetism is undesirable, and useful life longevity is poor,
Coating affects the mechanical property of laminated film simultaneously.
In conclusion Kapton and when conductive or magnetic fillers are compound or prepared by coating, generally existing filler
Dispersion is uneven, serious, caducous problem of reuniting, and causes the electric conductivity of laminated film and magnetism poor, while affecting multiple
The mechanical performance for closing film itself, limits it in the further development and application of electronic field, especially in electronic shield field
Research is using rare report at home and abroad.
Summary of the invention
As it can be seen that the Kapton of the prior art and when conductive, magnetic fillers are compound or coating, there are filler dispersions not
, easy to reunite, caducous defect, causes the electric conductivity of laminated film and magnetism poor, and affects the mechanicalness of film
Can, limit further development and application.In response to this, it is proposed that a kind of have both electric conductivity and magnetic polyimides
Laminated film and preparation method, can be effectively improved dispersibility of the filler in film matrix, and gained film has preferable conductive
Property and superparamagnetism, can be widely used for the fields such as electronic shield material.
To achieve the above object, specific technical solution of the present invention is as follows:
A kind of preparation method having both electric conductivity and magnetic polyimide composite film, the polyimide composite film preparation
Specific step is as follows:
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, react 16 ~ 20h at room temperature, then
4 ~ 6h is stirred under ice bath, is filtered, and by obtained solid adding into acetone, reducing agent is added, then 2 ~ 3h of heating reflux reaction takes out
Filter, filtrate is rotated, 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene is obtained；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film.
Preferably, step (1) reducing agent is at least one of hydrazine hydrate or phenylhydrazine.
Preferably, the parts by weight of step (1) each raw material are 1,2,3,4- tetrachloro triptycene, 15 ~ 20 parts by weight, acetic acid
20 ~ 25 parts by weight of acid anhydride, 2 ~ 4 parts by weight of nitric acid, 49 ~ 62 parts by weight of acetone, 1 ~ 2 parts by weight of reducing agent.
Preferably, step (2) catalyst is palladium/carbon catalyst, nickel carbon catalyst, cobalt/C catalyst, iron/carbon are urged
At least one of agent.
Preferably, the parts by weight of step (2) each raw material are 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene
18 ~ 22 parts by weight, 22 ~ 25 parts by weight of hexafluorodianhydride (6FDA), 5 ~ 8 parts by weight of ferric acetyl acetonade, 1 ~ 2 parts by weight of catalyst, parachlorophenol
43 ~ 54 parts by weight.
Preferably, step (2) reaction temperature is 160 ~ 200 DEG C, and the time is 16 ~ 20h.
Preferably, the parts by weight of step (3) each raw material are porous polyimide/Fe2O325 ~ 30 weight of composite material
Part, 8 ~ 12 parts by weight of aqueous polyurethane, 58 ~ 67 parts by weight of deionized water.
Preferably, step (4) strong base solution is one of potassium hydroxide solution, sodium hydroxide solution, when immersion
Between be 10 ~ 20min.
Preferably, the back end vacuum degree of step (4) described magnetron sputtering is 4 ~ 5kPa, and operating pressure is 1.5 ~ 1.8mm, target
Cardinal distance is 100 ~ 120mm, and sedimentation time is 5 ~ 10min.
Triptycene has unique D in organic compound3hSymmetry, biggish intramolecular hole and rigid celestial body shape three
Stereochemical structure is tieed up, when its unique three-dimensional rigid structure is introduced into polymer, can assign polymer biggish specific surface area, is made
Obtain porous material.The present invention exactly utilizes this principle, the polyimides of the structure containing triptycene is prepared, using its micropore to original position
The Fe of generation2O3It is loaded, the micropore of polyimide structures itself is Fe2O3Space is provided and promotes Fe2O3In the film
It is evenly dispersed.Further, due to containing triptycene structure in polyimides, so that be separated from each other between polymer chain and chain,
There is no strong interchain interactions, so that film has good ductility, under tension, between triptycene mutually
It is close, it is loaded in chain and interchain transmitting, and make film modulus with higher.
The present invention uses ferric acetyl acetonade in-situ preparation Fe at high temperature2O3, and it is uniformly wrapped on triptycene polyimides
In porous structure, after casting film-forming, silver conductive layer is formed in upper and lower surface by magnetron sputtering, has both superparamagnetism to be made
With the laminated film of electric conductivity.Whole preparation process is fairly simple, easily controllable, and energy consumption is lower, can be widely used for industrial production
In.
The polyimides for having both electric conductivity and magnetism being prepared the present invention also provides a kind of above-mentioned preparation method is multiple
Close film.The polyimide composite film is first to synthesize 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene, then with six
Fluorine dianhydride synthesizes the porous polyimide of the structure containing triptycene, while in-situ preparation Fe2O3It is coated on the porous structure of polyimides
In, then casting film-forming is carried out, and form silver conductive layer in the upper and lower surface of film using magnetron sputtering and be made.
The present invention provides a kind of polyimide composite films and preparation method for having both electric conductivity and magnetism, with existing skill
Art is compared, and the feature and excellent effect protruded is:
1. polyimide composite film prepared by the present invention has both good superparamagnetism and electric conductivity, can be used as being electromagnetically shielded
Material.
2. polyimide composite film prepared by the present invention has good ductility and higher modulus.
3. polyimide composite film prepared by the present invention, specific surface area and porosity with higher, Fe2O3For original position
It generates, and is coated in the porous structure of polyimides, therefore favorable dispersibility.
4. preparation method of the invention, silver conductive layer are formed by magnetron sputtering, process is simple, easily controllable.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, 19h is reacted at room temperature, then in ice
Bath is lower to stir 5h, filters, by obtained solid adding into acetone, reducing agent is added, and then heating reflux reaction 2.5h is filtered, will
Filtrate revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is hydrazine hydrate；The parts by weight of each raw material
For 1,2,3,4- tetrachloro triptycene, 17 parts by weight, 23 parts by weight of acetic anhydride, 3 parts by weight of nitric acid, 56 parts by weight of acetone, reducing agent 1
Parts by weight；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is palladium/carbon catalyst；Reaction temperature is 190 DEG C, time 17h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 21 parts by weight, 23 parts by weight of hexafluorodianhydride (6FDA), levulinic
7 parts by weight of ketone iron, 1 parts by weight of catalyst, 48 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O327 parts by weight of composite material, 9 parts by weight of aqueous polyurethane, 64 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is potassium hydroxide solution, soaking time 16min；Magnetic
The back end vacuum degree of control sputtering is 4.5kPa, operating pressure 1.7mm, target-substrate distance 110mm, sedimentation time 7min.
Test method:
(1) it superparamagnetism (saturation magnetization, coercive force, remanent magnetism): is shaken using U.S. LDJ Electronics VSM-4HF
Dynamic sample magnetometer is tested, and the laminated film produced by the present invention of arbitrary shape is taken, and test ambient temperature is 23 ± 2 DEG C,
Relative humidity is 55 ± 5%, obtains hysteresis loop, and then the coercive force, remanent magnetism and saturated magnetization that obtain magnetic coupling film are strong
Degree；
(2) electric conductivity (resistivity): it is that four-point probe is tested using Keithley 4200, takes the present invention of arbitrary shape
Laminated film obtained, test ambient temperature are 23 ± 2 DEG C, and relative humidity is 55 ± 5%, obtain the resistance of conductive composite film
Rate；
(3) it ductility, modulus (tensile strength, stretch modulus): is carried out using Japan's Shimadzu AGS-X5KN cupping machine
Test, test ambient temperature are 23 ± 2 DEG C, and relative humidity is 55 ± 5%, by polyimide composite film system produced by the present invention
At standard sample, its thickness of first precise measurement, rate of extension 5mm/min, test and calculate laminated film stretch modulus and
Tensile strength；
(4) it specific surface area: is tested using Bei Shide BET specific surface area tester, takes the produced by the present invention of arbitrary shape
Laminated film measures the specific surface area of laminated film；
(5) it porosity: is tested using PoreMaster series thin film porosity test instrument, takes the present invention of arbitrary shape
Laminated film obtained measures the porosity of laminated film；
The data obtained is as shown in table 1.
Embodiment 2
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, reacts 160h at room temperature, then exists
4h is stirred under ice bath, is filtered, by obtained solid adding into acetone, reducing agent is added, and then heating reflux reaction 2h is filtered, will
Filtrate revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is phenylhydrazine；The parts by weight of each raw material are,
15 parts by weight of 1,2,3,4- tetrachloro triptycene, 20 parts by weight of acetic anhydride, 2 parts by weight of nitric acid, 62 parts by weight of acetone, 1 weight of reducing agent
Measure part；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is nickel carbon catalyst；Reaction temperature is 160 DEG C, time 20h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 18 parts by weight, 22 parts by weight of hexafluorodianhydride (6FDA), levulinic
5 parts by weight of ketone iron, 1 parts by weight of catalyst, 54 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O325 parts by weight of composite material, 8 parts by weight of aqueous polyurethane, 67 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is sodium hydroxide solution, soaking time 10min；Magnetic
The back end vacuum degree of control sputtering is 4kPa, operating pressure 1.5mm, target-substrate distance 100mm, sedimentation time 10min.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 3
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, 20h is reacted at room temperature, then in ice
Bath is lower to stir 6h, filters, by obtained solid adding into acetone, reducing agent is added, then heating reflux reaction 3h is filtered, will be filtered
Liquid revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is hydrazine hydrate；The parts by weight of each raw material are,
20 parts by weight of 1,2,3,4- tetrachloro triptycene, 25 parts by weight of acetic anhydride, 4 parts by weight of nitric acid, 49 parts by weight of acetone, 2 weight of reducing agent
Measure part；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is cobalt/C catalyst；Reaction temperature is 200 DEG C, time 16h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 22 parts by weight, 25 parts by weight of hexafluorodianhydride (6FDA), levulinic
8 parts by weight of ketone iron, 2 parts by weight of catalyst, 43 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O330 parts by weight of composite material, 12 parts by weight of aqueous polyurethane, 58 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is potassium hydroxide solution, soaking time 20min；Magnetic
The back end vacuum degree of control sputtering is 5kPa, operating pressure 1.8mm, target-substrate distance 120mm, sedimentation time 5min.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 4
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, 17h is reacted at room temperature, then in ice
Bath is lower to stir 5.5h, filters, by obtained solid adding into acetone, reducing agent is added, and then heating reflux reaction 2h is filtered, will
Filtrate revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is phenylhydrazine；The parts by weight of each raw material are,
16 parts by weight of 1,2,3,4- tetrachloro triptycene, 22 parts by weight of acetic anhydride, 2 parts by weight of nitric acid, 59 parts by weight of acetone, 1 weight of reducing agent
Measure part；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is iron/C catalyst；Reaction temperature is 170 DEG C, time 19h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 19 parts by weight, 23 parts by weight of hexafluorodianhydride (6FDA), levulinic
6 parts by weight of ketone iron, 1 parts by weight of catalyst, 51 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O326 parts by weight of composite material, 9 parts by weight of aqueous polyurethane, 65 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is sodium hydroxide solution, soaking time 12min；Magnetic
The back end vacuum degree of control sputtering is 4kPa, operating pressure 1.6mm, target-substrate distance 105mm, sedimentation time 8min.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 5
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, 19h is reacted at room temperature, then in ice
Bath is lower to stir 5.5h, filters, by obtained solid adding into acetone, reducing agent is added, and then heating reflux reaction 3h is filtered, will
Filtrate revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is hydrazine hydrate or phenylhydrazine；Each raw material
Parts by weight are, 1,2,3,4- tetrachloro triptycene, 19 parts by weight, 24 parts by weight of acetic anhydride, 4 parts by weight of nitric acid, 51 parts by weight of acetone,
2 parts by weight of reducing agent；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is palladium/carbon catalyst；Reaction temperature is 190 DEG C, time 17h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 21 parts by weight, 24 parts by weight of hexafluorodianhydride (6FDA), levulinic
7 parts by weight of ketone iron, 2 parts by weight of catalyst, 46 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O329 parts by weight of composite material, 11 parts by weight of aqueous polyurethane, 60 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is potassium hydroxide solution, soaking time 18min；Magnetic
The back end vacuum degree of control sputtering is 5kPa, operating pressure 1.7mm, target-substrate distance 115mm, sedimentation time 7min.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Embodiment 6
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, 18h is reacted at room temperature, then in ice
Bath is lower to stir 5h, filters, by obtained solid adding into acetone, reducing agent is added, and then heating reflux reaction 2.5h is filtered, will
Filtrate revolving, obtains 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene；Reducing agent is phenylhydrazine；The parts by weight of each raw material are,
18 parts by weight of 1,2,3,4- tetrachloro triptycene, 22 parts by weight of acetic anhydride, 3 parts by weight of nitric acid, 55 parts by weight of acetone, 2 weight of reducing agent
Measure part；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；Catalyst is nickel carbon catalyst；Reaction temperature is 180 DEG C, time 18h；Each raw material
Parts by weight be 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 20 parts by weight, 24 parts by weight of hexafluorodianhydride (6FDA), levulinic
6 parts by weight of ketone iron, 2 parts by weight of catalyst, 48 parts by weight of parachlorophenol；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, casting film-forming,
Porous polyimide/Fe is made in infrared drying2O3/ polyurethane laminated film；The parts by weight of each raw material are that porous polyamides is sub-
Amine/Fe2O328 parts by weight of composite material, 10 parts by weight of aqueous polyurethane, 62 parts by weight of deionized water；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film；Strong base solution is sodium hydroxide solution, soaking time 15min；Magnetic
The back end vacuum degree of control sputtering is 4.5kPa, operating pressure 1.6mm, target-substrate distance 110mm, sedimentation time 8min.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Comparative example 1
Triptycene structure is introduced not in polyimides, but is raw material preparation with 4,4'- diaminodiphenyl ether and hexafluorodianhydride (6FDA)
Polyimides, other preparation conditions and embodiment 6 are consistent.
Test method and embodiment 1 are consistent, and the data obtained is as shown in table 1.
Table 1:
Claims (10)
1. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film, which is characterized in that the polyamides is sub-
Specific step is as follows for the preparation of amine laminated film:
(1) 1,2,3,4- tetrachloro triptycene is added in acetic anhydride, nitric acid solution is added dropwise, react 16 ~ 20h at room temperature, then
4 ~ 6h is stirred under ice bath, is filtered, and by obtained solid adding into acetone, reducing agent is added, then 2 ~ 3h of heating reflux reaction takes out
Filter, filtrate is rotated, 2,6- diaminostilbene, 3,14,15,16- tetrachloro triptycene is obtained；
(2) 2,6- diaminostilbene 3,14,15,16- tetrachloro triptycene, hexafluorodianhydride (6FDA), ferric acetyl acetonade, catalyst are added to chlorine
In phenol, heating reaction, dianhydride and diamine reactant generate the porous polyimide with triptycene structure, and ferric acetyl acetonade occurs
Pyrolytic in-situ preparation ferriferous oxide, and be uniformly wrapped in the porous structure of polyimides, it refilters, dry, be made more
Hole polyimides/Fe2O3Composite material；
(3) by porous polyimide/Fe2O3Composite material, waterborne polyurethane resin are scattered in deionized water, and casting film-forming is red
Outside line is dry, and porous polyimide/Fe is made2O3/ polyurethane laminated film；
(4) by porous polyimide/Fe2O3/ polyurethane laminated film, which is soaked in strong base solution, carries out surface etch, makes surface
The polyimides open loop of layer forms polyamic acid, then plates silver conductive layer respectively in upper and lower surface using magnetron sputtering, is made
Have both electric conductivity and magnetic polyimide composite film.
2. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: step (1) reducing agent is at least one of hydrazine hydrate or phenylhydrazine.
3. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: the parts by weight of step (1) each raw material are 1,2,3,4- tetrachloro triptycene, 15 ~ 20 parts by weight, acetic anhydride 20 ~ 25
Parts by weight, 2 ~ 4 parts by weight of nitric acid, 49 ~ 62 parts by weight of acetone, 1 ~ 2 parts by weight of reducing agent.
4. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: step (2) catalyst is palladium/carbon catalyst, in nickel carbon catalyst, cobalt/C catalyst, iron/C catalyst
It is at least one.
5. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: the parts by weight of step (2) each raw material are 2,6- 3,14,15,16- tetrachloro triptycene of diaminostilbene, 18 ~ 22 weight
Part, 22 ~ 25 parts by weight of hexafluorodianhydride (6FDA), 5 ~ 8 parts by weight of ferric acetyl acetonade, 1 ~ 2 parts by weight of catalyst, 43 ~ 54 weight of parachlorophenol
Part.
6. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: step (2) reaction temperature is 160 ~ 200 DEG C, and the time is 16 ~ 20h.
7. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: the parts by weight of step (3) each raw material are porous polyimide/Fe2O3It is 25 ~ 30 parts by weight of composite material, aqueous
8 ~ 12 parts by weight of polyurethane, 58 ~ 67 parts by weight of deionized water.
8. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: step (4) strong base solution be one of potassium hydroxide solution, sodium hydroxide solution, soaking time be 10 ~
20min。
9. a kind of preparation method for having both electric conductivity and magnetic polyimide composite film according to claim 1, special
Sign is: the back end vacuum degree of step (4) described magnetron sputtering is 4 ~ 5kPa, and operating pressure is 1.5 ~ 1.8mm, and target-substrate distance is
100 ~ 120mm, sedimentation time are 5 ~ 10min.
10. a kind of polyimides for having both electric conductivity and magnetism that any one of claim 1 ~ 9 preparation method is prepared
Laminated film.
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