CN106519668B - A kind of preparation method of electrically conductive polyamide acid imide composite material - Google Patents
A kind of preparation method of electrically conductive polyamide acid imide composite material Download PDFInfo
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- CN106519668B CN106519668B CN201610908194.4A CN201610908194A CN106519668B CN 106519668 B CN106519668 B CN 106519668B CN 201610908194 A CN201610908194 A CN 201610908194A CN 106519668 B CN106519668 B CN 106519668B
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- 239000002253 acid Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 239000004952 Polyamide Substances 0.000 title claims abstract description 21
- 150000003949 imides Chemical class 0.000 title claims abstract description 21
- 229920002647 polyamide Polymers 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 43
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 43
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 6
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 230000020477 pH reduction Effects 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000004962 Polyamide-imide Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229920002312 polyamide-imide Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000005954 phosphonylation reaction Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000002166 wet spinning Methods 0.000 claims description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims 2
- 230000009514 concussion Effects 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000011592 zinc chloride Substances 0.000 claims 1
- 235000005074 zinc chloride Nutrition 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 230000007123 defense Effects 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000010355 oscillation Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 239000011159 matrix material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—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 C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—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
- C08K2201/011—Nanostructured additives
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- 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
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of electrically conductive polyamide acid imide composite material, belong to the preparation technical field of polymer modification and nanocomposite.Conductive PAI material of the invention synthesizes in two steps.Firstly, PAI is reacted with carboxylic acid carbon nano tube, the conducting masterbatch that content of carbon nanotubes is 20-80% is prepared；Then, conducting masterbatch is mixed with ultrasonic oscillation instrument by high-speed emulsifying machine in a solvent with PAI, solution film forming or the spinning of uniform carbon nanotubes will be dispersed.There is electrically conductive polyamide acid imide material provided by the invention tensile strength height and excellent electric conductivity, conductivity to reach 100S/m or more, can be widely applied in industries such as electronic apparatus, aerospace, defense military.
Description
Technical field:
The present invention relates to a kind of electrically conductive polyamide acid imide and preparation method thereof, belong to high molecular material blending and modifying and
The preparation technical field of nanocomposite.
Background technique:
It is well known that high molecular material has the unexistent processing temperature of metal material low, moulding process is simple, corrosion-resistant
The advantages that, but the high molecular material of most one-components is difficult conduction.Although gripping conducting polymer altogether has relatively
Good electric conductivity, but poor processability, therefore largely limit it and be widely applied.Since carbon nanotube is with excellent
Electric conductivity and great draw ratio if a small amount of carbon nanotube is added in polymeric matrix can keep poly-
While the advantages that closing the excellent processing characteristics of object and low-density, the very big electric conductivity that must improve composite material.Therefore carbon nanometer
Managing polymer-modified composite material has very big application prospect in fields such as electromagnetic shielding, electrostatic spraying, static eliminations.But
It is since there are strong Van der Waals force and the surface inertness of carbon nanotube between carbon nanotube, so that carbon nanotube is in polymer
In be difficult to disperse.Therefore, by being modified to carbon nanotube, keep its surface-functionalized and group, improve interface binding power
And keeping it evenly dispersed in the polymer is all the emphasis studied at present.
Summary of the invention
It is an object of the invention to solve the technical problem of carbon nanotube difficult dispersion in a polymer matrix, realization can with compared with
Low carbon nanotube additive amount obtains the polymer matrix composite of high conduction performance.
The preparation method of electrically conductive polyamide acid imide composite material carries out as steps described below:
(1) acidification of carbon nanotube
Carbon nanotube is added in the strong oxidizing property acid solution of concentrated nitric acid and the concentrated sulfuric acid that volume ratio is 1:0~1:3, is added
Heat arrives 115-120 DEG C of reflux 0.5-3h, after reaction, standing to room temperature, then with distilled water repeatedly filtering and washing to neutrality,
Dry 2~6h in vacuum drying oven at 60-100 DEG C；
(2) preparation of conducting masterbatch
The carbon nanotube that acidification is crossed is prepared into conducting masterbatch by phosphonylation react with polyamidoimide.Under
It states step progress: N-Methyl pyrrolidone (NMP) is added in acidification carbon nanotube and polyamidoimide, condensing agent is then added
And water absorbing agent, under inert atmosphere, 80 DEG C -120 DEG C are warming up to, is reacted 2-8 hours；Reaction product passes through at ethyl alcohol or methanol sedimentation
Reason, is then embathed repeatedly with warm water, is dried in vacuo 8 hours under the conditions of 80 DEG C of products therefrom.
(3) preparation of electrically conductive polyamide acid imide composite material
Conducting masterbatch is added in preparatory prepared polyamidoimide/m-cresol solution, by high speed emulsification and
The carbon nanotube masterbatch handled well is homogeneously dispersed in polyamideimide solution by ultrasonic vibration；Then it is poured by solution
Film forming or the method for wet spinning prepare polyamidoimide/carbon nanotube conducting composite material.
Wherein Strong oxdiative acid is one or both of the concentrated sulfuric acid, concentrated nitric acid in step (1)；
Wherein carbon nanotube is one of single-walled carbon nanotube or multi-walled carbon nanotube or combinations thereof object in step (1)；
Wherein the mass volume ratio of carbon nanotube and acid with strong oxidizing property is 1:10-1:100 in step (1)；
The 20-80% that content of carbon nanotubes is polyamidoimide quality is wherein acidified in step (2)；
Wherein polyamidoimide/nmp solution concentration is 1g/50mL-1g/100mL in step (2)；
Wherein condensing agent described in step (2) is pyridine (Py), triphenyl phosphite (TPP)；
Wherein condensing agent dosage described in step (2) is the 10%-20% of NMP dosage,
Wherein water absorbing agent described in step (2) is anhydrous calcium chloride (CaCl2), anhydrous lithium chloride (LiCl), anhydrous chlorine
Change one of zinc or a variety of；
Wherein water absorbing agent dosage described in step (2) is 5-10 times of polyamidoimide quality.
Wherein polyamidoimide/m-cresol solution concentration is 1g/10mL-1g/40mL in step (3)；
Wherein in step (3) carbon nanotube content be polyamidoimide gross mass 0.1-20%；
Wherein the structural formula of the polyamidoimide is shown below:
Wherein Ar1For one kind of following structural formula:
Wherein Ar2For one kind of following structural formula:
Wherein x=1,2,3,5,7,8,9,10,11,13
Wherein n=10-200.
Using the above method, there is following technological merit:
Since carbon nanotube itself has a very high specific surface area, there are stronger Van der Waals forces between particle, existing big
In most technologies, it is evenly dispersed in polymeric matrix material to be difficult to realize carbon nanotube.And by using described in this patent
Method, carbon nanotube additive amount can be made to remain to be evenly dispersed in polymeric matrix when being up to 20%, assigned prepared
The higher intensity of polyamidoimide material and excellent electric conductivity.
Specific embodiment
With reference to embodiments, the present invention will be described in further detail, and specific embodiment described herein is only
To explain the present invention, it is not intended to limit the present invention.
Embodiment 1
Selected polyamide-imide resin (PAI-AU) structural formula is as follows:
(1) acidification of carbon nanotube: by 5g multi-walled carbon nanotube be added strong oxidizing property mixed acid (concentrated sulfuric acid 50ml and
Concentrated nitric acid 50ml) in solution, with being heated to 115 DEG C in churned mechanically three-necked flask, flow back 1.5h under mechanical stirring.Instead
It is cooled to room temperature, is filtered after answering, is washed with deionized until neutrality, obtains acidification carbon nanotube.
(2) preparation of conducting masterbatch: 2g is acidified carbon nanotube and the N- methyl pyrrole of 100mL is added in 8g polyamidoimide
Pyrrolidone (NMP), is then added phosphonylation reagent and solubilizer, under inert atmosphere, is warming up to 120 DEG C, reacts 4 hours.Reaction
Then product is embathed repeatedly with warm water by ethyl alcohol or methanol settlement treatment, is dried in vacuo 8h under the conditions of 80 DEG C of products therefrom.
(3) preparation of electrically conductive polyamide acid imide composite material
2.5g conducting masterbatch is added to 30mL prepared polyamidoimide/m-cresol solution (0.1g/mL) in advance
In, carbon nanotube masterbatch is homogeneously dispersed in polyamideimide solution by high speed emulsification and ultrasonic vibration；Then by molten
Liquid casting film forming.The conductivity of polyamidoimide conductive film is 7.0S/m, tensile strength 94MPa, and Young's modulus is
2.10GPa。
Embodiment 2
The present embodiment leads 50mg the difference from embodiment 1 is that in the preparation step of electrically conductive polyamide acid imide material
Goddess of lightning's material is added to 49.55mL in advance in prepared polyamidoimide/m-cresol solution (0.1g/mL), other processing hands
Duan Junyu embodiment 1 is consistent.The conductivity of polyamidoimide conductive film is 3.4 × 10-5S/m, tensile strength are
54.0MPa, Young's modulus 0.98GPa.
Embodiment 3
The acidification process and embodiment 1 of selected polyamide-imide resin and carbon nanotube in the present embodiment
Unanimously, difference is that step (2) and (3) treatment process are different, and details are as follows:
(2) preparation of conducting masterbatch: 1g is acidified carbon nanotube and the N- methyl of 100mL is added in 0.25g polyamidoimide
In pyrrolidones (NMP), it is then added phosphonylation reagent and solubilizer, under inert atmosphere, is warming up to 120 DEG C, reacts 4 hours.
Then reaction product is embathed repeatedly with warm water, is dried in vacuo under the conditions of 80 DEG C of products therefrom by ethyl alcohol or methanol settlement treatment
8h。
(3) preparation of electrically conductive polyamide acid imide composite material
1g conducting masterbatch is added to 38mL in advance in prepared polyamidoimide/m-cresol solution (0.1g/mL),
High speed emulsification and ultrasonic vibration, carbon nanotube masterbatch is homogeneously dispersed in polyamideimide solution；Then pass through solution
Casting film forming.The conductivity of polyamidoimide conductive film is 105S/m, tensile strength 112MPa, and Young's modulus is
2.49GPa。
Embodiment 4
The present embodiment is distinguished from embodiment 1 is that selected polyamide-imide resin is different, other processing means are equal
It is consistent with embodiment 1.Polyamide-imide resin structural formula used in the present embodiment is as follows:
The conductivity of polyamidoimide conductive film is 7.5S/m, tensile strength 103MPa, and Young's modulus is
2.19GPa。
Embodiment 5
The difference of the present embodiment and embodiment 4 is in the acidification step of carbon nanotube, by 5g multi-walled carbon nanotube
It is added in 500ml concentrated nitric acid solution, other processing means are consistent with embodiment 1.The conductance of polyamidoimide conductive film
Rate is 4.8S/m, tensile strength 91MPa, Young's modulus 1.95GPa.
Embodiment 6
The difference of the present embodiment and embodiment 4 is in the acidification step of carbon nanotube, by 5g multi-walled carbon nanotube
Be added strong oxidizing property mixed acid (concentrated sulfuric acid 37.5ml and concentrated nitric acid 12.5ml) solution in, other processing means with embodiment 1
Unanimously.The conductivity of polyamidoimide conductive film is 7.6S/m, tensile strength 98MPa, Young's modulus 2.11GPa.
The various embodiments described above are merely to illustrate the present invention, wherein the parameter of each step, implementation condition etc. are all can be
Variation, all equivalent variationss and improvement carried out based on the technical solution of the present invention should not be excluded of the invention
Except protection scope.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Conductivity (S/m) | 7.0 | 3.4×10-5 | 105 | 7.5 | 4.8 | 7.6 |
| Tensile strength (MPa) | 94 | 54 | 112 | 103 | 91 | 98 |
| Young's modulus (GPa) | 2.10 | 0.98 | 2.49 | 2.19 | 1.95 | 2.11 |
Claims (10)
1. the preparation method of electrically conductive polyamide acid imide composite material, it is characterised in that carry out as steps described below:
(1) acidification of carbon nanotube
Carbon nanotube is added in the strong oxidizing property acid solution of concentrated nitric acid and the concentrated sulfuric acid that volume ratio is 1:0~1:3, is heated to
115-120 DEG C of reflux 0.5-3h is stood to room temperature after reaction, then with distilled water repeatedly filtering and washing to neutrality, 60-
Dry 2~6h in vacuum drying oven at 100 DEG C；
(2) preparation of conducting masterbatch
The carbon nanotube that acidification is crossed is prepared into conducting masterbatch by phosphonylation react with polyamidoimide；
It carries out as steps described below: N-Methyl pyrrolidone (NMP) is added in acidification carbon nanotube and polyamidoimide, then
It is added phosphonylation reagent and solubilizer, under inert atmosphere, is warming up to 80 DEG C -120 DEG C, reacts 2-8 hours；Reaction product passes through second
Then alcohol or methanol settlement treatment are embathed repeatedly with warm water, be dried in vacuo 8 hours under the conditions of 80 DEG C of products therefrom；
(3) preparation of electrically conductive polyamide acid imide composite material
Conducting masterbatch is added in preparatory prepared polyamidoimide/m-cresol solution, high speed emulsification and ultrasound are passed through
The carbon nanotube masterbatch handled well is homogeneously dispersed in polyamideimide solution by concussion；Then it is poured and is formed a film by solution
Or the method for wet spinning prepares polyamidoimide/carbon nanotube conducting composite material.
2. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly Strong oxdiative acid is one or both of the concentrated sulfuric acid, concentrated nitric acid in (1).
3. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly carbon nanotube is one of single-walled carbon nanotube or multi-walled carbon nanotube or combinations thereof object in (1).
4. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly the mass volume ratio of carbon nanotube and acid with strong oxidizing property is 1:10-1:100 in (1).
5. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly the 20-80% that content of carbon nanotubes is polyamidoimide quality is acidified in (2).
6. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly polyamidoimide/nmp solution concentration is 1g/50mL-1g/100mL in (2).
7. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly phosphonylation reagent described in (2) is pyridine (Py), triphenyl phosphite (TPP).
8. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly phosphonylation reagent dosage described in (2) is the 10%-20% of NMP dosage；
Wherein solubilizer described in step (2) is anhydrous calcium chloride (CaCl2), anhydrous lithium chloride (LiCl), in anhydrous zinc chloride
It is one or more；
Wherein solubilizer dosage described in step (2) is 5-10 times of polyamidoimide quality.
9. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein walk
Suddenly polyamidoimide/m-cresol solution concentration is 1g/10mL-1g/40mL in (3)；
Wherein in step (3) carbon nanotube content be polyamidoimide gross mass 0.1-20%.
10. the preparation method of electrically conductive polyamide acid imide composite material according to claim 1, it is characterised in that wherein institute
The structural formula for the polyamidoimide stated is shown below:
Wherein n=10-200.
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