CN106519668A - Method for preparing conductive polyamideimide composite material - Google Patents
Method for preparing conductive polyamideimide composite material Download PDFInfo
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- CN106519668A CN106519668A CN201610908194.4A CN201610908194A CN106519668A CN 106519668 A CN106519668 A CN 106519668A CN 201610908194 A CN201610908194 A CN 201610908194A CN 106519668 A CN106519668 A CN 106519668A
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- polyamidoimide
- electrically conductive
- cnt
- conductive polyamide
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 229920002312 polyamide-imide Polymers 0.000 title claims abstract description 15
- 239000004962 Polyamide-imide Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 11
- 230000009514 concussion Effects 0.000 claims abstract 2
- 239000002253 acid Substances 0.000 claims description 26
- 239000004952 Polyamide Substances 0.000 claims description 18
- 150000003949 imides Chemical class 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 14
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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
- 239000002048 multi walled nanotube 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
- 238000005954 phosphonylation reaction Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 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
- 238000006243 chemical reaction Methods 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
- 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
- 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 12
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract description 2
- 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
- 238000009987 spinning Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000005411 Van der Waals force Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class 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
- 238000013019 agitation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 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
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
- 238000000967 suction filtration Methods 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
The invention discloses a method for preparing a conductive polyamideimide composite material, which belongs to the technical field of modification of a high-molecular material and preparation of a nano composite material. The conductive polyamideimide material is synthesized by two steps. The method comprises the following steps: PAI and carboxylated carbon nanotube are reacted, the content of the carbon nanotube in a prepared conductive mother material is 20-80%; then, a high speed emulsifying machine and a supersonic wave concussion instrument are used for mixing the conductive mother material and PAI in a solvent, and the uniformly dispersed solvent containing the carbon nanotube is subjected to film forming or spinning. The conductive polyamideimide composite material has high tensile strength and excellent conductive performance, the conductivity reaches 100S/m and more, and the conductive polyamideimide composite material is widely used in the industries of electric appliance, aviation spaceflight, national defense and military.
Description
Technical field：
The present invention relates to a kind of electrically conductive polyamide acid imide and preparation method thereof, belong to macromolecular material blending and modifying and
The preparing technical field of nano composite material.
Background technology：
It is well known that macromolecular material has the unexistent processing temperature of metal material low, moulding process is simple, corrosion-resistant
The advantages of, but the macromolecular material of most one-components is difficult conduction.Although gripping conducting polymer altogether to have relatively
Good electric conductivity, but poor processability, therefore largely limit which and be widely applied.Due to CNT have it is excellent
Electric conductivity and great draw ratio, if a small amount of CNT is added in polymeric matrix, can keep poly-
While the advantages of excellent processing characteristics of compound and low-density, the very big electric conductivity that must improve composite.Therefore carbon nanometer
Manage polymer-modified composite and there is very big application prospect in fields such as electromagnetic shielding, electrostatic spraying, static eliminations.But
It is due to the surface inertness that there is strong Van der Waals force and CNT between CNT so that CNT is in polymer
In be difficult dispersion.Therefore, by being modified to CNT so as to surface-functionalized and group, improve interface binding power
And make its in the polymer it is dispersed be all current research emphasis.
The content of the invention
It is an object of the invention to solve CNT difficult scattered technical barrier in polymeric matrix, realization can with compared with
Low CNT addition obtains the polymer matrix composite of high conduction performance.
The preparation method of electrically conductive polyamide acid imide composite, is carried out as steps described below：
(1) acidification of CNT
CNT is added to into volume ratio for 1：0～1：In 3 red fuming nitric acid (RFNA) and the strong oxidizing property acid solution of the concentrated sulfuric acid, plus
Heat, is stood to room temperature after reaction terminates to 115-120 DEG C of backflow 0.5-3h, then with distilled water repeatedly filtering and washing to neutrality,
2～6h is dried at 60-100 DEG C in vacuum drying oven；
(2) preparation of conducting masterbatch
The CNT that acidification is crossed prepares conducting masterbatch with polyamidoimide by phosphonylation reaction.According under
Stating step is carried out：CNT will be acidified and polyamidoimide will add 1-METHYLPYRROLIDONE (NMP), be subsequently adding condensing agent
And water absorbing agent, under inert atmosphere, 80 DEG C -120 DEG C are warming up to, react 2-8 hours；Product passes through at ethanol or methyl alcohol sedimentation
Reason, is then embathed repeatedly with warm water, is vacuum dried 8 hours under the conditions of 80 DEG C of products therefrom.
(3) preparation of electrically conductive polyamide acid imide composite
Conducting masterbatch is added in the polyamidoimide/m-cresol solution for preparing in advance, by high speed emulsification and
Ultrasonic vibration is homogeneously dispersed in the carbon nanotube masterbatch handled well in polyamideimide solution；Then poured into a mould by solution
The method of film forming or wet spinning prepares polyamidoimide/carbon nanotube conducting composite.
Wherein in step (1) Strong oxdiative acid be the concentrated sulfuric acid, one or two in red fuming nitric acid (RFNA)；
Wherein in step (1), CNT is SWCN or one kind or combinations thereof in multi-walled carbon nano-tubes；
Wherein in step (1), CNT is 1 with the mass volume ratio of acid with strong oxidizing property:10-1:100；
20-80% of the acidifying content of carbon nanotubes for polyamidoimide quality wherein in step (2)；
Wherein in step (2), polyamidoimide/nmp solution concentration is 1g/50mL-1g/100mL；
Condensing agent wherein described in step (2) is pyridine (Py), triphenyl phosphite (TPP)；
10%-20% of the condensing agent consumption wherein described in step (2) for NMP consumptions,
Water absorbing agent wherein described in step (2) is anhydrous calcium chloride (CaCl2), anhydrous Lithium chloride (LiCl), anhydrous chlorine
Change one or more in zinc；
5-10 times for polyamidoimide quality of water absorbing agent consumption wherein described in step (2).
Wherein in step (3), the concentration of polyamidoimide/m-cresol solution is 1g/10mL-1g/40mL；
0.1-20% of the content of CNT for polyamidoimide gross mass wherein in step (3)；
The structural formula of wherein described 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 said method, with following technological merit：
As CNT itself has very high specific surface area, between particle, there is stronger Van der Waals force, it is existing big
In most technologies, CNT is difficult to realize dispersed in polymeric matrix material.And pass through using described in this patent
Method, can make to remain to be evenly dispersed in polymeric matrix during CNT addition up to 20%, give 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 CNT：By 5g multi-walled carbon nano-tubes add strong oxidizing property mixed acid (concentrated sulfuric acid 50ml and
Red fuming nitric acid (RFNA) 50ml) in solution, the 1.5h that flows back under 115 DEG C, mechanical agitation is heated in churned mechanically there-necked flask.Instead
Room temperature should be cooled to after terminating, carry out suction filtration, be washed with deionized until neutrality, obtains being acidified CNT.
(2) preparation of conducting masterbatch：2g is acidified into the N- methyl pyrroles that CNT and 8g polyamidoimides add 100mL
Pyrrolidone (NMP), is subsequently adding phosphonylation reagent and solubilizer, under inert atmosphere, is warming up to 120 DEG C, reacts 4 hours.Reaction
Product passes through ethanol or methyl alcohol settlement treatment, is then embathed repeatedly with warm water, is vacuum dried 8h under the conditions of 80 DEG C of products therefrom.
(3) preparation of electrically conductive polyamide acid imide composite
2.5g conducting masterbatch is added to into polyamidoimide/m-cresol solution (0.1g/mL) that 30mL is prepared in advance
In, emulsification and ultrasonic vibration, carbon nanotube masterbatch is homogeneously dispersed in polyamideimide solution at a high speed；Then by molten
Liquid pours into a mould film forming.The electrical conductivity of polyamidoimide conductive film is 7.0S/m, and tensile strength is 94MPa, and Young's modulus is
2.10GPa。
Embodiment 2
During the difference of the present embodiment and embodiment 1 is the preparation process of electrically conductive polyamide acid imide material, 50mg is led
Goddess of lightning's material is added in polyamidoimide/m-cresol solution (0.1g/mL) that 49.55mL is prepared in advance, and other process hand
Duan Junyu embodiments 1 are consistent.The electrical conductivity of polyamidoimide conductive film is 3.4 × 10-5S/m, tensile strength is
54.0MPa, Young's modulus are 0.98GPa.
Embodiment 3
The acidification process of selected polyamide-imide resin and CNT and embodiment 1 in the present embodiment
Unanimously, difference is that step (2) and (3) processing procedure are different, and details are as follows：
(2) preparation of conducting masterbatch：1g is acidified the N- methyl that CNT and 0.25g polyamidoimides add 100mL
In pyrrolidones (NMP), phosphonylation reagent and solubilizer is subsequently adding, under inert atmosphere, is warming up to 120 DEG C, reacted 4 hours.
Product passes through ethanol or methyl alcohol settlement treatment, is then embathed repeatedly with warm water, is vacuum dried under the conditions of 80 DEG C of products therefrom
8h。
(3) preparation of electrically conductive polyamide acid imide composite
1g conducting masterbatch is added in polyamidoimide/m-cresol solution (0.1g/mL) that 38mL is prepared in advance,
Emulsification and ultrasonic vibration, carbon nanotube masterbatch is homogeneously dispersed in polyamideimide solution at a high speed；Then pass through solution
Cast film forming.The electrical conductivity of polyamidoimide conductive film is 105S/m, and tensile strength is 112MPa, and Young's modulus is
2.49GPa。
Embodiment 4
The present embodiment is that selected polyamide-imide resin is different from the difference of embodiment 1, and other processing means are equal
It is consistent with embodiment 1.Used by the present embodiment, polyamide-imide resin structural formula is as follows：
The electrical conductivity of polyamidoimide conductive film is 7.5S/m, and tensile strength is 103MPa, and Young's modulus is
2.19GPa。
Embodiment 5
During the difference of the present embodiment and embodiment 4 is the acidification step of CNT, by 5g multi-walled carbon nano-tubes
In adding 500ml concentrated nitric acid solutions, other processing means are consistent with embodiment 1.The conductance of polyamidoimide conductive film
Rate is 4.8S/m, and tensile strength is 91MPa, and Young's modulus is 1.95GPa.
Embodiment 6
During the difference of the present embodiment and embodiment 4 is the acidification step of CNT, by 5g multi-walled carbon nano-tubes
Add strong oxidizing property mixed acid (concentrated sulfuric acid 37.5ml and red fuming nitric acid (RFNA) 12.5ml) solution in, other processing means with embodiment 1
Unanimously.The electrical conductivity of polyamidoimide conductive film is 7.6S/m, and tensile strength is 98MPa, and Young's modulus is 2.11GPa.
It all can be that the various embodiments described above are merely to illustrate the present invention, the parameter of wherein each step, implementation condition etc.
Change, every equivalent variations carried out on the basis of technical solution of the present invention and improvement should not be excluded the present invention's
Outside protection domain.
Table 1
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 |
| Electrical 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, it is characterised in that carry out as steps described below：
(1) acidification of CNT
CNT is added to into volume ratio for 1：0～1：In 3 red fuming nitric acid (RFNA) and the strong oxidizing property acid solution of the concentrated sulfuric acid, it is heated to
115-120 DEG C of backflow 0.5-3h, after reaction terminates, stands to room temperature, then with distilled water repeatedly filtering and washing to neutrality, 60-
2～6h is dried at 100 DEG C in vacuum drying oven；
(2) preparation of conducting masterbatch
The CNT that acidification is crossed prepares conducting masterbatch with polyamidoimide by phosphonylation reaction；
Carry out as steps described below：CNT will be acidified and polyamidoimide will add 1-METHYLPYRROLIDONE (NMP), then
Condensing agent and water absorbing agent is added, under inert atmosphere, 80 DEG C -120 DEG C is warming up to, 2-8 hours are reacted；Product pass through ethanol or
Methyl alcohol settlement treatment, is then embathed repeatedly with warm water, is vacuum dried 8 hours under the conditions of 80 DEG C of products therefrom；
(3) preparation of electrically conductive polyamide acid imide composite
Conducting masterbatch is added in the polyamidoimide/m-cresol solution for preparing in advance, by high speed emulsification and ultrasound
Concussion is homogeneously dispersed in the carbon nanotube masterbatch handled well in polyamideimide solution；Then film forming is poured into a mould by solution
Or the method for wet spinning prepares polyamidoimide/carbon nanotube conducting composite.
2. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly in (1) Strong oxdiative acid be the concentrated sulfuric acid, one or two in red fuming nitric acid (RFNA).
3. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly in (1), CNT is SWCN or one kind or combinations thereof in multi-walled carbon nano-tubes.
4. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly in (1), CNT is 1 with the mass volume ratio of acid with strong oxidizing property:10-1:100.
5. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly in (2), acidifying content of carbon nanotubes is the 20-80% of polyamidoimide quality.
6. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly in (2), polyamidoimide/nmp solution concentration is 1g/50mL-1g/100mL.
7. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly the condensing agent described in (2) is pyridine (Py), triphenyl phosphite (TPP).
8. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein walk
Suddenly the condensing agent consumption described in (2) is the 10%-20% of NMP consumptions；
Water absorbing agent wherein described in step (2) is anhydrous calcium chloride (CaCl2), anhydrous Lithium chloride (LiCl), in anhydrous zinc chloride
One or more；
5-10 times for polyamidoimide quality of water absorbing agent consumption wherein described in step (2).
9. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that
Wherein in step (3), the concentration of polyamidoimide/m-cresol solution is 1g/10mL-1g/40mL；
0.1-20% of the content of CNT for polyamidoimide gross mass wherein in step (3).
10. the preparation method of electrically conductive polyamide acid imide composite according to claim 1, it is characterised in that wherein institute
The structural formula of the polyamidoimide stated 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.
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| CN109135279A (en) * | 2018-07-11 | 2019-01-04 | 常州大学 | A kind of preparation method based on polyamidoimide high-strength high-conductivity film |
| JP2022528262A (en) * | 2019-04-12 | 2022-06-09 | エムシーディ テクノロジーズ エスエーアールエル | How to Obtain Modifiers for Producing Composites Using Thermoplastic Polymers |
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| CN102382319A (en) * | 2011-07-28 | 2012-03-21 | 同济大学 | Method for preparing carbon nanotube grafted glass fiber multiscale reinforcement reinforced polyimide composite |
| CN105669971A (en) * | 2016-04-08 | 2016-06-15 | 南京工业大学 | Method for preparing nylon composite modified by in-situ polymerization carbon nanotube |
| CN106009629A (en) * | 2015-09-22 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Carbon nanotube/polyamide composite material and preparation method thereof |
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| CN102382319A (en) * | 2011-07-28 | 2012-03-21 | 同济大学 | Method for preparing carbon nanotube grafted glass fiber multiscale reinforcement reinforced polyimide composite |
| CN106009629A (en) * | 2015-09-22 | 2016-10-12 | 洛阳新巨能高热技术有限公司 | Carbon nanotube/polyamide composite material and preparation method thereof |
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| CN109135279A (en) * | 2018-07-11 | 2019-01-04 | 常州大学 | A kind of preparation method based on polyamidoimide high-strength high-conductivity film |
| JP2022528262A (en) * | 2019-04-12 | 2022-06-09 | エムシーディ テクノロジーズ エスエーアールエル | How to Obtain Modifiers for Producing Composites Using Thermoplastic Polymers |
| EP3954726A4 (en) * | 2019-04-12 | 2023-04-26 | MCD Technologies S.a.r.l | Method for producing a modifier for preparing a composite material based on a thermoplastic polymer |
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