CN105506981A - Polyamide/polyaniline electric conduction composite and preparation method thereof - Google Patents
Polyamide/polyaniline electric conduction composite and preparation method thereof Download PDFInfo
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- CN105506981A CN105506981A CN201510967331.7A CN201510967331A CN105506981A CN 105506981 A CN105506981 A CN 105506981A CN 201510967331 A CN201510967331 A CN 201510967331A CN 105506981 A CN105506981 A CN 105506981A
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- polyamide
- polyaniline
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 92
- 229920002647 polyamide Polymers 0.000 title claims abstract description 92
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000011065 in-situ storage Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 14
- 230000004048 modification Effects 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229920001778 nylon Polymers 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004677 Nylon Substances 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 abstract description 28
- 239000004744 fabric Substances 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 238000005660 chlorination reaction Methods 0.000 abstract 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- 229920002292 Nylon 6 Polymers 0.000 description 18
- 229920002302 Nylon 6,6 Polymers 0.000 description 17
- 229920001577 copolymer Polymers 0.000 description 17
- 239000000243 solution Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- 229920000305 Nylon 6,10 Polymers 0.000 description 8
- 239000004020 conductor Substances 0.000 description 8
- 229920006152 PA1010 Polymers 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 239000002657 fibrous material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 acrylic acid acyl chloride Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/08—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin
- D06M14/12—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M14/16—Polyamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
- D06M11/52—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with selenium, tellurium, polonium or their compounds; with sulfur, dithionites or compounds containing sulfur and halogens, with or without oxygen; by sulfohalogenation with chlorosulfonic acid; by sulfohalogenation with a mixture of sulfur dioxide and free halogens
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
- D06M13/335—Amines having an amino group bound to a carbon atom of a six-membered aromatic ring
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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- D06M2101/34—Polyamides
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Abstract
The invention relates to a polyamide/polyaniline electric conduction composite and a preparation method, and belongs to the technical field of composites. The polyamide/polyaniline electric conduction composite is characterized in that polyamide and polyaniline are bonded through chemical bonds. The electric conduction composite with polyamide and polyaniline combined through chemical bonds is obtained by grafting crylic acid on the surface of a polyamide product, conducting acylating chlorination on the grafted crylic acid, making the grafted crylic acid subjected to acylating chlorination react with para phenylene diamine to generate the active center of aniline chemical oxidative polymerization, and conducting in-situ polymerization on aniline monomers through the active center. By means of the method, the electric conductivity of the polyamide product is improved, and due to the fact that polyamide and polyaniline are bonded through chemical bonds, the bonding strength of polyamide and polyaniline is greatly improved. The method is suitable for improving the electric conductivity of resin, fiber, fabric, panels, sheets and the like, can be used for the fields of daily life, medical care, intelligent sensors, spinning, garments, military and the like, and has wide application prospects.
Description
Technical field
The invention belongs to the preparation field of conducing composite material, particularly relate to a kind of polyamide/polyaniline composite material and preparation method thereof.
Background technology:
Polyamide, also known as nylon, is the one that in five large-engineering plastics, consumption is maximum, is also important composite fibre materials.Conventional nylon can be obtained by diamines and diacid polycondensation, different nylon product can be obtained according to diamine is different with binary acid carbon number object, and distinguished by the numeral after nylon, last digit represents the carbon number of diamine, the carbon number (as NYLON610) of a rear numeral binary acid; Also can be obtained by lactam polycondensation or ring-opening polymerization, different polyamide products (as nylon 6) can be obtained according to carbon atom number contained by its cellular construction.Polyamide applications relates to the every field such as daily life and communications and transportation, fishery, military project.It has excellent mechanical property and wear-resisting, oil resistant, solvent resistant, self-lubricating, corrosion-resistant and good processing characteristics etc.Although polyamide material superior performance, its electrical conductivity about 10
-12s/m, has very high insulating properties, and the accumulation of electrostatic charge easily occurs, and can set off an explosion and fire time serious, therefore polyamide article not only requires that having higher mechanical property also requires to have anti-static function.In addition, polyamide is used in petroleum pipeline, electronic apparatus, requires higher during the fields such as auto parts machinery to its antistatic behaviour.Static resistant polyamide fiber is used for clothes industry can improve snugness of fit; Static resistant polyamide industrial yarn, cord fabric thread can be eliminated or reduce because of fricative electrostatic in tire, conveyer belt use procedure; Static resistant polyamide powdery paints can be sprayed at various product surface and improve safety in utilization.
Polyaniline as a kind of desirable conducting polymer have raw material cheap, synthesize easy and doping phenomenon is unique, electrical conductivity is higher, the advantage in atmosphere with good stability, be considered to one of the most promising conducting polymer.Be that conductive material prepared by raw material with polyaniline, excellent lasting electric conductivity can not only be obtained, the electrical conductivity of polyaniline can also be regulated by the mode changing dopant acid concentration.Polyaniline also has the performances such as excellent optical property, chemical property and electromagnetic wave absorption concurrently, in multiple research field, all there is very wide application prospect, utilize polyaniline can solve the antistatic problem of polyamide material high-efficient simple, also can solve polyaniline processing difficulties and the limited difficult problem of range of application simultaneously.
Utilize aniline can form the polyaniline of one deck conduction at polyamide surface in the method for polyamide material in situ Polymerization, as Kyung etc. to form the coating of electrically conductive polyaniline on the surface of polyamide 6 (nylon 6) fiber by in-situ polymerization, thus improve the electric conductivity (OhKW of this fiber, KimSH, KimE, Improvedsurfacecharacteristicsandtheconductivityofpolyan iline – nylon6fabricsbyplasmatreatment [J], JournalofAppliedPolymerScience, 2001, 81 (3): 684-694), Gregory is matrix with polyamide fiber, utilizes in-situ polymerization to obtain the excellent polyamide/polyaniline fiber of electric conductivity, (GregoryRV, KimbrellWC, KuhnHH., Conductivetextiles [J], SyntheticMetals, 1989,28 (1): 823-835), Han Ke is clear etc. probed into different types of dopant acid to aniline in-situ polymerization on fabric and becomes polyaniline on the impact (Han Keqing of electric conductivity, Jinhui is fragrant, polyaniline/terylene conductive fabric adulterates and the research [J] of scourability again, synthetic fiber industry, 2002,25 (5): 25-27).
But in the research of present stage aniline in-situ polymerization on polyamide, there is a serious problem: the polyaniline being exactly compound is strong not at the adhesion of polyamide surface, the conductive compositions of obtained polyamide/polyaniline composite material is not wear-resisting, easily come off, be easy to the forfeiture causing polyamide compoiste material electric conductivity, shorten the useful life of material, these significantly limit the practical application of polyamide/layer/polyaniline conductive material.Although researchers attempt using plasma, the surface modifying methods such as acidifying etching polyamide, to improve the interface bond strength of both polyamide and polyaniline, but the polyamide/polyaniline composite material adopting these methods to obtain still mainly is combined by physisorption at polyaniline and polyamide interface, bond strength is difficult to meet product application in practice.
Summary of the invention
Only physisorption is relied on for polyamide and polyaniline composite conducting material, in interface, bond strength is weak, cause obtained polyamide/layer/polyaniline conductive materials conductive composition not wear-resisting, the defect such as easily come off, the invention provides a kind of method that polyamide and polyaniline are combined with chemical covalent bonds, can effectively solve this defect, obtain and combine firmly polyamide polyaniline composite material.First at polyamide surface graft copolymerization acrylic acid, again by the acrylic acid chloride of graft copolymerization, then itself and p-phenylenediamine (PPD) is made to react, produce the chain carrier of aniline chemical oxidising polymerisation, aniline monomer carries out in-situ polymerization with this activated centre, obtains the polyamide/polyaniline composite material by covalent bonds.Chemical bonds is passed through between polyamide and polyaniline, improve the interface bond strength between polyaniline and polyamide, efficiently solve the defect that the adhesion of polyaniline on polyamide surface is not strong, improve the electric conductivity of product, the ABRASION RESISTANCE of conductive compositions and durability, extend the service life of product, there is very high practical value.
The present invention is achieved by the following technical solutions:
The surface modification of (a) polyamide article: add solvent in flask, polyamide, initator, acrylic monomers, be grafted to polyamide surface under nitrogen protection, washing is dry obtains the acrylic acid product of pure polyamide grafts;
B the acrylic acid acyl chloride reaction of () polyamide grafts: the product getting step (a), in flask, adds thionyl chloride, is heated to 70 DEG C, backflow, stirs 30min-8h, has reacted rear taking-up product, vacuumize, obtains the polyamide grafts acrylic acid of chloride;
(c) acid chloride product grafting p-phenylenediamine (PPD): have two kinds of methods can realize acid chloride product grafting p-phenylenediamine (PPD).One is spray process, and by p-phenylenediamine (PPD) solution, in right amount and spray equably in step (b) its surface 10-1000s, vacuumize is to constant weight; Another kind is immersion method, is the product of step (b) is immersed in 1-30min in the solution of p-phenylenediamine (PPD), and take out product, vacuumize is to constant weight;
(d) home position polymerization reaction: by dopant acid, aniline monomer, and the product of step (c) puts into water, add initator after stirring, cause aniline and obtain polyamide/polyaniline composite material in its surface in-situ polymerization of step (c).
Another object of the present invention is to provide a kind of composite of polyamide/polyaniline, and this composite is prepared by above-mentioned steps (a), (b), (c) and (d).
Polyamide material described in step (a) refers to the class material by being aggregated into by amido link containing carboxyl and amino monomer, be commonly called as nylon, its goods include but not limited to it is any one in the resin of polyamide, fiber, sheet material, sheet material; Described solvent is water, ethanol, ether, n-hexane, cyclohexane, acetone, benzene; Described initator can be but be not limited to be dibenzoyl peroxide, potassium permanganate, the ammonium persulfate in hot initiator system, also includes but not limited to it is hydrogen peroxide/sulfuric acid ferrous system, potassium permanganate/sulfuric acid system, potassium peroxydisulfate/sulfuric acid system, dimethylamine/copper sulphate system, the dimethylamine/copper nitrate system in redox system.
P-phenylenediamine (PPD) solution described in step (c) solvent used is benzene, toluene, ethanol, ether, hexane.
Dopant acid described in step (d) is hydrochloric acid, sulfuric acid, formic acid, acetic acid, DBSA; Initator is potassium peroxydisulfate, ammonium persulfate, iron chloride, potassium bichromate, hydrogen peroxide; The molar ratio of dopant acid, aniline monomer, initator is 0.5:1:0.5-0.1:1:4.
The preparation method of described a kind of polyamide/polyaniline composite material, the polymerization time of the in-situ polymerization described in step (d) is 30min-10h.
Advantage of the present invention:
(1) by polyamide and acrylic acid graft product chloride, then react with p-phenylenediamine (PPD), obtain the activated centre of aniline chemical oxidising polymerisation, make aniline with this activated centre for growing point is polymerized, obtain the polyamide/polyaniline composite material of chemical bonds.
(2) polyamide/polyaniline provided by the invention is with covalent bonds, solves polyamide and polyaniline only relies on physical absorption, the shortcoming that bond strength is weak therebetween, makes conducing composite material durable more.
(3) the present invention is applicable to improve all kinds of polyamide material as the electric conductivity of the materials such as resin, sheet material, sheet material, fiber, fabric and capability of electromagnetic shielding, applies very extensive.
(4) the present invention there is no particular/special requirement to Preparation equipment, easily realizes, and has broad application prospects.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, further detailed description is done to the present invention.What accompanying drawing 1-6 described is for initator with benzoyl peroxide (BPO), polyamide 6 is polyamide article is example, and polyamide 6 produces the activated centre of aniline chemical oxidising polymerisation after series reaction and aniline take activated centre as the course of reaction that growing point carries out in-situ polymerization.Fig. 7-9 is for nylon 66 fiber, is preparing in polyamide/polyaniline composite material process, fiber in the change of different stage surface topographies, wherein:
Fig. 1 is the chemical equation that initator benzoyl peroxide decomposes produces benzoic acid free radical and phenyl radical.
Fig. 2 is the chemical equation that initator free radical causes that polyamide 6 produces macromolecular radical.
Fig. 3 is the chemical equation of polyamide 6 macromolecular radical graft acrylic acid.
Fig. 4 is the acyl chloride reaction formula of polyamide 6 graft acrylic acid.
Fig. 5 is the chemical equation that polyamide 6 grafted polyacrylic acid acid chloride product and p-phenylenediamine (PPD) react.
Fig. 6 is the chemical equation of aniline monomer at polyamide surface in-situ polymerization.
Fig. 7 is the undressed surface topography of Nylon66.
Fig. 8 is the surface topography after Nylon66 surface grafting acrylic acid.
Fig. 9 is the pattern that polyaniline is aggregated in Nylon66 surface.
Detailed description of the invention
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
(1) surface modification of daiamid-6 fiber goods: add 45ml water in flask; 15ml n-hexane, 1g daiamid-6 fiber, 0.5g dibenzoyl peroxide; nitrogen protection; then flask is placed in 80 DEG C of constant temperature oil baths, adds 3g acrylic monomers, carry out the acrylic acid reaction of surface grafting of polyamide; 2h; after having reacted, fiber boiling water rinses 30min, puts into baking oven and is dried to constant weight in 60 DEG C and obtains pure daiamid-6 fiber grafted propylene acid copolymer.As shown in Figure 1-Figure 3, dibenzoyl peroxide decomposes, makes daiamid-6 fiber produce macromolecular radical, causes the graft reaction of acrylic monomers on macromolecular radical, make a certain amount of acrylic acid of daiamid-6 fiber surface grafting course of reaction.
(2) the copolymer chloride process of step (1): the copolymer getting step (1), in flask, adds 30ml thionyl chloride, heats at 70 DEG C, stirs, and backflow 12h, has reacted rear taking-up product, vacuumize at 30 DEG C.As shown in Figure 4, the carboxylic group of daiamid-6 fiber surface grafting is by chloride for course of reaction.
(3) reaction of step (2) product and p-phenylenediamine (PPD): get 0.5g p-phenylenediamine (PPD) and be dissolved in 30ml benzene, within the 15s time in right amount and its surface sprayed equably in step (2), at 40 DEG C, vacuumize is to constant weight.As shown in Figure 5, the carboxyl of daiamid-6 fiber surface grafting is reacted with p-phenylenediamine (PPD) by after chloride course of reaction, creates aniline activated centre.
(4) product of step (3) carries out home position polymerization reaction in aniline monomer solution: in beaker, add 150ml water, 5ml hydrochloric acid, 10ml aniline monomer, then the product of step (3) is put into mixed solution, 15g Ammonium Persulfate 98.5 is added after stirring 2h, reaction 2h, aniline, at polyamide surface in-situ polymerization, forms the covalently bound fibrous conductive material of polyamide 6/polyaniline, is labeled as sample A.As described in Figure 6, aniline monomer for growing point, becomes polyaniline at daiamid-6 fiber in situ Polymerization with the activated centre of chemical oxidising polymerisation to course of reaction.
As a comparison, according to document (OhKW, KimSH, KimE.Improvedsurfacecharacteristicsandtheconductivityofp olyaniline – nylon6fabricsbyplasmatreatment [J] .JournalofAppliedPolymerScience, 2001,81 (3): 684-694.) the nylon 6/ polyaniline complex fiber material prepared of method, is labeled as sample B.Test the unmodified nylon of 5cm length, the electric conductivity of sample A and sample B and surface friction property at identical conditions.The resistance of unmodified nylon 6 fiber is 10
12Ω; The sheet resistance of sample B is 10
8Ω, 5 the rear surface resistance that rub are 10
12Ω; The sheet resistance of sample A is 10
6Ω, 5 the rear surface resistance that rub are 10
6Ω, 50 the rear surface resistance that rub are 10
8Ω.Result shows, the present invention, by the polyamide 6/layer/polyaniline conductive complex fiber material of covalent bonds, has desirable electric conductivity and interface bond strength.
Embodiment 2:
(1) surface modification of polyamide 66 textile article: add 50ml water in flask; 20ml cyclohexane, 2cm × 2cm polyamide 66 fabric, 0.6g dibenzoyl peroxide; nitrogen protection; then flask is placed in 80 DEG C of constant temperature oil baths, adds 3g acrylic monomers, carry out the surface grafting acrylic acid reaction 3h of polyamide; after having reacted; graft is put into 50 DEG C of baking ovens, be dried to constant weight, obtain pure polyamide 66 fabric grafted propylene acid copolymer.
(2) copolymer of step (1) carries out chloride process: the copolymer getting step (1), in flask, adds 35ml thionyl chloride, is heated to 70 DEG C, 12h, product at 30 DEG C vacuumize to constant weight.
(3) product of step (2) and p-phenylenediamine (PPD) react: get 0.5g p-phenylenediamine (PPD) and be dissolved in 30ml hexane, the product of step (2) is immersed above-mentioned solution 10min, and take out, at 50 DEG C, vacuumize is to constant weight.
(4) home position polymerization reaction of step (3) product in aniline monomer solution: add 150ml water in beaker, 4.5ml hydrochloric acid, 5ml aniline monomer, then step (3) product is put into mixed solution, 15g ammonium persulfate is added after stirring 2h, reaction 3h, aniline at polyamide surface in-situ polymerization, formed polyamide 66/polyaniline covalency in conjunction with conductive fabric.
Performance test:
The surface resistivity of unmodified nylon66 fiber fabric is 10
14Ω cm, the nylon66 fiber/polyaniline surface resistivity of modification of the present invention is 10
6Ω m, the resistivity after 5 times that rubs is 10
6Ω m, the resistivity after 50 times that rubs is 10
7Ω m.Result shows, the polyamide 66 by covalent bonds/layer/polyaniline conductive composite fabric material obtained after surface modification, has desirable electric conductivity and interface bond strength.
Embodiment 3:
(1) surface modification of polyamide 610 resin particle goods: add 100ml water in flask; 3g polyamide 610 resin particle; 1g potassium permanganate; 1ml sulfuric acid; nitrogen protection; then flask is placed in 60 DEG C of constant temperature oil baths; add 5g acrylic monomers; carry out the surface grafting acrylic acid copolymer reaction 4h of polyamide; graft product apparatus,Soxhlet's is extracted 3h; graft after process is put into baking oven and is dried to constant weight in 60 DEG C, obtain pure polyamide 610 resin grafted propylene acid copolymer.
(2) the chloride process of the copolymer of step (1): the copolymer getting step (1), in flask, adds 40ml thionyl chloride, heats at 70 DEG C, stirs, and backflow 24h, has reacted rear taking-up product, vacuumize at 40 DEG C.
(3) reaction of step (2) product and p-phenylenediamine (PPD): by the product of step (2), is dissolved in the 30ml benzole soln of 0.5g p-phenylenediamine (PPD), and after 10min, at 50 DEG C, vacuumize is to constant weight.
(4) home position polymerization reaction of step (3) product in aniline monomer solution: add 150ml water in beaker, 5ml hydrochloric acid, 6ml aniline monomer, then step (3) product is put into mixed solution, add 25g hydrogen peroxide, reaction 3h, obtains aniline and forms the covalently bound resin conductive material of polyamide 610/polyaniline at polyamide surface in-situ polymerization.
Performance test: the resistivity of unmodified NYLON610 resin is 10
12Ω cm, the surface resistivity of polyamide 610/polyaniline of the present invention is 10
6Ω cm, 5 the rear surface resistivity that rub are 10
6Ω cm, 50 the rear surface resistivity that rub are 10
7Ω cm.Result shows, the polyamide 610 by covalent bonds/layer/polyaniline conductive composite resin material obtained after surface modification, has desirable electric conductivity and interface bond strength.
Embodiment 4:
(1) surface modification of polyamide 6 board product: add 100ml water in flask; 3g polyamide 6 sheet material; 0.5g potassium peroxydisulfate and 4ml sulfuric acid; nitrogen protection, is placed in 70 DEG C of constant temperature oil baths, adds 10g acrylic monomers by flask; carry out the surface grafting acrylic acid copolymer reaction 4h of polyamide; graft product apparatus,Soxhlet's is extracted 3h, and graft puts into 60 DEG C of oven dryings to constant weight, obtains pure polyamide 6 sheet material grafted propylene acid copolymer.
(2) the chloride process of the copolymer of step (1): the copolymer getting step (1), in flask, adds 40ml thionyl chloride, heats at 70 DEG C, stirs, and backflow 24h, has reacted rear taking-up product, vacuumize at 40 DEG C;
(3) product of step (2) and the reaction of p-phenylenediamine (PPD): by the product of step (2), be dissolved in the 25ml toluene solution of 0.5g p-phenylenediamine (PPD), take out after 8min, at 60 DEG C, vacuumize is to constant weight;
(4) home position polymerization reaction of step (3) product in aniline monomer solution: add 200ml water in beaker, 3ml nitric acid, 6ml aniline monomer, then step (3) product is put into mixed solution, 18g iron chloride is added after stirring at room temperature 2h, reaction 3h, aniline, at polyamide surface in-situ polymerization, forms polyamide 6/polyaniline sheet material conductive material.
The surface resistivity of composite is 10
6Ω cm, 5 the rear surface resistivity that rub are 10
6Ω cm, 50 the rear surface resistivity that rub are 10
8Ω cm.Result shows, the polyamide 6 by covalent bonds/layer/polyaniline conductive composite board material obtained after surface modification, has desirable electric conductivity and interface bond strength.
Embodiment 5:
(1) surface modification of polyamide 1010 sheet material products: add 100ml water in flask; 3g polyamide 1010 sheet material; 1ml hydrogen peroxide and 2g ferrous sulfate; nitrogen protection; then flask is placed in 70 DEG C of constant temperature oil baths; add 10ml acrylic monomers, carry out the surface grafting acrylic acid reaction 4h of polyamide, graft is put into baking oven and be dried to permanent quality in 60 DEG C and obtain pure polyamide 1010 sheet material grafted propylene acid copolymer.
(2) the chloride process of step (1) copolymer: the copolymer getting step (1), in flask, adds 40ml thionyl chloride, heats at 70 DEG C, stirs, and backflow 20h, has reacted rear taking-up product, vacuumize at 40 DEG C.
(3) reaction of step (2) product and p-phenylenediamine (PPD): get 0.5g p-phenylenediamine (PPD) and be dissolved in 30ml toluene, the product of step (2) is dissolved in this solution, 25min, and at 60 DEG C, vacuumize is to constant weight.
(4) home position polymerization reaction of step (3) product in aniline monomer solution: add 200ml water in beaker, 5ml formic acid, 6ml aniline monomer, then the product of step (3) is put into mixed solution, 17g iron chloride is added after stirring 2h, reaction 3h, aniline, at polyamide surface in-situ polymerization, forms polyamide 1010/polyaniline sheet material conductive material.
The resistivity of unmodified nylon 1010 sheet material is 10
12Ω cm, the surface resistivity of modified polyamide 1010/polyaniline is 10
6Ω cm, 5 the rear surface resistivity that rub are 10
6Ω cm, 50 the rear surface resistivity that rub are 10
8Ω cm.Result shows, the polyamide 1010 by covalent bonds/layer/polyaniline conductive compound sheet material obtained after surface modification, has desirable electric conductivity and interface bond strength.
Embodiment 6:
(1) in flask, 100ml water is added, 0.5g nylon 66 fiber, 1g potassium permanganate, 1ml sulfuric acid, add 5g acrylic monomers, 60 DEG C of constant temperature carry out polyamide surface grafted propylene acid reaction 4h, and then graft product is placed in baking oven and is dried to constant weight in 60 DEG C and obtains pure nylon 66 fiber graft acrylic acid, surface topography as shown in Figure 8.
(2) the chloride process of step (1) copolymer: the copolymer getting step (1), in flask, adds 40ml thionyl chloride, reflux at 70 DEG C 24h, reacted rear taking-up product, vacuumize at 40 DEG C;
(3) reaction of step (2) product and p-phenylenediamine (PPD): get 0.5g p-phenylenediamine (PPD) and be dissolved in 30ml benzene, appropriate and spray in step (2) its surface uniformly within the 20s time, then immediately at 70 DEG C vacuumize to constant weight;
(4) home position polymerization reaction of step (3) product in aniline monomer solution: add 150ml water in beaker, 5ml hydrochloric acid, 6ml aniline monomer, then step (3) product is put into mixed solution, ice bath, the hydrogen peroxide of 15ml30% is added after 2h, reaction 3h, aniline forms the covalently bound conductive fiber material of nylon66 fiber/polyaniline at nylon fiber in situ Polymerization, and surface topography as shown in Figure 9.
Performance test:
The surface resistivity of unmodified nylon 66 fiber is 10
14Ω cm, the nylon66 fiber/polyaniline surface resistivity of modification of the present invention is 10
6Ω cm, the resistivity after 5 times that rubs is 10
6Ω cm, the resistivity after 50 times that rubs is 10
7Ω cm.Result shows, the polyamide 66 by covalent bonds/layer/polyaniline conductive composite fabric material obtained after surface modification, has desirable electric conductivity and interface bond strength.
Although described above is the embodiment of polyamide/polyaniline composite material and preparation method thereof; but; under above-mentioned instruction of the present invention; those skilled in the art can carry out various improvement and distortion on the basis of above-described embodiment, and these improve or distortion drops in protection scope of the present invention.It will be understood by those skilled in the art that specific descriptions are above to explain object of the present invention, not for limiting the present invention.Protection scope of the present invention is by claim and equivalents thereof.
Claims (9)
1. polyamide/polyaniline composite material and preparation method thereof, is characterized in that polyamide/polyaniline is by chemical bonds, comprises the steps:
A the surface modification of () polyamide: add solvent in flask, polyamide, initator, acrylic monomers, arrives polyamide surface by acrylic acid-grafted under nitrogen protection, washing is dry obtains pure polyamide grafts acrylic acid product;
B () acyl chloride reaction: the product getting step (a), in flask, adds thionyl chloride, is heated to 70 DEG C, backflow, stirs 30min-8h, has reacted rear taking-up product, vacuumize, obtained the polyamide grafts acrylic acid of chloride;
(c) acid chloride product grafting p-phenylenediamine (PPD): the product getting step (b), with p-phenylenediamine (PPD) solution reaction, product at 40-80 DEG C vacuumize to constant weight;
(d) aniline home position polymerization reaction: by dopant acid, aniline monomer, and the product of step (c) puts into water, initator is added after stirring, cause its surface in-situ polymerization of aniline in step (c), reaction 30min-10h, obtains polyamide/polyaniline composite material.
2. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that described polyamide refers to the class material by being aggregated into by amido link containing carboxyl and amino monomer, being commonly called as nylon.
3. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that the solvent described in step (a) is water, ethanol, ether, n-hexane, cyclohexane, acetone, benzene.
4. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, it is characterized in that the initator described in step (a) is dibenzoyl peroxide, potassium permanganate, ammonium persulfate, hydrogen peroxide/sulfuric acid ferrous system, potassium permanganate/sulfuric acid system, potassium peroxydisulfate/sulfuric acid system, dimethylamine/copper sulphate system, dimethylamine/copper nitrate system.
5. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, it is characterized in that the described chloride method of step (c), it comprises: by p-phenylenediamine (PPD) solution, in right amount and spray equably in step (b) its surface 10-1000s, vacuumize is to constant weight; Or by 1-30min in the solution of the product of step (b) immersion p-phenylenediamine (PPD), take out product, vacuumize is to constant weight.
6. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that the solvent of described p-phenylenediamine (PPD) solution is benzene, toluene, ethanol, ether, hexane.
7. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that the dopant acid described in step (d) is hydrochloric acid, sulfuric acid, formic acid, acetic acid, DBSA; Described initator is potassium peroxydisulfate, ammonium persulfate, iron chloride, potassium bichromate, hydrogen peroxide.
8. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that the mol ratio of the dopant acid described in step (d), aniline monomer, initator is 0.5:1:0.5-0.1:1:4.
9. a kind of polyamide/polyaniline composite material according to claim 1 and preparation method thereof, is characterized in that the polyamide/polyaniline composite material adopting the method in claim 1 to 8 described in arbitrary claim to prepare.
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