CN105506981B - A kind of polyamide/polyaniline composite material and preparation method thereof - Google Patents
A kind of polyamide/polyaniline composite material and preparation method thereof Download PDFInfo
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- CN105506981B CN105506981B CN201510967331.7A CN201510967331A CN105506981B CN 105506981 B CN105506981 B CN 105506981B CN 201510967331 A CN201510967331 A CN 201510967331A CN 105506981 B CN105506981 B CN 105506981B
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- 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
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- 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
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- 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
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- 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
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- 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
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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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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- 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
- D06M15/61—Polyamines polyimines
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/34—Polyamides
Abstract
The present invention relates to a kind of polyamide/polyaniline composite material and preparation method, it is characterized in that polyamide/polyaniline belongs to technical field of composite materials by chemical bonds.The present invention is first in polyamide article surface grafting acrylic acid, again by the acrylic acid chloride of grafting, then the activated centre for producing aniline chemical oxidising polymerisation is reacted with p-phenylenediamine, aniline monomer, into polyaniline, obtains a kind of polyamide and polyaniline with the conducing composite material of chemical bonds with this activated centre in-situ polymerization.The method not only increases the electric conductivity of polyamide article, and polyaniline and polyamide are combined with chemical bond, drastically increase both bond strengths.This method is applied to improve various polyamide polymers, and such as electric conductivity of resin, fiber, fabric, sheet material, sheet material can be used for the fields such as daily life, health care, intelligence sensor, weaving, clothes, military affairs, be with a wide range of applications.
Description
Technical field
The invention belongs to the preparation field of conducing composite material, more particularly to a kind of polyamide/layer/polyaniline conductive composite wood
Material and preparation method thereof.
Background technology：
Polyamide is also known as nylon, is one kind of consumption maximum in five large-engineering plastics, is also important composite fibre materials.
Conventional nylon can be obtained by diamines and diacid polycondensation, can be obtained not according to diamine is different with binary acid carbon number purpose
Same nylon product, and can be distinguished by by the numeral after nylon, last digit represents the carbon number of diamine, latter number
Word represents the carbon number (such as NYLON610) of binary acid；Also it can be obtained by lactams polycondensation or ring-opening polymerisation, according to its cellular construction
Contained carbon atom number can obtain different polyamide products (such as nylon 6).Polyamide applications are related to daily life and traffic
The every field such as transport, fishery, military project.It has excellent mechanical property and wear-resisting, oil resistant, solvent resistant, self-lubricating, corrosion resistant
Erosion and good processing characteristics etc..Although polyamide material superior performance, its electrical conductivity about 10-12S/m, with very high exhausted
Edge, easily occur electrostatic charge accumulation, can set off an explosion and fire when serious, thus polyamide article do not require nothing more than with compared with
High mechanical property it is also desirable to have anti-static function.In addition, polyamide is used in petroleum pipeline, electronic apparatus, auto parts machinery etc. is led
Higher is required to its antistatic behaviour during domain.Static resistant polyamide fiber, which is used for clothes industry, can improve snugness of fit；It is anti-quiet
Polyamides industrial yarn, cord fabric thread can be eliminated or reduced during tire, conveyer belt use because of the electrostatic that friction is produced；It is anti-quiet
Polyamides powdery paints can be sprayed at various product surfaces and improve safety in utilization.
Polyaniline has raw material cheap, convieniently synthesized as a kind of preferable conducting polymer and phenomenon of adulterating is unique, electric
Conductance is higher, have the advantages that good stability in atmosphere, it is considered to be one of most promising conducting polymer.With poly-
Aniline is that raw material prepares conductive material, can not only obtain excellent lasting electric conductivity, additionally it is possible to by changing acid concentration of adulterating
Mode adjusts the electrical conductivity of polyaniline.Polyaniline also has the property such as excellent optical property, chemical property and electromagnetic wave absorption concurrently
Can, all there is extremely wide application prospect in a variety of research fields, polyamide can be solved with high-efficient simple using polyaniline
The antistatic problem of material, polyaniline processing difficulties and the limited problem of application can be also solved simultaneously.
Can be conductive in one layer of polyamide surface formation in the method for polyamide material in situ Polymerization using aniline
Polyaniline, such as Kyung form the painting of electrically conductive polyaniline by in-situ polymerization on the surface of polyamide 6 (nylon 6) fiber
Layer, so as to improve electric conductivity (Oh K W, Kim S H, Kim E, the Improved surface of the fiber
characteristics and the conductivity of polyaniline–nylon 6 fabrics by plasma
Treatment [J], Journal of Applied Polymer Science, 2001,81 (3):684-694)；Gregory with
Fypro is matrix, and the excellent polyamide/polyaniline fiber of electric conductivity has been obtained using in-situ polymerization；
(Gregory R V, Kimbrell W C, Kuhn H H., Conductive textiles [J], Synthetic Metals,
1989,28(1):823-835)；Han Ke is clear etc. probed into different types of dopant acid to aniline on fabric in-situ polymerization into poly-
Aniline to electric conductivity influence (Han Keqing, Jinhui is fragrant, polyaniline/terylene conductive fabric adulterate again and scourability research
[J], synthetic fiber industry, 2002,25 (5):25-27).
But aniline is on polyamide in the research of in-situ polymerization at this stage, exist one it is serious the problem of：It is compound
Polyaniline is not strong enough in the adhesion of polyamide surface, and the conductive compositions of obtained polyamide/polyaniline composite material are not
It is wear-resisting, it is easy to fall off, it is easy to cause the forfeiture of polyamide compoiste material electric conductivity, shorten the useful life of material, these poles
The earth limits the practical application of polyamide/layer/polyaniline conductive material.Although researchers attempt using plasma, acidifying is carved
The surface modifying method such as polyamide is lost, to improve polyamide and the interface bond strength both polyaniline, but these sides are used
Polyamide/polyaniline composite material that method is obtained still mainly passes through physical absorption in polyaniline and polyamide interface
Effect is combined, and bond strength is difficult to meet the application of product in practice.
The content of the invention
Physisorption is relied solely on for both polyamide and polyaniline composite conducting material, is combined in interface strong
Degree is weak, causes obtained polyamide/layer/polyaniline conductive materials conductive composition not wear-resisting, the defect such as easy to fall off, and the present invention is provided
A kind of method that polyamide is combined with polyaniline with chemical covalent bonds, can efficiently solve this defect, obtain and combine jail
Solid polyamide polyaniline composite material.First in polyamide surface graft copolymerization acrylic acid, then by the third of graft copolymerization
Olefin(e) acid chloride, then makes it be reacted with p-phenylenediamine, produces the chain carrier of aniline chemical oxidising polymerisation, aniline monomer
In-situ polymerization is carried out with this activated centre, polyamide/polyaniline composite material by Covalent bonding together is obtained.Polyamide
By chemical bonds between polyaniline, the interface bond strength between polyaniline and polyamide is improved, is efficiently solved
The not strong defect of adhesion of the polyaniline on polyamide surface, improves electric conductivity, the wearability of conductive compositions of product
And durability, the service life of product is extended, with very high practical value.
The present invention is achieved by the following technical solutions：
(a) surface of polyamide article is modified：Add solvent into flask, polyamide, initiator, acrylic monomers,
Polyamide surface is grafted under nitrogen protection, washing is dried to obtain the product of pure polyamide grafts acrylic acid；
(b) acyl chloride reaction of polyamide grafts acrylic acid：The product of step (a) is taken in flask, thionyl chloride is added,
70 DEG C are heated to, backflow stirs 30min-8h, product is taken out after the completion of reaction, is dried in vacuo, and the polyamide for obtaining chloride connects
Branch acrylic acid；
(c) acid chloride product grafting p-phenylenediamine：There are two methods to realize that acid chloride product is grafted p-phenylenediamine.One kind is
Spray process, it is appropriate and equably spray in step (b) its surface 10-1000s by p-phenylenediamine solution, it is dried under vacuum to perseverance
Weight；Another is immersion method, is that the product of step (b) is immersed in into 1-30min in the solution of p-phenylenediamine, takes out product, very
Sky is dried to constant weight；
(d) home position polymerization reaction：The product of dopant acid, aniline monomer, and step (c) is put into water, added after stirring
Enter initiator, trigger aniline to obtain polyamide/polyaniline composite material in its surface in-situ polymerization of step (c).
It is a further object of the present invention to provide a kind of composite of polyamide/polyaniline, this composite is to pass through
It is prepared by above-mentioned steps (a), (b), (c) and (d).
Polyamide material described in step (a) refers to aggregate into by amido link by the monomer containing carboxyl and amino
A class material, be commonly called as nylon, its product includes but is not limited to be any in the resin of polyamide, fiber, sheet material, sheet material
Kind；Described solvent is water, ethanol, ether, n-hexane, hexamethylene, acetone, benzene；Described initiator can be but not limited to
It is dibenzoyl peroxide, potassium permanganate, the ammonium persulfate in hot initiator system, also includes but is not limited to be redox system
In the ferrous system of hydrogen peroxide/sulfuric acid, potassium permanganate/sulfuric acid system, potassium peroxydisulfate/sulfuric acid system, dimethylamine/copper sulphate body
System, dimethylamine/copper nitrate system.
The solvent used in p-phenylenediamine solution described in step (c) is benzene, toluene, ethanol, ether, hexane.
Dopant acid described in step (d) is hydrochloric acid, sulfuric acid, formic acid, acetic acid, DBSA；Initiator is over cure
Sour potassium, ammonium persulfate, iron chloride, potassium bichromate, hydrogen peroxide；Dopant acid, aniline monomer, the molar ratio of initiator are 0.5:
1:0.5-0.1:1:4。
A kind of preparation method of described polyamide/polyaniline composite material, in-situ polymerization described in step (d)
Polymerization time is 30min-10h.
Advantages of the present invention：
(1) by the graft product chloride of polyamide and acrylic acid, then reacted with p-phenylenediamine, obtain aniline chemistry
The activated centre of oxidation polymerization so that aniline polymerize by growing point of this activated centre, obtains the polyamide of chemical bonds/poly-
Aniline conducing composite material.
(2) polyamide/polyaniline that the present invention is provided solves polyamide and polyaniline is relied solely on Covalent bonding together
Physical absorption, the weak shortcoming of bond strength, makes conducing composite material more durable therebetween.
(3) present invention is applied to improve leading for all kinds of polyamide material such as materials such as resin, sheet material, sheet material, fiber, fabric
Electrical property and capability of electromagnetic shielding, using quite varied.
(4) present invention has no particular/special requirement to Preparation equipment, easily realizes, has broad application prospects.
Brief description of the drawings
Further detailed description is done to the present invention below in conjunction with the accompanying drawings.Accompanying drawing 1-6 is described with benzoyl peroxide
(BPO) it is initiator, polyamide 6 is exemplified by polyamide article, polyamide 6 produces aniline chemical oxidation after series reaction
The course of reaction of the activated centre of polymerization and aniline using activated centre as growth point progress in-situ polymerization.Fig. 7-9 is with nylon66 fiber
Exemplified by fiber, during polyamide/polyaniline composite material is prepared, fiber different stage surface topographies change, its
In：
Fig. 1 is that initiator benzoyl peroxide is produced benzoic acid free radical by thermal decomposition and phenyl radical is chemically reacted
Formula.
Fig. 2 is the chemical equation that initiator free radical triggers polyamide 6 generation macromolecular radical.
Fig. 3 is the chemical equation of polyamide 6 macromolecular radical grafted propylene acid.
Fig. 4 is the acyl chloride reaction formula of polyamide 6 grafted propylene acid.
Fig. 5 is the chemical equation that polyamide 6 grafted polyacrylic acid acid chloride product reacts with p-phenylenediamine.
Fig. 6 is chemical equation of the aniline monomer in 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.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1：
(1) surface of daiamid-6 fiber product is modified：45ml water, 15ml n-hexanes, 1g polyamide 6s are added into flask
Then flask is placed in 80 DEG C of constant temperature oil baths, adds 3g acrylic acid lists by fiber, 0.5g dibenzoyl peroxides, nitrogen protection
Body, the reaction of the surface grafting acrylic acid of progress polyamide, 2h, after the completion of reaction, fiber rinses 30min with boiling water, is put into baking
Case obtains pure daiamid-6 fiber grafted propylene acid copolymer to constant weight in 60 DEG C of dryings.Course of reaction such as Fig. 1-Fig. 3 institutes
Show, dibenzoyl peroxide is thermally decomposed, daiamid-6 fiber is produced macromolecular radical, trigger acrylic monomers dividing greatly
Graft reaction on sub- free radical, makes a certain amount of acrylic acid of daiamid-6 fiber surface grafting.
(2) the copolymer chloride processing of step (1)：The copolymer of step (1) is taken in flask, 30ml dichloros are added sub-
Sulfone, is heated at 70 DEG C, stirring, and flow back 12h, is taken out and is dried in vacuo at product, 30 DEG C after the completion of reaction.Course of reaction such as Fig. 4 institutes
Show, the carboxylic group of daiamid-6 fiber surface grafting is by chloride.
(3) reaction of step (2) product and p-phenylenediamine：0.5g p-phenylenediamine is taken to be dissolved in 30ml benzene, within the 15s times
Spray in right amount and equably and be dried under vacuum to constant weight at its surface in step (2), 40 DEG C.Course of reaction is as shown in figure 5, poly-
The carboxyl of the fiber surface of acid amides 6 grafting is reacted after chloride with p-phenylenediamine, generates aniline activated centre.
(4) product of step (3) carries out home position polymerization reaction in aniline monomer solution：150ml water is added in beaker,
The product of step (3), is then put into mixed solution by 5ml hydrochloric acid, 10ml aniline monomers, and 15g persulfuric acid is added after stirring 2h
Amine, reacts 2h, and aniline forms the covalently bound fibrous conductive material of polyamide 6/polyaniline in polyamide surface in-situ polymerization,
Labeled as sample A.As described in Figure 6, aniline monomer is using the activated centre of chemical oxidising polymerisation as growing point, in polyamides for course of reaction
The fiber surface in-situ polymerization of amine 6 is into polyaniline.
As a comparison, according to document (Oh K W, Kim S H, Kim E.Improved surface
characteristics and the conductivity of polyaniline–nylon 6 fabrics by plasma
treatment[J].Journal of Applied Polymer Science,2001,81(3):684-694.) method preparation
The polyaniline complex fiber material of nylon 6/, labeled as sample B.Unmodified nylon, the sample of 5cm length are tested under the same conditions
Product A and sample B electric conductivity and surface friction property.The resistance of unmodified nylon 6 fiber is 1012Ω；Sample B surface
Resistance is 108Ω, sheet resistance is 10 after rubbing 5 times12Ω；Sample A sheet resistance is 106Ω, sheet resistance after rubbing 5 times
For 106Ω, sheet resistance is 10 after rubbing 50 times8Ω.As a result show, polyamide 6/polyphenyl that the present invention passes through Covalent bonding together
Amine electrically conductive composite fibre material, with preferable electric conductivity and interface bond strength.
Embodiment 2：
(1) surface of polyamide 66 textile article is modified：50ml water, 20ml hexamethylenes, 2cm × 2cm are added into flask
Then flask is placed in 80 DEG C of constant temperature oil baths, adds 3g by polyamide 66 fabric, 0.6g dibenzoyl peroxides, nitrogen protection
Acrylic monomers, carries out the surface grafting propylene acid reaction 3h of polyamide, after the completion of reaction, graft is put into 50 DEG C of baking ovens,
Dry to constant weight, obtain pure polyamide 66 fabric grafted propylene acid copolymer.
(2) copolymer of step (1) carries out chloride processing：The copolymer of step (1) is taken in flask, 35ml bis- is added
Chlorine sulfoxide, is heated to 70 DEG C, 12h, product is dried under vacuum to constant weight at 30 DEG C.
(3) product of step (2) reacts with p-phenylenediamine：0.5g p-phenylenediamine is taken to be dissolved in 30ml hexanes, by step (2)
Product immerse above-mentioned solution 10min, take out, constant weight be dried under vacuum at 50 DEG C.
(4) home position polymerization reaction of step (3) product in aniline monomer solution：150ml water is added in beaker,
Step (3) product, is then put into mixed solution by 4.5ml hydrochloric acid, 5ml aniline monomers, and 15g persulfuric acid is added after stirring 2h
Ammonium, reacts 3h, and aniline forms the covalent combination conductive fabric of polyamide 66/polyaniline in polyamide surface in-situ polymerization.
Performance test：
The surface resistivity of unmodified nylon66 fiber fabric is 1014Ω cm, the modified nylon66 fiber/polyaniline surface of the present invention
Resistivity is 106Ω m, resistivity is 10 after rubbing 5 times6Ω m, resistivity is 10 after rubbing 50 times7Ω·m.As a result table
It is bright, by the modified obtained polyamide 66/layer/polyaniline conductive composite fabric material by Covalent bonding together in surface, with reason
The electric conductivity and interface bond strength thought.
Embodiment 3：
(1) surface of polyamide 610 resin particle product is modified：100ml water, 3g polyamide 610 trees are added into flask
Then flask is placed in 60 DEG C of constant temperature oil baths, adds 5g acrylic acid by fat particle, 1g potassium permanganate, 1ml sulfuric acid, nitrogen protection
Monomer, carries out the surface grafting acrylic acid copolymer reaction 4h of polyamide, graft product is extracted into 3h with apparatus,Soxhlet's, will be handled
Graft afterwards is put into baking oven and dried in 60 DEG C to constant weight, obtains pure polyamide 610 resin grafted propylene acid copolymer.
(2) the chloride processing of the copolymer of step (1)：The copolymer of step (1) is taken in flask, 40ml dichloros are added
Sulfoxide, is heated at 70 DEG C, stirring, and flow back 24h, is taken out and is dried in vacuo at product, 40 DEG C after the completion of reaction.
(3) reaction of step (2) product and p-phenylenediamine：By the product of step (2), the 30ml of 0.5g p-phenylenediamine is dissolved in
In benzole soln, after 10min, constant weight is dried under vacuum at 50 DEG C.
(4) home position polymerization reaction of step (3) product in aniline monomer solution：150ml water, 5ml are added in beaker
Step (3) product, is then put into mixed solution by hydrochloric acid, 6ml aniline monomers, adds 25g hydrogen peroxide, reacts 3h, obtains
Aniline is in the polyamide surface in-situ polymerization formation covalently bound resin conductive material of polyamide 610/polyaniline.
Performance test：The resistivity of unmodified NYLON610 resin is 1012Ω cm, polyamide 610/polyphenyl of the invention
The surface resistivity of amine is 106Ω cm, surface resistivity is 10 after rubbing 5 times6Ω cm, surface resistivity is 10 after rubbing 50 times7
Ωcm.As a result show, tree is combined by the modified obtained polyamide 610/layer/polyaniline conductive by Covalent bonding together in surface
Fat material, with preferable electric conductivity and interface bond strength.
Embodiment 4：
(1) surface of polyamide 6 board product is modified：100ml water, 3g polyamide 6 sheet materials, 0.5g mistakes are added into flask
Potassium sulfate and 4ml sulfuric acid, nitrogen protection, flask is placed in 70 DEG C of constant temperature oil baths, adds 10g acrylic monomers, carries out polyamides
The surface grafting acrylic acid copolymer reaction 4h of amine, extracts 3h, graft is put into 60 DEG C of baking ovens by graft product with apparatus,Soxhlet's
Dry to constant weight, obtain pure polyamide 6 sheet material grafted propylene acid copolymer.
(2) the chloride processing of the copolymer of step (1)：The copolymer of step (1) is taken in flask, 40ml dichloros are added
Sulfoxide, is heated at 70 DEG C, stirring, and flow back 24h, is taken out and is dried in vacuo at product, 40 DEG C after the completion of reaction；
(3) reaction of the product and p-phenylenediamine of step (2)：By the product of step (2), 0.5g p-phenylenediamine is dissolved in
In 25ml toluene solutions, taken out after 8min, constant weight is dried under vacuum at 60 DEG C；
(4) home position polymerization reaction of step (3) product in aniline monomer solution：200ml water, 3ml are added in beaker
Step (3) product, is then put into mixed solution by nitric acid, 6ml aniline monomers, addition 18g iron chloride after 2h is stirred at room temperature, instead
3h is answered, aniline forms polyamide 6/polyaniline sheet material conductive material in polyamide surface in-situ polymerization.
The surface resistivity of composite is 106Ω cm, surface resistivity is 10 after rubbing 5 times6Ω cm, after rubbing 50 times
Surface resistivity is 108Ωcm.As a result show, by the modified obtained polyamide 6/polyphenyl by Covalent bonding together in surface
Amine conduction composite board material, with preferable electric conductivity and interface bond strength.
Embodiment 5：
(1) surface of polyamide 1010 sheet material products is modified：The addition 100ml water into flask, 3g polyamide 1010 sheet materials,
Flask, is then placed in 70 DEG C of constant temperature oil baths by 1ml hydrogen peroxide and 2g ferrous sulfate, nitrogen protection, adds 10ml acrylic acid
Monomer, carries out the surface grafting propylene acid reaction 4h of polyamide, and graft is put into baking oven obtains in 60 DEG C of drying to permanent quality
Pure polyamide 1010 sheet material grafted propylene acid copolymer.
(2) the chloride processing of step (1) copolymer：The copolymer of step (1) is taken in flask, 40ml dichloros are added sub-
Sulfone, is heated at 70 DEG C, stirring, and flow back 20h, is taken out and is dried in vacuo at product, 40 DEG C after the completion of reaction.
(3) reaction of step (2) product and p-phenylenediamine：0.5g p-phenylenediamine is taken to be dissolved in 30ml toluene, by step (2)
Product be dissolved in the solution, 25min is dried under vacuum to constant weight at 60 DEG C.
(4) home position polymerization reaction of step (3) product in aniline monomer solution：200ml water, 5ml are added in beaker
The product of step (3), is then put into mixed solution by formic acid, 6ml aniline monomers, and 17g iron chloride, reaction are added after stirring 2h
3h, aniline forms polyamide 1010/polyaniline sheet material conductive material in polyamide surface in-situ polymerization.
The resistivity of unmodified nylon 1010 sheet material is 1012Ω cm, the surface of modified polyamide 1010/polyaniline
Resistivity is 106Ω cm, surface resistivity is 10 after rubbing 5 times6Ω cm, surface resistivity is 10 after rubbing 50 times8Ωcm.Knot
Fruit shows, by the modified obtained polyamide 1010/layer/polyaniline conductive compound sheet material by Covalent bonding together in surface,
With preferable electric conductivity and interface bond strength.
Embodiment 6：
(1) 100ml water is added into flask, 0.5g nylon 66 fibers, 1g potassium permanganate, 1ml sulfuric acid adds 5g acrylic acid
Monomer, 60 DEG C of constant temperature carry out polyamide surface grafted propylene acid reaction 4h, and graft product then is placed in into baking oven in 60 DEG C of dryings
Pure nylon 66 fiber grafted propylene acid is obtained to constant weight, surface topography is as shown in Figure 8.
(2) the chloride processing of step (1) copolymer：The copolymer of step (1) is taken in flask, 40ml dichloros are added sub-
Sulfone, flow back at 70 DEG C 24h, takes out and is dried in vacuo at product, 40 DEG C after the completion of reaction；
(3) reaction of step (2) product and p-phenylenediamine：0.5g p-phenylenediamine is taken to be dissolved in 30ml benzene, within the 20s times
Appropriate and uniform spray is dried under vacuum to constant weight at 70 DEG C in step (2) its surface, immediately after；
(4) home position polymerization reaction of step (3) product in aniline monomer solution：150ml water, 5ml are added in beaker
Step (3) product, is then put into mixed solution, ice bath by hydrochloric acid, 6ml aniline monomers, and 15ml 30% peroxide is added after 2h
Change hydrogen, react 3h, aniline is in the nylon fiber in situ Polymerization formation covalently bound conductive fiber material of nylon66 fiber/polyaniline
Material, surface topography is as shown in Figure 9.
Performance test：
The surface resistivity of unmodified nylon 66 fiber is 1014Ω cm, the modified nylon66 fiber/polyaniline surface of the present invention
Resistivity is 106Ω cm, resistivity is 10 after rubbing 5 times6Ω cm, resistivity is 10 after rubbing 50 times7Ω·cm.As a result
Show, by the modified obtained polyamide 66/layer/polyaniline conductive composite fabric material by Covalent bonding together in surface, have
Preferable electric conductivity and interface bond strength.
Although described above is the embodiment of polyamide/polyaniline composite material and preparation method thereof, at this
Under the above-mentioned teaching of invention, those skilled in the art can carry out various improvement and deformation on the basis of above-described embodiment, and
These are improved or deformation is within the scope of the present invention.It will be understood by those skilled in the art that specific descriptions above
It is intended merely to explain the purpose of the present invention, is not intended to limit the present invention.Protection scope of the present invention is by claim and its waits
Jljl limits.
Claims (9)
1. a kind of preparation method of polyamide/polyaniline composite material, it is characterised in that polyamide/polyaniline passes through chemistry
Bond is closed, and is comprised the following steps：
（a）The surface of polyamide is modified：Solvent, polyamide, initiator, acrylic monomers, in nitrogen protection are added into flask
Lower to arrive polyamide surface by acrylic acid-grafted, washing is dried to obtain pure polyamide grafts acrylic acid product；
（b）Acyl chloride reaction：Take step（a）Product in flask, add thionyl chloride, be heated to 70 DEG C, flow back, stirring
Product is taken out after the completion of 30min-8h, reaction, is dried in vacuo, obtains the polyamide grafts acrylic acid of chloride；
（c）Acid chloride product is grafted p-phenylenediamine：Take step（b）Product, with p-phenylenediamine solution reaction, product is at 40-80 DEG C
Under be dried under vacuum to constant weight；
（d）Aniline home position polymerization reaction：By dopant acid, aniline monomer, and step（c）Product be put into water, after stirring plus
Enter initiator, trigger aniline in step（c）Its surface in-situ polymerization, react 30min-10h, obtain polyamide/polyaniline
Conducing composite material.
2. preparation method according to claim 1, wherein described polyamide refers to by the list containing carboxyl and amino
Body passes throughAmido linkThe class material aggregated into, is commonly called as nylon.
3. preparation method according to claim 1, it is characterised in that step（a）Described solvent be water, ethanol, ether,
N-hexane, hexamethylene, acetone, benzene.
4. preparation method according to claim 1, it is characterised in that step（a）Described initiator is diphenyl peroxide first
Acyl, potassium permanganate, ammonium persulfate, hydrogen peroxide/sulfuric acid ferrous iron system, potassium permanganate/sulfuric acid system, potassium peroxydisulfate/sulfuric acid body
System, dimethylamine/copper sulphate system, dimethylamine/copper nitrate system.
5. preparation method according to claim 1, it is characterised in that step (c) the chloride method, it includes：Will be right
Phenylenediamine solution, it is appropriate and equably spray in step（b）Its surface 10-1000 s, are dried under vacuum to constant weight；Either will
Step（b）Product immersion p-phenylenediamine solution in 1-30 min, take out product, be dried under vacuum to constant weight.
6. preparation method according to claim 1, it is characterised in that the solvent of described p-phenylenediamine solution is benzene, first
Benzene, ethanol, ether, hexane.
7. preparation method according to claim 1, it is characterised in that the dopant acid described in step (d) is hydrochloric acid, sulfuric acid, first
Acid, acetic acid, DBSA；Described initiator is potassium peroxydisulfate, ammonium persulfate, iron chloride, potassium bichromate, peroxidating
Hydrogen.
8. preparation method according to claim 1, it is characterised in that dopant acid, aniline monomer described in step (d), initiation
The mol ratio of agent is 0.5:1:0.5-0.1:1:4.
9. polyamide/layer/polyaniline conductive composite wood prepared by the method according to any claim in claim 1 to 8
Material.
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