CN102757642A - Preparation method of conductive nylon 66 composite material - Google Patents
Preparation method of conductive nylon 66 composite material Download PDFInfo
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- CN102757642A CN102757642A CN2011101146844A CN201110114684A CN102757642A CN 102757642 A CN102757642 A CN 102757642A CN 2011101146844 A CN2011101146844 A CN 2011101146844A CN 201110114684 A CN201110114684 A CN 201110114684A CN 102757642 A CN102757642 A CN 102757642A
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- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 29
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 73
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- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 57
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 229920000767 polyaniline Polymers 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000013067 intermediate product Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 21
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical group CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 20
- 239000003381 stabilizer Substances 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000004160 Ammonium persulphate Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 10
- GGHPAKFFUZUEKL-UHFFFAOYSA-M sodium;hexadecyl sulfate Chemical group [Na+].CCCCCCCCCCCCCCCCOS([O-])(=O)=O GGHPAKFFUZUEKL-UHFFFAOYSA-M 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000004927 fusion Effects 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 5
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- -1 polyoxyethylene octylphenol Polymers 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 3
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- 229920001778 nylon Polymers 0.000 abstract 2
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- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
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Abstract
The invention discloses a preparation method of a conductive nylon 66 composite material, comprising the following steps of: firstly sequentially mixing carbon nano tubes and phenylamine, stirring and ultrasonically homogenizing, then adding a co-stablizer to obtain a mixture, and then adding the mixture to an aqueous emulsifier solution, sequentially stirring and ultrasonically homogenizing to obtain a miniemulsion; then firstly adding an aqueous protonic acid solution to the miniemulsion, and then stirring to obtain a doped solution, then dripping an aqueous oxidant solution to the doped solution to obtain an intermediate product; then firstly carrying out centrifugalizing, washing and drying treatment on the intermediate product to obtain modified conductive carbon nano tube powder, and then melting the modified conductive carbon nano tube powder and nylons 66 and then mixing by using double screw rods and extruding to prepare the conductive nylon 66 composite material containing the nylons 66, polyaniline and the carbon nano tubes. The target product prepared by the method has good dispersity of the carbon nano tubes, high compatibility with a base body and wide conductivity regulating range and can be widely used for products of an automobile industry, an instrument shell, office equipment, and the like, which are easy to generate electrostatic hazards.
Description
Technical field
The present invention relates to a kind of preparation method of matrix material, especially a kind of preparation method of conducting electricity nylon 66 composite material.
Background technology
Nylon 66 (polyhexamethylene adipamide) is a kind of thermoplastic engineering plastic of excellent performance; In industrial circle and daily life, use very extensively, its Application Areas is from automobile, electronic apparatus, machinery, aerospace field to daily living article like silk stocking, clothing, carpet, fishing net etc.It has excellent mechanical property, electrical property and wear-resisting, oil resistant, anti-solvent, self-lubricating preferably, corrosion-resistant and good processing properties etc.Compare with nylon 6 (polycaprolactam), nylon 66 is applied even more extensively in automotive industry, Instrument shell and other and needs the product that shock resistance and HS require.Although the over-all properties of nylon 66 is superior, yet, because its high-ohmic that has, nylon 66 objects contacts or when rubbing with material with other materials, can produce that static is also continuous to be accumulated; Simultaneously, because the increase of surfaceness can strengthen the electrostatic accumulation, thereby cause the surface adsorption dust of nylon 66 goods, nylon 66 component in the office equipment even can produce spark and cause burning because static can cause damage to it.For further satisfying the requirement of market, need nylon 66 is carried out modification, to improve the electroconductibility of nylon 66 significantly to the nylon 66 material specialized property.
After the good electrochemical properties of carbon nanotube came to light, it had just served as packing material, and conductivity, mechanical property, the stability of matrix material are greatly improved.Numerous excellent properties of carbon nanotube make it in matrix material, play many-sided effect: superpower mechanical property can greatly be improved the intensity and the toughness of matrix material; The opto-electrical polymers matrix material that the specific conductivity that unique conduction and photoelectric properties can be improved polymer materials is novel with preparation; Its unique texture can prepare the one-dimensional nano-composite material of metal or MOX filling.Yet the carbon nanotube interfascicular has stronger Van der Waals force effect, makes carbon nanotube itself assemble bunchy easily, twines mutually, forms aggregate structure.In addition, carbon nano tube surface lacks polar group, and between polymeric matrix avidity very a little less than.
Based on above factor; People have made unremitting effort in order to obtain to conduct electricity nylon 66, like a kind of " preparation method of high-conductivity composition and preparation method thereof, molded article " who discloses among the disclosed Chinese invention patent Shen Qing Publication specification sheets CN 101624470A on January 13rd, 2010; This patent instruction book high-conductivity composition comprises modified carbon nano-tube and polymeric amide (can select nylon 66 for use as polymeric amide); The preparation method is for utilizing strong acid to carbon nano-tube modification earlier, it is scattered in to make compsn obtain high conductivity in the polymeric amide again.But, no matter be compsn, or its preparation method; All exist weak point, at first, use strong acid that carbon nanotube is carried out modification; The one, can cause great damage to carbon nanotube because of the deep-etching effect of strong acid, even carbon nanotube is blocked, advantage such as make the original high conductivity of carbon nanotube, intensity is big, rigidity is strong is destroyed or is lost; The 2nd, fail to overcome carbon nanotube and lack polar group because of its surface, and the very weak difficult problem of avidity between the polymeric matrix; Secondly, the preparation method fails to make the good dispersivity and the improved final product of the consistency between the matrix of carbon nanotube.For solving dispersion and the orientation problem of carbon nanotube in polymeric matrix, disclosed among the disclosed Chinese invention patent ublic specification of application CN 1410455A on April 16th, 2003 a kind of " preparation method of polymer/carbon nano-tube composite emulsion and in-situ emulsion polymerization thereof "; The raw material of composite emulsion wherein is monomer (optional aniline is as polymerization single polymerization monomer), carbon nanotube, water, tensio-active agent, initiator, pH regulator agent, and the preparation method adopts emulsion polymerization to come carbon nanotube is carried out modification.Yet; The also difficult people's will to the greatest extent of result, its cause is that letex polymerization is not the in-situ polymerization mode, can not guarantee that polyaniline is that template is carried out in-situ polymerization all the time with the carbon nanotube; Thereby realize the homodisperse of carbon nanotube, this perhaps is one of reason of not seeing in this patent application document the related data report.In addition, the preparation method is also more numerous and diverse, also nitrogen protection need be provided in the preparation process.
Summary of the invention
The technical problem that the present invention will solve is the limitation that overcomes above-mentioned various technical schemes, and the preparation method of the conduction nylon 66 composite material of the good dispersivity of the carbon nanotube in a kind of title product,, conductivity adjustment wide ranges high with the consistency of matrix is provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: the preparation method of conduction nylon 66 composite material comprises melt-blending process, and particularly completing steps is following:
Step 1; Be that 0.8～1.2: 0.8～1.2 ratio is mixed stirring and ultrasonic homogenizing at least behind 15min and the 10min, to wherein adding co-stabilizer, wherein successively according to mass ratio earlier with carbon nanotube and aniline; Mass ratio between co-stabilizer and the aniline is 0.8～1.2: 20～30; Obtain mixture, mixture is added in the emulsifier aqueous solution that concentration is 0.0075～0.0079mol/L stir successively and ultrasonic homogenizing 15min and 10min at least again, wherein; Mass ratio between the aniline in emulsifying agent and the mixture is 0.8～1.2: 20～30, obtains miniemulsion;
Step 2 stirs 10min at least behind the adding protonic acid aqueous solution earlier, wherein in miniemulsion; Mol ratio between the aniline in protonic acid and the miniemulsion is 0.8～1.2: 0.8～1.2, obtains the liquid that mixes, and in doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5～5.4mol/L; Wherein, Mol ratio between the aniline in oxygenant and the doping liquid is 0.8～1.2: 0.8～1.2, react 4h at least after, obtain intermediate product;
Step 3; Earlier middle product is carried out centrifugal, washing and exsiccant is handled; Obtain the modified carbon nano-tube conductive powder; Be to extrude with the twin screw blend after 1～10: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube.
As preparing method's the further improvement of conduction nylon 66 composite material, the pipe diameter of described carbon nanotube is that 10～30nm, pipe range are 2～30 μ m; Described co-stabilizer is a n-Hexadecane, or hexadecanol; Described emulsifying agent is a Sodium palmityl sulfate, or the hexadecyl Supragil GN, or polyoxyethylene octylphenol ether, or cetyl trimethylammonium bromide; Described protonic acid is a hydrochloric acid, or sulfuric acid, or phosphoric acid, or Witco 1298 Soft Acid; The concentration of described aqueous hydrochloric acid is 0.5～1.5mol/L; Described oxygenant is an ammonium persulphate, or hydrogen peroxide, or potassium permanganate; Rotating speed during described centrifugal treating is that 3000～5000r/min, time are 1～3min; Described carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively; Temperature during described drying treatment is that 70～90 ℃, time are 10～20h.
Beneficial effect with respect to prior art is; One of which; Use transmission electron microscope, X-ray diffractometer and four point probe resistivity tester to characterize respectively to the title product that makes; Can be known that by its result title product is the powder agglomates shape, it is 100: 1～10: 1～10 composition of proportions according to mass ratio by nylon 66, polyaniline and carbon nanotube; Wherein, for similar compatibility combines, be connected with conjugation between polyaniline and the carbon nanotube between nylon 66 and the polyaniline.The specific conductivity of title product is 10
-6～10
-13S/cm.Its two, preparing method's science, effectively, both having utilized polyaniline itself fully is conducting polymer; Has electroconductibility; And can not cause any damage, thereby make original performance of carbon nanotube destroyed or lose, bring into play the π-πGong Ezuoyong that exists between polyaniline and the carbon nanotube again effectively carbon nanotube; Come to improve significantly the dispersiveness of carbon nanotube; Utilized also that similar structure improves both consistencies widely between polyaniline and the nylon 66, more, guaranteed that it is that template is carried out in-situ polymerization from start to finish with the carbon nanotube that polyaniline is able to owing to adopted in-situ polymerization mode---fine emulsion polymerization; Thereby improved the dispersiveness of carbon nanotube widely, greatly strengthened the bonding force at interface between carbon nanotube and the nylon 66.In addition, polyaniline and carbon nanotube fully contacts the π-πGong Ezuoyong that has also promoted further between carbon nanotube outer wall and the polyaniline, the raising of the title product specific conductivity that is highly advantageous to.In addition; The co-stabilizer of introducing in the mini-emulsion polymerization system among the preparation method; The monomeric transporting action of inhibition is arranged; And processes such as emulsification, ultrasonic homogenizing have also been gone through in the preparation of miniemulsion, not only strengthened system stability, reduced the emulsifying agent consumption, also more help combining of carbon nanotube and polyaniline; Simultaneously, that the preparation method also has is simple to operate, reaction conditions is gentle, is suitable for the advantage of large-scale industrial production.
As the further embodiment of beneficial effect, the one, the pipe diameter of carbon nanotube is preferably 10～30nm, pipe range is preferably 2～30 μ m, is suitable for practical application generally; The 2nd, co-stabilizer is preferably n-Hexadecane, or hexadecanol, and emulsifying agent is preferably Sodium palmityl sulfate, or the hexadecyl Supragil GN; Or polyoxyethylene octylphenol ether, or cetyl trimethylammonium bromide, protonic acid is preferably hydrochloric acid; Or sulfuric acid, or phosphoric acid, or Witco 1298 Soft Acid; The concentration of aqueous hydrochloric acid wherein is preferably 0.5～1.5mol/L, and oxygenant is preferably ammonium persulphate, or hydrogen peroxide; Or potassium permanganate, not only make the source of raw material than horn of plenty, also make preparation technology more be prone to implement and flexibly; The 3rd, the rotating speed during centrifugal treating is preferably 3000～5000r/min, time and is preferably 1～3min, is easy to by isolating throw out in the intermediate product; The 4th, carrying out washing treatment is preferably uses the second alcohol and water respectively to clean respectively 3 times, is beneficial to the removal of impurity in the throw out; The 5th, the temperature during drying treatment is preferably 70～90 ℃, time and is preferably 10～20h, can under lower temperature, make the title product of higher quality with the short time.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 uses one of result that transmission electron microscope (TEM) characterizes to the modified carbon nano-tube conductive powder that obtains.Can find out that by this TEM photo the dispersiveness of carbon nanotube has obtained tangible improvement and not by brachymemma.
Fig. 2 uses one of result that transmission electron microscope characterizes to the section of the title product that makes.Can find out by this TEM photo, carbon nanotube dispersed very good, and formed fine and close conductive network each other.
Embodiment
At first buy or make with ordinary method from market:
The pipe diameter is that 10～30nm, pipe range are the carbon nanotube of 2～30 μ m; And as the n-Hexadecane and the hexadecanol of co-stabilizer; Sodium palmityl sulfate, hexadecyl Supragil GN, polyoxyethylene octylphenol ether and cetyl trimethylammonium bromide as emulsifying agent; As hydrochloric acid, sulfuric acid, phosphoric acid and the Witco 1298 Soft Acid of protonic acid, wherein, the concentration of aqueous hydrochloric acid is 0.5～1.5mol/L; Ammonium persulphate, hydrogen peroxide and potassium permanganate as oxygenant.
Then,
Embodiment 1
Step 1 is after 0.8: 1.2 ratio is mixed stirring and ultrasonic homogenizing 15min and 14min successively, to wherein adding co-stabilizer with carbon nanotube and aniline according to mass ratio earlier; Wherein, co-stabilizer is a n-Hexadecane, and the mass ratio between itself and the aniline is 0.8: 30, obtains mixture.Again mixture is added in the emulsifier aqueous solution that concentration is 0.0075mol/L and stir successively and ultrasonic homogenizing 15min and 14min; Wherein, emulsifying agent is a Sodium palmityl sulfate, and the mass ratio between the aniline in itself and the mixture is 0.8: 30, obtains miniemulsion.
Step 2 stirs 10min behind the adding protonic acid aqueous solution earlier in miniemulsion; Wherein, protonic acid is that concentration is the hydrochloric acid of 0.5mol/L, and the mol ratio between the aniline in itself and the miniemulsion is 0.8: 1.2, obtains the liquid that mixes.In doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5mol/L; Wherein, oxygenant is an ammonium persulphate, and the mol ratio between the aniline in itself and the doping liquid is 0.8: 1.2.Behind the reaction 4h, obtain intermediate product.
Step 3 is earlier carried out centrifugal, washing to middle product and exsiccant is handled; Wherein, the rotating speed during centrifugal treating is that 3000r/min, time are 3min, and carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively, and the temperature during drying treatment is that 70 ℃, time are 20h, obtains being similar to modified carbon nano-tube conductive powder shown in Figure 1.Be to extrude with the twin screw blend after 1: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make and be similar to the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube shown in Figure 2.
Embodiment 2
Step 1 is after 0.9: 1.1 ratio is mixed stirring and ultrasonic homogenizing 16min and 13min successively, to wherein adding co-stabilizer with carbon nanotube and aniline according to mass ratio earlier; Wherein, co-stabilizer is a n-Hexadecane, and the mass ratio between itself and the aniline is 0.9: 28, obtains mixture.Again mixture is added in the emulsifier aqueous solution that concentration is 0.0076mol/L and stir successively and ultrasonic homogenizing 16min and 13min; Wherein, emulsifying agent is a Sodium palmityl sulfate, and the mass ratio between the aniline in itself and the mixture is 0.9: 28, obtains miniemulsion.
Step 2 stirs 11min behind the adding protonic acid aqueous solution earlier in miniemulsion; Wherein, protonic acid is that concentration is the hydrochloric acid of 0.8mol/L, and the mol ratio between the aniline in itself and the miniemulsion is 0.9: 1.1, obtains the liquid that mixes.In doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5.1mol/L; Wherein, oxygenant is an ammonium persulphate, and the mol ratio between the aniline in itself and the doping liquid is 0.9: 1.1.Behind the reaction 4.5h, obtain intermediate product.
Step 3 is earlier carried out centrifugal, washing to middle product and exsiccant is handled; Wherein, the rotating speed during centrifugal treating is that 3500r/min, time are 2.5min, and carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively, and the temperature during drying treatment is that 75 ℃, time are 18h, obtains being similar to modified carbon nano-tube conductive powder shown in Figure 1.Be to extrude with the twin screw blend after 2.5: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make and be similar to the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube shown in Figure 2.
Embodiment 3
Step 1 is after 1: 1 ratio is mixed stirring and ultrasonic homogenizing 17min and 12min successively, to wherein adding co-stabilizer with carbon nanotube and aniline according to mass ratio earlier; Wherein, co-stabilizer is a n-Hexadecane, and the mass ratio between itself and the aniline is 1: 25, obtains mixture.Again mixture is added in the emulsifier aqueous solution that concentration is 0.0077mol/L and stir successively and ultrasonic homogenizing 17min and 12min; Wherein, emulsifying agent is a Sodium palmityl sulfate, and the mass ratio between the aniline in itself and the mixture is 1: 25, obtains miniemulsion.
Step 2 stirs 12min behind the adding protonic acid aqueous solution earlier in miniemulsion; Wherein, protonic acid is that concentration is the hydrochloric acid of 1mol/L, and the mol ratio between the aniline in itself and the miniemulsion is 1: 1, obtains the liquid that mixes.In doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5.2mol/L; Wherein, oxygenant is an ammonium persulphate, and the mol ratio between the aniline in itself and the doping liquid is 1: 1.Behind the reaction 5h, obtain intermediate product.
Step 3 is earlier carried out centrifugal, washing to middle product and exsiccant is handled; Wherein, the rotating speed during centrifugal treating is that 4000r/min, time are 2min, and carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively, and the temperature during drying treatment is that 80 ℃, time are 15h, obtains modified carbon nano-tube conductive powder as shown in Figure 1.Be to extrude with the twin screw blend after 5: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube as shown in Figure 2.
Embodiment 4
Step 1 is after 1.1: 0.9 ratio is mixed stirring and ultrasonic homogenizing 18min and 11min successively, to wherein adding co-stabilizer with carbon nanotube and aniline according to mass ratio earlier; Wherein, co-stabilizer is a n-Hexadecane, and the mass ratio between itself and the aniline is 1.1: 23, obtains mixture.Again mixture is added in the emulsifier aqueous solution that concentration is 0.0078mol/L and stir successively and ultrasonic homogenizing 18min and 11min; Wherein, emulsifying agent is a Sodium palmityl sulfate, and the mass ratio between the aniline in itself and the mixture is 1.1: 23, obtains miniemulsion.
Step 2 stirs 13min behind the adding protonic acid aqueous solution earlier in miniemulsion; Wherein, protonic acid is that concentration is the hydrochloric acid of 1.3mol/L, and the mol ratio between the aniline in itself and the miniemulsion is 1.1: 0.9, obtains the liquid that mixes.In doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5.3mol/L; Wherein, oxygenant is an ammonium persulphate, and the mol ratio between the aniline in itself and the doping liquid is 1.1: 0.9.Behind the reaction 5.5h, obtain intermediate product.
Step 3 is earlier carried out centrifugal, washing to middle product and exsiccant is handled; Wherein, the rotating speed during centrifugal treating is that 4500r/min, time are 1.5min, and carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively, and the temperature during drying treatment is that 85 ℃, time are 13h, obtains being similar to modified carbon nano-tube conductive powder shown in Figure 1.Be to extrude with the twin screw blend after 7.75: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make and be similar to the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube shown in Figure 2.
Embodiment 5
Step 1 is after 1.2: 0.8 ratio is mixed stirring and ultrasonic homogenizing 19min and 10min successively, to wherein adding co-stabilizer with carbon nanotube and aniline according to mass ratio earlier; Wherein, co-stabilizer is a n-Hexadecane, and the mass ratio between itself and the aniline is 1.2: 20, obtains mixture.Again mixture is added in the emulsifier aqueous solution that concentration is 0.0079mol/L and stir successively and ultrasonic homogenizing 19min and 10min; Wherein, emulsifying agent is a Sodium palmityl sulfate, and the mass ratio between the aniline in itself and the mixture is 1.2: 20, obtains miniemulsion.
Step 2 stirs 14min behind the adding protonic acid aqueous solution earlier in miniemulsion; Wherein, protonic acid is that concentration is the hydrochloric acid of 1.5mol/L, and the mol ratio between the aniline in itself and the miniemulsion is 1.2: 0.8, obtains the liquid that mixes.In doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5.4mol/L; Wherein, oxygenant is an ammonium persulphate, and the mol ratio between the aniline in itself and the doping liquid is 1.2: 0.8.Behind the reaction 6h, obtain intermediate product.
Step 3 is earlier carried out centrifugal, washing to middle product and exsiccant is handled; Wherein, the rotating speed during centrifugal treating is that 5000r/min, time are 1min, and carrying out washing treatment is respectively cleaned 3 times for using the second alcohol and water respectively, and the temperature during drying treatment is that 90 ℃, time are 10h, obtains being similar to modified carbon nano-tube conductive powder shown in Figure 1.Be to extrude with the twin screw blend after 10: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make and be similar to the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube shown in Figure 2.
Select n-Hexadecane or hexadecanol more respectively for use as co-stabilizer; Sodium palmityl sulfate or hexadecyl Supragil GN or polyoxyethylene octylphenol ether or cetyl trimethylammonium bromide as emulsifying agent; Hydrochloric acid or sulfuric acid or phosphoric acid or Witco 1298 Soft Acid as protonic acid; Ammonium persulphate or hydrogen peroxide or potassium permanganate as oxygenant; Repeat the foregoing description 1～5, made equally as or be similar to the conduction nylon 66 composite material of forming by conduction nylon 66, polyaniline and carbon nanotube shown in Figure 2.
Obviously, those skilled in the art can carry out various changes and modification to the preparation method of conduction nylon 66 composite material of the present invention and not break away from the spirit and scope of the present invention.Like this, belong within the scope of claim of the present invention and equivalent technologies thereof if of the present invention these are revised with modification, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. one kind conducts electricity the preparation method of nylon 66 composite material, comprises melt-blending process, it is characterized in that completing steps is following:
Step 1; Be that 0.8～1.2: 0.8～1.2 ratio is mixed stirring and ultrasonic homogenizing at least behind 15min and the 10min, to wherein adding co-stabilizer, wherein successively according to mass ratio earlier with carbon nanotube and aniline; Mass ratio between co-stabilizer and the aniline is 0.8～1.2: 20～30; Obtain mixture, mixture is added in the emulsifier aqueous solution that concentration is 0.0075～0.0079mol/L stir successively and ultrasonic homogenizing 15min and 10min at least again, wherein; Mass ratio between the aniline in emulsifying agent and the mixture is 0.8～1.2: 20～30, obtains miniemulsion;
Step 2 stirs 10min at least behind the adding protonic acid aqueous solution earlier, wherein in miniemulsion; Mol ratio between the aniline in protonic acid and the miniemulsion is 0.8～1.2: 0.8～1.2, obtains the liquid that mixes, and in doping liquid, dripping concentration again is the aqueous oxidizing agent solution of 5～5.4mol/L; Wherein, Mol ratio between the aniline in oxygenant and the doping liquid is 0.8～1.2: 0.8～1.2, react 4h at least after, obtain intermediate product;
Step 3; Earlier middle product is carried out centrifugal, washing and exsiccant is handled; Obtain the modified carbon nano-tube conductive powder; Be to extrude with the twin screw blend after 1～10: 100 the ratio fusion according to mass ratio with modified carbon nano-tube conductive powder and nylon 66 again, make the conduction nylon 66 composite material of forming by nylon 66, polyaniline and carbon nanotube.
2. the preparation method of conduction nylon 66 composite material according to claim 1, the pipe diameter that it is characterized in that carbon nanotube is that 10～30nm, pipe range are 2～30 μ m.
3. the preparation method of conduction nylon 66 composite material according to claim 1 is characterized in that co-stabilizer is a n-Hexadecane, or hexadecanol.
4. the preparation method of conduction nylon 66 composite material according to claim 1 is characterized in that emulsifying agent is a Sodium palmityl sulfate, or the hexadecyl Supragil GN, or polyoxyethylene octylphenol ether, or cetyl trimethylammonium bromide.
5. the preparation method of conduction nylon 66 composite material according to claim 1 is characterized in that protonic acid is a hydrochloric acid, or sulfuric acid, or phosphoric acid, or Witco 1298 Soft Acid.
6. the preparation method of conduction nylon 66 composite material according to claim 5, the concentration that it is characterized in that aqueous hydrochloric acid is 0.5～1.5mol/L.
7. the preparation method of conduction nylon 66 composite material according to claim 1 is characterized in that oxygenant is an ammonium persulphate, or hydrogen peroxide, or potassium permanganate.
8. the preparation method of conduction nylon 66 composite material according to claim 1, the rotating speed when it is characterized in that centrifugal treating is that 3000～5000r/min, time are 1～3min.
9. the preparation method of conduction nylon 66 composite material according to claim 1 is characterized in that carrying out washing treatment respectively cleans 3 times for using the second alcohol and water respectively.
10. the preparation method of conduction nylon 66 composite material according to claim 1, the temperature when it is characterized in that drying treatment are that 70～90 ℃, time are 10～20h.
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