CN101195709A - Method for producing high decentrality amido carbon nano-tube/nylon 66 composite material - Google Patents
Method for producing high decentrality amido carbon nano-tube/nylon 66 composite material Download PDFInfo
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Abstract
The invention relates to preparation method of aminated carbon nanotube with high dispersibility/nylon 66 composite material, which belongs to the material technology field. The preparation method comprises the following steps that firstly, acidification is performed to the carbon nanotube to produce carbon nanotube carried with a carboxyl group, and a series of surface modification is further performed to the carboxylated carbon nanotube, to prepare the amido carbon nanotube carried with the amine groups. The aminated carbon nanotube is polymerized with hexanediamine and adipic acid through the in-situ polymerization method, to ensure the amine groups on the carbon nanotube to take part in the polycondensation reaction, so as to obtain the required products. The invention improves the dispersilbility and the interface bonding force of the carbon nanotube in the nylon 66, and obtains the aminated carbon nanotube with good dispersion property/nylon 66 composite material.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material.
Background technology
Carbon nanotube has very excellent mechanical property, polymkeric substance such as the strength ratio common carbon fibers of carbon nanotube or glass fibre are used high 2～3 orders of magnitude of strongthener always, and toughness is very high, and therefore, carbon nanotube is the accurate one dimension lightweight of a matrix material ideal enhanced functional material.Constituting matrix material if carbon nanotube can add in some matrix equably, can greatly improve its performance, is matrix material ideal lightweight fortifying fibre.
Nylon 66 is one of morning, output maximum, most widely used kinds of exploitation in the nylon series product.It has physical strength height, characteristics that rigidity is big, is the principal item of engineering plastics, is usually used in production intensity height, wear-resisting, various trolley parts that self lubricity is good, mechanical part, electronic apparatus, wrapping material etc.Shortcomings such as but also there is low temperature in nylon 66 and the dry state shock strength is poor, water-intake rate is big, notched Izod impact strength is low.Study on the modification at these shortcomings is a lot, adopt nanoparticle to improve nylon 66 and obtained development at full speed, but the research of research carbon nanotube remodeling nylon 66 is few, only a few studies also concentrates on the method that adopts mechanical blending, the dispersiveness of carbon nanotube in matrix is not good, and performance improves limited.Present method adopts aminated carbon nanotube and hexanediamine, hexanodioic acid to carry out in-situ polymerization, improve the interface binding power of the dispersiveness of carbon nanotube in nylon matrix and enhancing carbon nanotube and nylon matrix, obtain the matrix material of polymolecularity, lay foundation for preparing high performance matrix material.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material.
The preparation method of the high decentrality amido carbon nano-tube/nylon 66 composite material that the present invention proposes, its concrete steps are as follows:
(1) be that 1～50nm, length are that the carbon nanotube of 0.1～50 μ m mixes with protonic acid with caliber, using ultra-sonic oscillation, reaction times down at 40 ℃～60 ℃ is 1～8h, products therefrom is neutral with washed with de-ionized water, oven dry promptly gets the acidifying carbon nanotube, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carbon nanotube
10～100 parts of protonic acids
(2) carbon nanotube after step (1) acidifying is mixed with protonic acid, use ultra-sonic oscillation down at 60 ℃～80 ℃, reaction times is 0.5～2h, products therefrom is neutral with washed with de-ionized water, evaporate to dryness under 40 ℃～100 ℃ temperature condition, obtain carboxylic carbon nano-tube, the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carbon nanotube after the acidifying
10～100 parts of protonic acids
(3) carboxylic carbon nano-tube that step (2) is made mixes with condensing agent, polyamine, reflux stirs under 100 ℃～150 ℃ temperature, reaction times is 12～96h, the products therefrom absolute ethanol washing, and under the ultra-sonic oscillation condition unnecessary amine, condensing agent and other by products of flush away, use filtering with microporous membrane, repeated washing (as 3～5 times), the carbon pipe that leaches is evaporate to dryness under 40 ℃～100 ℃ temperature condition, obtains aminated carbon nanotube, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carboxylic carbon nano-tube
10～30 parts of condensing agents
50～90 parts of polyamines
(4) aminated carbon nanotube and hexanediamine, the hexanodioic acid that step (3) is made is mixed with nylon salt, in nylon salt, add acetate, mix, under 190～200 ℃ of temperature, under 1.5～1.6Mpa, react 1～6h, obtain the matrix material prepolymer, with the prepolymer oven dry, carry out polycondensation, promptly get material requested, the consumption of acetate is the 0.5wt% of nylon salt, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
0.01～0.4 part of aminated carbon nanotube
20～50 parts of hexanediamines
20～50 parts of hexanodioic acids.
Among the present invention, described carbon nanotube comprises the single wall or the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over, template and the preparation of laser evaporation method, and caliber is 1～50nm, and length is 0.1～50 μ m, and acidified processing and purification process.
Among the present invention, described protonic acid be the vitriol oil, concentrated nitric acid, concentrated hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute hydrochloric acid, phosphoric acid, acetate or hydrogen peroxide one to several mixtures.
Among the present invention, described polyamine be quadrol, hexanediamine, mphenylenediamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, isophorone diamine, two (4-amino-3 first class cyclohexyl) methane, two (4-aminocyclohexyl) methane, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone or both-end amido oligopolymer etc. in any.
Among the present invention, described condensing agent adopts aliphatic carbon diimine type or aromatic series carbodiimide type condensing agent, aliphatic carbon diimine type condensing agent such as N ' N-dicyclohexylcarbodiimide (DCC), aromatic series carbodiimide type condensing agent such as DIC (N, N '-DIC) or 1-ethyl-3-dimethylamine propyl carbodiimide (EDC) medium one or more.
Advantage of the present invention is: carbon nanotube has amine groups through the chemically modified surface, can form amido linkage with hexanediamine, hexanodioic acid reaction, and ultrasonic dispersing and powerful dispersed with stirring have been passed through, therefore reduced the cluster phenomenon of carbon nanotube, improve the dispersiveness of carbon nanotube, and then obtained the good matrix material of dispersing property.The present invention is a purpose with the preparation high decentrality amido carbon nano-tube/nylon 66 composite material, earlier carbon nanotube is carried out finishing, make it carry amine groups, the polycondensation by amine groups participation nylon 66 improves the dispersing property of carbon nanotube in nylon matrix.
Description of drawings
Fig. 1 is embodiment 1 electron-microscope scanning figure.
Fig. 2 is embodiment 2 electron-microscope scanning figure.
Fig. 3 is embodiment 3 electron-microscope scanning figure.
Fig. 4 is embodiment 4 electron-microscope scanning figure
Fig. 5 is embodiment 5 electron-microscope scanning figure
Fig. 6 is comparative example 1 electron-microscope scanning figure.
Fig. 7 is comparative example 2 electron-microscope scanning figure.
Embodiment
Further specify the present invention below by embodiment, rather than limit the scope of the invention.
Embodiment 1:
The first step: the preparation of carboxylic carbon nano-tube
With caliber is 1～50nm, and length is that carbon nanotube 1g, vitriol oil 120ml and the concentrated nitric acid 40ml of 0.1～50 μ m mixes, at 40 ℃ of ultra-sonic oscillation 8h.After reaction is finished, remove nitration mixture and other by product with a large amount of deionized waters, be neutral with millipore filtration (diameter is 0.45 μ m) filtration until filtrate, oven dry obtains the acidifying carbon nanotube.Acidifying carbon nanotube 1g and vitriol oil 40ml and hydrogen peroxide 10ml are mixed, at 70 ℃ of ultra-sonic oscillation 0.5h.After reaction is finished, go out nitration mixture and other by product, filter until filtrate with millipore filtration (diameter is 0.45 μ m) and be neutrality, dry and obtain carboxylic carbon nano-tube with a large amount of deionized waters.
Second step: the preparation of aminated carbon nanotube
Carboxylic carbon nano-tube 1g, quadrol 150g and the dicyclohexylcarbodiimide 25g of above-mentioned preparation are mixed, at 120 ℃ of reflux 24h.After reaction is finished,, filter repeated washing 3 times with millipore filtration (diameter is 0.45 μ m) with unnecessary amine, DCC and other by product of the ultrasonic flush away of dehydrated alcohol.The carbon pipe that leaches is evaporate to dryness under 80 ℃ of temperature condition, obtains aminated carbon nanotube.
The 3rd step: aminated carbon nano-tube/nylon 66 composite material preparation
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing aminated multi-walled carbon nano-tubes 0.2726g according to 0.1% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, behind the ultra-sonic oscillation 0.5h it is added in solution of adipic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 200 ℃ gradually, under 1.5～1.6Mpa, react 2h, take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.Behind reaction 2.5h under this temperature, stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum 0.5h after 3 times so repeatedly, cool off matrix material.
Embodiment 2:
The first step: the preparation of carboxylic carbon nano-tube
With caliber is 1～50nm, and length is that carbon nanotube 1g, vitriol oil 120ml and the concentrated nitric acid 40ml of 0.1～50 μ m mixes, at 50 ℃ of ultra-sonic oscillation 4h.After reaction is finished, remove nitration mixture and other by product with a large amount of deionized waters, be neutral with millipore filtration (diameter is 0.45 μ m) filtration until filtrate, oven dry obtains the acidifying carbon nanotube.Acidifying carbon nanotube 1g and vitriol oil 40ml and hydrogen peroxide 10ml are mixed, at 60 ℃ of ultra-sonic oscillation 0.5h.After reaction is finished, go out nitration mixture and other by product, filter until filtrate with millipore filtration (diameter is 0.45 μ m) and be neutrality, dry and obtain carboxylic carbon nano-tube with a large amount of deionized waters.
Second step: the preparation of aminated carbon nanotube
Carboxylic carbon nano-tube 1g, quadrol 150g and the dicyclohexylcarbodiimide 25g of above-mentioned preparation are mixed, at 100 ℃ of reflux 96h.After reaction is finished,, filter repeated washing 3 times with millipore filtration (diameter is 0.45 μ m) with unnecessary amine, DCC and other by product of the ultrasonic flush away of dehydrated alcohol.The carbon pipe that leaches is evaporate to dryness under 40 ℃ of temperature condition, obtains aminated carbon nanotube.
The 3rd step: aminated carbon nano-tube/nylon 66 composite material preparation
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing aminated multi-walled carbon nano-tubes 1.363g according to 0.5% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, behind the ultra-sonic oscillation 0.5h it is added in solution of adipic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 200 ℃ gradually, under 1.5～1.6Mpa, react 4h, take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.Behind reaction 2.5h under this temperature, stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum half an hour so repeatedly after 3 times, cool off matrix material.
Embodiment 3:
The first step: the preparation of carboxylic carbon nano-tube
With caliber is 1～50nm, and length is that carbon nanotube 1g, vitriol oil 120ml and the concentrated nitric acid 40ml of 0.1～50 μ m mixes, at 50 ℃ of ultra-sonic oscillation 4h.After reaction is finished, remove nitration mixture and other by product with a large amount of deionized waters, be neutral with millipore filtration (diameter is 0.45 μ m) filtration until filtrate, oven dry obtains the acidifying carbon nanotube.Acidifying carbon nanotube 1g and vitriol oil 40ml and hydrogen peroxide 10ml are mixed, at 70 ℃ of ultra-sonic oscillation 0.5h.After reaction is finished, go out nitration mixture and other by product, filter until filtrate with millipore filtration (diameter is 0.45 μ m) and be neutrality, dry and obtain carboxylic carbon nano-tube with a large amount of deionized waters.
Second step: the preparation of aminated carbon nanotube
Carboxylic carbon nano-tube 1g, quadrol 150g and the dicyclohexylcarbodiimide 25g of above-mentioned preparation are mixed, at 150 ℃ of reflux 30h.After reaction is finished,, filter repeated washing 3 times with millipore filtration (diameter is 0.45 μ m) with unnecessary amine, DCC and other by product of the ultrasonic flush away of dehydrated alcohol.The carbon pipe that leaches is evaporate to dryness under 50 ℃ of temperature condition, obtains aminated carbon nanotube.
The 3rd step: aminated carbon nano-tube/nylon 66 composite material preparation
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing aminated multi-walled carbon nano-tubes 2.726g according to 1.0% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, ultra-sonic oscillation after half an hour add it in solution of adipic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 190 ℃ gradually, under 1.5～1.6Mpa, react 6h, take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.Behind reaction 2.5h under this temperature, stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum half an hour so repeatedly after 3 times, cool off matrix material.
Embodiment 4:
The first step: the preparation of carboxylic carbon nano-tube
With caliber is 1～50nm, and length is that carbon nanotube 1g, vitriol oil 120ml and the concentrated nitric acid 40ml of 0.1～50 μ m mixes, at 40 ℃ of ultra-sonic oscillation 4h.After reaction is finished, remove nitration mixture and other by product with a large amount of deionized waters, be neutral with millipore filtration (diameter is 0.45 μ m) filtration until filtrate, oven dry obtains the acidifying carbon nanotube.Acidifying carbon nanotube 1g and vitriol oil 40ml and hydrogen peroxide 10ml are mixed, at 60 ℃ of ultra-sonic oscillation 0.5h.After reaction is finished, go out nitration mixture and other by product, filter until filtrate with millipore filtration (diameter is 0.45 μ m) and be neutrality, dry and obtain carboxylic carbon nano-tube with a large amount of deionized waters.
Second step: the preparation of aminated carbon nanotube
Carboxylic carbon nano-tube 1g, quadrol 150g and the dicyclohexylcarbodiimide 25g of above-mentioned preparation are mixed, at 100 ℃ of reflux 24h.After reaction is finished,, filter repeated washing 3 times with millipore filtration (diameter is 0.45 μ m) with unnecessary amine, DCC and other by product of the ultrasonic flush away of dehydrated alcohol.The carbon pipe that leaches is evaporate to dryness under 100 ℃ of temperature condition, obtains aminated carbon nanotube.
The 3rd step: aminated carbon nano-tube/nylon 66 composite material preparation
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing aminated multi-walled carbon nano-tubes 2.726g according to 1.0% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, ultra-sonic oscillation after half an hour add it in solution of adipic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 190 ℃ gradually, under 1.5～1.6Mpa, react 4h, take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.Behind reaction 2.5h under this temperature, stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum half an hour so repeatedly after 3 times, cool off matrix material.
Embodiment 5
The first step: the preparation of carboxylic carbon nano-tube
With caliber is 1～50nm, and length is that carbon nanotube 1g, vitriol oil 120ml and the concentrated nitric acid 40ml of 0.1～50 μ m mixes, at 60 ℃ of ultra-sonic oscillation 4h.After reaction is finished, remove nitration mixture and other by product with a large amount of deionized waters, be neutral with millipore filtration (diameter is 0.45 μ m) filtration until filtrate, oven dry obtains the acidifying carbon nanotube.Acidifying carbon nanotube 1g and vitriol oil 40ml and hydrogen peroxide 10ml are mixed, at 80 ℃ of ultra-sonic oscillation 0.5h.After reaction is finished, go out nitration mixture and other by product, filter until filtrate with millipore filtration (diameter is 0.45 μ m) and be neutrality, dry and obtain carboxylic carbon nano-tube with a large amount of deionized waters.
Second step: the preparation of aminated carbon nanotube
Carboxylic carbon nano-tube 1g, quadrol 150g and the dicyclohexylcarbodiimide 25g of above-mentioned preparation are mixed, at 150 ℃ of reflux 12h.After reaction is finished,, filter repeated washing 3 times with millipore filtration (diameter is 0.45 μ m) with unnecessary amine, DCC and other by product of the ultrasonic flush away of dehydrated alcohol.The carbon pipe that leaches is evaporate to dryness under 50 ℃ of temperature condition, obtains aminated carbon nanotube.
The 3rd step: aminated carbon nano-tube/nylon 66 composite material preparation
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing aminated multi-walled carbon nano-tubes 2.726g according to 1.0% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, ultra-sonic oscillation after half an hour add it in solution of adipic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 200 ℃ gradually, under 1.5～1.6Mpa, react 3h, take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.Behind reaction 2.5h under this temperature, stop logical N
2Vacuumize.Have bubble to produce the back and continue logical N2 and stir, keep vacuum half an hour so repeatedly after 3 times, cool off matrix material.
Comparative example 1:
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 200 ℃ gradually, under 1.5～1.6Mpa, react 2h (two hours), take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.React under this temperature 2.5h (hour) after stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum half an hour so repeatedly after 3 times, cool off nylon 66.
Comparative example 2:
The hexanodioic acid 176g and the hexanediamine 140g that mol ratio such as get are dissolved in the dehydrated alcohol respectively.Take by weighing not modified multi-walled carbon nano-tubes 2.726g according to 1.0% of nylon 66 total amounts that make after the polycondensation, be ground into fine powder, be dissolved in the dehydrated alcohol, ultra-sonic oscillation after half an hour add it in hexanodioic acid behind the uniform mixing.Hexanediamine solution is slowly added in the solution of adipic acid, leave standstill cooling back suction filtration and obtain nylon salt, dried for standby.Nylon salt is made into 50% the aqueous solution, adds molecular weight regulator acetate.After mixing it is added in the autoclave, be warmed up to about 200 ℃ gradually, under 1.5～1.6Mpa, react 2h (two hours), take out prepolymer, 100 ℃ of oven dry.Prepolymer is added in the there-necked flask N
2Protection slowly is warmed up to 270～280 ℃ down.React under this temperature 2.5h (hour) after stop logical N
2Vacuumize.Do not have bubble to produce the back and continue logical N
2Stir, keep vacuum half an hour so repeatedly after 3 times, cool off the unmodified carbon nano-tube/nylon 66 composite material.
Subordinate list 1: the light transmission of matrix material formic acid solution is (T=50d) relatively
| The matrix material formic acid solution | Transmittance/% | |
| λ＝480nm | λ＝ | |
| Embodiment | ||
| 1 | 34.8 | 40.8 |
| Embodiment 2 | 2.0 | 4.3 |
| Embodiment 3 | 0 | 0 |
| Embodiment 4 | 0 | 0 |
| Embodiment 5 | 0 | 0 |
| Comparative example 1 | 78.2 | 92.1 |
| Comparative example 2 | 2.5 | 5 |
Claims (5)
1. the preparation method of a high decentrality amido carbon nano-tube/nylon 66 composite material is characterized in that concrete steps are as follows:
(1) be that 1～50nm, length are that the carbon nanotube of 0.1～50 μ m mixes with protonic acid with caliber, using ultra-sonic oscillation, reaction times down at 40 ℃～70 ℃ is 1～8h, products therefrom is neutral with washed with de-ionized water, oven dry promptly gets the acidifying carbon nanotube, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carbon nanotube
10～100 parts of protonic acids
(2) carbon nanotube after step (1) acidifying is mixed with protonic acid, use ultra-sonic oscillation down at 50 ℃～80 ℃, reaction times is 0.5～2h, products therefrom is neutral with washed with de-ionized water, evaporate to dryness under 40 ℃～100 ℃ temperature condition, obtain carboxylic carbon nano-tube, the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carbon nanotube after the acidifying
10～100 parts of protonic acids
(3) carboxylic carbon nano-tube that step (2) is made mixes with condensing agent, polyamine, reflux stirs under 50 ℃～150 ℃ temperature, reaction times is 12～96h, the products therefrom absolute ethanol washing, and under the ultra-sonic oscillation condition unnecessary amine, condensing agent and other by products of flush away, use filtering with microporous membrane, repeated washing, the carbon pipe that leaches is evaporate to dryness under 40 ℃～100 ℃ temperature condition, obtains aminated carbon nanotube, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
1～20 part of carboxylic carbon nano-tube
10～30 parts of condensing agents
50～90 parts of polyamines
(4) aminated carbon nanotube and hexanediamine, the hexanodioic acid that step (3) is made is mixed with nylon salt, in nylon salt, add acetate, mix, under 190～200 ℃ of temperature, under 1.5～1.6Mpa, reacted 1～6 hour, obtain the matrix material prepolymer, with the prepolymer oven dry, carry out polycondensation, promptly get material requested, the consumption of acetate is the 0.5wt% of nylon salt, and the proportion of composing of its raw material is as follows:
Raw material consumption (mass parts)
0.01～0.4 part of aminated carbon nanotube
20～50 parts of hexanediamines
20～50 parts of hexanodioic acids.
2. the preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material according to claim 1, it is characterized in that described carbon nanotube comprises the single wall or the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over, template and the preparation of laser evaporation method, caliber is 1～50nm, length is 0.1～50 μ m, and acidified processing and purification process.
3. the preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material according to claim 1, it is characterized in that described protonic acid be the vitriol oil, concentrated nitric acid, concentrated hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute hydrochloric acid, phosphoric acid, acetate or hydrogen peroxide one to several mixtures.
4. the preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material according to claim 1, it is characterized in that described polyamine be quadrol, hexanediamine, mphenylenediamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, isophorone diamine, two (4-amino-3 first class cyclohexyl) methane, two (4-aminocyclohexyl) methane, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone or both-end amido oligopolymer in any.
5. the preparation method of high decentrality amido carbon nano-tube/nylon 66 composite material according to claim 1 is characterized in that described condensing agent adopts aliphatic carbon diimine type or aromatic series carbodiimide type condensing agent,
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