CN101205363A - Preparation method of carboxylic carbon nano-tube /nylon 66 composite material - Google Patents
Preparation method of carboxylic carbon nano-tube /nylon 66 composite material Download PDFInfo
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- CN101205363A CN101205363A CNA2007101718207A CN200710171820A CN101205363A CN 101205363 A CN101205363 A CN 101205363A CN A2007101718207 A CNA2007101718207 A CN A2007101718207A CN 200710171820 A CN200710171820 A CN 200710171820A CN 101205363 A CN101205363 A CN 101205363A
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Abstract
The invention pertains to the field of material technology, in particular to a preparation method for a carboxylic carbon nanotube/nylon 66 composite material.The particular preparation procedure is as follows: preparing a carbon nanotube with carboxyl by acidulating the carbon nanotube; Preparing the carboxylic carbon nanotube/nylon 66 composite material by polymerizing the carboxylic carbon nanotube and the raw material (such as polybasic acid and polybasic amine) which is used for preparing the nylon 66 through in situ polymerization. The polycondensation of carboxy group on the carbon nanotube improves the dispersity and interfacial binding force of the carbon nanotube in nylon matrix, and carboxylic carbon nanotube/nylon composite material with excellent dispersive property is obtained.
Description
Technical field
The invention belongs to the material technology field, be specifically related to a kind of preparation method of carboxylic 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 belongs to AABB type nylon, AABB type nylon has physical strength height, characteristics that rigidity is big, be the principal item of engineering plastics, be 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 AABB type nylon 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 AABB type nylon and obtained development at full speed, but the research of research carbon nanotube remodeling AABB type nylon is few, only research also concentrates on the method that adopts mechanical blending, the dispersiveness of carbon nanotube in matrix is not good, and performance improves limited.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of carboxylic carbon nano-tube/nylon 66 composite material.
The preparation method of the carboxylic carbon nano-tube/nylon 66 composite material that the present invention proposes adopts acid that carbon nanotube is carried out finishing, makes it carry carboxylic group.Adopt carboxylic carbon nano-tube and raw material polyamine, the polyprotonic acid of preparation nylon 66 to carry out in-situ polymerization then, make the carboxylic group on the carbon nanotube participate in polyreaction, improve the interface binding power of the dispersiveness of carbon nanotube in nylon matrix and enhancing carbon nanotube and nylon matrix, lay foundation for preparing high performance matrix material.
The preparation method of the carboxylic carbon nano-tube/nylon 66 composite material that the present invention proposes, concrete steps are:
(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, and products therefrom is neutral with washed with de-ionized water, promptly get the acidifying carbon nanotube, the mass ratio of raw material is:
Raw material consumption (mass parts)
1～20 part of unmodified carbon nanotube
10～100 parts of protonic acids
(2) step (1) gained acidifying carbon nanotube and protonic acid are mixed, use ultra-sonic oscillation down at 60 ℃～80 ℃, reaction times is 0.5～4h, products therefrom is extremely neutral with washed with de-ionized water, filter, dry under 40 ℃～100 ℃ temperature, promptly obtain carboxylic carbon nano-tube, the mass ratio of raw material is:
Raw material consumption (mass parts)
1～20 part of acidifying carbon nanotube
10～100 parts of protonic acids
(3) step (2) gained carboxylic carbon nano-tube is mixed with polyamine, polyprotonic acid, the preparation nylon salt, the gained nylon salt mixes with acetate, under 200 ℃ of temperature, 1.5～1.6Mpa reaction 1～6h down obtains the matrix material prepolymer, carry out polycondensation after the oven dry of gained prepolymer, the reaction later stage is removed excessive moisture under vacuum condition, promptly get desired product; The consumption of acetate is the 0.5wt% of nylon salt, and the mass ratio of raw material is:
Raw material consumption (mass parts)
Carboxylic carbon nano-tube 0.01～0.4
Polyamine 20～50
Polyprotonic acid 20～50.
Among the present invention, described carbon nanotube comprises the single wall merit 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 is an one to multiple kind in the vitriol oil, concentrated nitric acid, concentrated hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute hydrochloric acid, phosphoric acid, acetate or the hydrogen peroxide etc.
Among the present invention, described polyamine be in hexanediamine, decamethylene diamine, butanediamine or the dodecane diamines etc. any.
Among the present invention, described polyprotonic acid be in hexanodioic acid, sebacic acid or the dodecanedioic acid etc. any.
Advantage of the present invention is: carbon nanotube has carboxylic group through the chemically modified surface, can form amido linkage with polyamine, polyprotonic 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 matrix material of good dispersion property.
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 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 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: carboxylic 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, 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 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 half an hour so repeatedly after 3 times, 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 hydrochloric 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 1h.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: carboxylic 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 dilute sulphuric acid 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: carboxylic 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.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 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: carboxylic 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, behind the ultra-sonic oscillation 1h 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 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 3h.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 dilute hydrochloric acid 40ml and hydrogen peroxide 10ml are mixed, at 80 ℃ of ultra-sonic oscillation 1h.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: carboxylic 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, 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 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.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.
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, 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 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, behind the ultra-sonic oscillation 0.5h it is added 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, 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 the unmodified carbon nano-tube/nylon 66 composite material.
Table 1: the light transmission of matrix material formic acid solution is (T=50d) relatively
| The matrix material formic acid solution | Transmittance/% | |
| λ＝480nm | λ＝600nm | |
| Embodiment 1 | 36.2 | 43.2 |
| Embodiment 2 | 2.8 | 7.0 |
| |
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 carboxylic carbon nano-tube/nylon 66 composite material is characterized in that concrete steps are:
(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, and products therefrom is neutral with washed with de-ionized water, promptly get the acidifying carbon nanotube, the mass ratio of raw material is:
The raw material consumption, mass parts
1～20 part of unmodified carbon nanotube
10～100 parts of protonic acids
(2) step (1) gained acidifying carbon nanotube and protonic acid are mixed, use ultra-sonic oscillation down at 60 ℃～80 ℃, reaction times is 0.5～4h, products therefrom is extremely neutral with washed with de-ionized water, filter, dry under 40 ℃～100 ℃ temperature, promptly obtain carboxylic carbon nano-tube, the mass ratio of raw material is:
The raw material consumption, mass parts
1～20 part of acidifying carbon nanotube
10～100 parts of protonic acids
(3) step (2) gained carboxylic carbon nano-tube is mixed with polyamine, polyprotonic acid, the preparation nylon salt, the gained nylon salt mixes with acetate, under 190-210 ℃ of temperature, 1.5～1.6Mpa reaction 1～6h down obtains the matrix material prepolymer, carry out polycondensation after the oven dry of gained prepolymer, the reaction later stage is removed excessive moisture under vacuum condition, promptly get desired product; The consumption of acetate is the 0.5wt% of nylon salt, and the mass ratio of raw material is:
The raw material consumption, mass parts
Carboxylic carbon nano-tube 0.01～0.4
Polyamine 20～50
Polyprotonic acid 20～50.
2. the preparation method of carboxylic 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 carboxylic carbon nano-tube/nylon 66 composite material according to claim 1 is characterized in that described protonic acid is an one to multiple kind in the vitriol oil, concentrated nitric acid, concentrated hydrochloric acid, dilute sulphuric acid, rare nitric acid, dilute hydrochloric acid, phosphoric acid, acetate or the hydrogen peroxide.
4. the preparation method of carboxylic carbon nano-tube/nylon 66 composite material according to claim 1, it is characterized in that described polyamine be in hexanediamine, decamethylene diamine, butanediamine or the dodecane diamines any.
5. the preparation method of carboxylic carbon nano-tube/nylon 66 composite material according to claim 1, it is characterized in that described polyprotonic acid be in hexanodioic acid, sebacic acid or the dodecanedioic acid any.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101612420B (en) * | 2009-08-13 | 2013-01-09 | 湖南大学 | Multiple mesh nanometer carbon-hydroxyapatite composite material and preparation method thereof |
| CN105669971A (en) * | 2016-04-08 | 2016-06-15 | 南京工业大学 | Preparation method of in-situ polymerized carbon nanotube modified nylon composite material |
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| CN114196202A (en) * | 2022-01-21 | 2022-03-18 | 湖北洋田塑料制品有限公司 | Heat-conducting nylon composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101746747B (en) * | 2008-12-04 | 2011-08-24 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of nylon-6 grafting modified carbon nano tubes |
| CN101612420B (en) * | 2009-08-13 | 2013-01-09 | 湖南大学 | Multiple mesh nanometer carbon-hydroxyapatite composite material and preparation method thereof |
| CN105669971A (en) * | 2016-04-08 | 2016-06-15 | 南京工业大学 | Preparation method of in-situ polymerized carbon nanotube modified nylon composite material |
| CN105669971B (en) * | 2016-04-08 | 2019-01-04 | 南京工业大学 | Preparation method of in-situ polymerized carbon nanotube modified nylon composite material |
| CN111117226A (en) * | 2019-12-30 | 2020-05-08 | 湖南华曙高科技有限责任公司 | Nylon powder for selective laser sintering and preparation method thereof |
| CN114196202A (en) * | 2022-01-21 | 2022-03-18 | 湖北洋田塑料制品有限公司 | Heat-conducting nylon composite material and preparation method thereof |
| CN114196202B (en) * | 2022-01-21 | 2024-04-26 | 湖北洋田塑料制品有限公司 | Heat-conducting nylon composite material and preparation method thereof |
| CN116162238A (en) * | 2023-03-14 | 2023-05-26 | 广州明晖新材料有限公司 | In-situ polymerization preparation method of spinning-grade conductive carbon nanotube nylon composite material |
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