CN1259373C - Method for preparing in-situ polycondensation enhanced carbon nanotube/nylon composite materials - Google Patents
Method for preparing in-situ polycondensation enhanced carbon nanotube/nylon composite materials Download PDFInfo
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- CN1259373C CN1259373C CN 200410084741 CN200410084741A CN1259373C CN 1259373 C CN1259373 C CN 1259373C CN 200410084741 CN200410084741 CN 200410084741 CN 200410084741 A CN200410084741 A CN 200410084741A CN 1259373 C CN1259373 C CN 1259373C
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Abstract
The present invention discloses a preparation method of a reinforced composite carbon nanometer tube / nylon material through original position polycondensation. The method comprises the following steps: firstly, carbon nanometer tubes are acidified, and then, an original position polycondensation reaction is carried out between the acidified carbon nanometer tubes and nylon monomers or nylon monomer salt. The acidified carbon nanometer tubes have excellent performance and present better mechanical properties in compounding nylon in an original position polycondensation mode than other nanometer materials, such as montmorillonite or other compounding methods, such as a cross blend method, etc. The original position polycondensation reaction can realize the uniform dispersion of the carbon nanometer tubes and can keep the nanometer characteristics of the carbon nanometer tubes. Through one-step polymerization molding, degradation generated due to hot processing is avoided, other performance is kept stable, and the preparation method is simple.
Description
Technical field:
The present invention relates to a kind of preparation method of polymer composite, particularly the preparation method of in-situ polycondensation enhanced carbon nanotube/nylon composite materials.
Background technology:
Nylon has good physics, mechanical property, the tensile strength height, and the wear resisting property excellence, self lubricity is good, and toughness is good, and chemical-resistant resistance and oil-proofness are outstanding, are a kind of application engineering plastics very widely.But owing to there is more polar group, its water-intake rate is higher, and heat-drawn wire is lower, and modulus and intensity are also not high enough.When using under strong external force and heating condition, rigidity and thermotolerance are not good, make the stability and the electrical property variation of goods, and its application in a lot of fields is restricted, and therefore must carry out modification, to improve its performance.People once adopted several different methods that nylon is carried out enhancing modified, had improved its use properties to a certain extent, but effect is not very good.The enhancing modified that appears as nylon of nanotechnology provides a brand-brand-new way.Nano material has the characteristic of many novelties, and its application in plastics also gives body material many new performances except that strengthening toughening effect.Nano material is dispersed in the polymeric matrix with nano-scale, can obtains nano plastic.Nano plastic has the not available excellent properties of general matrix material, is a kind of brand-new hi tech and new material, has good commercial development and application prospect.
Carbon nanotube (CarbonNanotube is called for short CNT) is just found a kind of novel carbon structure in 1991, is the body that is rolled into by the graphite flake layer that carbon atom forms.According to the quantity of its graphite flake layer, carbon nanotube be divided into Single Walled Carbon Nanotube (Single-walledCarbonNanotube, SWNT), double-walled carbon nano-tube (Double-walledCarbonNanotube, DWNT), and multi-walled carbon nano-tubes (Multi-walledCarbonNanotube, MWNT).Carbon nanotube is the seamless hollow tube that is surrounded by the former sub-grid of hexagonal carbon, two ends are covered by hemispheric big fullerene molecule usually, diameter zero point several nanometers to tens nanometers, length then is several to a hundreds of micron, as a kind of novel material, the strength ratio steel of carbon nanotube is high more than 100 times, and Young's modulus can be up to 1TPa, and proportion has only 1/6 of steel.Because diameter is very little, length-to-diameter ratio is big, carbon nanotube is regarded as quasi-one-dimensional nanometer material.Confirmed now that carbon nanotube has peculiar electric property, superpower mechanical property, good adsorption property, thereby caused very big attention in the material field.
At present, (Polym.Eng.Sci, 2003 such as existing Zhang Guosheng, 43 (1), 204～213) adopt nylon 1010 and polynite to carry out intercalation polymeric and obtain the intercalation polymeric thing, when the content of polynite when 0% is increased to 17%, the Young's modulus of intercalated compound has increased by 34.9%.OlafMeincke (Polymer45 (2004) 739-748) carries out blend with nylon 6 and carbon nanotube, when the content of carbon nanotube when 0% is increased to 10%, the Young's modulus of its blend has increased by 59%.
Summary of the invention:
The objective of the invention is to by chemical reaction, carbon nanotube is carried out acid treatment, make the NH in carbon nano tube surface generation carboxyl-COOH and nylon monomer or the nylon monomer salt
2Condensation generation-CONH-, carbon nanotube and nylon molecule couple together by covalent linkage, generate the carbon nano-tube/nylon matrix material, thereby as a kind of important nano material, satisfy the needs of Application Areas such as novel material.
The concrete preparation method of in-situ polycondensation enhanced carbon nanotube/nylon composite materials of the present invention is as follows:
1) acid treatment of carbon nanotube:
Carbon nanotube is mixed with acid with strong oxidizing property, wherein the weight proportion of carbon nanotube and acid with strong oxidizing property is 0.1～100, behind 0～100kHz ultrasonication, 0.1～2hr, stir down in 30～180 ℃, reaction 0.5～100hr, use tetrafluoroethylene millipore filtration suction filtration then, use the deionized water repetitive scrubbing again, obtain the acidifying carbon nanotube behind 80 ℃ of vacuum-drying 24hr repeatedly to neutral;
2) in-situ polycondensation reaction:
Nylon monomer or nylon monomer salt are joined in the there-necked flask, sealing, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing, begin to be heated to 150～300 ℃ then, until nylon monomer or the complete fusion of monomer salt, start stirring reaction 0.5～5hr, again the acidifying carbon nanotube is added, wherein the weight proportion of acidifying carbon nanotube and nylon monomer or nylon monomer salt is 0.01/100～70/30, reacts 1～24hr under 150～350 ℃ again, obtains in-situ polycondensation enhanced carbon nanotube/nylon composite materials;
Wherein nylon monomer comprises hexosamine or 11-amino acid; Nylon monomer salt comprises nylon salt, nylon 1010 salt or nylon 1212 salt.
The carbon nanotube that the present invention uses is single wall, double-walled or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
The acid with strong oxidizing property that the present invention uses comprises nitric acid, sulfuric acid, nitric acid and vitriolic mixing acid or contains the sulfuric acid of potassium permanganate, and wherein the concentration of nitric acid is that 60wt%, vitriolic concentration are that the proportioning of 98wt%, nitric acid and vitriolic mixing acid is that 10/1～1/10ml/ml, the potassium permanganate concentration in sulfuric acid is 1～10g/100ml.
The preparation method's of in-situ polycondensation enhanced carbon nanotube/nylon composite materials of the present invention advantage is:
1) the acidifying carbon nanotube has excellent performance, and reveals better mechanical property than other nano materials (if you would take off soil) or other complex methods (as blending method) with the nylon composite table by the in-situ polycondensation mode; Compare with polynite/nylon 1010 intercalation polymeric thing, when the content of polynite when 0% is increased to 17%, the Young's modulus of intercalated compound has only increased by 34.9%, and when the content of carbon nanotube when 0% is increased to 20%, the Young's modulus of the carbon nanotube of in-situ polycondensation-nylon 1010 mixture has but increased by 77.6%; Compare with carbon nano-tube/nylon 6 intermingling materials, when the content of carbon nanotube when 0% is increased to 10%, its Young's modulus has increased by 59%, the Young's modulus of in-situ polycondensation enhanced carbon nanotube/nylon 1010 matrix material has then increased by 71.2%, and visible in-situ polycondensation enhanced carbon nanotube/nylon composite materials has stronger mechanical property.
2) because carbon nanotube has nano-grade size, therefore, the substrate molecule that directly links to each other with carbon nanotube in the matrix material of same mass content is more, and the enhancement of carbon nanotube is also bigger;
3) the in-situ polycondensation reaction can realize the homodisperse of his nanotube, can keep the nano-meter characteristic of carbon nanotube again; Having formed in matrix material is the interlinkage structure of node with the carbon nanotube, has increased the nylon matrix resistance to deformation, and the tensile strength of matrix material is improved;
4), avoid the degraded that produces because of hot-work, thereby keep the stable of other every performances, and the preparation method is simple because a polymerization forming.
Description of drawings:
Fig. 1: the Young's modulus of nylon 1010-carbon nano tube compound material and elongation at break are with the changing conditions of the content of carbon nanotube.
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 1wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, adding 0.7g exsiccant carbon nanotube and 20ml contains in the sulfuric acid of potassium permanganate, wherein sulfuric acid concentration is 98wt%, the concentration of potassium permanganate in sulfuric acid is 5g/100ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 0.26g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 150 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 0.5hr under this temperature; add the carbon nanotube 0.253g after the acidification again, switch to vacuum again, continue reaction 4hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 1wt%.
Embodiment 2: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 2.5wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, adding 1.75g exsiccant carbon nanotube and 30mL contains in the sulfuric acid of potassium permanganate, wherein sulfuric acid concentration is 98wt%, the concentration of potassium permanganate in sulfuric acid is 4g/100ml, with 50kHz ultrasonication 40min post-heating to 120 ℃, reaction 48hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 0.64g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 190 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 2hr under this temperature; add the carbon nanotube 0.64g after the acidification again, switch to vacuum again, continue reaction 6hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 2.5wt%.
Embodiment 3: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 5wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 3.5g exsiccant carbon nanotube and 30ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 1ml/ml, with 20kHz ultrasonication 60min post-heating to 150 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 1.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 250 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 3hr under this temperature; add the carbon nanotube 1.32g after the acidification again, switch to vacuum again, continue reaction 10hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 5wt%.
Embodiment 4: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 10wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 6g exsiccant carbon nanotube and 50ml nitric acid and the vitriolic mixing solutions, wherein the concentration of the nitric acid that uses of present embodiment is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 2ml/ml, with 80kHz ultrasonication 70min post-heating to 160 ℃, reaction 55hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 2.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 20g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 270 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4hr under this temperature; add the carbon nanotube 2.22g after the acidification again, switch to vacuum again, continue reaction 16hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 10wt%.
Embodiment 5: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 20wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 12.5g exsiccant carbon nanotube and 100ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 10ml/ml, with 40kHz ultrasonication 30min post-heating to 200 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 5g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 20g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 290 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4.5hr under this temperature; add the carbon nanotube 5g after the acidification again, switch to vacuum again, continue reaction 20hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 20wt%.
Embodiment 6: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1010 matrix materials of 30wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 500ml that the magnetic agitation rotor is housed, add in 16g exsiccant carbon nanotube and 150ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 10: lml/ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 6g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 15g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 300 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 5hr under this temperature; add the carbon nanotube 6.4g after the acidification again, switch to vacuum again, continue reaction 24hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 30wt%.
Embodiment 7: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 11 matrix materials of 2.5wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, adding 1.75g exsiccant carbon nanotube and 30mL contains in the sulfuric acid of potassium permanganate, wherein sulfuric acid concentration is 98wt%, the concentration of potassium permanganate in sulfuric acid is 4g/100ml, with 50kHz ultrasonication 40min post-heating to 120 ℃, reaction 48hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 0.64g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g11-amino acid, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 210 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 2hr under this temperature; add the carbon nanotube 0.64g after the acidification again, switch to vacuum again, continue reaction 6hr; obtain carbon nano-tube/nylon 11 matrix materials, wherein carbon nanotubes 2.5wt%.
Embodiment 8: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 11 matrix materials of 10wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 6g exsiccant carbon nanotube and 50ml nitric acid and the vitriolic mixing solutions, wherein the concentration of the nitric acid that uses of present embodiment is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 2ml/ml, with 80kHz ultrasonication 70min post-heating to 160 ℃, reaction 55hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 2.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 20g11-amino acid, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 270 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4hr under this temperature; add the carbon nanotube 2.22g after the acidification again, switch to vacuum again, continue reaction 16hr; obtain carbon nano-tube/nylon 11 matrix materials, wherein carbon nanotubes 10wt%.
Embodiment 9: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 11 matrix materials of 20wt%
(1) double-walled carbon nano-tube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 12.5g exsiccant carbon nanotube and 100ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 10ml/ml, with 40kHz ultrasonication 30min post-heating to 200 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 5g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 20g11-amino acid, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 290 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4.5hr under this temperature; add the carbon nanotube 5g after the acidification again, switch to vacuum again, continue reaction 20hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 20wt%.
Embodiment 10: contain the preparation of the carbon nanotube in-situ polycondensation carbon nano-tube/nylon 66 composite material of 1wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, adding 0.7g exsiccant carbon nanotube and 20ml contains in the sulfuric acid of potassium permanganate, wherein sulfuric acid concentration is 98wt%, the concentration of potassium permanganate in sulfuric acid is 5g/100ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 0.26g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 25g nylon salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 150 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 0.5hr under this temperature; add the carbon nanotube 0.253g after the acidification again, switch to vacuum again, continue reaction 4hr; obtain carbon nano-tube/nylon 66 composite material, wherein carbon nanotubes 1wt%.
Embodiment 11: contain the preparation of the carbon nanotube in-situ polycondensation carbon nano-tube/nylon 66 composite material of 5wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 3.5g exsiccant carbon nanotube and 30ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 1ml/ml, with 20kHz ultrasonication 60min post-heating to 150 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 1.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 25g nylon salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 250 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 3hr under this temperature; add the carbon nanotube 1.32g after the acidification again, switch to vacuum again, continue reaction 10hr; obtain carbon nano-tube/nylon 66 composite material, wherein carbon nanotubes 5wt%.
Embodiment 12: contain the preparation of the carbon nanotube in-situ polycondensation carbon nano-tube/nylon 66 composite material of 20wt%
(1) double-walled carbon nano-tube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 12.5g exsiccant carbon nanotube and 100ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 10ml/ml, with 40kHz ultrasonication 30min post-heating to 200 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 5g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 20g nylon salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 290 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4.5hr under this temperature; add the carbon nanotube 5g after the acidification again, switch to vacuum again, continue reaction 20hr; obtain carbon nano-tube/nylon 1010 matrix materials, wherein carbon nanotubes 20wt%.
Embodiment 13: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 6 matrix materials of 5wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 3.5g exsiccant carbon nanotube and 30ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 1ml/ml, with 20kHz ultrasonication 60min post-heating to 150 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 1.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 25g hexosamine, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 250 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 3hr under this temperature; add the carbon nanotube 1.32g after the acidification again, switch to vacuum again, continue reaction 10hr; obtain carbon nano-tube/nylon 6 matrix materials, wherein carbon nanotubes 5wt%.
Embodiment 14: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 6 matrix materials of 10wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 6g exsiccant carbon nanotube and 50ml nitric acid and the vitriolic mixing solutions, wherein the concentration of the nitric acid that uses of present embodiment is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 2ml/ml, with 80kHz ultrasonication 70min post-heating to 160 ℃, reaction 55hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 2.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 20g hexosamine, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 270 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4hr under this temperature; add the carbon nanotube 2.22g after the acidification again, switch to vacuum again, continue reaction 16hr; obtain carbon nano-tube/nylon 6 matrix materials, wherein carbon nanotubes 10wt%.
Embodiment 15: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 6 matrix materials of 30wt%
(1) double-walled carbon nano-tube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 500ml that the magnetic agitation rotor is housed, add in 16g exsiccant carbon nanotube and 150ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 10: 1ml/ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 6g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add the 15g hexosamine, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 300 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 5hr under this temperature; add the carbon nanotube 6.4g after the acidification again, switch to vacuum again, continue reaction 24hr; obtain carbon nano-tube/nylon 6 matrix materials, wherein carbon nanotubes 30wt%.
Embodiment 16: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1212 matrix materials of 5wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 3.5g exsiccant carbon nanotube and 30ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 1ml/ml, with 20kHz ultrasonication 60min post-heating to 150 ℃, reaction 96hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 1.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g nylon 1212 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 250 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 3hr under this temperature; add the carbon nanotube 1.32g after the acidification again, switch to vacuum again, continue reaction 10hr; obtain carbon nano-tube/nylon 1212 matrix materials, wherein carbon nanotubes 5wt%.
Embodiment 17: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1212 matrix materials of 10wt%
(1) Single Walled Carbon Nanotube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 100ml that the magnetic agitation rotor is housed, add in 6g exsiccant carbon nanotube and 50ml nitric acid and the vitriolic mixing solutions, wherein the concentration of the nitric acid that uses of present embodiment is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 1: 2ml/ml, with 80kHz ultrasonication 70min post-heating to 160 ℃, reaction 55hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 2.4g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 20g nylon 1212 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 270 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 4hr under this temperature; add the carbon nanotube 2.22g after the acidification again, switch to vacuum again, continue reaction 16hr; obtain carbon nano-tube/nylon 1212 matrix materials, wherein carbon nanotubes 10wt%.
Embodiment 18: contain the preparation of carbon nanotube in-situ polycondensation carbon nano-tube/nylon 1212 matrix materials of 30wt%
(1) double-walled carbon nano-tube with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 500ml that the magnetic agitation rotor is housed, add in 16g exsiccant carbon nanotube and 150ml nitric acid and the vitriolic mixing solutions, wherein the concentration of nitric acid is 60wt%, vitriolic concentration is 98wt%, the proportioning of sulfuric acid and nitric acid is 10: 1ml/ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 6g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) in the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 15g nylon 1212 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 300 ℃ under protection of nitrogen gas; after the complete fusion of thing to be mixed; start stirring; behind reaction 5hr under this temperature; add the carbon nanotube 6.4g after the acidification again, switch to vacuum again, continue reaction 24hr; obtain carbon nano-tube/nylon 1212 matrix materials, wherein carbon nanotubes 30wt%.
Comparative example 1: the preparation of pure nylon 1010
In the 100ml three neck round-bottomed flasks that mechanical stirrer is housed, add 25g nylon 1010 salt, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing.Then reactive system is warming up to 100～300 ℃ under protection of nitrogen gas, after the complete fusion of thing to be mixed, starts stirring, behind reaction 2hr under this temperature, switches to vacuum again, continues to obtain nylon 1010 at 150～350 ℃ of reaction 4hr.
Comparative example 2: contain the preparation of carbon nano-tube/nylon 1010 blended compound materials of 1wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 500ml that the magnetic agitation rotor is housed, adding 7g exsiccant carbon nanotube and 100ml contains in the sulfuric acid of potassium permanganate, wherein vitriolic concentration is 98wt%, the concentration of potassium permanganate in sulfuric acid is 1g/100ml, with 40kHz ultrasonication 30min post-heating to 120 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 4.2g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) with the carbon nanotube 2.5g after 47.5g particulate state commercial nylon 1010 and the acidification, put into Haake together, obtain containing carbon nano-tube/nylon 1010 intermingling materials of 5wt% carbon nanotube 230 ℃ of following blend 5～8 minutes.
Comparative example 3: contain the preparation of carbon nano-tube/nylon 1010 blended compound materials of 10wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 500ml that the magnetic agitation rotor is housed, add 10g exsiccant carbon nanotube and 100ml nitric acid,, wherein the concentration of this nitric acid is 60wt%, with behind the 40kHz ultrasonication 30min under normal temperature, stir and back flow reaction 24hr, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 5g behind 80 ℃ of vacuum-drying 24hr with the deionized water repetitive scrubbing;
(2) with the carbon nanotube 5g after 45g particulate state commercial nylon 1010 and the acidification, put into Haake together, obtain containing carbon nano-tube/nylon 1010 intermingling materials of 10wt% carbon nanotube 230 ℃ of following blend 5～8 minutes.
Comparative example 4: contain the preparation of carbon nano-tube/nylon 1010 blended compound materials of 30wt%
(1) multi-walled carbon nano-tubes with the catalytic pyrolysis method preparation is a raw material, in the single neck round-bottomed flask of the 1000ml that the magnetic agitation rotor is housed, add in 30g exsiccant carbon nanotube and the 500ml sulfuric acid, wherein vitriolic concentration is 98wt%, with 40kHz ultrasonication 30min post-heating to 80 ℃, reaction 24hr down stirs and refluxes, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, repeatedly to neutral, obtain acidifying carbon nanotube 15g with the deionized water repetitive scrubbing behind 80 ℃ of vacuum-drying 24hr;
(2) with the carbon nanotube 15g after 35g particulate state commercial nylon 1010 and the acidification, put into Haake together, obtain containing carbon nano-tube/nylon 1010 intermingling materials of 30wt% carbon nanotube 230 ℃ of following blend 5～8 minutes.
The mechanical property of in-situ polycondensation enhanced carbon nanotube/nylon 1010 matrix material and carbon nano-tube/nylon 1010 intermingling materials is done test, the results are shown in Figure 1 and table 1,
The Young's modulus of table 1 nylon 1010-carbon nano tube compound material and elongation at break are with the variation of the content of carbon nanotube
Nylon 1010-carbon nano tube compound material that on behalf of blend, suffix " B " obtain
| Sample | Content of carbon nanotubes (wt%) | Young's modulus (MPa) | Elongation at break (%) |
| Commercial nylon 1010 embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 comparative examples 1 comparative example 2 comparative examples 3 comparative examples 4 | 0 1 2.5 5 10 20 30 0 5 10 30 | 1203 1301 1302 1449 1748 1813 1912 1021 1226 1694 1769 | 40 35 31 23 17 9 5 37 27 19 8 |
Can see, the modulus of in-situ polycondensation enhanced carbon nanotube/nylon 1010 matrix material is better than pure nylon 1010, carbon nanotube nylon/1010 blends, when the content of carbon nanotube was increased to 30%, Young's modulus had improved 87.3%, and modulus is increased to 1912MPa from 1021MPa.Though and the Young's modulus of blend has also improved 73.3%, what do not have that the former improves is many, illustrates that the matrix material that matrix material that the in-situ polycondensation reaction obtains obtains than blend has stronger bonding force.
Simultaneously with Zhang Guosheng (Polym.Eng.Sci, 2003,43 (1), 204～213) Zhi Bei polynite/nylon 1010 intercalation polymeric thing is compared, in-situ polycondensation enhanced carbon nanotube/nylon 1010 matrix material has better mechanical property, when the content of polynite when 0% is increased to 17%, the Young's modulus of intercalated compound has only increased by 34.9%, and when the content of carbon nanotube when 0% is increased to 20%, the Young's modulus of the carbon nanotube of in-situ polycondensation-nylon 1010 mixture has but increased by 77.6%.OlafMeincke (Polymer45 (2004) 739-748) carries out blend with nylon 6 and carbon nanotube, when the content of carbon nanotube when 0% is increased to 10%, the Young's modulus of its intermingling material has increased by 59%, the Young's modulus of in-situ polycondensation enhanced carbon nanotube/nylon 1010 matrix material has then increased by 71.2%, and visible in-situ polycondensation enhanced carbon nanotube/nylon composite materials has stronger mechanical property.
Claims (3)
1. the preparation method of in-situ polycondensation enhanced carbon nanotube/nylon composite materials is characterized in that concrete preparation method is as follows:
1) acid treatment of carbon nanotube:
Carbon nanotube is mixed with acid with strong oxidizing property, wherein to get weight proportion be 0.1～100 for carbon nanotube and acid with strong oxidizing property, behind 0～100kHz ultrasonication, 0.1～2hr, stir down in 30～180 ℃, reaction 0.5～100hr, use tetrafluoroethylene millipore filtration suction filtration then, use the deionized water repetitive scrubbing again, obtain the acidifying carbon nanotube behind 80 ℃ of vacuum-drying 24hr repeatedly to neutral;
2) in-situ polycondensation reaction:
Nylon monomer or nylon monomer salt are joined in the there-necked flask, sealing, vacuumize then, charge into high purity nitrogen, this process repeatedly three times with the air in the system of removing, begin to be heated to 150～300 ℃ then, until nylon monomer or the complete fusion of monomer salt, start stirring reaction 0.5～5hr, again the acidifying carbon nanotube is added, wherein the weight proportion of acidifying carbon nanotube and nylon monomer or nylon monomer salt is 0.01/100～70/30, reacts 1～24hr under 150～350 ℃ again, obtains in-situ polycondensation enhanced carbon nanotube/nylon composite materials;
Wherein nylon monomer comprises hexosamine or 11-amino acid; Nylon monomer salt comprises nylon salt, nylon 1010 salt or nylon 1212 salt.
2. the preparation method of in-situ polycondensation enhanced carbon nanotube/nylon composite materials according to claim 1 is characterized in that carbon nanotube is single wall, double-walled or the multi-walled carbon nano-tubes of catalyse pyrolysis, arc-over, template or the preparation of laser evaporation method.
3. the preparation method of in-situ polycondensation enhanced carbon nanotube/nylon composite materials according to claim 1, it is characterized in that acid with strong oxidizing property comprises nitric acid, sulfuric acid, nitric acid and vitriolic mixing acid or contains the sulfuric acid of potassium permanganate, wherein the concentration of nitric acid is that 60wt%, vitriolic concentration are that the proportioning of 98wt%, nitric acid and vitriolic mixing acid is that 10/1～1/10ml/ml, the potassium permanganate concentration in sulfuric acid is 1～10g/100ml.
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