CN101746747B - Preparation method of nylon-6 grafting modified carbon nano tubes - Google Patents
Preparation method of nylon-6 grafting modified carbon nano tubes Download PDFInfo
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- CN101746747B CN101746747B CN2008102040686A CN200810204068A CN101746747B CN 101746747 B CN101746747 B CN 101746747B CN 2008102040686 A CN2008102040686 A CN 2008102040686A CN 200810204068 A CN200810204068 A CN 200810204068A CN 101746747 B CN101746747 B CN 101746747B
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Abstract
The invention relates to a preparation method of nylon-6 grafting modified carbon nano tubes, which comprises the following steps: adding multi-wall carbon nano tubes, styrene and maleic anhydride into phenylmethane to carry out a free radical polymerization, then obtaining styrene maleic anhydride grafting multi-wall carbon nano tubes; and adding the styrene maleic anhydride grafting multi-wall carbon nano tubes into caprolactam monomer as a macromolecule cocatalyst for anion ring-opening polymerization, then obtaining the nylon-6 grafting modified carbon nano tubes. Compared with the prior method, the invention grafts PA6 molecular chains on the surface of the multi-wall carbon nano tubes, so that the multi-wall carbon nano tubes can be uniformly dispersed in various solvents, and meanwhile, the PA6 molecular chains can be used as a good macromolecule compatilizer to improve the dispersibility of MWNTs in various polyamides. The invention prevents the structure of the carbon nano tubes from being destroyed since the carbon nano tubes are oxidized by strong acid, and avoids using lots of virulent phenylmethane 2,4-diisocyanate. Thus, the method is convenient and safe.
Description
Technical field
The present invention relates to carbon nanotube, relate in particular to a kind of preparation method of nylon 6 grafted modified carbon nano tubes.
Background technology
(Carbon nanotubes is called for short: CNTs) have excellent mechanics and electric property, from finding just to cause people's very big concern carbon nanotube.CNTs is dispersed in the polymer materials, improves the mechanics of polymer materials and electric property and be the focus of nano composite material research field in recent years.Yet there is intensive Van der Waals interaction force between the carbon nanotube, intensive π-π interaction and itself high length-to-diameter ratio also arranged between the carbon nanotube benzene ring structure unit, make carbon nanotube in many solvents and polymeric matrix, reunite seriously, be difficult to reach nano level dispersion.In order to address these problems, must carry out surface modification to carbon nanotube.
The method of surface modification of carbon nanotube comprises: (1) physics coating modification, (2) grafting modification.Because the smooth surface of carbon nanotube, only rely on physics interaction force between additive and the carbon nanotube to carry out the physics coating modification and have significant limitation, so more research concentrates on grafting modification.Grafting modification has following several big classification again: (1) Sun Yaping (Acc.Chem.Res.2002,35:1096) grade is utilized nitric acid and sulfuric acid mixing acid oxide/carbon nanometer tube, prepare carboxylated carbon nanotube, utilize carboxyl to carry out a series of chemical reaction, the material that grafting is different; (2) (Macromolecules.2006 39:9035) waits the two keys by free radical attack carbon nano tube surface to produce the carbon nanotube free radical to Guo Guiquan, carries out free radical grafting.Because the mixing acid oxidation style has very big destruction to the structure of carbon nanotube itself,, uses free radical grafting so having more widely.
Carlos (Chem.Mater.2003,15:4470) grade is utilized the free radical grafting reaction, at carbon nano tube surface grafting polymethylmethacrylate, this polymethylmethacrylate functionalized carbon nanotube has excellent more dispersiveness than primary carbon nanotube in the methyl methacrylate matrix.(Macromolecules 2004,37:3965-3967) wait and utilize the radical polymerization polyvinyl P-TOLUENE SULFO ACID 99 sodium that has been combined in carbon nano tube surface success grafting, and prepared product has good dispersion stabilization in water for Ford.
In sum, at present to the method for carbon nano-tube modification have that carbon nanotube structure is destroyed, carbon nano tube modified only in the solvent of limited classification homodisperse, use problems such as reagent is dangerous poisonous.
Summary of the invention
Purpose of the present invention be exactly provide in order to overcome the defective that above-mentioned prior art exists a kind of technology rationally, the preparation method of nylon 6 grafted modified carbon nano tubes of easy-to-operate, good product dispersibility.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method adds multi-walled carbon nano-tubes, vinylbenzene and maleic anhydride in the toluene earlier carries out Raolical polymerizable, make styrene-maleic anhydride grafted multi-wall carbon nanotube, again styrene-maleic anhydride grafted multi-wall carbon nanotube is joined in the caprolactam monomer, as the macromole promotor of anionic ring-opening polymerization, make nylon 6 grafted modified carbon nano tubes;
Described method may further comprise the steps:
(1) preparation of styrene-maleic anhydride grafted multi-wall carbon nanotube:
With multi-walled carbon nano-tubes, carry out ultra-sonic dispersion in vinylbenzene and the maleic anhydride adding toluene, multi-walled carbon nano-tubes, vinylbenzene, the part by weight of maleic anhydride and toluene is 0.1-1: 12.5: 10: 200, ultra-sonic dispersion 0.5-1.5 hour, mixture behind the ultra-sonic dispersion is added in the reaction flask, add radical initiator again, after dispersed with stirring is even, stirred Raolical polymerizable 1-8 hour down, temperature of reaction is 50-90 ℃, reaction after finishing is filtered reaction mixture, washing, suction filtration with filter cake 60-80 ℃ of drying 24 hours in vacuum drying oven, makes styrene-maleic anhydride grafted multi-wall carbon nanotube;
(2) preparation of nylon 6 grafted modified carbon nano tubes:
Under nitrogen protection, styrene-maleic anhydride grafted multi-wall carbon nanotube is joined in the strict caprolactam monomer that dewaters of its weight 50-500 process doubly, add anionic catalyst again, stir, after mixing, be heated to 130 ℃-180 ℃, stirring reaction 1-3 hour, remove the nylon 6 that unreacted caprolactam monomer and physical package overlay on the multi-wall carbon nano-tube tube-surface, vacuum-drying promptly gets nylon 6 grafted modified carbon nano tubes;
Radical initiator in the described step (1) is azo radical polymerization initiator or peroxide radical polymerization starter;
Described azo radical polymerization initiator is selected from one or more in azo diisopropyl cyanogen, the azo-bis-isobutyl cyanide, and described peroxide radical polymerization starter is selected from one or more in dicumyl peroxide, the benzoyl peroxide;
Anionic catalyst in the described step (2) is selected from basic metal, alkali-metal hydride, alkali-metal oxyhydroxide, alkali-metal alcoholate or sodium caprolactam(ate).
Described multi-walled carbon nano-tubes is selected from the multi-walled carbon nano-tubes of different diameter, different lengths or different length-to-diameter ratios.
The add-on of the radical initiator in the described step (1) is 0.5-1.5 a times of multi-walled carbon nano-tubes weight.
The used reagent of washing is acetone in the described step (1).
Described basic metal is Na or Li, and described alkali-metal hydride is NaH, and described alkali-metal oxyhydroxide is LiOH or NaOH, and described alkali-metal alcoholate is a sodium ethylate.
The add-on of the anionic catalyst in the described step (2) is 2 ‰ of a caprolactam monomer weight-15 ‰; Removing the method that nylon 6 that unreacted caprolactam monomer and physical package overlay on the multi-wall carbon nano-tube tube-surface adopts in the described step (2) is with a large amount of distilled water dilutings, washing reaction mixture, repeatedly behind Xi Di the sample filtering, washs repeatedly with formic acid.
Zelan 338 (SMA) is a kind of widely used compatilizer, and a spot of SMA of interpolation can greatly improve the interface compatibility between the polymkeric substance in blend polymer, reduces dispersed phase size, improves the mechanical property of blend.Maleic anhydride structural unit in the SMA molecular chain also can be used as the promotor of hexanolactam anionic ring-opening polymerization simultaneously, can cause the hexanolactam ring-opening polymerization and prepare the nylon 6/poly compound.The present invention adopts these reagent to unite multi-walled carbon nano-tubes (MWNTs) to be carried out modification, obtain good result.
Compare with existing method, the present invention at the multi-walled carbon nano-tubes surface grafting PA6 molecular chain, make its can be in multiple solvent homodisperse, these PA6 molecular chains also can be used as good macromole compatilizer and improve the dispersiveness of MWNTs in various polymeric amide simultaneously; Simultaneously, avoid because of use strong acid oxide/carbon nanometer tube causes the structure of carbon nanotube to be destroyed, and avoid a large amount of toluene 2 that use severe toxicity, the 4-vulcabond is the method for a kind of convenience, safety.
Description of drawings
Fig. 1 is a preparation were established synoptic diagram of the present invention;
Fig. 2 is the Raman collection of illustrative plates of pure MWNTs and MWNTs-g-SMA of the present invention;
Fig. 3 is pure MWNTs, the infared spectrum of MWNTs-g-SMA of the present invention and MWNTs-g-PA6;
Fig. 4 is pure MWNTs (a), the TEM synoptic diagram of MWNTs-g-SMA of the present invention (b) and MWNTs-g-PA6 (c);
Fig. 5 is that MWNTs is respectively at formic acid (a), fused hexanolactam (b) and MWNTs-g-PA6 of the present invention dispersed synoptic diagram in formic acid (c), fused hexanolactam (d) respectively.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
As shown in Figure 1, a kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method may further comprise the steps:
(1) preparation of styrene-maleic anhydride grafted multi-wall carbon nanotube (MWNTs-g-SMA):
With part by weight is 0.1: 12.5: 10: 200 MWNTs, vinylbenzene, maleic anhydride and toluene carried out ultra-sonic dispersion 0.5 hour after mixing, drop in the reaction flask then, 0.5 times the radical initiator azo diisopropyl cyanogen that adds MWNTs weight again, after mixing, 50 ℃ of reactions of constant temperature are 1 hour under stirring condition, reaction finishes the back suction filtration and removes toluene, the gained crude product is scattered in the acetone, with washing with acetone, suction filtration, repeatedly after five times with the gained filter cake 60 ℃ of vacuum-dryings 24 hours, make MWNTs-g-SMA;
(2) preparation of nylon 6 grafted modified carbon nano tubes (MWNTs-g-PA6):
Under nitrogen protection; prepared MWNTs-g-SMA is joined through in the strict caprolactam monomer that dewaters; the add-on of hexanolactam is 50 times of weight of MWNTs-g-SMA; 2 ‰ the sodium that adds caprolactam monomer weight again; starting stirring rod stirs; mix post-heating to 130 ℃; reacted 1 hour; reaction finishes back with a large amount of distilled water dilutings, washing reaction mixture; repeatedly behind Xi Di the sample filtering, wash repeatedly the PA6 that flush away physics coats with formic acid; with last black powder vacuum-drying 24 hours, promptly get MWNTs-g-PA6.
Embodiment 2
Referring to shown in Figure 1, a kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method may further comprise the steps:
(1) preparation of MWNTs-g-SMA:
With part by weight is 0.3: 12.5: 10: 200 MWNTs, vinylbenzene, maleic anhydride and toluene carried out ultra-sonic dispersion 0.8 hour after mixing, drop in the reaction flask then, 0.7 times the radical initiator benzoyl peroxide that adds MWNTs weight again, after mixing, 65 ℃ of reactions of constant temperature are 2.5 hours under stirring condition, reaction finishes the back suction filtration and removes toluene, the gained crude product is scattered in the acetone, with washing with acetone, suction filtration, repeatedly after five times with the gained filter cake 66 ℃ of vacuum-dryings 24 hours, make MWNTs-g-SMA;
(2) preparation of MWNTs-g-PA6:
Under nitrogen protection; prepared MWNTs-g-SMA is joined through in the strict caprolactam monomer that dewaters; the add-on of hexanolactam is 150 times of weight of MWNTs-g-SMA; 5 ‰ the NaH that adds caprolactam monomer weight again; starting stirring rod stirs; mix post-heating to 140 ℃; reacted 2 hours; reaction finishes back with a large amount of distilled water dilutings, washing reaction mixture; repeatedly behind Xi Di the sample filtering, wash repeatedly the PA6 that flush away physics coats with formic acid; with last black powder vacuum-drying 24 hours, promptly get MWNTs-g-PA6.
Embodiment 3
Referring to shown in Figure 1, a kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method may further comprise the steps:
(1) preparation of MWNTs-g-SMA:
With part by weight is 0.5: 12.5: 10: 200 MWNTs, vinylbenzene, maleic anhydride and toluene carried out ultra-sonic dispersion 1 hour after mixing, drop in the reaction flask then, 0.95 times the radical initiator azo-bis-isobutyl cyanide that adds MWNTs weight again, after mixing, 72 ℃ of reactions of constant temperature are 4 hours under stirring condition, reaction finishes the back suction filtration and removes toluene, the gained crude product is scattered in the acetone, with washing with acetone, suction filtration, repeatedly after five times with the gained filter cake 70 ℃ of vacuum-dryings 24 hours, make MWNTs-g-SMA;
(2) preparation of MWNTs-g-PA6:
Under nitrogen protection; prepared MWNTs-g-SMA is joined through in the strict caprolactam monomer that dewaters; the add-on of hexanolactam is 300 times of weight of MWNTs-g-SMA; 8 ‰ the LiOH that adds caprolactam monomer weight again; starting stirring rod stirs; mix post-heating to 155 ℃; reacted 3 hours; reaction finishes back with a large amount of distilled water dilutings, washing reaction mixture; repeatedly behind Xi Di the sample filtering, wash repeatedly the PA6 that flush away physics coats with formic acid; with last black powder vacuum-drying 24 hours, promptly get MWNTs-g-PA6.
Embodiment 4
Referring to shown in Figure 1, a kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method may further comprise the steps:
(1) preparation of MWNTs-g-SMA:
With part by weight is 0.75: 12.5: 10: 200 MWNTs, vinylbenzene, maleic anhydride and toluene carried out ultra-sonic dispersion 1.2 hours after mixing, drop in the reaction flask then, 1.3 times the radical initiator dicumyl peroxide that adds MWNTs weight again, after mixing, 80 ℃ of reactions of constant temperature are 6 hours under stirring condition, reaction finishes the back suction filtration and removes toluene, the gained crude product is scattered in the acetone, with washing with acetone, suction filtration, repeatedly after five times with the gained filter cake 75 ℃ of vacuum-dryings 24 hours, make MWNTs-g-SMA;
(2) preparation of MWNTs-g-PA6:
Under nitrogen protection; prepared MWNTs-g-SMA is joined through in the strict caprolactam monomer that dewaters; the add-on of hexanolactam is 400 times of weight of MWNTs-g-SMA; 12 ‰ the sodium ethylate that adds caprolactam monomer weight again; starting stirring rod stirs; mix post-heating to 170 ℃; reacted 1.5 hours; reaction finishes back with a large amount of distilled water dilutings; the washing reaction mixture; repeatedly behind Xi Di the sample filtering, wash repeatedly the PA6 that flush away physics coats with formic acid; with last black powder vacuum-drying 24 hours, promptly get MWNTs-g-PA6.
Embodiment 5
Referring to shown in Figure 1, a kind of preparation method of nylon 6 grafted modified carbon nano tubes, this method may further comprise the steps:
(1) preparation of MWNTs-g-SMA:
With part by weight is 1: 12.5: 10: 200 MWNTs, vinylbenzene, maleic anhydride and toluene carried out ultra-sonic dispersion 1.5 hours after mixing, drop in the reaction flask then, 1.5 times the radical initiator azo diisopropyl cyanogen that adds MWNTs weight again, after mixing, 90 ℃ of reactions of constant temperature are 8 hours under stirring condition, reaction finishes the back suction filtration and removes toluene, the gained crude product is scattered in the acetone, with washing with acetone, suction filtration, repeatedly after five times with the gained filter cake 80 ℃ of vacuum-dryings 24 hours, make MWNTs-g-SMA;
(2) preparation of MWNTs-g-PA6:
Under nitrogen protection; prepared MWNTs-g-SMA is joined through in the strict caprolactam monomer that dewaters; the add-on of hexanolactam is 500 times of weight of MWNTs-g-SMA; 15 ‰ the sodium caprolactam(ate) that adds caprolactam monomer weight again; starting stirring rod stirs; mix post-heating to 180 ℃; reacted 2.5 hours; reaction finishes back with a large amount of distilled water dilutings; the washing reaction mixture; repeatedly behind Xi Di the sample filtering, wash repeatedly the PA6 that flush away physics coats with formic acid; with last black powder vacuum-drying 24 hours, promptly get MWNTs-g-PA6.
Prepare MWNTs-g-SMA and MWNTs-g-PA6 by the foregoing description, the sign of product is seen Fig. 2-4, and performance is seen Fig. 5.
By Fig. 2-4 as can be seen, SMA and PA6 have been grafted on the surface of carbon nanotube by covalent linkage.
As seen from Figure 5, in all kinds of SOLVENTS of PA6, has a good dispersiveness through the MWNTs after the PA6 graft modification.
Claims (6)
1. the preparation method of nylon 6 grafted modified carbon nano tubes, it is characterized in that, this method adds multi-walled carbon nano-tubes, vinylbenzene and maleic anhydride in the toluene earlier carries out Raolical polymerizable, make styrene-maleic anhydride grafted multi-wall carbon nanotube, again styrene-maleic anhydride grafted multi-wall carbon nanotube is joined in the caprolactam monomer, as the macromole promotor of anionic ring-opening polymerization, make nylon 6 grafted modified carbon nano tubes;
Described method may further comprise the steps:
(1) preparation of styrene-maleic anhydride grafted multi-wall carbon nanotube:
With multi-walled carbon nano-tubes, carry out ultra-sonic dispersion in vinylbenzene and the maleic anhydride adding toluene, multi-walled carbon nano-tubes, vinylbenzene, the part by weight of maleic anhydride and toluene is 0.1-1: 12.5: 10: 200, ultra-sonic dispersion 0.5-1.5 hour, mixture behind the ultra-sonic dispersion is added in the reaction flask, add radical initiator again, after dispersed with stirring is even, stirred Raolical polymerizable 1-8 hour down, temperature of reaction is 50-90 ℃, reaction after finishing is filtered reaction mixture, washing, suction filtration with filter cake 60-80 ℃ of drying 24 hours in vacuum drying oven, makes styrene-maleic anhydride grafted multi-wall carbon nanotube;
(2) preparation of nylon 6 grafted modified carbon nano tubes:
Under nitrogen protection, styrene-maleic anhydride grafted multi-wall carbon nanotube is joined in the strict caprolactam monomer that dewaters of its weight 50-500 process doubly, add anionic catalyst again, stir, after mixing, be heated to 130 ℃-180 ℃, stirring reaction 1-3 hour, remove the nylon 6 that unreacted caprolactam monomer and physical package overlay on the multi-wall carbon nano-tube tube-surface, vacuum-drying promptly gets nylon 6 grafted modified carbon nano tubes;
Radical initiator in the described step (1) is azo radical polymerization initiator or peroxide radical polymerization starter;
Described azo radical polymerization initiator is selected from one or more in azo diisopropyl cyanogen, the azo-bis-isobutyl cyanide, and described peroxide radical polymerization starter is selected from one or more in dicumyl peroxide, the benzoyl peroxide;
Anionic catalyst in the described step (2) is selected from basic metal, alkali-metal hydride, alkali-metal oxyhydroxide, alkali-metal alcoholate or sodium caprolactam(ate).
2. the preparation method of nylon 6 grafted modified carbon nano tubes according to claim 1 is characterized in that described multi-walled carbon nano-tubes is selected from the multi-walled carbon nano-tubes of different diameter, different lengths or different length-to-diameter ratios.
3. the preparation method of nylon 6 grafted modified carbon nano tubes according to claim 1 is characterized in that, the add-on of the radical initiator in the described step (1) is 0.5-1.5 a times of multi-walled carbon nano-tubes weight.
4. the preparation method of nylon 6 grafted modified carbon nano tubes according to claim 1 is characterized in that, the used reagent of washing is acetone in the described step (1).
5. the preparation method of nylon 6 grafted modified carbon nano tubes according to claim 1, it is characterized in that described basic metal is Na or Li, described alkali-metal hydride is NaH, described alkali-metal oxyhydroxide is LiOH or NaOH, and described alkali-metal alcoholate is a sodium ethylate.
6. the preparation method of nylon 6 grafted modified carbon nano tubes according to claim 1 is characterized in that, the add-on of the anionic catalyst in the described step (2) is 2 ‰ of a caprolactam monomer weight-15 ‰; Removing the method that nylon 6 that unreacted caprolactam monomer and physical package overlay on the multi-wall carbon nano-tube tube-surface adopts in the described step (2) is with a large amount of distilled water dilutings, washing reaction mixture, repeatedly behind Xi Di the sample filtering, washs repeatedly with formic acid.
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| CN102876038B (en) * | 2012-10-24 | 2014-06-04 | 江苏科技大学 | Polyimide siloxane and carbon nanotube composite material and preparation method thereof |
| TWI503458B (en) * | 2013-07-04 | 2015-10-11 | Taiwan Textile Res Inst | Modified nylon, modified nylon fibers and preparation thereof |
| CN103726129B (en) * | 2013-12-04 | 2017-01-18 | 太仓荣文合成纤维有限公司 | Preparation method of anti-static chinlon/terylene compounded hybrid fiber |
| CN104357941B (en) * | 2014-11-04 | 2016-04-06 | 天津工业大学 | Graphene and multi-walled carbon nano-tubes work in coordination with enhanced polymer fiber and preparation method thereof |
| CN104593901B (en) * | 2014-12-25 | 2016-08-17 | 东华大学 | A kind of preparation method of polyamide grafts carbon nano tube composite fibre |
| CN104609388B (en) * | 2014-12-25 | 2016-06-22 | 东华大学 | A kind of preparation method of polyamide grafts carbon nano tube compound material |
| CN107759752A (en) * | 2017-11-03 | 2018-03-06 | 西南石油大学 | A kind of preparation method of kayexalate/multi-walled carbon nanotube compound |
| CN108285138B (en) * | 2018-05-08 | 2021-06-04 | 西南石油大学 | Preparation method of anionic polymer modified multi-walled carbon nanotube |
| CN110818963A (en) * | 2019-11-28 | 2020-02-21 | 安徽微威减震降噪技术研究院 | Impact-resistant elastomer composite rubber material and preparation method thereof |
| CN111518396B (en) * | 2020-05-07 | 2022-03-11 | 江门市融泰新材料科技有限公司 | High-ductility and high-strength polyamide material and preparation method thereof |
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| US3539664A (en) * | 1968-02-14 | 1970-11-10 | Allied Chem | Homogeneous nylon graft copolymers onto ethylene copolymer backbones |
| CN101205363A (en) * | 2007-12-06 | 2008-06-25 | 同济大学 | Preparation method of carboxylic carbon nano-tube /nylon 66 composite material |
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