CN103333333A - Preparation method of nano copper-polyamide composite - Google Patents
Preparation method of nano copper-polyamide composite Download PDFInfo
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- CN103333333A CN103333333A CN2013102952669A CN201310295266A CN103333333A CN 103333333 A CN103333333 A CN 103333333A CN 2013102952669 A CN2013102952669 A CN 2013102952669A CN 201310295266 A CN201310295266 A CN 201310295266A CN 103333333 A CN103333333 A CN 103333333A
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Abstract
The invention belongs to the technical field of polymer matrix nano composite preparation, and particularly relates to a preparation method of a nano copper-polyamide composite. The method belongs to an in-situ reaction technique, and adopts the main design principle that in a process that a polyamide monomer is polymerized to form a polymer, a copper compound is reduced to nano metal particles of pure copper in a reducing atmosphere of the polyamide monomer or under the action of an additional reducing agent, the nano metal particles are uniformly dispersed in a polyamide base material, and then the nano copper-polyamide composite is prepared by one step. The method can allow nano copper to be dispersed in the base material in a primary particle state, so that aggregation of the nano particles is avoided, and the chemical stability of the nano copper particles is kept; and compared with the prior art, a technology of preparing the polymer nano metal composite is simplified, and the method has better industrial application prospects.
Description
Technical field
The invention belongs to the polymer based nanocomposites preparing technical field, be specifically related to a kind of preparation method of nanometer copper-polyamide compoiste material.
Background technology
Nano material is compared the performance with many excellences with conventional material, prepare polymer based nanocomposites as filler, can significantly improve the over-all properties of the aspect such as mechanics, tribology, heat, electricity of polymer materials, have simultaneously that addition is few, the obvious results advantage.Prepare the method that polymer based nanocomposites adopts melt blending usually, still, this method only is difficult to reach nano material aim of even dispersion in polymer matrix material by the conversion velocity of shear, is unfavorable for the embodiment of nano material nano-meter characteristic.Especially in the preparation process of metal nanometer composite material, metal nano material is easy to oxidation, is difficult to embody the characteristic of metal nano material, also is difficult to reach the homodisperse effect of metallic nano-particle.For solving the problem of metallic nano-particle oxidation and reunion, Chen etc. prepare the core-shell particles of silicon-dioxide-polymethylmethacrylate clad nano silver particles with chemical reduction method, then prepare methyl methacrylate base nano silver composite material (Ag nanoparticles-coated silica – PMMA core-shell microspheres and hollow PMMA microspheres with Ag nanoparticles in the interior surfaces by emulsion polymerization, Colloids and Surfaces A:Physi cochem. Eng. Aspects, 2006,272:151-156).Vasilyeva etc. have prepared polypyrrole base nanotube-palladium composite material (Synthesis and characterization of palladium nanoparticle/polypyrrole composites by the original position method of formation, J. Phys. Chem. C, 2008,112:19878-19885).Zhu etc. have utilized microwave-assisted technology one-step synthesis polyamide-based nanometer silver, platinum, copper nano composite material (Microwave-assisted one-step synthesis of polyacrylamide-metal (M=Ag, Pt, Cu), J. Phys. Chem. B, 2006,110:8593-8597).Among the preparation method of a kind of nano copper particle that Chinese patent 200810037326.6 is announced, utilize the strong coordination of a plurality of amino that exist in the dendrimer of phenyl ring for nuclear to prepare nanometer copper, have effect preferably.But above these methods can solve the metallic nano-particle agglomeration traits, but always have complex process, the easy oxidation of nanometer copper, are unfavorable for drawbacks such as commercial application.
Summary of the invention
The object of the invention is to provide that operation is easy, the preparation method of a kind of nanometer copper-polyamide compoiste material of being easy to commercial application.
The present invention adopts following technical scheme.
A kind of preparation method of nanometer copper-polyamide compoiste material may further comprise the steps:
(1) monomer of polyamide, distilled water, copper compound and catalyzer are added in the reaction vessel;
Above-mentioned monomer of polyamide is hexanolactam, or the salt of diamine and diprotic acid formation, or 6-aminocaprolc acid;
Above-mentioned copper compound is cupric oxide, copper hydroxide;
Above-mentioned catalyzer be mineral acid or organic acid any;
(2) under 1 ~ 16 atmospheric pressure, the reacting by heating container is warming up to 180 ~ 220 ℃, keeps constant temperature and pressure 1 ~ 3.5h;
(3) under 1 ~ 16 atmospheric pressure, the reacting by heating container is warming up to 230 ~ 265 ℃, keeps constant temperature and pressure 1 ~ 2h;
(4) after reaction finishes, reaction vessel is vacuumized, when vacuum tightness reach-0.07 ~-during 0.08MP, namely make nanometer copper-polyamide compoiste material.
The salt that the described diamine of step (1) and diprotic acid form is nylon salt (nylon salt) or sebacic acid decamethylene diamine salt (nylon 1010 salt).
According to the mass fraction, monomer of polyamide is 100.0 parts in the step (1), and distilled water is 0.1 ~ 5.0 part, and copper compound is 0.1 ~ 1.0 part, and catalyzer is 0.5 ~ 3.0 part.
Step can add reductive agent in (1).
Add the mixture that reductive agent is one or more arbitrary proportions in hydrazine hydrate, ethylene glycol, formaldehyde, amino acid, the quadrol in the step (1).
Adding reductive agent reductive agent mass fraction in the step (1) is 0.1 ~ 1.0 part.
Step (2), step feed nitrogen in (3) in reaction vessel, avoid the copper that is reduced oxidized again.
Need to prove that monomer of polyamide and distilled water can replace with the aqueous solution of monomer of polyamide or the ethanolic soln of monomer of polyamide described in the step (1).
The main principle of design of invention is: form in the polymer process in the monomer of polyamide polymerization, copper compound is under the reducing atmosphere of monomer of polyamide or be reduced into the nano metal particulate of elemental copper under the additional reducing agent effect, be dispersed in the polyamide substrate material, thereby a step is made nanometer copper-polyamide compoiste material.The effect of distilled water is to make the lactan open loop and form active group in the reaction system, is beneficial to the carrying out of polyreaction; The effect of catalyzer is to be conducive to generate polymeric amide and control molecular weight.
The invention belongs to a kind of original position generation technique, this method can make nanometer copper be dispersed in the body material with the primary partical state, avoided the reunion of nanoparticle, the chemical stability that has kept nanometer copper particulate, simultaneously compared with prior art, simplify the technology of preparation polymer nanocomposite metal composite, had good industrialized application prospect.
Description of drawings
Fig. 1 is the transmission electron microscope picture of nanometer copper-polyamide 6 composite material;
Fig. 2 is nanometer copper-polyamide 6 composite material X-ray diffraction (XRD) curve.
Embodiment
Below in conjunction with embodiment the present invention will be further explained explanation.
Embodiment 1
(1) with hexanolactam 100g, catalyzer hexanodioic acid 1g, distilled water 2mL, cupric oxide 0.5g joins in the reaction vessel;
(2) the reacting by heating container is warming up to 190 ℃ under normal pressure, reaction 3h, and in this process, copper oxide reduction is red-brown nanometer copper;
(3) feed N
2, discharge the water vapor in the reaction system simultaneously, reaction vessel is continued heating, make system be warming up to 230 ℃, continue reaction 1.5h;
(4) stop logical N
2, keep 230 ℃ of conditions, begin to vacuumize, vacuum tightness progressively improves process, also is the small molecules process of progressively removing, when vacuum tightness reach-during 0.08MPa, reaction finishes, and namely gets nanometer copper-polyamide compoiste material.
Present embodiment gained nanometer copper-polyamide compoiste material, it is nanometer copper-polyamide 6 that the contriver names its code name, and it is carried out electron-microscope scanning, the result shows that nanometer copper can evenly disperse as shown in Figure 1 in the polyamide substrate material; It is carried out X-ray diffraction analysis, and as shown in Figure 2, the absorption peak of the nanometer copper that wherein generates is consistent with the absorption peak of copper simple substance, show nanometer copper can stable existence in the polyamide substrate material.
(1) with 6-aminocaprolc acid 100g, catalyzer hexanodioic acid 1g, distilled water 2mL, copper hydroxide 0.5g joins in the reaction vessel;
(2) under the condition of normal pressure, to reaction vessel heat temperature raising to 200 ℃, reaction 3h, in this process, copper oxide reduction is red-brown nanometer copper;
(3) feed N
2, discharge the water vapor in the reaction system simultaneously, reaction vessel is continued heating, make system temperature rise to 260 ℃, continue reaction 1h,
(4) stop logical N
2, keep 235 ℃ of conditions, begin to vacuumize, when be decompressed to-during 0.08MPa, reaction finishes, and namely gets nanometer copper-polyamide compoiste material.
Embodiment 3
(1) aqueous solution, catalyzer acetic acid 1mL, reductive agent quadrol 0.6mL and the copper hydroxide 0.5g with 100g nylon salt (nylon salt) 60% adds in the reaction vessel,
(2) under 10 atmospheric pressure conditions, be warming up to 200 ℃ gradually, reaction 3h obtains prepolymer, and copper hydroxide is reduced to red-brown nanometer copper;
(3) unload and be depressed into normal pressure, feed N
2, reaction system is continued heat temperature raising to 260 ℃, keep 2h;
(4) stop logical N
2, under the condition of 260 ℃ of maintenances, beginning to vacuumize, pressure reduces to-0.08MPa, gets nanometer copper-polyamide compoiste material.
Embodiment 4
(1) 500g is contained in ethanolic soln, reductive agent hydrazine hydrate 0.5mL and the cupric oxide 0.5g adding reaction vessel of 20% sebacic acid decamethylene diamine salt (nylon 1010 salt);
(2) vacuumize 20 minutes, to be decompressed to-to charge into behind the 0.09MPa nitrogen and to return to normal pressure (this step main purpose is in order vacuumizing in advance, avoid copper to be reduced after oxidized again), the reacting by heating system is warming up to 180 ℃, the fusion of nylon 1010 salt, copper oxide reduction are red-brown nanometer copper
(3) continue to feed nitrogen and make system pressure rise to 12 normal atmosphere, when the reacting by heating system was warming up to 230 ℃, insulation 1h discharged steam then, is depressurized to normal pressure, and cooling obtains nanometer copper-polyamide compoiste material.
Above embodiment is the most preferred embodiment of the claimed technical scheme of the present invention, is not to concrete restriction of the present invention.On embodiment provided by the present invention basis, those skilled in the art make amendment to the correlation technique parameter can obtain the parameters value of the technical scheme that the present invention asks for protection, so the present invention embodiment of no longer providing the relevant parameter that too repeats to change.
Claims (7)
1. the preparation method of a nanometer copper-polyamide compoiste material is characterized in that this method may further comprise the steps:
(1) monomer of polyamide, distilled water, copper compound and catalyzer are added in the reaction vessel;
Above-mentioned monomer of polyamide is hexanolactam, or the salt of diamine and diprotic acid formation, or 6-aminocaprolc acid;
Above-mentioned copper compound is cupric oxide, copper hydroxide;
Above-mentioned catalyzer be mineral acid or organic acid any;
(2) under 1 ~ 16 atmospheric pressure, the reacting by heating container is warming up to 180 ~ 220 ℃, keeps constant temperature and pressure 1 ~ 3.5h;
(3) under 1 ~ 16 atmospheric pressure, the reacting by heating container is warming up to 230 ~ 265 ℃, keeps constant temperature and pressure 1 ~ 2h;
(4) after reaction finishes, reaction vessel is vacuumized, when vacuum tightness reach-0.07 ~-during 0.08MP, namely make nanometer copper-polyamide compoiste material.
2. the preparation method of nanometer copper-polyamide compoiste material according to claim 1, it is characterized in that: the salt that the described diamine of step (1) and diprotic acid form is nylon salt or sebacic acid decamethylene diamine salt.
3. the preparation method of nanometer copper-polyamide compoiste material according to claim 1, it is characterized in that: according to the mass fraction, monomer of polyamide is 100.0 parts in the step (1), and distilled water is 0.1 ~ 5.0 part, copper compound is 0.1 ~ 1.0 part, and catalyzer is 0.5 ~ 3.0 part.
4. the preparation method of nanometer copper-polyamide compoiste material according to claim 1, it is characterized in that: step can add reductive agent in (1).
5. as the preparation method of nanometer copper-polyamide compoiste material as described in the claim 4, it is characterized in that: described reductive agent is the mixture of one or more arbitrary proportions in hydrazine hydrate, ethylene glycol, formaldehyde, amino acid, the quadrol.
6. as the preparation method of nanometer copper-polyamide compoiste material as described in the claim 5, it is characterized in that: the reductive agent mass fraction is 0.1 ~ 1.0 part.
7. the preparation method of nanometer copper-polyamide compoiste material according to claim 1, it is characterized in that: step (2), step feed nitrogen in (3) in reaction vessel.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105295029A (en) * | 2015-12-04 | 2016-02-03 | 黄淮学院 | Nano zinc oxide and polyamide composite and preparation method thereof |
| CN105332083A (en) * | 2015-12-01 | 2016-02-17 | 东华大学 | Preparation method for nano copper oxide-loaded mesoporous zirconium phosphate antibacterial polyamide fiber |
| CN105350104A (en) * | 2015-12-01 | 2016-02-24 | 东华大学 | Method for preparing mesoporous zirconium phosphate supported copper oxide antibacterial polyvinyl alcohol fibers |
| EP3073321A1 (en) * | 2015-03-26 | 2016-09-28 | Centre National de la Recherche Scientifique (C.N.R.S.) | Metal-polymer composite material |
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| US20020068795A1 (en) * | 2000-12-04 | 2002-06-06 | Jongok Won | Inorganic-organic hybrid polymers composed of nano-particles on the surface using dendrimers and manufacturing method thereof |
| CN101864074A (en) * | 2010-06-04 | 2010-10-20 | 河南大学 | Preparation method of nanometer SiO2/nylon 6 nanometer composite material |
| CN102585493A (en) * | 2010-12-28 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method and application thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020068795A1 (en) * | 2000-12-04 | 2002-06-06 | Jongok Won | Inorganic-organic hybrid polymers composed of nano-particles on the surface using dendrimers and manufacturing method thereof |
| CN101864074A (en) * | 2010-06-04 | 2010-10-20 | 河南大学 | Preparation method of nanometer SiO2/nylon 6 nanometer composite material |
| CN102585493A (en) * | 2010-12-28 | 2012-07-18 | 上海杰事杰新材料(集团)股份有限公司 | Nano particle/polyamide composite material, preparation method and application thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3073321A1 (en) * | 2015-03-26 | 2016-09-28 | Centre National de la Recherche Scientifique (C.N.R.S.) | Metal-polymer composite material |
| WO2016151141A1 (en) * | 2015-03-26 | 2016-09-29 | Centre National De La Recherche Scientifique | Metal-polymer composite material |
| US10808138B2 (en) | 2015-03-26 | 2020-10-20 | Centre National De La Recherche Scientifique | Metal-polymer composite material |
| CN105332083A (en) * | 2015-12-01 | 2016-02-17 | 东华大学 | Preparation method for nano copper oxide-loaded mesoporous zirconium phosphate antibacterial polyamide fiber |
| CN105350104A (en) * | 2015-12-01 | 2016-02-24 | 东华大学 | Method for preparing mesoporous zirconium phosphate supported copper oxide antibacterial polyvinyl alcohol fibers |
| CN105350104B (en) * | 2015-12-01 | 2017-10-27 | 东华大学 | A kind of preparation method of Mesoporous zirconium phosphate loaded copper oxide antibacterial polyethylene alcohol fiber |
| CN105295029A (en) * | 2015-12-04 | 2016-02-03 | 黄淮学院 | Nano zinc oxide and polyamide composite and preparation method thereof |
| CN105295029B (en) * | 2015-12-04 | 2018-10-30 | 黄淮学院 | A kind of nano zine oxide-polyamide compoiste material and preparation method thereof |
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