CN102189268A - Core-shell nanometer copper/polyacrylonitrile composite material and preparation method thereof - Google Patents
Core-shell nanometer copper/polyacrylonitrile composite material and preparation method thereof Download PDFInfo
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- CN102189268A CN102189268A CN 201110107368 CN201110107368A CN102189268A CN 102189268 A CN102189268 A CN 102189268A CN 201110107368 CN201110107368 CN 201110107368 CN 201110107368 A CN201110107368 A CN 201110107368A CN 102189268 A CN102189268 A CN 102189268A
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Abstract
The invention discloses a core-shell nanometer copper/polyacrylonitrile composite material and a preparation method thereof, relates to a polyacrylonitrile composite material and a preparation method thereof, and solves the problem of low anti-static and fireproof properties of the conventional polyacrylonitrile. The composite material is prepared from nanometer copper, polyvinylpyrrolidone, polyoxyethylene octylphenol ether (OP-10), sodium dodecyl benzene sulfonate, azodiisobutyronitrile, acrylonitrile and polyvinyl alcohol, wherein the nanometer copper is prepared from anhydrous copper sulfate, OP-10, sodium hydroxide and hydrazine hydrate. The method comprises the following steps of: reacting mixed solution of the copper sulfate, the OP-10, the sodium hydroxide and the hydrazine hydrate under heating, and washing and drying the filtered solid matter to obtain the nanometer copper; and adding the OP-10, the sodium dodecyl benzene sulfonate and the nanometer copper into mixed solution of the polyvinylpyrrolidone and the nanometer copper, performing ultrasonic treatment, adding the polyvinyl alcohol, introducing nitrogen, dripping mixed solution of the azodiisobutyronitrile and the acrylonitrile, raising the temperature for reaction, and washing and drying to obtain a product. The product can be used for the field of anti-static and fireproof materials.
Description
Technical field
The present invention relates to polyacrylonitrile composite and preparation method thereof.
Background technology
Nano composite material is different with the inorganic filler/polymer composite body of routine, be not organic with inorganic simple the mixing, but two-phase is composited in nano-scale range.Because area is very big between decentralized photo and the continuous phase, has very strong interaction between the interface, produces desirable adhesive property, make the interface fuzzy.Nano metal/polymer core-shell type composite material can be realized the mutual supplement with each other's advantages or the reinforcement of group element material, utilize the special performance of metal nanoparticle constituent element cost-effectively, it is the effective way of high surface energy metal nanoparticle stabilisation, for development high-performance, nano material multi-functional, low-cost, practicability provide new approaches, wide application prospect is arranged at aspects such as antibiotic, clean, antistatic certainly, electromagnetic shielding, cell separation, Separation of Proteins, metal ultrafine powder immobilization carrier, catalyst.Research application at electromagnetic shielding material, electrically-conducting paint has far-reaching and significant meaning.Polyacrylonitrile is one of most important synthetic fibers, and its product is widely used in the top grade decoration.But, the range of application of polyacrylonitrile is restricted because the antistatic and the fire line of polyacrylonitrile are poor.
Summary of the invention
The present invention is the technical problem that will solve the antistatic of existing polyacrylonitrile and fire line difference, and core-shell type nanometer copper/polyacrylonitrile composite and preparation method thereof is provided.
Core-shell type nanometer copper of the present invention/polyacrylonitrile composite is made by the poly-vinyl alcohol solution that is 1% (quality) by 1 part of nanometer copper of ratio of quality and the number of copies, 0.80～0.86 part of polyvinylpyrrolidone, 0.30～0.35 part of OP-10,0.50～0.53 part of neopelex, 0.080～0.086 part of azodiisobutyronitrile, acrylonitrile and concentration, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.5mL～1.7mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.3mL～8.6mL; Nanometer copper is made by 1 part of anhydrous cupric sulfate, 4～5 parts of OP-10,0.5～0.6 part of NaOH and 2.2～2.3 parts of hydrazine hydrates by ratio of quality and the number of copies.
The preparation method of above-mentioned core-shell type nanometer copper/polyacrylonitrile composite carries out according to the following steps: one, take by weighing 1 part of anhydrous cupric sulfate, 4 parts～5 parts OP-10,0.5 part～0.6 part NaOH and 2.2 parts～2.3 parts hydrazine hydrates by ratio of quality and the number of copies; Two, be that the proportional quantities of 1g: 12mL～13mL is removed ionized water by the mass volume ratio of anhydrous cupric sulfate and water, the anhydrous cupric sulfate that step 1 is taken by weighing is dissolved in the deionized water, obtains copper-bath; Three, be that the proportional quantities of 1g: 3mL～3.5mL is removed ionized water by the mass volume ratio of OP-10 and water, the OP-10 that step 1 is taken by weighing is dissolved in the deionized water, obtains OP-10 solution; Four, be that the proportional quantities of 1g: 25mL～27mL is removed ionized water by the mass volume ratio of NaOH and water, the NaOH that step 1 is taken by weighing is dissolved in the deionized water, obtains sodium hydroxide solution; Five, be that the proportional quantities of 1g: 5mL～6mL is removed ionized water by the mass volume ratio of hydrazine hydrate and water, the hydrazine hydrate that step 1 is taken by weighing is dissolved in the deionized water, obtains hydrazine hydrate solution; Six, the copper-bath of step 2 preparation, the OP-10 solution of step 3 preparation, the sodium hydroxide solution of step 4 preparation and the hydrazine hydrate solution of step 5 preparation are joined in the copper-bath of step 2 preparation successively, join in the there-necked flask with backflow agitating device after stirring again, low whipping speed is under the condition of 300r/min～400r/min, be warming up to 70 ℃～75 ℃ and keep 1h～1.5h, be cooled to room temperature, obtain mixture; Seven, the mixture that step 6 is obtained filters, after solid formation disperseed with acetone, wash, use again absolute ethanol washing earlier with water, at last with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain nanometer copper; Eight, take by weighing the nanometer copper of 1 part of step 7 preparation, 0.80～0.86 part polyvinylpyrrolidone, 0.30～0.35 part OP-10,0.50～0.53 part neopelex, 0.080～0.086 part azodiisobutyronitrile by ratio of quality and the number of copies, in nanometer copper and concentration is that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is that the ratio of 1g: 1.5mL～1.7mL takes by weighing the poly-vinyl alcohol solution that concentration is 1% (quality), is that the ratio of 1g: 8.3mL～8.6mL takes by weighing acrylonitrile in the mass volume ratio of nanometer copper and acrylonitrile; Nine, in nanometer copper and deionized water mass volume ratio be that the ratio of 1g: 35mL～37mL takes by weighing deionized water, the nanometer copper and the polyvinylpyrrolidone that step 8 are taken by weighing join in the deionized water again, ultrasonic processing 30min～35min obtains solution A; Ten, by the mass volume ratio of OP-10 and water is that the proportional quantities of 1g: 20mL～25mL is removed ionized water, the OP-10 that step 8 is taken by weighing is dissolved in the deionized water, obtain OP-10 solution, be that the proportional quantities of 1g: 20mL～25mL is removed ionized water by the mass volume ratio of neopelex and water again, the neopelex that step 8 is taken by weighing is dissolved in the deionized water, obtain neopelex solution, again the OP-10 solution of this step preparation and neopelex are joined in the solution A that step 9 obtains, ultrasonic processing 30min～35min obtains solution B; 11, the azodiisobutyronitrile that step 8 is taken by weighing is dissolved in the acrylonitrile that step 8 takes by weighing, and joins in the constant pressure funnel this acrylonitrile solution standby; 12, the concentration that step 8 is taken by weighing is that the poly-vinyl alcohol solution of 1% (quality) joins in the there-necked flask with stirring and refluxing device, the solution B that step 10 is obtained also joins in the there-necked flask again, low whipping speed is to heat up under the condition of 180r/min～200r/min, when temperature reaches 60 ℃～63 ℃, feed nitrogen protection, acrylonitrile solution in the described constant pressure funnel of step 11 is dropwise splashed in the there-necked flask, is back flow reaction 8h～9h under 60 ℃～63 ℃ the condition in temperature; 13, measure acetone by the volume ratio 1: 0.5～3 of liquid in the there-necked flask and acetone, and acetone joined in the there-necked flask, stir 30min～40min, refilter, with solid formation with wash with water earlier, again with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain core-shell type nanometer copper/polyacrylonitrile composite.
The present invention uses OP-10 as surfactant earlier, and the hydrazine hydrate liquid phase reduction is prepared the pure metallic copper nano particle with face-centred cubic structure, and particle diameter is 30nm～50nm, and controllable size, and hydrazine hydrate generates N in course of reaction simultaneously
2Can prevent the metallic copper oxidation.And then be nuclear with nanometer copper, with the polyacrylonitrile is the core-shell type of shell, preparation core-shell type nanometer copper/polyacrylonitrile composite, because nanometer copper is uniformly dispersed in the composite, thereby make core-shell type nanometer copper/polyacrylonitrile composite have electric conductivity preferably, its body resistivity is compared five orders of magnitude that descend with the virgin pp nitrile, for the antistatic material technology of preparing provides new research direction; The oxidate temperature of the core-shell type nanometer copper/polyacrylonitrile composite of preparation improves 10 ℃ than polyacrylonitrile, and this material can be used as fire proofing material and uses.
Core-shell type nanometer copper of the present invention/polyacrylonitrile composite can be used for antistatic, fire proofing material field.
Description of drawings
The stereoscan photograph of Fig. 1 nanometer copper that to be the specific embodiment 40 obtain once step 7; Fig. 2 is the stereoscan photograph of the core-shell type nanometer copper/polyacrylonitrile composite of the specific embodiment 41 preparations.
The specific embodiment
The specific embodiment one: the core-shell type nanometer copper/polyacrylonitrile composite of present embodiment is by 1 part of nanometer copper pressing ratio of quality and the number of copies, 0.80～0.86 part of polyvinylpyrrolidone, 0.30～0.35 part of OP-10,0.50～0.53 part of neopelex, 0.080～0.086 part of azodiisobutyronitrile, acrylonitrile and concentration are that the poly-vinyl alcohol solution of 1% (quality) is made, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.5mL～1.7mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.3mL～8.6mL; Nanometer copper is made by 1 part of anhydrous cupric sulfate, 4～5 parts of OP-10,0.5～0.6 part of NaOH and 2.2～2.3 parts of hydrazine hydrates by ratio of quality and the number of copies.
Present embodiment uses OP-10 as surfactant earlier, and the hydrazine hydrate liquid phase reduction is prepared the pure metallic copper nano particle with face-centred cubic structure, and particle diameter is 30nm～50nm, and controllable size, and hydrazine hydrate generates N in course of reaction simultaneously
2Can prevent the metallic copper oxidation.And then be nuclear with nanometer copper, with the polyacrylonitrile is the core-shell type of shell, preparation core-shell type nanometer copper/polyacrylonitrile composite, because nanometer copper is uniformly dispersed in the composite, thereby make core-shell type nanometer copper/polyacrylonitrile composite have electric conductivity preferably, its body resistivity is compared five orders of magnitude that descend with the virgin pp nitrile, for the antistatic material technology of preparing provides new research direction; The oxidate temperature of the core-shell type nanometer copper/polyacrylonitrile composite of preparation improves 10 ℃ than polyacrylonitrile, and this material can be used as fire proofing material and uses.
The specific embodiment two: what present embodiment and the specific embodiment one were different is: core-shell type nanometer copper/polyacrylonitrile composite is by 1 part of nanometer copper pressing ratio of quality and the number of copies, 0.81～0.85 part of polyvinylpyrrolidone, 0.31～0.34 part of OP-10,0.51～0.52 part of neopelex, 0.082～0.085 part of azodiisobutyronitrile, acrylonitrile and concentration are that the poly-vinyl alcohol solution of 1% (quality) is made, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.55mL～1.65mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.4mL～8.5mL.Other is identical with the specific embodiment one.
The specific embodiment three: what present embodiment and the specific embodiment one were different is: core-shell type nanometer copper/polyacrylonitrile composite is made by the poly-vinyl alcohol solution that is 1% (quality) by 1 part of nanometer copper of ratio of quality and the number of copies, 0.83 part of polyvinylpyrrolidone, 0.33 part of OP-10,0.515 part of neopelex, 0.083 part of azodiisobutyronitrile, acrylonitrile and concentration, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.6mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.45mL.Other is identical with the specific embodiment one.
The specific embodiment four: what present embodiment was different with one of specific embodiment one to three is: nanometer copper is made by 1 part of anhydrous cupric sulfate, 4.1～4.9 parts of OP-10,0.51～0.59 part of NaOH and 2.21～2.29 parts of hydrazine hydrates by ratio of quality and the number of copies.Other is identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different with one of specific embodiment one to three is: nanometer copper is made by 1 part of anhydrous cupric sulfate, 4.5 parts of OP-10,0.55 part of NaOH and 2.25 parts of hydrazine hydrates by ratio of quality and the number of copies.Other is identical with one of specific embodiment one to three.
The specific embodiment six: the preparation method of the core-shell type nanometer copper/polyacrylonitrile composite of present embodiment carries out according to the following steps: one, take by weighing 1 part of anhydrous cupric sulfate, 4 parts～5 parts OP-10,0.5 part～0.6 part NaOH and 2.2 parts～2.3 parts hydrazine hydrates by ratio of quality and the number of copies; Two, be that the proportional quantities of 1g: 12mL～13mL is removed ionized water by the mass volume ratio of anhydrous cupric sulfate and water, the anhydrous cupric sulfate that step 1 is taken by weighing is dissolved in the deionized water, obtains copper-bath; Three, be that the proportional quantities of 1g: 3mL～3.5mL is removed ionized water by the mass volume ratio of OP-10 and water, the OP-10 that step 1 is taken by weighing is dissolved in the deionized water, obtains OP-10 solution; Four, be that the proportional quantities of 1g: 25mL～27mL is removed ionized water by the mass volume ratio of NaOH and water, the NaOH that step 1 is taken by weighing is dissolved in the deionized water, obtains sodium hydroxide solution; Five, be that the proportional quantities of 1g: 5mL～6mL is removed ionized water by the mass volume ratio of hydrazine hydrate and water, the hydrazine hydrate that step 1 is taken by weighing is dissolved in the deionized water, obtains hydrazine hydrate solution; Six, the copper-bath of step 2 preparation, the OP-10 solution of step 3 preparation, the sodium hydroxide solution of step 4 preparation and the hydrazine hydrate solution of step 5 preparation are joined in the copper-bath of step 2 preparation successively, join in the there-necked flask with backflow agitating device after stirring again, low whipping speed is under the condition of 300r/min～400r/min, be warming up to 70 ℃～75 ℃ and keep 1h～1.5h, be cooled to room temperature, obtain mixture; Seven, the mixture that step 6 is obtained filters, after solid formation disperseed with acetone, wash, use again absolute ethanol washing earlier with water, at last with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain nanometer copper; Eight, take by weighing the nanometer copper of 1 part of step 7 preparation, 0.80～0.86 part polyvinylpyrrolidone, 0.30～0.35 part OP-10,0.50～0.53 part neopelex, 0.080～0.086 part azodiisobutyronitrile by ratio of quality and the number of copies, in nanometer copper and concentration is that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is that the ratio of 1g: 1.5mL～1.7mL takes by weighing the poly-vinyl alcohol solution that concentration is 1% (quality), is that the ratio of 1g: 8.3mL～8.6mL takes by weighing acrylonitrile in the mass volume ratio of nanometer copper and acrylonitrile; Nine, in nanometer copper and deionized water mass volume ratio be that the ratio of 1g: 35mL～37mL takes by weighing deionized water, the nanometer copper and the polyvinylpyrrolidone that step 8 are taken by weighing join in the deionized water again, ultrasonic processing 30min～35min obtains solution A; Ten, by the mass volume ratio of OP-10 and water is that the proportional quantities of 1g: 20mL～25mL is removed ionized water, the OP-10 that step 8 is taken by weighing is dissolved in the deionized water, obtain OP-10 solution, be that the proportional quantities of 1g: 20mL～25mL is removed ionized water by the mass volume ratio of neopelex and water again, the neopelex that step 8 is taken by weighing is dissolved in the deionized water, obtain neopelex solution, again the OP-10 solution of this step preparation and neopelex are joined in the solution A that step 9 obtains, ultrasonic processing 30min～35min obtains solution B; 11, the azodiisobutyronitrile that step 8 is taken by weighing is dissolved in the acrylonitrile that step 8 takes by weighing, and joins in the constant pressure funnel this acrylonitrile solution standby; 12, the concentration that step 8 is taken by weighing is that the poly-vinyl alcohol solution of 1% (quality) joins in the there-necked flask with stirring and refluxing device, the solution B that step 10 is obtained also joins in the there-necked flask again, low whipping speed is to heat up under the condition of 180r/min～200r/min, when temperature reaches 60 ℃～63 ℃, feed nitrogen protection, acrylonitrile solution in the described constant pressure funnel of step 11 is dropwise splashed in the there-necked flask, is back flow reaction 8h～9h under 60 ℃～63 ℃ the condition in temperature; 13, measure acetone in the ratio of the volume ratio 1: 0.5～3 of liquid in the there-necked flask and acetone, and acetone joined in the there-necked flask, stir 30min～40min, refilter, with solid formation with wash with water earlier, again with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain core-shell type nanometer copper/polyacrylonitrile composite.
Present embodiment uses OP-10 as surfactant earlier, and the hydrazine hydrate liquid phase reduction is prepared the pure metallic copper nano particle with face-centred cubic structure, and particle diameter is 30nm～50nm, and controllable size, and hydrazine hydrate generates N in course of reaction simultaneously
2Can prevent the metallic copper oxidation.And then be nuclear with nanometer copper, with the polyacrylonitrile is the core-shell type of shell, preparation core-shell type nanometer copper/polyacrylonitrile composite, because nanometer copper is uniformly dispersed in the composite, thereby make core-shell type nanometer copper/polyacrylonitrile composite have electric conductivity preferably, its body resistivity is compared five orders of magnitude that descend with the virgin pp nitrile, for the antistatic material technology of preparing provides new research direction; The oxidate temperature of the core-shell type nanometer copper/polyacrylonitrile composite of preparation improves 10 ℃ than polyacrylonitrile, and this material can be used as fire proofing material and uses.
The specific embodiment seven: what present embodiment and the specific embodiment six were different is: take by weighing 1 part of anhydrous cupric sulfate, 4.1 parts～4.9 parts OP-10,0.51 part～0.59 part NaOH and 2.21 parts～2.29 parts hydrazine hydrates in the step 1.Other is identical with the specific embodiment one.
The specific embodiment eight: what present embodiment and the specific embodiment six were different is: take by weighing 1 part of anhydrous cupric sulfate, 4.5 parts of OP-10,0.55 part of NaOH and 2.25 parts of hydrazine hydrates in the step 1.Other is identical with the specific embodiment one.
The specific embodiment nine: what present embodiment was different with one of specific embodiment six to eight is: the mass volume ratio of anhydrous cupric sulfate and water is 1g: 12.2mL～12.8mL in the step 2.Other is identical with one of specific embodiment six to eight.
The specific embodiment ten: what present embodiment was different with one of specific embodiment six to eight is: the mass volume ratio of anhydrous cupric sulfate and water is 1g: 12.5mL in the step 2.Other is identical with one of specific embodiment six to eight.
The specific embodiment 11: what present embodiment was different with one of specific embodiment six to ten is: the mass volume ratio of OP-10 and water is 1g: 3.1mL～3.4mL in the step 3.Other is identical with one of specific embodiment six to ten.
The specific embodiment 12: what present embodiment was different with one of specific embodiment six to ten is: the mass volume ratio of OP-10 and water is 1g: 3.3mL in the step 3.Other is identical with one of specific embodiment six to ten.
The specific embodiment 13: what present embodiment was different with one of specific embodiment six to 12 is: the mass volume ratio of NaOH and water is 1g: 25.2mL～26.8mL in the step 4.Other is identical with one of specific embodiment six to 12.
The specific embodiment 14: what present embodiment was different with one of specific embodiment six to 12 is: the mass volume ratio of NaOH and water is 1g: 26mL in the step 4.Other is identical with one of specific embodiment six to 12.
The specific embodiment 15: what present embodiment was different with one of specific embodiment six to 14 is: the mass volume ratio of step 5 hydrazine hydrate and water is 1g: 5.1mL～5.9mL.Other is identical with one of specific embodiment six to 14.
The specific embodiment 16: what present embodiment was different with one of specific embodiment six to 14 is: the mass volume ratio of step 5 hydrazine hydrate and water is 1g: 5.5mL.Other is identical with one of specific embodiment six to 14.
The specific embodiment 17: what present embodiment was different with one of specific embodiment six to 16 is: the mixing speed of there-necked flask is 310r/min～390r/min in the step 6.Other is identical with one of specific embodiment six to 16.
The specific embodiment 18: what present embodiment was different with one of specific embodiment six to 16 is: the mixing speed of there-necked flask is 350r/min in the step 6.Other is identical with one of specific embodiment six to 16.
The specific embodiment 19: what present embodiment was different with one of specific embodiment six to 18 is: be warming up to 71 ℃～74 ℃ in the step 6 and keep 11h～1.4h.Other is identical with one of specific embodiment six to 18.
The specific embodiment 20: what present embodiment was different with one of specific embodiment six to 18 is: be warming up to 73 ℃ in the step 6 and keep 1.3h.Other is identical with one of specific embodiment six to 18.
The specific embodiment 21: what present embodiment was different with one of specific embodiment six to 20 is: vacuum drying temperature is that 51 ℃～54 ℃, vacuum are that 0.082MPa～0.088MPa, drying time are 25h～27h in the step 7.Other is identical with one of specific embodiment six to 20.
The specific embodiment 22: what present embodiment was different with one of specific embodiment six to 20 is: vacuum drying temperature is that 53 ℃, vacuum are that 0.085MPa, drying time are 26h in the step 7.Other is identical with one of specific embodiment six to 20.
The specific embodiment 23: what present embodiment was different with one of specific embodiment six to 22 is: take by weighing 1 part of nanometer copper by ratio of quality and the number of copies in the step 8,0.81～0.85 part polyvinylpyrrolidone, 0.31～0.34 part OP-10,0.51～0.52 part neopelex, 0.081～0.085 part azodiisobutyronitrile, in nanometer copper and concentration is that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is that the ratio of 1g: 1.55mL～1.65mL takes by weighing the poly-vinyl alcohol solution that concentration is 1% (quality), is that the ratio of 1g: 8.4mL～8.5mL takes by weighing acrylonitrile in the mass volume ratio of nanometer copper and acrylonitrile.Other is identical with one of specific embodiment six to 22.
The specific embodiment 24: what present embodiment was different with one of specific embodiment six to 22 is: take by weighing 1 part of nanometer copper by ratio of quality and the number of copies in the step 8,0.83 the polyvinylpyrrolidone of part, 0.33 the OP-10 of part, 0.515 the neopelex of part, 0.083 the azodiisobutyronitrile of part, in nanometer copper and concentration is that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is that the ratio of 1g: 1.60mL takes by weighing the poly-vinyl alcohol solution that concentration is 1% (quality), is that the ratio of 1g: 8.45mL takes by weighing acrylonitrile in the mass volume ratio of nanometer copper and acrylonitrile.Other is identical with one of specific embodiment six to 22.
The specific embodiment 25: what present embodiment was different with one of specific embodiment six to 24 is: in the step 9 nanometer copper and deionized water mass volume ratio be 1g: 35.5mL～36.5mL.Other is identical with one of specific embodiment six to 24.
The specific embodiment 26: what present embodiment was different with one of specific embodiment six to 24 is: in the step 9 nanometer copper and deionized water mass volume ratio be 1g: 36mL.Other is identical with one of specific embodiment six to 24.
The specific embodiment 27: what present embodiment was different with one of specific embodiment six to 26 is: nanometer copper and polyvinylpyrrolidone join the ultrasonic processing 31min～34min in back in the deionized water in the step 9.Other is identical with one of specific embodiment six to 26.
The specific embodiment 28: what present embodiment was different with one of specific embodiment six to 26 is: nanometer copper and polyvinylpyrrolidone join the ultrasonic processing 33min in back in the deionized water in the step 9.Other is identical with one of specific embodiment six to 26.
The specific embodiment 29: what present embodiment was different with one of specific embodiment six to 28 is: the mass volume ratio of OP-10 and water is 1g: 21mL～24mL in the step 10, and the mass volume ratio of neopelex and water is 1g: 21mL～24mL.Other is identical with one of specific embodiment six to 28.
The specific embodiment 30: what present embodiment was different with one of specific embodiment six to 28 is: the mass volume ratio of OP-10 and water is 1g: 23mL in the step 10, and the mass volume ratio of neopelex and water is 1g: 22mL.Other is identical with one of specific embodiment six to 28.
The specific embodiment 31: what present embodiment was different with one of specific embodiment six to 30 is: ultrasonic processing 31min～34min in the step 10.Other is identical with one of specific embodiment six to 30.
The specific embodiment 32: what present embodiment was different with one of specific embodiment six to 30 is: ultrasonic processing 33min in the step 10.Other is identical with one of specific embodiment six to 30.
The specific embodiment 33: what present embodiment was different with one of specific embodiment six to 32 is: mixing speed is 185r/min～195r/min in the step 12.Other is identical with one of specific embodiment six to 32.
The specific embodiment 34: what present embodiment was different with one of specific embodiment six to 32 is: mixing speed is 190r/min in the step 12.Other is identical with one of specific embodiment six to 32.
The specific embodiment 35: what present embodiment was different with one of specific embodiment six to 34 is: in the step 12 when temperature reaches 60.5 ℃～62.5 ℃; feed nitrogen protection; and the acrylonitrile solution in the described constant pressure funnel of step 11 dropwise splashed in the there-necked flask, in temperature back flow reaction 8.2h～8.8h under 60.5 ℃～62.5 ℃ the condition.Other is identical with one of specific embodiment six to 34.
The specific embodiment 36: what present embodiment was different with one of specific embodiment six to 34 is: in the step 12 when temperature reaches 61.5 ℃; feed nitrogen protection; and the acrylonitrile solution in the described constant pressure funnel of step 11 dropwise splashed in the there-necked flask, in temperature back flow reaction 8.5h under 61.5 ℃ the condition.Other is identical with one of specific embodiment six to 34.
The specific embodiment 37: what present embodiment was different with one of specific embodiment six to 36 is: liquid in the step 13 in the there-necked flask and the volume ratio of acetone 1: 0.5～3.Other is identical with one of specific embodiment six to 36.
The specific embodiment 38: what present embodiment was different with one of specific embodiment six to 36 is: the liquid in the step 13 in the there-necked flask and the volume ratio of acetone 1: 1.Other is identical with one of specific embodiment six to 36.
The specific embodiment 39: what present embodiment was different with one of specific embodiment six to 38 is: vacuum drying temperature is that 51 ℃～54 ℃, vacuum are that 0.082MPa～0.088MPa, drying time are 25h～27h in the step 13.Other is identical with one of specific embodiment six to 38.
The specific embodiment 40: what present embodiment was different with one of specific embodiment six to 38 is: vacuum drying temperature is that 52 ℃, vacuum are that 0.085MPa, drying time are 26h in the step 13.Other is identical with one of specific embodiment six to 38.
The specific embodiment 41: the preparation method of the core-shell type nanometer copper/polyacrylonitrile composite of present embodiment carries out according to the following steps: one, take by weighing 4g anhydrous cupric sulfate, 16gOP-10,2g NaOH and 8.9g hydrazine hydrate; Two, measure the 50mL deionized water, the anhydrous cupric sulfate that step 1 is taken by weighing is dissolved in the deionized water, obtains copper-bath; Three, measure the 50mL deionized water, the OP-10 that step 1 is taken by weighing is dissolved in the deionized water, obtains OP-10 solution; Four, measure the 50mL deionized water, the NaOH that step 1 is taken by weighing is dissolved in the deionized water, obtains sodium hydroxide solution; Five, measure the 50mL deionized water, the hydrazine hydrate that step 1 is taken by weighing is dissolved in the deionized water, obtains hydrazine hydrate solution; Six, the OP-10 solution of step 3 preparation, the sodium hydroxide solution of step 4 preparation and the hydrazine hydrate solution of step 5 preparation are joined in the copper-bath of step 2 preparation successively, join in the there-necked flask with backflow agitating device after stirring again, low whipping speed is under the condition of 300r/min, be warming up to 70 ℃ and keep 1h, be cooled to room temperature, obtain mixture; Seven, the mixture that step 6 is obtained filters, after the dispersion of solid formation usefulness 30mL acetone, wash, use again absolute ethanol washing earlier with water, at last with after the acetone washing, be placed on temperature and be 50 ℃, vacuum and be dry 24h in the vacuum drying chamber of 0.09MPa, obtain nanometer copper; Eight, take by weighing OP-10, the 0.6g neopelex of polyvinylpyrrolidone, 0.4g part of nanometer copper, the 1g of 1.18g step 7 preparation, the azodiisobutyronitrile of 0.1g, 2mL concentration is the poly-vinyl alcohol solution of 1% (quality), the 10mL acrylonitrile; Nine, measure the 40mL deionized water, the nanometer copper and the polyvinylpyrrolidone that step 8 are taken by weighing join in the deionized water again, and ultrasonic processing 30min obtains solution A; Ten, measure the 10mL deionized water, the OP-10 that step 8 is taken by weighing is dissolved in the deionized water, obtain OP-10 solution, measure the 10mL deionized water again, the neopelex that step 8 is taken by weighing is dissolved in the deionized water, obtains neopelex solution, the OP-10 solution of this step preparation and neopelex is joined in the solution A that step 9 obtains again, ultrasonic processing 30min obtains solution B; 11, the azodiisobutyronitrile that step 8 is taken by weighing is dissolved in the acrylonitrile that step 8 takes by weighing, and joins in the constant pressure funnel this acrylonitrile solution standby; 12, the concentration that step 8 is taken by weighing is that the poly-vinyl alcohol solution of 1% (quality) joins in the there-necked flask with stirring and refluxing device, the solution B that step 10 is obtained also joins in the there-necked flask again, low whipping speed is to heat up under the condition of 180r/min, when temperature reaches 60 ℃, feed nitrogen protection, acrylonitrile solution in the described constant pressure funnel of step 11 is dropwise splashed in the there-necked flask, is back flow reaction 8h under 60 ℃ the condition in temperature; 13, by the volume ratio 1 of liquid in the there-necked flask and acetone: 30mL is measured acetone, and acetone joined in the there-necked flask, stir 30min～40min, refilter, with solid formation with wash with water earlier, again with after the acetone washing, be placed on temperature and be 50 ℃, vacuum and be dry 24h in the vacuum drying chamber of 0.09MPa, obtain core-shell type nanometer copper/polyacrylonitrile composite.
The stereoscan photograph of the nanometer copper of present embodiment through obtaining through step 7 as shown in Figure 1, as can be seen from Figure 1, nanometer copper has face-centred cubic structure, particle diameter is 28nm～30nm.
The stereoscan photograph of core-shell type nanometer copper/polyacrylonitrile composite that present embodiment obtains as shown in Figure 2, as can be seen from Figure 2, the pattern of core-shell type nanometer copper/polyacrylonitrile composite changes nanoparticle subclass sphere into by the cotton-shaped amorphous state of polyacrylonitrile, compare with the nanometer copper particle particle diameter of preparation shown in Figure 1, the core-shell type nanometer copper of Fig. 2/polyacrylonitrile composite particle diameter obviously increases, thereby this explanation polyacrylonitrile wraps up nanometer copper particle and makes grain diameter become big.
It is 1.6 * 10 that the core-shell type nanometer copper that present embodiment obtains/polyacrylonitrile composite is measured body resistivity
9Ω cm.
Is the oxidate temperature of core-shell type nanometer copper/polyacrylonitrile composite that present embodiment obtains? ℃, improving 10 ℃ than polyacrylonitrile, this material can be used as fire proofing material and uses.
Claims (10)
1. core-shell type nanometer copper/polyacrylonitrile composite, it is characterized in that core-shell type nanometer copper/polyacrylonitrile composite is by 1 part of nanometer copper by ratio of quality and the number of copies, 0.80～0.86 part of polyvinylpyrrolidone, 0.30～0.35 part of OP-10,0.50～0.53 part of neopelex, 0.080～0.086 part of azodiisobutyronitrile, acrylonitrile and concentration are that the poly-vinyl alcohol solution of 1% (quality) is made, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.5mL～1.7mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.3mL～8.6mL; Nanometer copper is made by 1 part of anhydrous cupric sulfate, 4～5 parts of OP-10,0.5～0.6 part of NaOH and 2.2～2.3 parts of hydrazine hydrates by ratio of quality and the number of copies.
2. core-shell type nanometer copper according to claim 1/polyacrylonitrile composite, it is characterized in that core-shell type nanometer copper/polyacrylonitrile composite is by 1 part of nanometer copper by ratio of quality and the number of copies, 0.81～0.85 part of polyvinylpyrrolidone, 0.31～0.34 part of OP-10,0.51～0.52 part of neopelex, 0.082～0.085 part of azodiisobutyronitrile, acrylonitrile and concentration are that the poly-vinyl alcohol solution of 1% (quality) is made, wherein nanometer copper and concentration are that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is 1g: 1.55mL～1.65mL, and the mass volume ratio of nanometer copper and acrylonitrile is 1g: 8.4mL～8.5mL.
3. core-shell type nanometer copper according to claim 1 and 2/polyacrylonitrile composite is characterized in that nanometer copper made by 1 part of anhydrous cupric sulfate, 4.1～4.9 parts of OP-10,0.51～0.59 part of NaOH and 2.21～2.29 parts of hydrazine hydrates by ratio of quality and the number of copies.
4. the preparation method of core-shell type nanometer copper as claimed in claim 1/polyacrylonitrile composite is characterized in that the preparation method of core-shell type nanometer copper/polyacrylonitrile composite carries out according to the following steps: one, take by weighing 1 part of anhydrous cupric sulfate, 4 parts～5 parts OP-10,0.5 part～0.6 part NaOH and 2.2 parts～2.3 parts hydrazine hydrates by ratio of quality and the number of copies; Two, be that the proportional quantities of 1g: 12mL～13mL is removed ionized water by the mass volume ratio of anhydrous cupric sulfate and water, the anhydrous cupric sulfate that step 1 is taken by weighing is dissolved in the deionized water, obtains copper-bath; Three, be that the proportional quantities of 1g: 3mL～3.5mL is removed ionized water by the mass volume ratio of OP-10 and water, the OP-10 that step 1 is taken by weighing is dissolved in the deionized water, obtains OP-10 solution; Four, be that the proportional quantities of 1g: 25mL～27mL is removed ionized water by the mass volume ratio of NaOH and water, the NaOH that step 1 is taken by weighing is dissolved in the deionized water, obtains sodium hydroxide solution; Five, be that the proportional quantities of 1g: 5mL～6mL is removed ionized water by the mass volume ratio of hydrazine hydrate and water, the hydrazine hydrate that step 1 is taken by weighing is dissolved in the deionized water, obtains hydrazine hydrate solution; Six, the copper-bath of step 2 preparation, the OP-10 solution of step 3 preparation, the sodium hydroxide solution of step 4 preparation and the hydrazine hydrate solution of step 5 preparation are joined in the copper-bath of step 2 preparation successively, join in the there-necked flask with backflow agitating device after stirring again, low whipping speed is under the condition of 300r/min～400r/min, be warming up to 70 ℃～75 ℃ and keep 1h～1.5h, be cooled to room temperature, obtain mixture; Seven, the mixture that step 6 is obtained filters, after solid formation disperseed with acetone, wash, use again absolute ethanol washing earlier with water, at last with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain nanometer copper; Eight, take by weighing the nanometer copper of 1 part of step 7 preparation, 0.80～0.86 part polyvinylpyrrolidone, 0.30～0.35 part OP-10,0.50～0.53 part neopelex, 0.080～0.086 part azodiisobutyronitrile by ratio of quality and the number of copies, in nanometer copper and concentration is that the mass volume ratio of the poly-vinyl alcohol solution of 1% (quality) is that the ratio of 1g: 1.5mL～1.7mL takes by weighing the poly-vinyl alcohol solution that concentration is 1% (quality), is that the ratio of 1g: 8.3mL～8.6mL takes by weighing acrylonitrile in the mass volume ratio of nanometer copper and acrylonitrile; Nine, in nanometer copper and deionized water mass volume ratio be that the ratio of 1g: 35mL～37mL takes by weighing deionized water, the nanometer copper and the polyvinylpyrrolidone that step 8 are taken by weighing join in the deionized water again, ultrasonic processing 30min～35min obtains solution A; Ten, by the mass volume ratio of OP-10 and water is that the proportional quantities of 1g: 20mL～25mL is removed ionized water, the OP-10 that step 8 is taken by weighing is dissolved in the deionized water, obtain OP-10 solution, be that the proportional quantities of 1g: 20mL～25mL is removed ionized water by the mass volume ratio of neopelex and water again, the neopelex that step 8 is taken by weighing is dissolved in the deionized water, obtain neopelex solution, again the OP-10 solution of this step preparation and neopelex are joined in the solution A that step 9 obtains, ultrasonic processing 30min～35min obtains solution B; 11, the azodiisobutyronitrile that step 8 is taken by weighing is dissolved in the acrylonitrile that step 8 takes by weighing, and joins in the constant pressure funnel this acrylonitrile solution standby; 12, the concentration that step 8 is taken by weighing is that the poly-vinyl alcohol solution of 1% (quality) joins in the there-necked flask with stirring and refluxing device, the solution B that step 10 is obtained also joins in the there-necked flask again, low whipping speed is to heat up under the condition of 180r/min～200r/min, when temperature reaches 60 ℃～63 ℃, feed nitrogen protection, acrylonitrile solution in the described constant pressure funnel of step 11 is dropwise splashed in the there-necked flask, is back flow reaction 8h～9h under 60 ℃～63 ℃ the condition in temperature; 13, measure acetone in the ratio of the volume ratio 1: 0.5～3 of liquid in the there-necked flask and acetone, and acetone joined in the there-necked flask, stir 30min～40min, refilter, with solid formation with wash with water earlier, again with after the acetone washing, be placed on temperature and be 50 ℃～55 ℃, vacuum and be dry 24h～28h in the vacuum drying chamber of 0.08MPa～0.09MPa, obtain core-shell type nanometer copper/polyacrylonitrile composite.
5. the preparation method of core-shell type nanometer copper according to claim 4/polyacrylonitrile composite is characterized in that mixing speed is 310r/min～390r/min in the step 6.
6. according to the preparation method of claim 4 or 5 described core-shell type nanometer copper/polyacrylonitrile composites, it is characterized in that being warming up in the step 6 71 ℃～74 ℃ and keep 11h～1.4h.
7. according to the preparation method of claim 4 or 5 described core-shell type nanometer copper/polyacrylonitrile composites, it is characterized in that in the step 7 that vacuum drying temperature is that 51 ℃～54 ℃, vacuum are that 0.082MPa～0.088MPa, drying time are 25h～27h.
8. according to the preparation method of claim 4 or 5 described core-shell type nanometer copper/polyacrylonitrile composites, it is characterized in that mixing speed is 185 rev/mins～195 rev/mins in the step 12.
9. according to the preparation method of claim 4 or 5 described core-shell type nanometer copper/polyacrylonitrile composites; it is characterized in that in the step 12 when temperature reaches 60.5 ℃～62.5 ℃; feed nitrogen protection; and the acrylonitrile solution in the described constant pressure funnel of step 11 dropwise splashed in the there-necked flask, in temperature back flow reaction 8.2h～8.8h under 60.5 ℃～62.5 ℃ the condition.
10. according to the preparation method of claim 4 or 5 described core-shell type nanometer copper/polyacrylonitrile composites, it is characterized in that in the step 13 that vacuum drying temperature is that 51 ℃～54 ℃, vacuum are that 0.082MPa～0.088MPa, drying time are 25h～27h.
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