CN101161705A - Functional polymer nano composite material and preparation method and uses thereof - Google Patents
Functional polymer nano composite material and preparation method and uses thereof Download PDFInfo
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Abstract
The present invention relates to a polymer nano-composite of the functional inorganic nano-particle with intermingle prepared by electrospinning method, and the use of the composite. The precursory sol of the functional inorganic nano-particle is prepared by the sol-gel method, and is mixed with the polymer solution to form spinning fluid, adding precursor of dopant if necessary, and then the mixed spinning fluid is sprayed on to the electric collecting board with the action of the electric field force by electrospinning method to obtain functional polymer nano-composite with intermingle. The equipment of the invention is simple, the operation is easy, the components, structure and characteristics of the composite is easy to control, the structure is stable, the inorganic nano-particle is dispersed uniformly. According to the difference of the functionality of the inorganic nano-particles, the composite can be used in conducting material, antistatic material, magnetic material, electrochromic material, photocatalysis and ecology environment material, antibiosis material and biomaterial.
Description
Technical field
The invention belongs to the functional polymer nano composite material field, particularly a kind of polymer nanocomposites that contains adulterated functional inorganic nano-particle that utilizes electrical spinning method to prepare, and the purposes of this matrix material.
Background technology
Inorganic nano-particle is meant the mineral compound ultrafine particle of size between 1～100nm.Because nanoscale effect, big specific surface area, surface atom are in the height active state, inorganic nano-particle has performances such as unique sound, light, heat, electricity, magnetic.Therefore, by giving some special functional, for example antibiotic, antiultraviolets of polymer based nanocomposites, anti-electrostatic, automatically cleaning, photochemical catalysis etc. with the polymer-based carbon volume recombination.Particularly along with the continuous research and development of nano material; the continuous progress of particle surface treatment technology; nano-material modified polymkeric substance will progressively develop to the industrialization direction; it can be applied even more extensively in fields such as military affairs, aerospace, electronics, environment protection, serve the progress and development of society.
The subject matter that polymer nanocomposites exists in actual processed and applied is that the interface compatibility of nano material and polymeric matrix is relatively poor, often can not get good dispersion, form the bigger coacervate of particle easily, thereby reduced the nano effect of inorganic particulate, limited its application greatly.Traditional compounding technology and equipment are difficult to overcome the problems referred to above, and occur the leakage of nanoparticle easily, and nanoparticle is because its easy imbedibility and high-penetrability, and (ToxicologicalSciences 2004 may to have sizable toxic side effect; 77:126～34; Nature Materials 2006; 5:245～8).At present, people utilize the method for sol-gel method original position generation nanoparticle can obtain some dispersed better polymerization thing nano composite materials.
The thirties in 20th century U.S. Pat 2123992 at first the electrical spinning method of report obtain gradually along with the development of nanotechnology paying attention to.The principle of solution electrospinning silk is: high-voltage dc is applied between the polymkeric substance drop and fiber collecting device of spinning nozzle, when drop is subjected to making its splitted electrostatic repulsion forces be enough to overcome and makes its and keeps the surface tension of globality, solution penetrates spinning nozzle, form charged jet flow, solvent evaporates forms the film that fiber or fiber constitute on the fiber collecting device.The nanofiber diameter of utilizing electrical spinning method to prepare can be hanged down and be reached 1nm, and specific surface area is big, and homogeneity is good, and aperture and thickness are adjustable.Chinese patent literature CN01804242.2 discloses a kind of electrical spinning method pharmaceutical compositions, the patent No. be US 6743273 U.S. Patent Publication a kind of electrospinning silk prepare polymer fiber.At present, utilize report that electrical spinning method prepares functional polymer nano composite material also seldom, Chinese patent literature CN1467314A has reported a kind of preparation method of antibacterial nano fiber material, this method is that the antiseptic-germicide ultrafine particle is dispersed in the macromolecular solution, obtains by electrical spinning method then.Because the nanometer ultrafine particle is very easily reunited, this method can not fundamentally solve the scattering problem of nanoparticle in polymer, thereby products obtained therefrom may not reach maximum antibacterial.The present invention utilizes sol-gel method to prepare inorganic nano-particle presoma and mixture of polymers, obtain containing the polymer nanofiber of inorganic nano-particle presoma again by electrical spinning method, generate inorganic nano-particle by the aftertreatment original position then, thereby realize the polymer composites of real nano-dispersed.Simultaneously, add the small amounts of dopants presoma in early stage in the preparation process, in last handling process, be accompanied by the formation of inorganic nano-particle, doping agent can form lattice imperfection, thereby has improved the performance of functional polymer nano composite material as aspects such as electro-conductive material, antistatic material, magneticsubstance, electrochromic material, photochemical catalysis and ecological environment material nd, anti-biotic material, biomaterials.
Summary of the invention
The object of the present invention is to provide the functional polymer matrix material that contains adulterated functional inorganic nano-particle.
A further object of the present invention is to provide the preparation method of the functional polymer nano composite material that contains adulterated inorganic nano-particle.
An also purpose of the present invention is to provide the purposes of the functional polymer nano composite material that contains adulterated inorganic nano-particle.
The present invention combines sol-gel technique and electrospinning silk technology, functional inorganic nano-particle precursor sol is mixed with polymers soln, add suitable dopant precursor body, prepare the polymer composite fibrous of the functional inorganic nano-particle presoma that contains doping agent by the electrospinning silk then, carry out aftertreatment with polymer composite fibrous at last, the precursor in situ of functional inorganic nano-particle changes into the nanoparticle of functional inorganic oxide, obtain containing the functional polymer matrix material of inorganic nano-particle, simultaneously, the dopant precursor body changes into oxide form, at the inner lattice imperfection that forms of inorganic nano-particle, can greatly improve the functional of inorganic nano-particle.Functional inorganic nano-particle in the functional polymer matrix material of the present invention is uniformly dispersed in polymkeric substance, Stability Analysis of Structures, function is controlled, can be used as aspects such as electro-conductive material, antistatic material, magneticsubstance, electrochromic material, photochemical catalysis and ecological environment material nd, anti-biotic material, biomaterial, Application Areas is extensive.
Contain adulterated functional inorganic nano-particle in the functional polymer nano composite material of the present invention as functional component, the mass percent of the functional inorganic nano-particle in the matrix material is 1%～30%, the mass percent of doping agent is 0%～10%, and the mass percent of polymkeric substance is 60%～99%.The particle diameter of functional inorganic nano-particle can be regulated by changing sol-gel prescription, electrospinning silk parameter and post-treatment condition, and the Stability Analysis of Structures of matrix material is controlled.By doping, can realize the function controlling of functional polymer nano composite material to functional inorganic nano-particle.
Functional polymer nano composite material of the present invention, functional inorganic nano-particle wherein is selected from the nanoparticle of inorganic oxide, comprises nano silicon, nano titanium oxide, nano zine oxide, nano-stannic oxide, nano-nickel oxide, nano-sized iron oxide, nano manganic manganous oxide, nano chromium oxide, nano tungsten trioxide, nano cupric oxide, nano phase ag_2 o, nano vanadium dioxide etc.In functional polymer matrix material of the present invention, can contain a kind of in these inorganic nano-particles, also can contain wherein more than one mixture.These oxide nano-particles are generated in-situ in the preparation process of functional polymer nano composite material, are uniformly dispersed in matrix material, and the size of particle and function can be controlled by material prescription and preparation technology's adjustment.
Functional polymer nano composite material of the present invention, the doping agent of functional inorganic nano-particle wherein is to regulate and control the functional component of inorganic nano-particle, comprises the oxide compound of metal platinum, iron, zinc, manganese, silver, cobalt, molybdenum, niobium, lanthanum, neodymium, yttrium, cerium, zirconium, praseodymium, samarium, gadolinium, europium etc.Among the present invention, inorganic nano-particle can mix, and also can undope; Can be a kind of in the doping agent, also can be more than one mixture.
Functional polymer nano composite material of the present invention, polymkeric substance wherein can be selected from polyester, comprises that polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate, poly terephthalic acid diallyl, PDAIP, poly terephthalic acid hexanaphthene are to dimethyl ester, poly-naphthalic acid fourth diester, polypropylene adipate (PPA), polycarbonate, polylactide, poly-glycollide, polycaprolactone, poly butyric ester; Also polyacrylic acid be can be selected from, butyl polyacrylate, polymethyl acrylate, polymethylmethacrylate, Vinalac 5920, poly-methyl comprised; Also polymeric amide be can be selected from, polycaprolactam, PA 66, poly-sebacic acid decamethylene diamine comprised; Also can be selected from other polymkeric substance such as urethane, polyvinyl acetate (PVA), Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral acetal, polyoxyethylene.These polymkeric substance can be homopolymer, also can be multipolymers; Can use wherein a kind of, also can use more than one mixture.
The preparation method of functional polymer nano composite material of the present invention may further comprise the steps:
(1) with polymer dissolution in solvent, form polymers soln A;
(2),, form sol B with presoma hydrolysis in solvent of functional inorganic nano-particle by sol-gel method;
(3) sol B that step (2) is obtained joins among the polymers soln A that step (1) obtains, and mixes the back and adds the dopant precursor body and stir, and forms spinning solution C; Wherein, the mass percent concentration of polymkeric substance is 0.5%～30% among the spinning solution C, and the mass percent concentration of inorganic nano-particle presoma is 0.5%～50%, and the mass percent concentration of dopant precursor body is 0%～10%;
(4) the spinning solution C that step (3) is obtained joins in the spray fiber tube of electrospinning silk equipment, by the electrospinning silk spinning solution C is ejected on the conduction collecting board, obtains containing the polymer composite fibrous D of adulterated functional inorganic nano-particle presoma or the film E that fiber constitutes;
(5) conjugated fibre D or the film E that step (4) is obtained carries out aftertreatment, obtains functional polymer nano composite material.
The preparation method of functional polymer nano composite material of the present invention, used solvent is meant and can dissolves the solvent of specifying polymkeric substance, be selected from trifluoroacetic acid, trichoroacetic acid(TCA), ethylene dichloride, methylene dichloride, acetone, trichloromethane, trichloroethane, tetrahydrofuran (THF), N, the mixture of one or more in dinethylformamide, formic acid, acetate, ethanol, the water etc.
The preparation method of functional polymer nano composite material of the present invention, the presoma of used functional inorganic nano-particle is meant the compound of the silicon that can form colloidal sol, titanium, zinc, tin, nickel, iron, manganese, chromium, tungsten, copper, silver, vanadium etc.; Comprise alkoxy compound, for example tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (butoxy oxyethyl group) silane, tetraethyl titanate, titanium isopropylate, tetra-n-butyl titanate, tetraisopropoxide tin, six isopropoxy tungsten, oxidation three isopropoxy vanadium etc.; Metal organic salt, for example, zinc acetate, nickelous acetate, manganous acetate, chromium acetate, venus crystals, silver acetate etc.; Metal inorganic salt, for example zinc chloride, zinc nitrate, zinc sulfate, nickelous chloride, nickelous nitrate, single nickel salt, manganous chloride, chromium trichloride, chromium nitrate, sodium wolframate, ammonium tungstate, tungsten hexachloride, titanium tetrachloride, tin tetrachloride, iron trichloride, iron nitrate, ferric sulfate, cupric chloride, copper sulfate, cupric nitrate etc.Among the present invention, can use a kind of in the presoma, also can use more than one mixture.
The preparation method of functional polymer nano composite material of the present invention, used dopant precursor body is meant metal platinum, iron, zinc, manganese, silver, cobalt, molybdenum, niobium, lanthanum, neodymium, yttrium, cerium, zirconium, praseodymium, samarium, gadolinium, the nitrate of europium, hydrochloride, vitriol, the carboxylate salt that can be dissolved in designated solvent; Comprise Platinic chloride, iron nitrate, zinc nitrate, manganous nitrate, Silver Nitrate, lanthanum nitrate, neodymium nitrate, Yttrium trinitrate, cerous nitrate, zirconium nitrate, acetic acid yttrium, praseodymium nitrate, samaric nitrate, Gadolinium trinitrate, europium nitrate etc.In the preparation of functional polymer nano composite material, can use doping agent, also can not use doping agent; Can use wherein a kind of, also can use more than one mixture.
The preparation method of functional polymer nano composite material of the present invention, used aftertreatment is meant that the presoma of inorganic nano-particle among the film E that can cause polymer composite fibrous D or fiber formation transforms, is grown to serve as the processing mode of functional inorganic nano-particle, comprise with frequency being the microwave treatment 1 second～100 minutes of 100MHz～5GHz, or be room temperature to 250 ℃ hydrothermal treatment consists 1 hour～48 hours with temperature, or room temperature to 250 ℃ drying, wherein hydrothermal treatment consists can be carried out under acidic conditions, also can carry out under neutrality or alkaline condition.By the electrospinning silk obtain contain functional inorganic nano-particle presoma polymer composite fibrous through aftertreatment, further reaction takes place in the presoma of functional inorganic nano-particle, converted in-situ becomes functional inorganic oxide nanoparticles, the dopant precursor body that contains simultaneously also changes into oxide form and forms lattice imperfection, realizes the doping to functional inorganic nano-particle.
Method equipment used of the present invention is simple, processing ease, and the composition of matrix material, structure, performance can be controlled easily, have Stability Analysis of Structures, finely dispersed characteristics.According to the functional difference of contained inorganic nano-particle, this matrix material can be used for the purposes of aspects such as electro-conductive material, antistatic material, magneticsubstance, electrochromic material, photochemical catalysis and ecological environment material nd, anti-biotic material, biomaterial.
The advantage of functional polymer nano composite material of the present invention is:
(1) resulting polymer nanocomposites Stability Analysis of Structures, nanoparticle is uniformly dispersed in polymkeric substance;
(2) preparation condition gentleness, energy consumption is little, and cost is low;
(3) the electrical spinning method equipment of Cai Yonging is simple to operation;
(4) performance of products obtained therefrom and gauge are adjustable.
Description of drawings
Fig. 1. the functional PET/TiO of the embodiment of the invention 1
2The stereoscan photograph of nano-composite fiber.
Fig. 2. the functional PET/TiO of the embodiment of the invention 2
2The transmission electron microscope photo of nano-composite fiber.
Embodiment
Embodiment 1
(1) 0.63g polyethylene terephthalate (PET) is dissolved in the mixed solvent (v: v=1) of 3ml trifluoroacetic acid and methylene dichloride; The 1ml tetra-n-butyl titanate joins the mixed solvent (v: v=1), behind the room temperature magnetic agitation 3h, with the two mixing, join in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min of 3ml trifluoroacetic acid and methylene dichloride;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the electricity spinning fibre that obtains dry air 24h at room temperature, vapor away solvent, be immersed in then in 70 ℃ the pure water and keep 10h, take out dryly, can obtain containing TiO
2Particle diameter is at the PET/TiO of 3nm
2The photocatalytic nanometer matrix material.Stereoscan photograph as shown in Figure 1.
Embodiment 2
(1) 0.63g polyethylene terephthalate (PET) is dissolved in the mixed solvent (v: v=1) of 1ml trifluoroacetic acid and ethylene dichloride; The 1ml tetra-n-butyl titanate joins the mixed solvent (v: v=1), behind the room temperature magnetic agitation 3h, with the two mixing, join in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min of 2ml trifluoroacetic acid and ethylene dichloride;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the electricity spinning fibre that obtains dry air 24h at room temperature, vapor away solvent, be immersed in then in 90 ℃ the pure water and keep 15h, take out dryly, can obtain containing TiO
2Particle diameter is at the PET/TiO of 3.7nm
2The photocatalytic nanometer matrix material.Stereoscan photograph as shown in Figure 2.
Embodiment 3
(1) 0.63g polyethylene terephthalate (PET) is dissolved in the mixed solvent (v: v=1) of 5ml trifluoroacetic acid and methylene dichloride; The 1ml tetra-n-butyl titanate joins the mixed solvent (v: v=1) of 1ml trifluoroacetic acid and methylene dichloride, behind the room temperature magnetic agitation 3h, the two is mixed, and adding 300 μ L concentration is the Platinic chloride of 0.05mol/L, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the electricity spinning fibre that obtains dry air 24h at room temperature, pass through the microwave radiation 3min of 300W then, radiation frequency is 2GHz, can obtain containing TiO
2Particle diameter is at 3nm, PtO
2Mass percent be 0.39% PET/TiO
2The photocatalytic nanometer matrix material.
Embodiment 4
(1) 1g polyvinyl alcohol (PVA) is dissolved in the 15ml water; 0.4g zinc acetate joins in the 3ml acetate, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.The electricity spinning fibre that obtains at 60 ℃ of following dry air 24h, is immersed in the alkaline solution of pH=12 40 ℃ then and keeps 12h, take out dryly, can obtain containing the ZnO particle diameter at the PVA/ZnO of 18nm antimicrobial nano matrix material.
Embodiment 5
(1) 2g polycaprolactam (PA6) is dissolved in the 10ml formic acid; 0.2g FeCl
36H
2O joins in the 3ml formic acid, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.The electricity spinning fibre that obtains in 200 ℃ of dry air 10h, can be obtained containing Fe
2O
3Particle diameter is at the PA6/Fe of 20nm
2O
3Magnetic nanometer composite material.
Embodiment 6
(1) 0.5g polycaprolactone (PCL) is dissolved in the 3ml tetrahydrofuran (THF); The 1ml tetra-n-butyl titanate joins the mixed solvent (v: v=1), behind the room temperature magnetic agitation 3h, with the two mixing, join in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min of 2ml trifluoroacetic acid and ethylene dichloride;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 20kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 24h of the electricity spinning fibre air at room temperature that obtains, in 80 ℃ pure water, keep 10h then, take out drying, can obtain containing TiO
2Particle diameter is at the PCL/TiO of 3nm
2The biological antibiotic nano composite material.
Embodiment 7
(1) 0.8g polyterephthalate (PTP) is dissolved in the mixed solvent of 3ml trifluoroacetic acid and ethylene dichloride; 0.5g cupric nitrate joins in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 20h of the electricity spinning fibre air at room temperature that obtains, 70 ℃ of hydrothermal treatment consists 30h in the alkaline solution of pH=8 take out drying then, can obtain containing the CuO particle diameter at the PTP/CuO of 15nm conductive nano composite material.
Embodiment 8
(1) 0.8g polycaprolactam (PA6) is dissolved in the 3ml formic acid; 0.7g zinc acetate joins in the 3ml acetate, behind the room temperature magnetic agitation 3h, with the two mixing, adds the 1.9mg Silver Nitrate then, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 40kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 24h of the electricity spinning fibre air at room temperature that obtains, be immersed in 80 ℃ of hydrothermal treatment consists 10h in the alkaline solution of pH=9 then, take out dryly, can obtain containing the ZnO particle diameter at 13nm, Ag
2The mass percent of O is 0.11% PA6/ZnO antimicrobial nano matrix material.
Embodiment 9
(1) 0.7g polybutylene terephthalate (PBT) is dissolved in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride; The 1g nickelous acetate is dissolved in the ethanol that contains 0.5g PEO, and 70 ℃ of magnetic agitation 3h are to be cooled to room temperature, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 24h of the electricity spinning fibre air at room temperature that obtains, in bathing, 100 ℃ pure water keeps 40h then, take out drying, can obtain containing the NiO particle diameter in the PBT/NiO of 4.5nm electrochromism nano composite material.
Embodiment 10
(1) 0.6g Poly(Trimethylene Terephthalate) (PTT) is dissolved in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride; The 1ml tetra-n-butyl titanate joins in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride, behind the room temperature magnetic agitation 3h, with the two mixing, adds the 1mg lanthanum nitrate then, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 20h of the electricity spinning fibre air at room temperature that obtains, through the microwave radiation 2min of 600W, radiation frequency is 1GHz, can obtain containing TiO then
2Particle diameter is at 4.5nm, La
2O
3Mass percent be 0.05% PTT/TiO
2The photocatalytic nanometer matrix material.
Embodiment 11
(1) 0.7g polymethyl acrylate (PMAC) is dissolved in the 3ml acetone; The 1ml tetra-n-butyl titanate joins in the 3ml trifluoroacetic acid, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the dry 15h of the electricity spinning fibre air at room temperature that obtains, be immersed in then in 70 ℃ the pure water and keep 10h, take out dryly, can obtain containing TiO
2Particle diameter is at the PMAC/TiO of 10nm
2The photocatalytic nanometer matrix material.
Embodiment 12
(1) 0.63g polyethylene terephthalate (PET) is dissolved in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride; The 1ml titanium isopropylate joins in the mixed solvent of 3ml trifluoroacetic acid and methylene dichloride, behind the room temperature magnetic agitation 3h, with the two mixing, adds the 5mg cerous nitrate then, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.The electricity spinning fibre that obtains is first at the dry 24h of air at room temperature, in 200 ℃ of vacuum-drying 5h, can obtain containing TiO then
2Particle diameter is at 2nm, CeO
2Mass percent be 0.24% PET/TiO
2The photocatalytic nanometer matrix material.
Embodiment 13
(1) 1g polyethylene terephthalate (PET) is dissolved in the mixed solvent (v: v=1) of 3ml trifluoroacetic acid and methylene dichloride; 0.4g zinc acetate joins in the 3ml acetate, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.The electricity spinning fibre that obtains at 60 ℃ of following dry air 24h, is immersed in the alkaline solution of pH=12 40 ℃ then and keeps 12h, take out dryly, can obtain containing the ZnO particle diameter at the PET/ZnO of 20nm anti-electrostatic nano matrix material.
Embodiment 14
(1) 0.9g Polyethylene Naphthalate (PEN) is dissolved in the mixed solvent of 6ml trifluoroacetic acid and ethylene dichloride; The 1g sodium wolframate joins in the mixed solvent of 3ml trifluoroacetic acid and ethylene dichloride, behind the room temperature magnetic agitation 3h, with the two mixing, joins in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.Through 100 ℃ of hydrothermal treatment consists 10h, take out dryly the electricity spinning fibre that obtains, can obtain containing WO
3Particle diameter is at the PEN/WO of 5nm
3The photocatalytic nanometer matrix material.
Embodiment 15
(1) 0.8g polytrimethylene terephthalate (PTT) is dissolved in the mixed solvent of 6ml trifluoroacetic acid and ethylene dichloride; 5ml TiCl
4Join in the mixed solvent of 3ml trifluoroacetic acid and ethylene dichloride, behind the room temperature magnetic agitation 3h,, add the 60mg iron nitrate then, join in the electrospinning silk shower nozzle needle tubing after continuing to stir 30min the two mixing;
(2) control from the spinning nozzle of electrospinning device to the voltage the collecting board at 30kV, collect electricity spinning fibre with the aluminium foil plate.With the electricity spinning fibre that obtains dry air 24h at room temperature, immerse 80 ℃ of hydrothermal treatment consists 8h in the alkaline solution of pH=8 then, take out dryly, can obtain containing TiO
2Particle diameter is 4nm, Fe
2O
3Mass percent be 0.68% PTT/TiO
2The photocatalytic nanometer matrix material.
Embodiment 16
Getting area is the PET/TiO of embodiment 1 preparation of 2cm * 4cm
2The photocatalytic nanometer composite material film is dipped in the methyl orange aqueous solution that concentration is 15mg/L, and the concentration of tropeolin-D is 10mg/L with the uv-visible absorption spectra test result behind the lucifuge absorption 3h, is that 300nm, light intensity are 200 μ W/cm through wavelength
2UV-irradiation 6h after, the concentration of tropeolin-D is reduced to 0.5mg/L, the photocatalytic degradation rate of tropeolin-D reaches 96.7%.
Embodiment 17
The PVA/ZnO nano composite material with anti-microbial property of embodiment 4 preparation is added in the fabric fibre, adopt national standard FZ/T73023-2006 antibiosis knitting product to test, the antibiotic rate of streptococcus aureus more than 99%, is reached the A level.
Embodiment 18
PCL/FiO with embodiment 6 preparations
2The biological antibiotic nano composite material adopts national standard QB/T2591-2003 " antibiotic plastic: anti-microbial property test method and antibacterial effect " test, to streptococcus aureus, intestinal bacteria, Candida albicans are antibiotic the obvious suppression effect arranged all, the mildew-resistant grade reaches 1 grade.
Embodiment 19
Getting area is the La of embodiment 10 preparations of 2cm * 4cm
2O
3Doped P TT/TiO
2The photocatalytic nanometer composite material film is dipped in the methyl orange aqueous solution that concentration is 20mg/L, and the concentration of tropeolin-D is 12mg/L with the uv-visible absorption spectra test result behind the lucifuge absorption 3h, is that 300nm, light intensity are 200 μ W/cm through wavelength
2UV-irradiation 6h after, the concentration of tropeolin-D is reduced to 0.8mg/L, the photocatalytic degradation rate of tropeolin-D reaches 96%.
Embodiment 20
Getting area is the PEN/WO with photocatalytic activity of embodiment 14 preparations of 2cm * 4cm
3Nanocomposite films is dipped in the methyl orange aqueous solution that concentration is 20mg/L, and the concentration of tropeolin-D is 11mg/L with the uv-visible absorption spectra test result behind the lucifuge absorption 3h, is that 300nm, light intensity are 200 μ W/cm through wavelength
2UV-irradiation 6h after, the concentration of tropeolin-D is reduced to 0.3mg/L, the photocatalytic degradation rate of tropeolin-D reaches 98.5%.
Claims (10)
1. functional polymer nano composite material, it is characterized in that: contain adulterated functional inorganic nano-particle in this matrix material, the mass percent of the functional inorganic nano-particle in the matrix material is 1%～30%, the mass percent of doping agent is 0%～10%, and the mass percent of polymkeric substance is 60%～99%.
2. functional polymer nano composite material according to claim 1 is characterized in that: described functional inorganic nano-particle is selected from one or more the mixture in nano silicon, nano titanium oxide, nano zine oxide, nano-stannic oxide, nano-nickel oxide, nano-sized iron oxide, nano manganic manganous oxide, nano chromium oxide, nano tungsten trioxide, nano cupric oxide, nano phase ag_2 o, the nano vanadium dioxide.
3. functional polymer nano composite material according to claim 1 is characterized in that: described doping agent is selected from one or more the mixture in the oxide compound of metal platinum, iron, zinc, manganese, silver, cobalt, molybdenum, niobium, lanthanum, neodymium, yttrium, cerium, zirconium, praseodymium, samarium, gadolinium, europium.
4. functional polymer nano composite material according to claim 1 is characterized in that: described polymkeric substance is selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate, the poly terephthalic acid diallyl, PDAIP, the poly terephthalic acid hexanaphthene is to dimethyl ester, poly-naphthalic acid fourth diester, polypropylene adipate (PPA), polycarbonate, polylactide, poly-glycollide, polycaprolactone, poly butyric ester, butyl polyacrylate, polymethyl acrylate, polymethylmethacrylate, Vinalac 5920, poly-methyl, polycaprolactam, PA 66, poly-sebacic acid decamethylene diamine, polyurethane, polyvinyl acetate (PVA), Polyvinylpyrolidone (PVP), polyoxyethylene glycol, polyvinyl alcohol, polyacrylonitrile, polyvinyl butyral acetal, the homopolymer of polyoxyethylene or one or more the mixture in the multipolymer.
5. the preparation method according to each described functional polymer nano composite material of claim 1～4 is characterized in that, this method may further comprise the steps:
(1) with polymer dissolution in solvent, form polymers soln A;
(2),, form sol B with presoma hydrolysis in solvent of functional inorganic nano-particle by sol-gel method;
(3) sol B that step (2) is obtained joins among the polymers soln A that step (1) obtains, and mixes the back and adds the dopant precursor body and stir, and forms spinning solution C; Wherein, the mass percent concentration of polymkeric substance is 0.5%～30% among the spinning solution C, and the mass percent concentration of inorganic nano-particle presoma is 0.5%～50%, and the mass percent concentration of dopant precursor body is 0%～10%;
(4) the spinning solution C that step (3) is obtained joins in the spray fiber tube of electrospinning silk equipment, by the electrospinning silk spinning solution C is ejected on the conduction collecting board, obtains containing the polymer composite fibrous D of adulterated functional inorganic nano-particle presoma or the film E that fiber constitutes;
(5) conjugated fibre D or the film E that step (4) is obtained carries out aftertreatment, obtains functional polymer nano composite material.
6. method according to claim 5, it is characterized in that: described solvent is selected from trifluoroacetic acid, trichoroacetic acid(TCA), ethylene dichloride, methylene dichloride, acetone, trichloromethane, trichloroethane, tetrahydrofuran (THF), N, the mixture of one or more in dinethylformamide, formic acid, acetate, ethanol, the water.
7. method according to claim 5 is characterized in that: the presoma of described functional inorganic nano-particle is selected from tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four (butoxy oxyethyl group) silane, tetraethyl titanate, titanium isopropylate, tetra-n-butyl titanate, tetraisopropoxide tin, six isopropoxy tungsten, oxidation three isopropoxy vanadium, zinc acetate, nickelous acetate, manganous acetate, chromium acetate, venus crystals, silver acetate, zinc chloride, zinc nitrate, zinc sulfate, nickelous chloride, nickelous nitrate, single nickel salt, manganous chloride, chromium trichloride, chromium nitrate, sodium wolframate, ammonium tungstate, tungsten hexachloride, titanium tetrachloride, tin tetrachloride, iron trichloride, iron nitrate, ferric sulfate, cupric chloride, copper sulfate, the mixture of one or more in the cupric nitrate.
8. method according to claim 5 is characterized in that: described dopant precursor body is selected from one or more the mixture in the nitrate, hydrochloride, vitriol, carboxylate salt of metal platinum, iron, zinc, manganese, silver, cobalt, molybdenum, niobium, lanthanum, neodymium, yttrium, cerium, zirconium, praseodymium, samarium, gadolinium, europium.
9. method according to claim 5 is characterized in that: described aftertreatment comprises with frequency being the microwave treatment 1 second～100 minutes of 100MHz～5GHz, or is room temperature to 250 ℃ hydrothermal treatment consists 1 hour～48 hours with temperature, or room temperature to 250 ℃ drying.
10. purposes according to each described functional polymer nano composite material of claim 1～4, it is characterized in that: this matrix material can be used as electro-conductive material, antistatic material, magneticsubstance, electrochromic material, photochemical catalysis and ecological environment material nd, anti-biotic material or biomaterial.
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