CN100478074C - Catalyst-supporting fiber structure and method for producing same - Google Patents
Catalyst-supporting fiber structure and method for producing same Download PDFInfo
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- CN100478074C CN100478074C CNB2004800164415A CN200480016441A CN100478074C CN 100478074 C CN100478074 C CN 100478074C CN B2004800164415 A CNB2004800164415 A CN B2004800164415A CN 200480016441 A CN200480016441 A CN 200480016441A CN 100478074 C CN100478074 C CN 100478074C
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- fiber construct
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Abstract
A catalyst-supporting fiber structure is disclosed wherein a catalyst is supported by fibers constituting a fiber structure. The fiber structure has an average fiber diameter of 1 mum or less and substantially contains no fibers having a fiber length of 20 mum or less. The fiber structure has sufficient flexibility and catalyst-supporting properties at the same time. Since the fiber structure is excellent in catalyst-supporting properties, it can be formed into, for example, a fiber structure having an extremely strong power of decomposing harmful substances.
Description
Technical field
The present invention relates to catalyst-loaded fiber construct catalyst-loaded on the fiber that constitutes fiber construct and preparation method thereof.
Background technology
In recent years, along with the deterioration of earth environment, environmental problem becomes social concern day by day, and people strengthen day by day to the care of environmental problem.Along with the sternness of environmental problem, people wish to develop the technology that can highly remove harmful chemical pollutant.Wherein, people worry VOC such as benzene, trichloro-ethylene (VOC), phthalic acid ester etc. and upset the profound influence of endocrine material to human body, particularly for the waste water that contains these materials, except hope is provided with extensive treatment facility, people also begin to seek take place separately that the source removes in fact fully way.
The method of removing about these chemical pollutants, someone has studied the method that microorganism is used as the catalyst that decomposes harmful substance in the waste water, for example there is scheme to propose: on the knitted fabric of synthetic fibers, to support microorganism, the method for decomposing harmful substances (for example with reference to patent documentation 1).But in this method, the loading of microorganism has the limit, and therefore the problem of treatment effeciency difference is arranged.
The research and development that are used for removing the adsorbent of the harmful substance of decomposing waste water or catalyst etc. are also being carried out, and wherein, but people are conceived to have the catalyst of the titanium oxide of photocatalysis as decomposing harmful substances.Promptly, the photochemical catalyst irradiation that contains titanium oxide is had the light of the wavelength of the above energy of band gap,, on conduction band, produce electronics by optical excitation, on valence band, produce the hole, electronics and the high reducing power in hole and the decomposition that oxidability is used for harmful substance that this optical excitation can be generated.
For example, the someone proposes: the photocatalyst oxidizes titanium is supported on the porous whisker with specific specific area, makes photocatalytic whisker (for example with reference to patent documentation 2).But, in order to be used for actual wastewater treatment, also this whisker must be contained in coating or the rubber etc. by the whisker that this method obtains, trivial operations, and the catalyst loading quantitative change in the final type of service is little.
The somebody proposes: titanium oxide is supported in specific specific area or following titania fiber surface, make photocatalysis titania fiber (for example with reference to patent documentation 3).But the titania fiber of this method also has the little problem of catalyst loading amount.In addition, titania fiber lacks flexibility, so type of service is restricted.
Have more the raw-material example of flexibility as use, showing makes photocatalyst-supporting on woven cloths or non-weaving cloth, more particularly, make the possibility (for example with reference to patent documentation 4) of photocatalyst-supporting, but still have the few problem of catalyst loading amount in aramid fibre cloth, fluororesin cloth etc.
[patent documentation 1] TOHKEMY 2000-288569 communique
[patent documentation 2] TOHKEMY 2000-271488 communique
[patent documentation 3] TOHKEMY 2000-218170 communique
[patent documentation 4] Japanese kokai publication hei 9-267043 communique
Summary of the invention
First purpose of the present invention is to eliminate the problem points that above-mentioned conventional art has, and the fiber construct that has sufficient flexibility and catalyst loading performance concurrently is provided.
Another object of the present invention is to provide method preparation to have the method for the fiber construct of high harmful substance capacity of decomposition with extremely easy.
The accompanying drawing summary
Fig. 1 is the preparation facilities ideograph that is used to illustrate a preparation method's of the present invention scheme.
Fig. 2 is the preparation facilities ideograph that is used to illustrate a preparation method's of the present invention scheme.
Fig. 3 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of fiber construct that the operation by embodiment 1 is obtained is taken.
Fig. 4 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the fiber construct that the operation by embodiment 1 obtained with SEM is taken.
Fig. 5 is the electron micrograph figure (taking 5000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 1 obtained with SEM is taken.
Fig. 6 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of the fiber construct that the operation by embodiment 2 obtained with SEM is taken.
Fig. 7 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the fiber construct that the operation by embodiment 2 obtained with SEM is taken.
Fig. 8 is the electron micrograph figure (taking 20000 times of multiplying powers) that the surface of the fiber construct that the operation by embodiment 3 obtained with SEM is taken.
Fig. 9 is the electron micrograph figure (taking 20000 times of multiplying powers) that the surface of the fiber construct that the operation by embodiment 4 obtained with SEM is taken.
Figure 10 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 5 obtained with SEM is taken.
Figure 11 is the electron micrograph figure (taking 20000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 5 obtained with SEM is taken.
Figure 12 is the X-ray diffraction figure of the catalyst-loaded fiber construct that obtains of the operation by embodiment 5, and in the curve map of Figure 12, the longitudinal axis is X-ray diffraction intensity (cps), and transverse axis is the angle of diffraction 2 θ (deg.).
Figure 13 is the X-ray diffraction figure of the fiber construct that obtains of the operation by comparative example 3, and in the curve map of Figure 13, the longitudinal axis is X-ray diffraction intensity (cps), and transverse axis is the angle of diffraction 2 θ (deg.).
Figure 14 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 6 obtained with SEM is taken.
Figure 15 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 7 obtained with SEM is taken.
Figure 16 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 8 obtained with SEM is taken.
Figure 17 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 9 obtained with SEM is taken.
Figure 18 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 10 obtained with SEM is taken.
Figure 19 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 11 obtained with SEM is taken.
Figure 20 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 12 obtained with SEM is taken.
Figure 21 is the electron micrograph figure (taking 2000 times of multiplying powers) that the surface of the catalyst-loaded fiber construct that the operation by embodiment 13 obtained with SEM is taken.
Figure 22 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the fiber construct that the operation by comparative example 4 obtained with SEM is taken.
Figure 23 is the electron micrograph figure (taking 8000 times of multiplying powers) that the surface of the fiber construct that the operation by comparative example 5 obtained with SEM is taken.
The best mode that carries out an invention
The present invention below is described in detail in detail.
Among the present invention, " fiber construct " is meant the stereoisomer that operation such as, lamination knitting, woven by fiber is carried out forms, and preferably example has non-weaving cloth.
The fiber diameter that forms the fiber of fiber construct of the present invention is necessary for 1 μ m or following.Fiber diameter surpasses 1 μ m, and then fiber specific surface area diminishes, and therefore the amount of the catalyst that can support reduces.In addition, as the average diameter of fruit fiber be 0.01 μ m or more than, then the intensity of gained fiber construct is enough.The average diameter of fiber that constitutes this fiber construct is preferably in the scope of 0.01-0.7 μ m.
Fiber construct essence of the present invention does not contain the fiber with 20 μ m or following fiber length.Essence described here does not contain and is meant: use the sem observation optional position, all do not observe and have 20 μ m or the long fiber of following fiber.It is long to have 20 μ m or following fiber, and then the mechanical strength of gained fiber construct is not enough, and is not preferred.Among the present invention, preferably do not contain fiber, more preferably do not contain fiber with 1mm or following fiber length with 40 μ m or following fiber length.
But support on the fiber that constitutes fiber construct catalyst so long as the catalyst of decomposing harmful substances get final product, be not particularly limited, inorganic compounds such as photochemical catalyst, allophane, flying dust such as titanium oxide are for example arranged, microbial catalysts such as whiterot fungi, trichloro-ethylene decomposer, various enzymes etc.Wherein, consider that preferably use inorganic compound, special preferred light catalyst especially preferably uses titanium oxide from operability, active equal angles.When using titanium oxide, particulate supports on fiber easily, thereby preferred.
When using photochemical catalyst as catalyst, the part on the surface of this photochemical catalyst is covered by other inorganic compound, shows high catalytic activity when then making catalyst-loaded fiber construct, more preferably.Other inorganic compound of lining photocatalyst surface for example has potteries such as silica, apatite.
Among the present invention, as long as above-mentioned catalyst loading is on the fiber that constitutes fiber construct, it can be any state that supports, it for example can be the state that (a) is attached to the fiber surface that constitutes fiber construct, (b) be contained in fibrous inside, the state that part catalyst exposure contains in fiber surface, (c) its state is, catalyst is rendered as the particle of particle diameter 1-100 mu m range, be wrapped in the fiber construct in this particle, and the catalyst particles intragranular of interior bag wraps in the existing part of noncontact part of this catalyst granules and the fiber that constitutes fiber construct, and the catalyst granules surface of interior bag comprise this catalyst granules and with the noncontact part of fiber.Here, among the present invention, interior bag is meant and keeps and make the catalyst can be by the state of fiber construct landing that special preferred catalyst particle contacts with one or more fiber at least on its surface, and catalyst granules is embedded in the state in the fiber construct.
In the fiber construct of the state that supports of above-mentioned (a), catalyst is by the possibility height that comes off on the fiber construct, but can effectively utilize catalyst surface, therefore can be used for being difficult to taking place catalyst such as mechanical stress or distortion and comes off in the purposes of factor.
In the fiber construct of the state that supports of above-mentioned (b), the exposed area of catalyst surface than above-mentioned (a) to support state little, but catalyst is difficult to come off from the catalyst fiber structure, the easy generation catalyst of fiber construct that therefore can be used for being not suitable for the state that supports of above-mentioned (a) purposes of factor that comes off.
The fiber construct of the state that supports of above-mentioned (c) is in the state that supports of above-mentioned (a) and supporting between the state of above-mentioned (c).
Here, above-mentioned (c) supports in the state, and above-mentioned catalyst particle size must be in the scope of 1-100 μ m.1 μ m is little for size ratio, then can the specific area of reacting contributive catalyst be increased, but absolute surface area is too small, thereby not preferred.In addition, surpass 100 μ m, then can the absolute area of reacting contributive catalyst be increased, but the specific area of catalyst is too small.
Particle diameter described here is meant the mean value of the value of the best part in the particle diameter that supports in the fiber construct, it can be the one-level particle diameter, it also can be catalyst granules condenses the particle diameter of the condensation product (so-called secondary flocculated particle) that forms in fiber construct value, the one-level particle diameter shows higher activity at the catalyst of the scope of 1-100 μ m, thereby preferred.Preferred particle diameter is 1.5 μ m-30 μ m.
Among the present invention, obtain the state that supports of above-mentioned (a)-(c), can suitably select according to the target purposes, can also a plurality of fiber constructs are overlapping, make complex form by applying etc., for example the fiber construct with the state that supports of above-mentioned (b) is disposed at outermost, be disposed at the fiber construct of the state that supports of above-mentioned (a) the most inboard, this can make the reduction that comes off of the catalyst of fiber construct integral body, perhaps by opposite configuration, make the whole catalyst that keeps of fiber construct, make a part of catalyst of fiber construct have a mind to come off simultaneously.
Consider that from mechanics rerum natura, operability the fiber that forms fiber construct of the present invention is to contain the organic macromolecule fiber.
Above-mentioned organic macromolecule example has: polyacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, poly-n-propyl methacrylate, Vinalac 5920, PMA, polyethyl acrylate, butyl polyacrylate, polyacrylonitrile/methacrylate copolymer, polyvinylidene chloride, polyvinyl chloride, polyvinylidene chloride/acrylate copolymer, polyethylene, polypropylene, poly--4-methylpentene-1, polystyrene, aromatic polyamides, PPTA, PPTA/3,4 '-oxygen diphenylene base terephthalamide copolymer, poly, polybenzimidazoles, poly-equal benzene tetramethyl acyl is to the benzene diimine, poly--4, the equal diimides of 4 '-oxygen diphenylene base, polyvinyl alcohol, cellulose, cellulose diacetate, cellulosic triacetate, methylcellulose, propyl cellulose, benzylcellulose, acetate/cellulose butyrate, poly-ethylidene sulphur, polyvinyl acetate, PETG, PEN, PLA, polyglycolic acid, the polylactic acid/polyglycolic acid copolymer, polycaprolactone, polyglutamic acid, the polyaryl thing, Merlon, polyether sulfone, polyether ethersulfone, polyvinylidene fluoride, polyurethane, poly-butanedioic acid Aden ester, poly-butanedioic acid ethyl, the own ester of polymerized thylene carbonate, the polyvinyl isocyanates, poly-butyl isocyanate, polyvinyl acetate, polyvinyl methyl ether, the polyvinyl ethylether, the polyvinyl n-propyl ether, the polyvinyl isopropyl ether, the polyvinyl n-butyl ether, polyvinyl isobutyl ether, the polyvinyl tertbutyl ether, poly-(N-vinyl pyrrolidone), poly-(N-VCz), poly-(4-vinylpridine), polyvinyl methyl ketone, poly-methyl isopropenyl ketone, PEO, PPOX, the polyoxygenated cyclopentene, the polystyrene sulfone, nylon 6, nylon 66, nylon 11, nylon 12, NYLON610, nylon 612, polyvinylidene fluoride, polyvinyl bromide, polychlorotrifluoroethylene, polychlorobutadiene, the ring-opening polymerization polymer of norborneol alkene monomer and hydride thereof, fibroin, natural rubber, chitin, deacetyl chitin, collagen, zein etc., they can be the materials of copolymerization, also can be mixture, can be by various angle Selection.
Example as above-mentioned selection, for example from operability, the rerum natura equal angles is considered, can use polyacrylonitrile and their copolymer, perhaps use it is heat-treated the compound that obtains, in order to guarantee no matter to be subjected to influence from being supported on which kind of catalyst on the fiber, itself does not decompose fiber construct yet, can use the organic polymer that contains halogen element (polyvinyl chloride for example, polyvinylidene chloride, polyvinylidene chloride-acrylate copolymer, polyvinylidene fluoride, polyvinyl bromide, polychlorotrifluoroethylene, polychlorobutadiene etc.), especially preferably use polyvinyl chloride, make fiber construct have biological degradability, can be in soil after long-time the use natural decomposition, can also use PLA.
After forming fiber, can use it is implemented heat treatment or chemically treated fiber, also can be as required, the powder of mixed emulsion or organic and inorganic thing uses in above-mentioned macromolecule.
Catalyst-loaded fiber construct of the present invention can use separately, and also binding operation or other require item, are used in combination with other member.For example, collect ground and use non-weaving cloth or woven cloths, the film etc. that can be used as supporting substrate,, can make the member that supporting substrate and this superimposed fiber thing combine by forming the superimposed fiber thing thereon.
As long as can obtain having the catalyst-loaded fiber construct of above-mentioned fiber diameter, fibre length, catalyst-loaded fiber construct of the present invention can adopt any preparation method.
Below, in the scheme of preparation catalyst-loaded structure of the present invention, the method for the state that supports of above-mentioned to preparing (a)-(c) describes.
Fiber construct with the state that supports of above-mentioned (a) for example can obtain by the preparation method who comprises with the catalyst-loaded fiber construct of next stage: make into the dissolving of fibroid organic polymer, the stage of preparation solution; By the stage of electrostatic spinning with above-mentioned solution spinning; Obtain being accumulated in the stage of collecting the fiber construct on the ground by above-mentioned spinning; Make the stage of catalyst loading in above-mentioned fiber construct.
Here, method of electrostatic spinning is with the dissolving of one-tenth fibroid compound, makes solution, this solution is sprayed onto in the electrostatic field that forms between electrode, this solution to the electrode direction wire drawing, is accumulated in the fibrous material that forms on the collection ground, obtains the method for fiber construct thus; Fibrous material is not only and is heated up in a steamer the solvent that makes into the dissolving of fibroid compound, the state that forms the superimposed fiber body, represents that also this solvent also is contained in the state in the fibrous material.
Then, the employed device of method of electrostatic spinning is described.
Above-mentioned electrode can be metal, inorganic matter or organic any material, can use as long as show electric conductivity, and in addition, also can be the form that has the metal, inorganic matter or the organic film that show electric conductivity on the insulant.
Electrostatic field forms between a pair of or a plurality of electrodes, can be to arbitrary electrode applying high voltage.This also comprises for example different high-voltage electrode (for example 15kV and 10kV) of two magnitudes of voltage and the earth electrode situation of totally three electrodes of use, perhaps also comprises the situation of using the electrode that outnumbers 3.
Then, in order the fiber preparation method that constitutes fiber construct of the present invention by method of electrostatic spinning is described.
At first, make into the dissolving of fibroid organic polymer, preparation solution, here, the one-tenth fibroid organic macromolecule concentration in the preferred solution is 1-30 weight %.1 weight % is little for this concentration ratio, and then concentration is low excessively, is difficult to form fiber construct, and is not preferred.In addition, bigger than 30 weight %, then the average diameter of gained fiber increases, and is not preferred.Preferred concentration is 2-20 weight %.
Above-mentionedly make the solvent of organic polymer dissolving, be not particularly limited so long as be dissolved into the fibroid organic polymer and can evaporate so that forming the solvent of fiber gets final product in the stage of carrying out spinning by method of electrostatic spinning.Acetone, chloroform, ethanol, isopropyl alcohol, methyl alcohol, toluene, oxolane, water, benzene, benzylalcohol, 1 are for example arranged, 4-diox, propyl alcohol, carrene, carbon tetrachloride, cyclohexane, cyclohexanone, phenol, pyridine, trichloroethanes, acetate, formic acid, hexafluoroisopropanol, Hexafluoro acetone, N, dinethylformamide, acetonitrile, N-methylmorpholine-N-oxide, 1, the mixed solvent of 3-dioxolanes, methyl ethyl ketone, N-methyl pyrrolidone, above-mentioned solvent etc.
Wherein,, preferably use N, dinethylformamide, oxolane, chloroform, N, the mixed solvent of dinethylformamide and oxolane from considerations such as operability, rerum naturas.
Then, to describing by the stage of method of electrostatic spinning with above-mentioned solution spinning.The method that this solution sprays in electrostatic field can be used any method, for example the solution supply nozzle can be positioned over position suitable in the electrostatic field with solution,, solution by wire drawing in this nozzle, be formed fiber by electric field.
Below, use Fig. 1 further to specify.
The top ends setting that keeps groove (Fig. 1 3) at the tubular solution of syringe applies the injection needle-like solution nozzle (Fig. 1 1) of voltage by proper device (for example high-voltage generator (Fig. 1 6)), solution (Fig. 1 2) is guided to the top ends of solution nozzle.Apart from the fibrous material passive electrode of ground connection (Fig. 1 5), the top of this solution nozzle (Fig. 1 1) is set with suitable distance, solution (Fig. 1 2) is by the top ends ejection of this solution nozzle (Fig. 1 1), can form fibrous material between the head portion of this nozzle and fibrous material passive electrode (Fig. 1 5).
Other scheme describes with Fig. 2.The fine droplets (not shown) of this solution can be imported electrostatic field, unique important document of this moment is that solution (Fig. 2 2) is placed electrostatic field, keeps forming the distance of fiber with fibrous material passive electrode (Fig. 2 5).For example, can in keeping solution (2 figure 2) in the groove (Fig. 2 3), directly insert the solution with solution nozzle (2 figure 1) and fibrous material passive electrode electrode of opposite (2 figure 4).
When this solution is supplied with electrostatic field by nozzle, can use a plurality of nozzles side by side, to improve the speed of production of fibrous material.In addition, interelectrode distance and carried charge, jet size, solution are relevant by the amount of nozzle ejection, solution concentration etc., and the distance of maintenance 5-20cm is suitable during the 10kV left and right sides.In addition, the electrostatic potential that applies is generally 3-100kV, preferred 5-50kV, more preferably 5-30kV.Required current potential can be by the known acquisition of proper method arbitrarily in the past.
Above-mentioned two kinds of schemes are situations that the electrode double as is collected ground, can be used as the object of collecting ground by being provided with between electrode, can be independent of electrode and the collection ground is set, and collect the superimposed fiber body thereon.In this case, for example, as collecting ground, can produce continuously like this with this by banded material is set between electrode.
Then, describe obtaining to be accumulated in the stage of collecting the fiber construct on the ground.Among the present invention, with this solution during collecting the ground wire drawing, according to condition, the solvent evaporation forms fibrous material.If common room temperature, then before being collected on the collection ground, solvent evaporates fully, if but the solvent evaporation is insufficient, then can under reduced pressure, carry out wire drawing.In the time of on being collected into this collection ground, having formed and satisfied above-mentioned average fibre diameter and the long fiber construct of fiber at least.In addition, the evaporation proterties of wire-drawing temperature and solvent or the viscosity of spinning solution are relevant, are generally 0-50 ℃ scope.
Then, can be catalyst-loaded on the fiber construct that obtains by above-mentioned method of electrostatic spinning, catalyst-loaded method is not particularly limited, by above-mentioned fiber construct being impregnated in the liquid that contains catalyst, the method that catalyst is contacted with fiber surface, perhaps the liquid that will contain catalyst by operations such as sprayings is coated on the above-mentioned fiber construct, this from the simplicity of operation or can evenly support consider preferred.Preferably contain and also contain the composition that can make fiber construct and catalyst bonding in the liquid of catalyst.
Then, the fiber construct with the state that supports of above-mentioned (b) for example can obtain by the preparation method who comprises with the catalyst-loaded fiber construct of next stage: make into the stage that fibroid organic polymer and catalyst precarsor are dissolved in preparation solution in the solvent; By the stage of method of electrostatic spinning with above-mentioned solution spinning; Obtain being accumulated in the stage of collecting the fiber construct on the ground by above-mentioned spinning; The catalyst precarsor that is contained in the above-mentioned fiber construct is handled, formed the stage of catalyst.
Among this preparation method, at first be to make into fibroid organic polymer and catalyst precarsor to be dissolved in and to prepare solution in the solvent, here, catalyst precarsor for example can use the inorganic compound that can form catalyst by sol gel reaction, and the example of this inorganic compound has metal alcoholate or metal chloride.Specifically have: alkoxytitanium, alkoxyl tin, alkoxyl silicone, aluminum alkoxide etc., wherein, especially preferably use alkoxytitanium.Consider that from buying easy equal angles above-mentioned alkoxytitanium can preferably use tetraisopropoxy titanium, four titanium butoxide etc.
Become the fibroid organic polymer to be preferably 1-30 weight % with respect to the concentration of the solvent in the solution.Become fibroid organic macromolecule concentration ratio 1 weight % little, then concentration is low excessively, is difficult to form fiber construct, and is not preferred.Bigger than 30 weight %, then the fibre diameter of gained fiber construct increases, and is not preferred.Becoming the fibroid organic polymer is 2-20 weight % with respect to the preferred concentration of the solvent in the solution.
Catalyst precarsor is preferably 1-30 weight % with respect to the concentration of the solvent in the solution.The concentration ratio 1 weight % of catalyst precarsor is little, and then the catalytic amount that generates reduces, and is not preferred.Bigger than 30 weight %, then be difficult to form fiber construct, not preferred.Catalyst precarsor is 2-20 weight % with respect to the preferred concentration of the solvent in the solution.
Solvent can be used alone, also can be with multiple solvent combination.As long as this solvent can be dissolved into fibroid organic polymer and catalyst precarsor, and, get final product, be not particularly limited so that can form fiber in the phase evaporation by the method for electrostatic spinning spinning, can use prepare above-mentioned (a) support state the time solvent that uses.
Among the preparation method of the present invention, can be further with coordination compound and solvent combination.This coordination compound is so long as controlled controlling catalyst precursors reaction, and the material that forms fiber construct gets final product, and is not particularly limited, and carboxylic acids, amide-type, ester class, ketone, phosphine class, ethers, alcohols, thio-alcohol etc. are for example arranged.
Among this preparation method, catalyst precarsor contained in the fiber construct that is obtained by method of electrostatic spinning is handled, formed catalyst.
When using metal alcoholate or metal chloride, can implement hydrothermal treatment consists as required, in the closed containers such as the autoclave that is about to pack into, carry out heat treated in solution or in its steam by the fiber construct that above-mentioned method of electrostatic spinning obtains as catalyst precarsor.As long as hydro-thermal treatment method can promote the crystallization of the hydrolysis of kish alcoholates contained in the above-mentioned fiber construct, the polycondensation reaction that promotes metal hydroxides, promotion metal oxide, be not particularly limited.Preferred 50 ℃-250 ℃ of treatment temperature, more preferably 70 ℃-200 ℃.Treatment temperature is lower than 50 ℃, then can't promote the crystallization of metal oxide, and is not preferred, and than 250 ℃ high, then the organic macromolecule intensity of using as base material reduces, and is not preferred.Liquid uses pure water usually, preferred pH 2-10, more preferably pH 3-9.
Also can be as required, above-mentioned fiber construct is dry under hot blast.By dry under hot blast, can promote the crystallization of metal oxide.Preferred 50 ℃-150 ℃ of said temperature, more preferably 80 ℃-120 ℃.
The not item of the record record of method of fiber construct that can directly quote the state that supports of preparation (a) among this preparation method.
Fiber construct with the state that supports of above-mentioned (c) for example can obtain by the preparation method who comprises with the catalyst-loaded fiber construct of next stage: make into the fibroid compound and be dissolved in and prepare solution in the solvent, make catalyst granules disperse the stage that wherein prepares dispersion soln again; By the stage of electrostatic spinning with above-mentioned dispersion soln spinning; Obtain being accumulated in the stage of collecting the catalyst-loaded fiber construct on the ground by above-mentioned spinning.
At first be to make into the fibroid compound to be dissolved in and to prepare solution in the solvent, make catalyst granules disperse the stage that wherein prepares dispersion soln again.One-tenth fibroid compound concentrations in the dispersion soln among the bright preparation method of this law is preferably 1-30 weight %.Become the fibroid compound concentrations littler than 1 weight %, then concentration is low excessively, is difficult to form fiber construct, and is not preferred.Bigger than 30 weight %, then the fibre diameter of the fiber construct of gained increases, and is not preferred.Preferred one-tenth fibroid compound concentrations is 2-20 weight %.
The dispersion concentration of catalyst granules is preferably 0.1-30 weight % in the dispersion soln among the preparation method of the present invention.The dispersion concentration ratio 0.1 weight % of catalyst granules is little, and then the catalyst activity of gained fiber construct is low excessively, and is not preferred.Than 30 weight % height, then the intensity of gained fiber construct reduces, and is not preferred.The dispersion concentration of preferred catalyst granules is 0.5-25 weight %.
Among the preparation method of the present invention, can prepare solution in the solvent with becoming the fibroid compound to be dissolved in earlier, catalyst granules is disperseed, also can also make into the fibroid compound and be dissolved in the solvent that has added catalyst granules in advance becoming fibroid compound and catalyst granules to add simultaneously in the solvent.The method that catalyst granules is disperseed is not particularly limited, and stirring, ultrasonic wave processing etc. are arranged.
The not item of the record record of method of fiber construct that can directly quote the state that supports of preparation (a) among this preparation method.
Embodiment
Further specify the present invention by the following examples, the present invention is not subjected to the qualification of these embodiment.Each following embodiment, the assessment item in the comparative example are implemented by following method.
The average diameter of fiber:
With SEM (Hitachi Co., Ltd makes S-2400) (taking 8000 times of multiplying powers) taken on the surface of gained fiber construct, 20 positions of picked at random from the photo that obtains, measure fibre diameter, obtain the mean value of whole fibre diameters (n=20), with this average diameter as fiber.
Affirmation to the existence of long 20 μ m of fiber or following fiber:
With SEM (Hitachi Co., Ltd makes S-2400) (taking 2000 times of multiplying powers) taken on the surface of gained fiber construct, observable photo confirms whether to exist long 20 μ m of fiber or following fiber.
Catalyst particle size:
With SEM (Hitachi Co., Ltd makes S-2400) (taking 8000 times of multiplying powers) taken on the surface of gained fiber construct, 5 positions of picked at random from the photo that obtains, measure the diameter of catalyst granules part, obtain the mean value of whole diameters (n=5), with this as catalyst particle size.
With the longest part of the scope catalyst particles that can in photo, confirm as diameter.
Catalyst activity is estimated:
The fiber construct sample is cut into vertical 2cm, horizontal 2cm, is impregnated in the aqueous solution of methylene blue of 5ml10ppm.
Use Iwasaki Electric Co., Ltd.'s system EYE SUPER UV tester " SUV-F11 ", with 60mW/cm
2Intensity, penetrate the stipulated time with the illumination in 295-450nm district.In addition, with not catalyst-loaded fiber construct sample in contrast, the aqueous solution of methylene blue that floods this control sample is also shone.
Use Shimano Inc to make " UV-2400PC " of manufacturing, the gained aqueous solution of methylene blue is measured the absorbance of 665nm.Dipping has supported in the aqueous solution of methylene blue of the aqueous solution of methylene blue of fiber construct of catalyst and the not catalyst-loaded fiber construct of dipping, aqueous solution of methylene blue one side's the absorbance of fiber construct that dipping has supported catalyst is little, can be by the decomposition evaluation of catalyst activity size of methylene blue.
Preparation contains 1 weight portion polyacrylonitrile (Wako Pure Chemical Industries, Ltd.'s manufacturing), 9 weight portion N, the solution of dinethylformamide (Wako Pure Chemical Industries, Ltd.'s manufacturing, reagent superfine).Use device shown in Figure 2, this solution was ejected to fibrous material passive electrode (Fig. 2 5) 30 minutes.The internal diameter of nozzle (Fig. 2 1) is 0.8mm, and voltage is 12kV, and the distance of (Fig. 2 5) is 10cm from nozzle (Fig. 2 1) to the fibrous material passive electrode.The order of the fiber construct of gained is paid and is 3g/m
2With SEM (Hitachi Co., Ltd makes S-2400) the gained fiber construct is observed, fiber diameter is 0.2 μ m, and not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of gained fiber construct as shown in Figure 3, Figure 4.
Then, the gained fiber construct was flooded 10 minutes in photochemical catalyst smears (Japanese Parkerizing Co., Ltd.'s system " PALTITAN 5607 "), dry then, obtain catalyst-loaded fiber construct, the catalyst activity evaluation result that finally obtains is as shown in table 1.The electron scanning micrograph figure of the fiber construct that gained is catalyst-loaded as shown in Figure 5.
Among the embodiment 1, form after the fiber construct,, in addition carry out same operation 300 ℃ of heat treatments 3 hours.
Observe the fiber construct that obtains after the heat treatment with SEM (Hitachi Co., Ltd makes S-2400), fiber diameter is 0.2 μ m, and not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of gained fiber construct such as Fig. 6, shown in Figure 7.
To gained fiber construct enforcement operation similarly to Example 1, obtain catalyst-loaded fiber construct.The catalyst activity evaluation result that finally obtains is as shown in table 1.
Comparative example 1
Polyacrylonitrile (Wako Pure Chemical Industries, Ltd.'s manufacturing) is dissolved in N, dinethylformamide (Wako Pure Chemical Industries, Ltd.'s manufacturing, reagent superfine), the preparation polymer concentration is 7.5% rubber cement.
It is extruded in the coagulating bath of water as solidification liquid, carry out the wet type spinning, then in coagulating bath, be stretched to 3 times, obtain the fiber of 15 μ m fibre diameters.Pay by this fiber production order and to be 6g/m
2Non-weaving cloth.
To gained fiber assembly enforcement operation similarly to Example 1, obtain catalyst-loaded fiber construct.The catalyst activity evaluation result that finally obtains is as shown in table 1.The gained fiber construct lacks flexibility.
It is 1300 polyvinyl chloride, 4.5 weight portion N that preparation contains the 1 weight portion degree of polymerization, the solution of dinethylformamide (Wako Pure Chemical Industries, Ltd. makes, superfine), 4.5 weight portion oxolanes (Wako Pure Chemical Industries, Ltd. makes, superfine).Then, use device shown in Figure 1, with this solution to fibrous material passive electrode (Fig. 1 5) ejection 60 minutes.The internal diameter of nozzle (Fig. 1 1) is 0.8mm, and the solution feed speed is 20 μ l/ minutes, and voltage is 12kV, and nozzle (Fig. 1 1) to the distance of fibrous material passive electrode (Fig. 1 5) is 20cm.The order of gained fiber construct is paid and is 36g/m
2, be the non-weaving cloth shape of 0.2mm for thickness.Observation post gets fiber construct with SEM (Hitachi Co., Ltd makes S-2400), and fiber diameter is 0.4 μ m, and not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of gained fibre structure surface as shown in Figure 8.
Then, photochemical catalyst smears (Japanese Parkerizing Co., Ltd.'s system " PALTITAN 5607 ") used methanol/isopropanol (1/1; Weight ratio) the mixed solvent dilution is catalyst concn 1 weight %, the preparation coating solution.With its with air-brush (KisoPower Tool Co., Ltd. system " E1306 ": nozzle diameter 0.4mm), with 0.1ml/cm
2Coating weight coated fiber structure, obtain catalyst-loaded fiber construct.The catalyst activity evaluation result is as shown in table 1.
Among the embodiment 3, ejection time of solution was become 15 minutes by 60 minutes, in addition carry out same operation, form order and pay and be 7.8g/m
2, thickness is the fiber construct of the non-weaving cloth shape of 0.05mm.
Observation post gets fiber construct with SEM (Hitachi Co., Ltd makes S-2400), and fiber diameter is 0.3 μ m, and not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of gained fibre structure surface as shown in Figure 9.
Then, dipping is 10 minutes in the coating solution that above-mentioned fiber construct is prepared in embodiment 3, carries out drying then, obtains catalyst-loaded fiber construct.The catalyst activity evaluation result is as shown in table 1.
Comparative example 2
(order is paid 83g/m will to contain the cloth and silk of polyvinyl chloride multifilament (single fiber diameter is about 17.54 μ m) of 84dtex/25 monofilament
2) be impregnated into similarly to Example 2 in the coating solution, obtain catalyst-loaded fiber construct.The catalyst activity evaluation result is as shown in table 1.The gained non-weaving cloth lacks flexibility.
It is 1300 polyvinyl chloride, 4.5 weight portion oxolanes (Wako Pure Chemical Industries, Ltd. makes, superfine), 4.5 weight portion N that preparation contains the 1 weight portion degree of polymerization, the solution of dinethylformamide (Wako Pure Chemical Industries, Ltd. makes, superfine), 1.1 weight portions, four titanium butoxide (Wako Pure Chemical Industries, Ltd. makes, superfine).Use device shown in Figure 2, this solution is sprayed 60 minutes to the fibrous material passive electrode.The internal diameter of nozzle is that 0.8mm, voltage are 12kV, and nozzle to the distance of fibrous material passive electrode is 15cm.
With the gained fiber construct autoclave of packing into, in the aqueous solution of pH 3, kept 17 hours, sample with ion-exchange water washing, drying, is obtained order and pays and be 32g/cm at 80 ℃
2Catalyst-loaded fiber construct.Observation post gets catalyst-loaded fiber construct with SEM (Hitachi Co., Ltd makes " S-2400 "), and fiber diameter is 0.5 μ m, and not observing fiber length is 20 μ m or following fiber.In the X-ray diffraction result of the catalyst-loaded fiber construct of gained, as seen ° visible peak in 2 θ=25.3 generates the Detitanium-ore-type crystal of titanium oxide, as seen forms the photocatalyst oxidizes titanium by catalyst precarsor.The electron scanning micrograph figure of the fibre structure surface that gained is catalyst-loaded such as Figure 10 and shown in Figure 11, X-ray diffraction figure are as shown in figure 12, the catalyst activity evaluation result is as shown in table 1.
Comparative example 3
Among the embodiment 5, it is 1300 polyvinyl chloride, 4.5 weight portion oxolanes (Wako Pure Chemical Industries, Ltd. makes, superfine), 4.5 weight portion N that use contains the 1 weight portion degree of polymerization, the solution of dinethylformamide (Wako Pure Chemical Industries, Ltd.'s manufacturing, superfine), in addition carry out same operation, obtain order and pay and be 11g/m
2Fiber construct.In the X-ray diffraction result of gained fiber construct, ° do not see the peak in 2 θ=25.3.The X-ray diffraction figure of gained fiber construct as shown in figure 13, the catalyst activity evaluation result is as shown in table 1.
Preparation contains 1 weight portion polyacrylonitrile (Wako Pure Chemical Industries, Ltd.'s manufacturing), 9 weight portion N, and dinethylformamide (Wako Pure Chemical Industries, Ltd.'s manufacturing, reagent superfine) and 1 weight portion are as the solution of the porous silica lining titanium oxide (peaceful chemical Industry Co., Ltd system " MUSKMELON type photochemical catalyst ", particle diameter 2 μ m) of catalyst.Then, use device shown in Figure 1, with this solution to fibrous material passive electrode (Fig. 1 5) ejection 30 minutes.The internal diameter of nozzle (Fig. 1 1) is 0.8mm, and the solution feed speed is 20 μ l/ minutes, and voltage is 12kV, and the distance of (Fig. 1 5) is 15cm from nozzle (Fig. 1 1) to the fibrous material passive electrode.The order of the fiber construct of gained is paid and is 5g/m
2The electron scanning micrograph figure of gained fibre structure surface as shown in figure 14, fiber diameter is 0.15 μ m, not observing fiber length is 20 μ m or following fiber.In addition, catalyst particle size is 3 μ m.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 7
Among the embodiment 6, use porous silica lining titanium oxide (peaceful chemical Industry Co., Ltd system " MUSKMELON type photochemical catalyst ", particle diameter 5 μ m), in addition to carry out same operation as catalyst.
The order of gained fiber construct is paid and is 5g/m
2, fiber diameter is 0.15 μ m, and not observing fiber length is 20 μ m or following fiber, and catalyst particle size is 5 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 15.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 8
Among the embodiment 6, use porous silica lining titanium oxide (peaceful chemical Industry Co., Ltd system " MUSKMELON type photochemical catalyst ", particle diameter 15 μ m), in addition to carry out same operation as catalyst.
The order of gained fiber construct is paid and is 5g/m
2, fiber diameter is 0.15 μ m, and not observing fiber length is 20 μ m or following fiber, and catalyst particle size is 13 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 16.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 9
Among the embodiment 6, use the titanium oxide (peaceful chemical Industry Co., Ltd system " photochemical catalyst APATITE ", particle diameter 5 μ m) of lining apatite to replace porous silica lining titanium oxide, in addition carry out same operation as catalyst.The order of gained fiber construct is paid and is 5g/m
2, fiber diameter is 0.15 μ m, and not observing fiber length is 20 μ m or following fiber, and catalyst particle size is 9 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 17.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Among the embodiment 6, use titanium oxide (Titan Industrial Co., Ltd system " PC-101A ", particle diameter 40nm) to replace porous silica lining titanium oxide, in addition carry out same operation as catalyst.
The order of gained fiber construct is paid and is 5g/m
2, fiber diameter is 0.15 μ m, and not observing fiber length is 20 μ m or following fiber, and catalyst particle size is 4 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 18.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 11
Preparation contains 1 weight portion polyvinyl chloride (Wako Pure Chemical Industries, Ltd.'s manufacturing), 4.5 weight portion N, the solution of dinethylformamide (Wako Pure Chemical Industries, Ltd.'s manufacturing, superfine), 4.5 weight portion oxolanes (Wako Pure Chemical Industries, Ltd.'s manufacturing, superfine), 0.5 weight portion porous silica lining titanium oxide (peaceful chemical Industry Co., Ltd system " MUSKMELON type photochemical catalyst ", particle diameter 2 μ m).Then, use device shown in Figure 1, with this solution to fibrous material passive electrode (Fig. 1 5) ejection 30 minutes.The internal diameter of nozzle (Fig. 1 1) is that 0.8mm, solution feed speed are that 20 μ l/ minutes, voltage are 12kV, and nozzle (Fig. 1 1) to the distance of fibrous material passive electrode (Fig. 1 5) is 15cm.The order of gained fiber construct is paid and is 7g/m
2Now examine the surface of gained fiber construct with SEM, fiber diameter is 0.2 μ m, and now not examining fiber length is 20 μ m or following fiber.Catalyst particle size is 11 μ m.
The electron scanning micrograph figure of gained fiber construct as shown in figure 19.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 12
Among the embodiment 11, use the titanium oxide (peaceful chemical Industry Co., Ltd system " photochemical catalyst APATITE ", particle diameter 5 μ m) of lining apatite to replace porous silica lining titanium oxide, in addition carry out same operation as catalyst.The order of gained fiber construct is paid and is 7g/m
2, fiber diameter is 0.2 μ m, and now not examining fiber length is 20 μ m or following fiber, and catalyst particle size is 10 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 20.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Embodiment 13
Among the embodiment 11, use titanium oxide (Titan Industrial Co., Ltd system " PC-101A ", particle diameter 40nm) to replace porous silica lining titanium oxide, in addition carry out same operation as catalyst.
The order of gained fiber construct is paid and is 7g/m
2, fiber diameter is 0.2 μ m, and not observing fiber length is 20 μ m or following fiber, and catalyst particle size is 9 μ m.The electron scanning micrograph figure of fiber construct as shown in figure 21.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Comparative example 4
Among the embodiment 6, do not use porous silica lining titanium oxide, in addition carry out same operation.The order of gained fiber construct is paid and is 5g/m
2, fiber diameter is 0.15 μ m, not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of fiber construct as shown in figure 22.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Comparative example 5
Among the embodiment 11, do not use porous silica lining titanium oxide, in addition carry out same operation.The order of gained fiber construct is paid and is 7g/m
2, fiber diameter is 0.2 μ m, not observing fiber length is 20 μ m or following fiber.The electron scanning micrograph figure of fiber construct as shown in figure 23.The catalyst activity evaluation result of the fiber construct that gained is catalyst-loaded is as shown in table 1.
Table 1
| The UV irradiation time (minute) | The | |
| Embodiment | ||
| 1 | 30 | 0.07 |
| |
30 | 0.06 |
| |
30 | 0.08 |
| |
30 | 0.42 |
| |
60 | 0.37 |
| |
60 | 0.19 |
| Embodiment 7 | 60 | 0.20 |
| Embodiment 8 | 60 | 0.47 |
| Embodiment 9 | 60 | 0.27 |
| |
60 | 0.83 |
| Embodiment 11 | 60 | 0.13 |
| Embodiment 12 | 60 | 0.38 |
| Embodiment 13 | 60 | 0.93 |
| The 10ppm aqueous solution of methylene blue | Not irradiation | 1.80 |
| |
30 | 1.06 |
| Blank | 60 | 1.16 |
| Not catalyst-loaded fiber construct | 60 | 1.25 |
| Comparative example 1 | 30 | 0.33 |
| Comparative example 2 | 60 | 0.58 |
| Comparative example 3 | 60 | 1.38 |
| Comparative example 4 | 60 | 1.39 |
| Comparative example 5 | 60 | 1.40 |
Claims (11)
1. the preparation method of catalyst-loaded fiber construct, this method comprise makes into the dissolving of fibroid organic polymer, the stage of preparation solution; By the stage of method of electrostatic spinning with above-mentioned solution spinning; Obtain being accumulated in the stage of collecting the fiber construct on the ground by above-mentioned spinning; With the stage that makes catalyst loading in above-mentioned fiber construct.
2. the preparation method of claim 1, the solvent that wherein is used for above-mentioned dissolving is a volatile organic solvent.
3. the preparation method of claim 1, wherein, supporting of catalyst is to be undertaken by fiber construct be impregnated in the liquid that contains catalyst.
4. the preparation method of claim 1, wherein, supporting of catalyst is to coat the fibre structure surface by the liquid that will contain catalyst to carry out.
5. the preparation method of catalyst-loaded fiber construct, this method comprise the stage that fibroid organic polymer and catalyst precarsor are dissolved in preparation solution in the solvent that makes into; By the stage of method of electrostatic spinning with above-mentioned solution spinning; Obtain being accumulated in the stage of collecting the fiber construct on the ground by above-mentioned spinning; With the catalyst precarsor that is contained in the above-mentioned fiber construct is handled, form the stage of catalyst.
6. the preparation method of claim 5, wherein, the employed solvent of above-mentioned dissolving is a volatile organic solvent.
7. the preparation method of claim 5, wherein, the method for handling above-mentioned catalyst precarsor is a hydrothermal treatment consists.
8. the preparation method of catalyst-loaded fiber construct, this method comprise to be made into the fibroid compound and is dissolved in and prepares solution in the solvent, and catalyst granules is disperseed wherein and the stage of preparation dispersion soln; By the stage of method of electrostatic spinning with above-mentioned dispersion soln spinning; With the stage that obtains being accumulated in the catalyst-loaded fiber construct on the collection ground by above-mentioned spinning.
9. the preparation method of the catalyst-loaded fiber construct of claim 8, wherein above-mentioned catalyst granules is the particle of particle diameter in the scope of 1-100 μ m.
10. the preparation method of the catalyst-loaded fiber construct of claim 9, wherein the one-level particle diameter of above-mentioned catalyst is 1-100 μ m.
11. the preparation method of claim 8, wherein, the employed solvent of above-mentioned dissolving is a volatile organic solvent.
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