CN100532460C - Composite nanofiber, composite nanofiber mass, composite structure, and processes for producing these - Google Patents

Abstract

Silica nanofibers are derived from crystalline polymer filaments comprising a polymer which has a linear polyethyleneimine skeleton and can form a water-insoluble crystalline structure in the presence of water molecules at room temperature. The crystalline polymer filaments in the silica concentrate metal ions, whereby composite nanofibers can be realized in which the silica contains a metal or metal ions inside. The composite nanofibers can be easily produced by fixing, within silica, a polymer structure serving as a scaffold for metal ions and either concentrating metal ions on the scaffold or reducing the metal ions. Furthermore, metal-containing silica nanofibers can be easily obtained by removing the polymer ingredient from the composite nanofibers or from a mass or structure of the composite nanofibers. These nanofibers can be aggregated or gathered. The mass or structure obtained through aggregation or gathering can have various shapes.

Description

Composite nano fiber, composite nano fiber association body, complex structure body and their manufacture method thereof

Technical field

The present invention relates to a kind of nanofiber (nanofiber) that contains metal or metal ion in silica nano fibrous, association body (association) that this nanofiber gatheringization forms or the manufacture method of structure and these nanofibers or nanofiber association body.

The application advocates to the right of priority that the spy that the spy is willing to 2004-No. 161234 and on August 24th, 2004 applied for to the Japan special permission Room of Japan's special permission Room application is willing to 2004-No. 243580, to quote its content at this on May 31st, 2004.

Background technology

As everyone knows, material with nano-scale structure can show the characteristic that is different from the large size state, and wherein have the nano level thickness and count the nanofiber of the length that decuples its thickness, because its high aspect ratio, can show the distinctive dimensional effect of fiber shape, therefore receive concern as one of tip materials.Because silica nano fibrous have distinctive high aspect ratio of nanofiber and a big surface-area, have all rerum naturas such as inorganic materials inherent characteristic of semiconductor, electroconductibility, surface physical property, physical strength simultaneously, be expected to be applied with the various tip materials field headed by field of electronic materials, the biological life science.In addition, by a nanofiber (one dimension) is being kept forming flush type (cloth shape, two dimension) or build (bulk, three-dimensional) through gatheringization under the constant prerequisite of its nano-meter characteristic, make it become structure, thereby might make silica nano fibrous purposes be able to enlarge tremendously.

Especially the silica nano fibrous material that combines with functional materials such as other inorganic materials or organic materialss had applicability widely, for example, by with the combination of inorganic materials such as metal, be expected to be applied in various fields such as electronic material, optical material, catalyzer, colorant, transmitters.

As the material with silicon-dioxide and metal or metal ion combination, the matrix material that metal complex is fixed in mesoporosity silicon-dioxide has been used in chemical reaction catalyst, electrochemical sensor, the solid polymer electrolyte etc.Can predict, metal complex is directed in the matrix material of mesoporosity silicon-dioxide when being used for practical application, therefore plurality of advantages such as high surface area, the coordination compound active site that can embody silica sphere distributes at the homogeneous in nanometer cavity, the thermotolerance of the rapid diffusion of matrix compounds, support of the catalyst, acid resistance have received numerous concern (with reference to Non-Patent Document 1) with mesoporosity silicon-dioxide as the metal complex immobilization technology of carrier.

But, these in the past metal complex and the matrix material of silicon-dioxide in the silicon-dioxide that uses only limit to the silicon-dioxide of large size (bulk) powder and particle state.Because this complex body micropartical is the particle shape that aspect ratio is almost 1:1, therefore only can not gathering, integrated by this complex body micropartical, be difficult to form the structure that has kept the distinctive character of nano structural material.

In addition, with regard to manufacture method, need be provided with amino, imino-etc. are directed in the operation of silicon dioxide skeleton with chemical bond, described amino, imino-are used for and metal ion forms coordinate bond, and described operation is very miscellaneous.

Carried out many research at present for fine matrix material as silicon-dioxide and metal, for example study for the mesoporosity silicon-dioxide/metal nano silk complex body that in the mesoporosity silicon-dioxide duct of MCM-41 series, the metal ion solution reduction is formed in Non-Patent Document 2, the Non-Patent Document 3, studied in the Non-Patent Document 4 metal ion is incorporated into the silicon dioxide particles/metal nanoparticle complex body that forms in the silicon dioxide particles.

But these the metal nanoparticle nano threads in the past and the complex body of other material, if the fixed space of the material that is fixed with shape is not a condition, just be difficult to form metal nanoparticle and nano thread, therefore the degree of freedom of silicon-dioxide shape is low, be subject to and have the large-sized silicon-dioxide that forms hole wiry and the material of particle shape, the shape of complex body is difficult to control.So be difficult to make complex body or inner wire Highgrade integration.

Non-Patent Document 1:B.Lee et al.Langmuir, (2003), 19, p4246-4252

Non-Patent Document 2:G.Hornyak et al.Chem.Eur.J.1997,3, No.12, p1951-1956

Non-Patent Document 3:Yong-Jin Han, Chem.Mater.,, 12, p2068-2069 in 2000

Non-Patent Document 4:V.G.Pol et al., Chem.Mater., 2003,15, p1111-1118

Goal of the invention

The object of the present invention is to provide a metal ion species or atom to be fixed in the structure and can realize the metallic silica nano fibrous of gatheringization highly, functional polymer again compoundization in this metallic silica nano fibrous composite nano fiber, the association body of these fiber height gatheringizations or structure and their simple manufacture method.

Among the present invention, crystalline polymer long filament by the polymkeric substance with straight chain type polymine skeleton derives silica nano fibrous, and by the crystalline polymer long filament concentrating metals ion in this silicon-dioxide, can realize making metal or metal ion to be contained in the composite nano fiber of silicon-dioxide inside, described straight chain type polymine skeleton can form the water-insoluble xln in the presence of room temperature, water molecules.This composite nano fiber can gathering, integrated, and gatheringization or integrated association body or structure have multiple shape.In addition, composite nano fiber of the present invention can be fixed in the silicon-dioxide by the polymer structure that will become the metal ion support and metal ion concentrated in this support or makes this metal ion reduction and easily make.Remove component of polymer by association body, structure, also can easily obtain containing the silica nano fibrous of metal from this composite nano fiber or composite nano fiber.

Promptly, the invention provides the complex structure body that composite nano fiber, this composite nano fiber of containing following polymkeric substance in silica nano fibrous associate mutually and associate and form again between the association body that forms, this association body, described polymkeric substance has the straight chain type polymine skeleton that coordination has at least a metal or metal ion.

In addition, the invention provides from above-mentioned composite nano fiber, composite nano fiber association body and complex structure body and removed metallic silica nano fibrous, the silica nano fibrous association body that contains metal of component of polymer, the silica nano fibrous structure that contains metal.

The present invention also provides the manufacture method of the composite nano fiber that comprises following operation,

(1) make have straight chain type polymine skeleton polymer dissolution in solvent, in the presence of water, separate out then, obtain having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton;

(2) in the presence of water, contact with organoalkoxysilane by making above-mentioned crystalline polymer long filament, cover above-mentioned crystalline polymer long filament with silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance;

(3) make and above-mentionedly contain the silica nano fibrous of polymkeric substance and be dissolved with metal ion solution and contact, make straight chain type polymine skeleton in metal ion and the above-mentioned polymkeric substance form the operation of coordinate bond.The present invention also is provided at the manufacture method that above-mentioned operation also has the composite nano fiber of operation (4) afterwards, and operation (4) is to make the transition metal ion reductive operation that is incorporated into the straight chain type polymine skeleton in the above-mentioned polymkeric substance by coordinate bond.

The present invention also provides has the metallic silica nano fibrous manufacture method that (5) remove the operation of the component of polymer in this composite nano fiber after obtaining composite nano fiber by above-mentioned operation.

The effect of invention

Composite nano fiber of the present invention and metallic silica nano fibrous can be realized highly gatheringization, integrated by mutual association, can form the association body with micron～millimetre-sized two dimension or three-dimensional space shape.This association shape can be adjusted into as different shapes such as lettuce shape, fibrous, spongy, aster shape, celestial being's palmate, taraxacum shapes.By maybe should the combination of association body between the composite nano fiber association body, can form a structure again with the above large size outer shape of millimeter level by means of other composite nano fiber.The profile of this structure can be configured as shape arbitrarily, can be shaped to collar plate shape, cylinder shape, sheet type, filter type, membranous type, ball-type, stripe shape etc. according to the requirement of concrete application, can be processed into various states such as powder, particle, polyhedron, round tube type.There is the association shape of above-mentioned association body in this structure inside, composite nano fiber of the present invention and metallic silica nano fibrous be the basis of this association body.Therefore, this structure has the complex three-dimensional reticulated structure that is formed by these nanofibers.

Metal ion or metal are contained in composite nano fiber of the present invention and metallic silica nano fibrous portion within it.As metal ion, contain the ion of basic metal, alkaline-earth metal, transition metal etc., so these nanofibers are expected to be applied in solid electrolyte, solid catalyst, nanometer additive, the nano film material.

In addition, by making the spontaneous reduction of metal ion or utilizing thermal treatment or reductive agent makes its reduction, can make metal ion become particle shape or wire-shaped through metal beam.The sponge-like structure that the film like structures body that is made of the nanofiber that contains the metal nano silk can be provided thus, constitute by the nanofiber that contains the metal nano silk, the reticulated structure body that constitutes by the nanofiber that contains the metal nano silk.In addition, metal nanoparticle is distributed in the complex structure body of these shapes.

Wherein, contain transition metal, particularly to contain the silica nano fibrous applicability of precious metal crystalline very high, be expected to be used widely in whole field of nanometer technology as metallic catalyst, nano metal electro-conductive material, nano metal look material, nano metal transmitter, light image material, photoelectric material, medical material etc.

Manufacturing method according to the invention, can be by the solgel reaction of the silica source of only carrying out at the crystalline polymer filament surface of nanometer thickness, make certain thickness silicon-dioxide cover this crystalline polymer long filament, make the metal ion immobilization afterwards, or restore metal ion as required, can easily make composite nano fiber within a short period of time thus.

In addition, because the component of polymer in the composite nano fiber of the present invention can be removed simply by sintering etc., the therefore inner silica nano fibrous manufacturing that contains metal that comprises metal nanoparticle or metal nano silk also is easy to.

Description of drawings

Fig. 1 is the transmission electron microscope photo of the composite nano fiber structure in the embodiments of the invention 1.

Fig. 2 is the very high resolution transmission electron microscope photo of the metal nano silk in the composite nano fiber structure in the embodiments of the invention 1.

Fig. 3 is the transmission electron microscope photo of the composite nano fiber structure in the embodiments of the invention 2.

Fig. 4 is the very high resolution transmission electron microscope photo of the platinum nano thread in the composite nano fiber structure in the embodiments of the invention 2.

Fig. 5 is the scanning electron microscope photo of the composite nano fiber structure in the embodiments of the invention 4.

Embodiment

Composite nano fiber of the present invention is, metal or metal ion and the polymkeric substance with straight chain type polymine skeleton are contained in the matrix material in silica nano fibrous.

[polymkeric substance] with straight chain type polymine skeleton

The said straight chain type polymine of the present invention skeleton is meant that with the ethyleneimine unit as secondary amine be the unitary straight chain type polymer backbone of primary structure.Also can have ethyleneimine unit structural unit in addition in this skeleton, but in order to form the crystalline polymer long filament, the certain chain length of preferred polymers chain is made of successive ethyleneimine unit.The length of this straight chain type polymine skeleton, as long as in the polymkeric substance with this skeleton can form the scope of crystalline polymer long filament, just have no particular limits, in order to form suitable crystalline polymer long filament, the unitary number of repeat unit of ethyleneimine of this skeleton part is preferably more than 10, is preferably 20～10000 scope especially.

The polymkeric substance that uses among the present invention gets final product so long as have the material of above-mentioned straight chain type polymine skeleton in its structure, and its shape can be line style, star-like, comb type, as long as can form the crystalline polymer long filament in the presence of water.

In addition, the polymkeric substance of these line styles, star-like, comb type, can only constitute, also can constitute by the segmented copolymer of the block that constitutes by straight chain type polymine skeleton (following brief note is the polymine block) with other polymer blocks by straight chain type polymine skeleton.As other polymer blocks; can use as water-soluble polymers blocks such as polyoxyethylene glycol, poly-propionyl ethyleneimine, polyacrylamides, or hydrophobic polymer blocks such as the polymethylmethacrylate of the Ju Ben oxazolin of polystyrene, Ju oxazoline class, poly-Xin oxazolin, poly-Shi Er Wan oxazolin, polyacrylate(s), poly-n-butyl methacrylate.By forming the segmented copolymer with these other polymer blocks, can adjust the shape and the characteristic of crystalline polymer long filament.

Having in the polymkeric substance of straight chain type polymine skeleton has under the situation of other polymer blocks etc., the ratio of straight chain type polymine skeleton in this polymkeric substance, as long as in the scope that can form the crystalline polymer long filament, just have no particular limits, but in order to form suitable crystalline polymer long filament, the ratio of straight chain type polymine skeleton is preferably 25 moles more than the % in the polymkeric substance, more preferably 40 moles more than the %, especially be preferably 50 moles more than the %.

Above-mentioned polymkeric substance with straight chain type polymine skeleton, can be under acidic conditions or under the alkaline condition, by as the adding water decomposition of polymkeric substance (following brief note is a precursor polymer) with straight chain type skeleton that You Ju oxazoline class constitutes of its precursor and easily obtain.Therefore, have shapes such as the line style of the polymkeric substance of straight chain type polymine skeleton, star-like or comb type, can easily design by the shape of controlling this precursor polymer.In addition, the polymerization degree or end structure also can easily be adjusted by the polymerization degree or the functional end-group of control precursor polymer.Also have, form when having the segmented copolymer of straight chain type polymine skeleton, can be with precursor polymer as segmented copolymer, hydrolysis optionally takes place and obtains in the straight chain type skeleton that constitutes by the You Ju oxazoline class that makes in this precursor polymer.

Precursor polymer can synthesize with synthetic methods such as cationic polymerization or big (マ Network ロ) simplex methods to use oxazoline class monomer, by suitable selection synthetic method or initiator, can synthesize the precursor polymer of different shapes such as line style, star-like or comb type.

Monomer as forming the straight chain type skeleton that You Ju oxazoline class constitutes can use oxazoline monomers such as Jia oxazolin, ethyl oxazoline, Jia base Yi Xi oxazolin, Ben oxazolin.

As polymerization starter, can use have the chlorine alkyl in the molecule, the compound of functional group such as bromine alkyl, iodine alkyl, tosyloxy or three fluoro sulfonyloxy methyl oxygen bases.These polymerization starters can be converted into other functional group by the hydroxyl with multiple alcohol compound and obtain.Wherein, finished its polymerization efficiency of initiation height of material of bromination, iodate, toluenesulphonic acidsization and three fluoro methylsulphonic acidizations as functional group's conversion, thereby be preferred, preferred especially bromination alkyl, toluenesulphonic acids alkyl.

In addition, the material that the terminal hydroxyl of polyoxyethylene glycol is converted into the material of bromine or iodine or is converted into methyl sulphonyl also can be used as polymerization starter and uses.This moment, the polymerization degree of polyoxyethylene glycol was preferably 5～100 scope, was preferably 10～50 scope especially.

In addition, contain the functional group of tool positively charged ion open loop living polymerization initiating power and contain have the photoluminescence function, the pigment of any skeleton in porphyrin skeleton, phthalocyanine frame or the pyrene skeleton of energy forwarding function, transfer transport function can give resulting polymers with special function.

The line style precursor polymer can be by obtaining Shang Shu oxazoline monomer by the polymerization starter polymerization with 1 valency or divalent functional group.As such polymerization starter, can enumerate as chloromethylbenzene, brooethyl benzene, iodomethyl benzene, toluenesulphonic acids methyl phenyl ester, three and fluoridize methylsulphonic acid methyl phenyl ester, monobromethane, methyl iodide, toluenesulphonic acids methane or toluenesulphonic acids acid anhydride, three fluoro methylsulphonic acid acid anhydrides, 5-(4-2-bromomethylphenyl)-10,15, the material of 1 valencys such as 20-three (phenyl) porphyrins or brooethyl pyrene, the material of divalents such as dibromomethylbenzene, two toluene iodides, two bromomethylbiphenyls or dibromo methyl-benzene.In addition, poly-(first oxazolin), poly-(ethyl oxazoline) or the poly-oxazoline of poly-industrial line styles such as (first base second alkene oxazolins) can directly use as precursor polymer.

Star-like precursor polymer can be by obtaining Shang Shu oxazoline monomer by the polymerization starter polymerization with the above functional group of 3 valencys.As the polymerization starter more than 3 valencys; can enumerate the above materials of 5 valencys such as material, hexabromo toluene, four (3,5-dimethylbenzene alkylsulfonyl ethyl oxygen phenyl) porphyrin of 4 valencys such as material as 3 valencys such as toluene tribromides, tetrabromo toluene, four (4-chloromethyl phenyl) porphyrin, tetrabromo oxyethyl group phthalocyanine.

In order to obtain comb type precursor polymer; can use simple linear polymer with multivalence polymerization initiating radical; by this polymerization initiating radical Shi oxazoline monomer polymerization; for example; with bromine or iodine etc. side chains such as common Resins, epoxy or polyvinyl alcohol are contained the hydroxyl halogenation of the polymkeric substance of hydroxyl, or it also can be obtained this transform portion as the polymerization initiating radical after changing tosyl group into.

As the method that obtains comb type precursor polymer, also can use the polyamine type polymerization terminator.For example, use after the 1 valency polymerization starter Shi oxazoline polymerization, the amino of polyamine such as the end and the polymine of this Ju oxazoline, polyvinylamine, poly-propyl group amine is combined, just can obtain comb type De Ju oxazoline.

The hydrolysis of the straight chain type skeleton that is made of above-mentioned gained precursor polymer De Ju oxazoline class all can be carried out under any condition of acidic conditions or alkaline condition.

In the hydrolysis under the acidic conditions,, can obtain the hydrochloride of polymine for example by heated and stirred Ju oxazoline in aqueous hydrochloric acid.With the excess of ammonia water treatment of gained hydrochloride, can obtain the crystalline powder of alkaline polymine.The used salt aqueous acid can be a concentrated hydrochloric acid, also can be the aqueous solution about 1mol/L, but for hydrolysis is effectively carried out, preferably use the aqueous hydrochloric acid of 5mol/L.And temperature of reaction is preferably about 80 ℃.

In the hydrolysis under the alkaline condition,, can make poly-oxazoline be converted into polymine for example by using aqueous sodium hydroxide solution.Alkaline condition is cleaned reaction solution with dialysis membrane after reacting down, just can remove excessive sodium hydroxide, obtains the polymine crystalline powder.Used concentration sodium hydroxide can be the scope of 1～10mol/L, but for reaction is more effectively carried out, is preferably the scope of 3～5mol/L.Temperature of reaction is preferably about 80 ℃.

In the hydrolysis under acidic conditions or the alkaline condition, the usage quantity of acid or alkali can be 1～10 equivalent with respect to polymkeric substance Zhong De oxazoline unit, but in order to improve reaction efficiency and to simplify aftertreatment, is preferably about 3 equivalents.

By said hydrolyzed, the straight chain type skeleton that the You Ju oxazoline class in the precursor polymer constitutes becomes straight chain type polymine skeleton, thereby can obtain containing the polymkeric substance of this polymine skeleton.

In addition, when forming the segmented copolymer of straight chain type polymine block and other polymer blocks, can be by precursor polymer being constituted the segmented copolymer that the straight chain type polymer blocks that formed by Yi Ju oxazoline class and other polymer blocks constitute, and the straight chain type block that the Yi Ju oxazoline class in this precursor polymer is constituted optionally is hydrolyzed and obtains.

Under other the situation of polymer blocks, can utilize poly-(N-propionyl ethyleneimine) that the solvability of organic solvent is higher than the characteristics of poly-(N-formyl radical ethyleneimine) or poly-(N-ethanoyl ethyleneimine) and forms segmented copolymer for poly-water-soluble polymers blocks such as (N-propionyl ethyleneimine).Promptly; in the presence of above-mentioned polymerization initiation compound; make 2 — oxazolines or 2-methyl-2 — oxazoline carry out positively charged ion open loop living polymerization; make the polymerization of 2-ethyl-2 — oxazoline in the gained reactive polymer afterwards again, obtain thus by poly-(N-formyl radical ethyleneimine) block or poly-(N-ethanoyl ethyleneimine) block and the precursor polymer that gathers (N-propionyl ethyleneimine) block formation.This precursor polymer is dissolved in the water, and will be mixed in this aqueous solution with the immiscible organic solvent of the water of poly-(N-propionyl ethyleneimine) block of dissolving and stirs, form emulsion thus.Make poly-(N-formyl radical ethyleneimine) block or poly-(N-ethanoyl ethyleneimine) block selective hydrolysis by water interpolation acid or alkali, thereby form segmented copolymer with straight chain type polymine block and poly-(N-propionyl ethyleneimine) block to this emulsion.

To cause the valence mumber of compound be 1 and 2 o'clock in polymerization as used herein, becomes the straight chain type segmented copolymer, if be the valence mumber more than it, then can obtain star block copolymer.In addition, as if the segmented copolymer that precursor polymer is made as multistage, resulting polymers also may become the block structure of multistage.

[metal, metal ion]

Metal ion among the present invention, under the strong coordination ability effect that polymine skeleton in the above-mentioned polymkeric substance that contains straight chain type polymine skeleton is had, can form coordinate bond with the polyethyleneimine: amine unit in this skeleton and form metal complex.This metal complex is the product of metallic ion coordination in polyethyleneimine: amine unit gained, and is different with the forming process of ionic linkage, and no matter metal ion is positively charged ion or negatively charged ion, can form coordination compound by the coordination of polymine.Therefore, with regard to the metal kind of metal ion, so long as the material that can form coordinate bond with polyethyleneimine: amine unit in the polymkeric substance that contains straight chain type polymine skeleton just without limits, can enumerate basic metal, alkaline-earth metal, transition metal, metalloid, lanthanide series metal, polyoxometalate metal compound etc., the preferred metal ion that uses with these metal kinds.

As above-mentioned alkalimetal ion, can enumerate Li, Na, K, the ion of Cs etc.As the balance anion of alkalimetal ion, Cl can suitably be used, Br, I, NO ₃, SO ₄, PO ₄, ClO ₄, PF ₆, BF ₄, F ₃CSO ₃Deng.

As alkaline-earth metal ions, can enumerate Mg, Ba, the ion of Ca etc.

As transition metal ion, no matter it is transition-metal cation (Mn ⁺), the still acid radical anion (MOxn that constitutes by the bonding of transition metal and oxygen ^-) or the negatively charged ion (MLxn that constitutes by the halogen generic key ^-), all applicable to the formation of coordination compound.The transition metal of this specification sheets indication is meant the Sc of the periodic table of elements the 3rd family, the Y and the transition metal in the 4th～6 cycle of the 4th～12 family.

As transition-metal cation, can enumerate following transition-metal cation (Mn ⁺), as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Ru, Rh, Pd, Ag, Cd, W, Os, Ir, Pt, Au, the monovalence of Hg, divalence, trivalent or quaternary positively charged ion etc.The negatively charged ion of these positively charged ion correspondences can be Cl, NO ₃, SO ₄, or polyoxometallate (polyoxometalate) anionoid, carboxylic-acid organic anion in any.Ag wherein, Au, Pt etc. preferably modulate coordination compound by the pH value being made as control reduction reactions such as acidic conditions easily by polymine skeleton reductive metal.

In addition, as the transition metal negatively charged ion, can enumerate following transition metal negatively charged ion (MOxn ^-), MnO for example ₄, MoO ₄, ReO ₄, WO ₃, RuO ₄, CoO ₄, CrO ₄, VO ₃, NiO ₄, UO ₂Negatively charged ion.

As metal ion of the present invention, can be above-mentioned transition metal negatively charged ion is fixed on the polyoxometalate metal compound in the silicon-dioxide by being coordinated in the unitary metallic cation of ethyleneimine in the polymkeric substance that contains straight chain type polymine skeleton form.As the object lesson of this polyoxometalate class, can enumerate molybdate, tungstate, vanadic acid salt with the transition-metal cation combination.

In addition, following metallic negatively charged ion (MLxn ^-), AuCl for example ₄, PtCl ₆, RhCl ₄, ReF ₆, NiF ₆, CuF ₆, RuCl ₆, In ₂Cl ₆And so on metal-complexing also go for the formation of coordination compound in the negatively charged ion of halogen.

As the metalloid ion, can enumerate Al, Ga, In, Tl, Ge, Sn, Pb, Sb, the ion of Bi wherein is preferably Al, Ga, In, Sn, Pb, Tl.

As lanthanide metal ion, can enumerate as La Eu, Gd, Yb, the positively charged ion of 3 valencys such as Eu.

Metal among the present invention is so long as getting final product of reducible metal ion gained as this metal ion kind, can be enumerated above-mentioned metal ion as an example.Wherein preferably use transition metal such as Au, Ag, Cu, Pt, Pd, Mn, Ni, Rh, Co, Ru, Re, Mo, in these transition metal, particularly Au, Ag, Pt, Pd, because its metallic ion coordination is behind polymine, can spontaneous reduction under room temperature or heated condition, thereby preferred the use.

Metal in the composite nano fiber or metal ion can be a kind of, also can be more than two kinds.

[silica nano fibrous]

What constitute composite nano fiber of the present invention silica nano fibrously has several nm～hundreds of nm left and right sides thickness, a fiber shape that preferably has 15～100nm thickness.This silica nano fibrous length has no particular limits, and is preferably the scope of 0.1 μ m～3mm.Because this is silica nano fibrous to be to form by the crystalline polymer long filament that covers by the polymer formation with straight chain type polymine skeleton with silicon-dioxide, therefore has the shape of hollow.

Silicon-dioxide as this in silica nano fibrous can use the silicon-dioxide by the solgel reaction gained of known silica source commonly used.

[composite nano fiber, contain the silica nano fibrous of metal]

Composite nano fiber of the present invention is that the polymkeric substance with straight chain type polymine skeleton is contained in silica nano fibrous material, coordination has at least a metal or metal ion on the described polymine skeleton, and the key character of this composite nano fiber is to construct multiple shape.

The shape of composite nano fiber of the present invention is identical with the silica nano fibrous shape that constitutes it, to count about nm～hundreds of nm, the fiber shape of preferred 15～100nm thickness is as foundation structure, composite nano fiber of the present invention can form multiple shape with the basis that is shaped as of this primary structure by the association between this primary structure.The fiber shape length of this primary structure has no particular limits, and is preferably the scope of 0.1 μ m～3mm.

Metal in the composite nano fiber or metal ion and have the polymer formation coordinate bond of straight chain type polymine skeleton and exist.Owing to metal ion and the polymer formation coordinate bond with straight chain type polymine skeleton constitute coordination compound, therefore think this metal complex be present in hollow shape silica nano fibrous in.

In addition, can think metal be with the crystalline state that the metal ion that forms this metal complex is reduced be present in silica nano fibrous in.This metal can and form thread or the particle shape through pencil by reduction.Particle shape can be the contacted state of a plurality of particles, and threadly in silica nano fibrous can mix existence with emboliform.The thickness that this is thread or the particle diameter of particle shape are the nano level littler than the thickness of above-mentioned primary structure, if thread, its thickness is preferably about 2～20nm, if particle shape, its particle diameter is preferably about 2～20nm.

Composite nano fiber of the present invention by the association between this nanofiber shape, can form the association body (claiming in this specification sheets that this association body is a composite nano fiber association body) with micron～millimetre-sized two dimension or three-dimensional space shape.This association shape can be adjusted into as different shapes such as romaine lettuce shape, fibrous, spongy, aster shape, celestial being's palmate, taraxacum shapes.These association shapes can be by having straight chain type polymine skeleton polymer architecture geometrical shape, molecular weight, import non-ethyleneimine part in this polymkeric substance, the crystalline formation condition etc. that forms this polymkeric substance in addition controls, and is subjected to the influence of modulator approach of molecular structure, the polymerization degree, composition and the polymer crystallization of the polymkeric substance that uses especially.

By other composite nano fiber combination, can form a structure (claiming in this specification sheets that this structure is a complex structure body) by the combination between composite nano fiber association body or this composite nano fiber association body with the above large size outer shape of millimeter level.The profile of this structure can form shape arbitrarily, requirement according to concrete application, collar plate shape, cylinder shape, sheet type, filter type, membranous type, ball-type, stripe shape etc. can be formed, various states such as powder, particle, polyhedron, round shape can be processed into.The association shape that has above-mentioned composite nano fiber association body in this structure inside, this association body are the association bodies based on composite nano fiber of the present invention.Therefore, this structure has three reticulated structures that formed by the composite nano fiber intricately.

As the content of the silicon-dioxide in the composite nano fiber of the present invention, just have no particular limits as long as can construct above-mentioned various structure, form above-mentioned various structures because the scope of 30～80 quality % can be stablized, thereby be preferred.In addition, the content of metal or metal ion can suitably be adjusted according to various uses.

The polymkeric substance that inside has in the composite nano fiber of the present invention of reductive metal can easily be removed by sintering, can become the nanofiber (claiming in this specification sheets that this nanofiber is contain metal silica nano fibrous) that contains the metal of nanoparticle or nano thread shape in silica nano fibrous thus.Because therefore silica nano fibrous association shape or structure shape when can former state keeping removing polymkeric substance that this contains metal can form silica nano fibrous association body or the structure that contains metal.

As above-mentioned, because composite nano fiber of the present invention has metal or metal ion with the silica nano fibrous inside of containing metal, and can construct different shape, therefore be expected to every field, as being used widely as metallic catalyst, nano metal electro-conductive material, nano metal look material, nano metal transmitter, medical material in nanotechnology.Has possibility of its application particularly because composite nano fiber contains the polymkeric substance of tool straight chain type polymine skeleton, thereby in fields such as biological field or the corresponding goods of environment fields.

[manufacture method of composite nano fiber]

If will make composite nano fiber of the present invention, to the control of silicon-dioxide shape with can be necessary in the existence of the inner concentrating metals ionic of silicon-dioxide coordination molecule.In the manufacture method of the present invention, use has the polymkeric substance of straight chain type polymine skeleton as this coordination molecule, and form different shape by polymer associate with straight chain type polymine skeleton by (i), carry out solgel reaction in the association surface of this polymkeric substance and fixing silicon-dioxide, (ii) by the polymkeric substance height concentrating metals ion that is present in this silicon-dioxide with straight chain type polymine skeleton, in case of necessity at this place's reducing metal ion, can realize inner containing metal or metal ion thus and can construct the composite nano fiber of different shape.

In above-mentioned (i), the straight chain type polymine skeleton that has in the polymkeric substance of straight chain type polymine skeleton is soluble in water, but at room temperature exist with insoluble association body, therefore form crystallization by dividing, can form the crystalline polymer long filament of nanometer thickness with crystallographic property by the straight chain type polymine skeleton portion between the polymkeric substance.This crystalline polymer long filament plays the effect of template.In addition, can have a lot of chains of polymine freely that have nothing to do with crystallization inevitably at this crystalline polymer filament surface, these freely chain be in the state that hangs in the crystalline polymer filament surface.These chains become the support of polymeric silica stationary in its vicinity, play the effect that makes silica source polymeric catalyzer simultaneously.

At this, by carrying out solgel reaction, this crystalline polymer filament surface is covered by silicon-dioxide at crystalline polymer filament surface with straight chain type polymine skeleton, become and contain the silica nano fibrous of polymkeric substance.The constructed shape of crystalline polymer long filament this moment can be transferred to silicon-dioxide, can make the silica nano fibrous derivable multiple shape of this crystalline polymer long filament of constructing that contains polymkeric substance thus.

In addition, provide the hydrogel that in the presence of water, can easily control shape owing to have the crystalline polymer long filament of straight chain type polymine skeleton, therefore this hydrogel is configured as arbitrarily after the shape crosslinked with chemical bond between the crystalline polymer long filament in the hydrogel by compound with two above functional groups, carry out solgel reaction then, just can obtain by the silica nano fibrous structure that constitutes that contains polymkeric substance of having introduced each polymer associate shape in the big silica dioxide gel piece.Because the profile of this hydrogel may be configured as different shape, so the control of this structure macroshape becomes possibility.

Can construct multiple shape like this by making, containing the silica nano fibrous of polymkeric substance contacts with the metal ion aqueous solution, by above-mentioned effect (ii), draw a large amount of metal ions in this contains polymkeric substance silica nano fibrous, because the polymer formation coordinate bond of the tool straight chain type polymine skeleton in this metal ion and the silicon-dioxide, therefore the association body of this polymkeric substance is disintegrated in silicon-dioxide, replacing forms polymer/metal ion coordination compound, obtains containing the polymkeric substance of tool straight chain type polymine skeleton and the composite nano fiber of metal ion in silica nano fibrous.

This polymer/metal ion coordination compound can spontaneously reduce herein, or adds other reductive agent and be reduced, and becomes metallic crystal through metal beam.When metal is reduced, because it is silica nano fibrous or do not change by silica nano fibrous structure shape of constructing, the polymkeric substance of silica nano fibrous inside also can not be from silica nano fibrous outflow, therefore can obtain being contained in composite nano fiber in silica nano fibrous by the polymkeric substance polymer controls shape with straight chain type polymine skeleton, that have straight chain type polymine skeleton and metal.

As the concrete grammar of making composite nano fiber of the present invention, can enumerate the method for the operation that comprises following (1)～(3),

(1) polymer dissolution that will have straight chain type polymine skeleton separates out it in the presence of water in solvent then, obtains having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton,

(2) in the presence of water, contact with organoalkoxysilane by making above-mentioned crystalline polymer long filament, above-mentioned crystalline polymer long filament is covered by silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance,

(3) contain the silica nano fibrous of polymkeric substance and contact above-mentioned, make metal ion be incorporated into the operation of the straight chain type polymine skeleton in the above-mentioned polymkeric substance by coordinate bond with being dissolved with metal ion solution,

The method that perhaps comprises the operation of following (1)～(4),

(1) polymer dissolution that will have straight chain type polymine skeleton separates out it in the presence of water in solvent then, obtains having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton,

(2) in the presence of water, contact with organoalkoxysilane by making above-mentioned crystalline polymer long filament, above-mentioned crystalline polymer long filament is covered by silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance,

(3) contain the silica nano fibrous of polymkeric substance and contact above-mentioned, make metal ion be incorporated into straight chain type polymine skeleton in the above-mentioned polymkeric substance to operation by coordinate bond with being dissolved with metal ion solution,

(4) make the transition metal ion reductive operation that is incorporated into the straight chain type polymine skeleton in the above-mentioned polymkeric substance by coordinate bond.

[obtaining the operation of crystalline polymer long filament]

Manufacture method of the present invention, at first, the polymer dissolution that will have straight chain type polymine skeleton by (1) is in the presence of water it being separated out behind the solvent, obtain having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton, form crystalline polymer long filament with straight chain type polymine skeleton as the shape template of composite nano fiber of the present invention.Same as described above at this operable polymkeric substance with straight chain type polymine skeleton.

This has the polymkeric substance of straight chain type polymine skeleton, embodies crystallinity and this knot intergranular after the crystallization associates formation crystalline polymer long filament mutually in aqueous medium by straight chain type polymine skeleton.This crystalline polymer long filament also can form the hydrogel with tridimensional network by the physical bond between the crystalline polymer long filament in the presence of the water, can also be by with becoming the cross-linked hydrogel with chemical crossbond between linking agent cross-linking crystal polymer filaments.By using these hydrogels, can easily adjust the shape of composite nano fiber association body through regulating hydrogel manufacturing conditions gained, in addition, when forming the composite nano fiber structure, the control of its outer shape becomes easily, thereby is preferred.

This crystalline polymer long filament is, a plurality of straight chain type polymine skeletons crystallization in the presence of water molecules in the primary structure of the polymkeric substance by having straight chain type polymine skeleton, polymkeric substance associates mutually and with the product of fibrous growth, has crystalline character in its structure.

This crystalline polymer long filament has that thickness is about 1～10nm, is preferably 2～30nm, more preferably scope and the length of 2～10nm are more than 10 times of thickness, are preferably fiber shape more than 100 times (following claim that sometimes the fiber shape of this crystalline polymer long filament is the one-level shape).

The polymine that in the past was widely used is, the branched chain type polymkeric substance of the ring-opening polymerization gained by the ring-type ethyleneimine, and its primary structure exists primary amine, secondary amine, tertiary amine.Therefore the branched chain type polymine is water miscible, does not have crystallinity, therefore if will make hydrogel with the branched chain type polymine, must give reticulated structure by the covalent linkage that derives from linking agent.Yet the straight chain type polymine that has as skeleton in the polymkeric substance that the present invention uses only be made of secondary amine, and this secondary amine type straight chain type polymine is water miscible that crystallization also is possible simultaneously.

As everyone knows, the crystallization of such straight chain type polymine, there is very big difference (Y.Chatani et al., Macromolecules,, the 14th volume in 1981, p.315～321) in the crystalline texture of its polymkeric substance according to the unitary crystallization water number of ethyleneimine that is contained in this polymkeric substance.It is the crystalline texture of feature that anhydrous polymine is preferentially selected with the double-helix structure, if monomeric unit contains the water of 2 molecules, then to grow into the zigzag structure be the xln of feature to polymkeric substance.The crystallization of the straight chain type polymine that in fact obtains from water is the crystallization that a monomeric unit contains 2 molecular waters, and its crystallization is water-fast at room temperature state.

The crystalline polymer long filament of polymkeric substance that has straight chain type polymine skeleton among the present invention is identical with above-mentioned situation, producing crystallization by straight chain type polymine skeleton forms, polymer form can be line style, star-like or comb type, so long as have the polymkeric substance of straight chain type polymine skeleton in the primary structure, just can obtain the crystalline polymer long filament.

The existence of crystalline polymer long filament can be confirmed by X-ray diffraction, can confirm according near the peak value that derive from straight chain type polymine skeleton in the crystallinity water-sol of 2 θ angles in the wide-angle X ray diffractor (WAXS) 20 °, 27 °, 28 °.

In addition, the fusing point of the crystalline polymer long filament of being measured by differential scanning calorimeter (DSC) also exists with ... the primary structure of the polymkeric substance of polymine skeleton, probably is 45～90 ℃.

The crystalline polymer long filament is in the presence of water, can form hydrogel by the secondary or physical bond between the crystalline polymer long filament, can also be cross-linked to form cross-linked hydrogel by linking agent between the crystalline polymer long filament with chemical crossbond with tridimensional network.

In the hydrogel of crystalline polymer long filament, mutual associating crystalline polymer long filament has formed the 3D shape (below claim that sometimes this fine 3D shape is a secondary shape) of micron～mm size in the presence of water.Have between the association body of these secondary shape, the crystalline polymer long filament in the association body carries out the physics association again and forms crosslinking structure, forms the tridimensional network that all is made of the crystalline polymer long filament.Because these are to generate, can be formed on the aqueous hydrogel of bag in this tridimensional network in the presence of water.Use under the situation of linking agent, carry out chemically crosslinked between the crystalline polymer long filament, form this tridimensional network by the immobilized cross-linked hydrogel of chemically crosslinked.

Here said tridimensional network, different with common macromolecule hydrogel, be meant between the crystalline polymer long filament by being present in the hydrogen bond of its surperficial free ethylene imines chain the reticulated structure that forms by physical crosslinking.Therefore, in this temperature more than crystalline melt point, be dissolved in the water fully to crystallization, tridimensional network also can be disintegrated.In a single day and return room temperature, and generate the crystalline polymer long filament again, between crystallization, form the physical crosslinking that produces because of hydrogen bond, again tridimensional network can appear therefore.

In the hydrogel, the secondary shape that the crystalline polymer long filament forms, geometrical shape or molecular weight that can be by adjusting polymer architecture, can import the non-ethyleneimine part in the primary structure and the formation condition of crystalline polymer long filament etc., be controlled to be as fibrous, brush shape, different shape such as starlike.In addition, though hydrogel can keep profile (following claim that sometimes the outer shape of this hydrogel is three grades of shapes) roughly, owing to can be out of shape arbitrarily under external force, so its shape can easily be controlled.

Above-mentioned crystalline polymer long filament can obtain as follows, promptly, the polymkeric substance that utilization has a straight chain type polymine skeleton is insoluble to the character of room temperature water, makes polymer dissolution with straight chain type polymine skeleton in making it separate out and obtain behind the solvent in the presence of water.

As concrete method, can enumerate make polymer dissolution with straight chain type polymine skeleton in the mixed solvent (claiming these to be aqueous medium in this specification sheets) of water or water and hydrophilic organic solvent afterwards with the method for this solution heating postcooling or make polymer dissolution as an example in hydrophilic organic solvent and method etc. from water to this solvent that add with straight chain type polymine skeleton.

Have the solvent of the polymkeric substance of straight chain type polymine skeleton as dissolving, preferably use aqueous medium or hydrophilic organic solvent.As this hydrophilic organic solvent, can enumerate as hydrophilic organic solvents such as methyl alcohol, ethanol, tetrahydrofuran (THF), acetone, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), diepoxide for example, pyrrolidone.

If the crystalline polymer long filament is separated out from the solution of polymkeric substance with straight chain type polymine skeleton, the existence of water is indispensable, and therefore separating out is to take place in aqueous medium.

In addition, in the aforesaid method, have the amount of the polymkeric substance of straight chain type polymine skeleton, can obtain the hydrogel that constitutes by the crystalline polymer long filament by adjustment.For example, the polymer dispersed that at first will have straight chain type polymine skeleton is in a certain amount of water, heat this dispersion liquid, obtain having the transparent aqueous solution of the polymkeric substance of straight chain type polymine skeleton, then, be cooled to room temperature by the aqueous solution, just can obtain this hydrogel the polymkeric substance of heated condition.This hydrogel has and can deform because of external force such as shearing forces but can keep the state that is similar to ice cream of general shape, may be deformed into multiple shape.

In the aforesaid method, Heating temperature is preferably below 100 ℃, more preferably 90～95 ℃ scope.In addition, the polymer content in the polymer dispersion liquid as long as just have no particular limits, is preferably the scope of 0.01～20 quality % in the scope that can obtain hydrogel, in order to obtain the hydrogel of dimensionally stable, and 0.1～10 quality % more preferably.So, among the present invention, if use polymkeric substance, even very a spot of polymer concentration also can form hydrogel with straight chain type polymine skeleton.

The process of utilizing the temperature of above-mentioned aqueous solutions of polymers to drop to room temperature can be adjusted the secondary shape of the crystalline polymer long filament in the gained hydrogel.If example reduces method of temperature once, can enumerate aqueous solutions of polymers was kept 1 hour at 80 ℃, reduced to 60 ℃ with 1 hour then, kept again 1 hour in this temperature, thereafter with reducing to the method for reducing to room temperature after 40 ℃ naturally in 1 hour; Above-mentioned aqueous solutions of polymers is cooled off with the frozen water of freezing point or the cooling agent of the methyl alcohol/dry ice under the freezing point or acetone/dry ice quickly, keep the method for this state then with the water-bath of room temperature; Or with above-mentioned aqueous solutions of polymers with the water-bath of room temperature or air at room temperature environment temperature reduction to the method for room temperature etc.

The above-mentioned process that the temperature of aqueous solutions of polymers is reduced can produce great influence to the association between the crystalline polymer long filament in the gained hydrogel, therefore the formed secondary shape of crystalline polymer long filament in the hydrogel that obtains by above-mentioned different methods and inequality.

When the temperature of above-mentioned aqueous solutions of polymers reduced stage by stage under keeping the concentration certain condition, the secondary shape that the crystalline polymer long filament in the hydrogel forms can become fibrous shape.With returning behind its chilling under the situation of room temperature, can become petal-like form.In addition, with the acetone of dry ice shape once again with its chilling, return under the situation of room temperature, can become wavy form.As mentioned above, the form of the secondary shape that the crystalline polymer long filament in the hydrogel of the present invention forms can be set different shape for.

By above-mentioned gained hydrogel is opaque gel, is formed with the crystalline polymer long filament that is made of the polymkeric substance with polymine skeleton in gel, forms physical crosslinking by hydrogen bond between this crystalline polymer long filament, has formed three-dimensional netted physical structure.Crystalline polymer long filament in the formed hydrogel keeps insoluble state in room temperature, in case heating, the crystalline polymer long filament will dissociate, and hydrogel becomes collosol state.Therefore, physical hydrogel of the present invention can be finished from colloidal sol to the gel by thermal treatment, or reversible change from the gel to colloidal sol.

The said hydrogel of the present invention contains water at least in tridimensional network, add the hydrogel that hydrophilic organic solvent just can obtain containing organic solvent when modulating this hydrogel.As this hydrophilic organic solvent, can enumerate as hydrophilic organic solvents such as methyl alcohol, ethanol, tetrahydrofuran (THF), acetone, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), diepoxide for example, pyrrolidone.

The content of organic solvent is preferably 0.1～5 times scope of the volume of water, more preferably 1～3 times scope.

By containing above-mentioned hydrophilic organic solvent, can change the form of crystalline polymer long filament, the crystallization with simple water system different shape can be provided.For example, even in water, have the branched chain type secondary shape of fibrous divergence,, just can obtain being similar to the spheric secondary shape that contraction has taken place fiber if modulation the time makes it contain a certain amount of methyl alcohol.

The said hydrogel of the present invention by adding other water-soluble polymers, can obtain containing the hydrogel of water-soluble polymers when modulation.As this water-soluble polymers, can enumerate as polyoxyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, poly-(N-N-isopropylacrylamide), poly-hydroxyethylmethacry,ate, Ju Jia oxazolin, Ju ethyl oxazoline etc.

The content of water-soluble polymers is preferably 0.1～5 times scope of the polymer quality with straight chain type polymine skeleton, more preferably 0.5～2 times scope.

By making it contain the form that above-mentioned hydrophilic polymer also can change the crystalline polymer long filament, can give secondary shape with simple water system different shape.In addition, help increasing the viscosity of hydrogel, improve the stability of hydrogel.

With containing more than 2 and the functional group's of the amino reaction of polymine compound treatment hydrogel, just can obtain between the crystalline polymer filament surface in the hydrogel cross-linked hydrogel by the chemical bond connection by the aforesaid method gained.

As contain more than 2 room temperature state can with the functional group's of above-mentioned amino reaction compound, can use aldehydes linking agent, epoxies linking agent, acyl chlorides linking agent, acid anhydrides, ester class linking agent.As the aldehydes linking agent, can enumerate as mda, suceinic aldehyde, glutaraldehyde, o-phthalaldehyde(OPA), m-terephthal aldehyde, terephthalaldehyde etc.As the epoxies linking agent, can enumerate as polyethyleneglycol diglycidylether, bisphenol A diglycidyl ether, glycidyl muriate, glycidyl bromide etc.As acyl chloride, can enumerate malonyl chloride, succinic chloride, glutaryl chlorine, hexanedioyl chlorine, phthalyl chloride, m-phthaloyl chloride, p-phthaloyl chloride etc.As acid anhydrides, can enumerate as phthalate anhydride, Succinic anhydried, Pyroglutaric acid etc.As ester class linking agent, can enumerate propanedioic acid methyl esters, Succinic Acid methyl esters, pentanedioic acid methyl esters, phthalic acid methyl esters, polyoxyethylene glycol carboxylate methyl ester etc.

Crosslinking reaction can take the gained hydrogel is soaked in the method for cross-linking agent solution, also can take cross-linking agent solution is added method in the hydrogel.At this moment, linking agent is penetrated into hydrogel inside with the variation of the osmotic pressure in the system, connects the chemical reaction of the nitrogen-atoms of initiation and ethyleneimine between this is with the crystalline polymer long filament with hydrogen bond.

Crosslinking reaction can be by carrying out with the reaction of the free ethyleneimine of crystalline polymer filament surface, in order not cause this reaction as far as possible in crystalline polymer long filament inside, preferably the temperature below the fusing point of the crystalline polymer long filament that forms hydrogel is reacted, and most preferably carries out crosslinking reaction in room temperature.

Carry out in room temperature under the situation of crosslinking reaction, hydrogel to place with cross-linking agent solution blended state, just can be obtained cross-linked hydrogel.The time of crosslinking reaction can be several minutes to a few days, probably place can carry out an evening suitable crosslinked.

Cross-linked dosage is with respect to the ethyleneimine unit mole number in the polymkeric substance with the polymine skeleton that is used to form hydrogel, can be 0.05～20%, 1～10% more suitable.

Therefore above-mentioned hydrogel can embody the gel structure of variform because gelating agent is the crystalline polymer long filament.In addition, even because a spot of crystalline polymer long filament also can suitably form tridimensional network in water, therefore has high water-retentivity.In addition, the structure design of used polymkeric substance or synthetic all be easy to straight chain type polymine skeleton, and also the adjustment of hydrogel is simple.By will be between the crystalline polymer long filament in this hydrogel crosslinked with linking agent, the fixing shape of hydrogel just.

[acquisition contains the silica nano fibrous operation of polymkeric substance]

In the manufacture method of the present invention, after the operation of above-mentioned (1), has operation (2), promptly, in the presence of water, by above-mentioned crystalline polymer long filament is contacted with organoalkoxysilane, the operation of the nanofiber that obtains above-mentioned crystalline polymer long filament is covered by silicon-dioxide (claiming in this specification sheets that this nanofiber is contain polymkeric substance silica nano fibrous).In addition, the crystalline polymer long filament is crosslinked the crosslinked state of agent with the state that forms hydrogel or this hydrogel and contacts with silica source to be crosslinked the crosslinked state of agent, crystalline polymer long filament, just can obtain by the silica nano fibrous structure that constitutes that contains polymkeric substance.

As the method that the crystalline polymer long filament is contacted with organoalkoxysilane, can be listed below method, promptly, silica source is dissolved in solution in the operable solvent of common solgel reaction, join in the hydrogel or cross-linked hydrogel of the aqueous dispersions of crystalline polymer long filament or crystalline polymer long filament, at room temperature carry out the method for solgel reaction.By this method, can easily obtain to contain silica nano fibrous, the silica nano fibrous structure that this contains polymkeric substance of polymkeric substance.

As organoalkoxysilane, can enumerate the above organoalkoxysilane (having substituent organoalkoxysilane more than 3) of 3 valencys such as tetraalkoxysilane class, alkyltrialkoxysilaneand class as silica source.

As the tetraalkoxysilane class, can enumerate as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane, four butoxy silanes, four-t-butoxy silane etc.

As the alkyltrialkoxysilaneand class, can enumerate methyltrimethoxy silane, Union carbide A-162, ethyl trimethoxy silane, ethyl triethoxysilane, n-propyl trimethoxy silicane, n-propyl-triethoxysilicane, iso-propyl trimethoxy silicane, iso-propyl-triethoxysilicane, 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl-triethoxysilicane, 3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl triethoxyl silane, 3,3,3-trifluoro propyl Trimethoxy silane, 3,3,3-trifluoro propyl triethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl triethoxyl silane, phenyltrimethoxysila,e, phenyl triethoxysilane, p-chloromethyl phenyl Trimethoxy silane, p-chloromethyl phenyl triethoxyl silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, diethyl dimethoxy silane, diethyl diethoxy silane etc.

The silica nano fibrous above-mentioned solgel reaction that contains polymkeric substance is provided, in aqueous medium, the crystalline polymer long filament in the presence of carry out, but at aqueous medium this reaction does not take place in mutually, reaction is to carry out on the surface of crystalline polymer long filament.Therefore only otherwise make the dissolving of crystalline polymer long filament, compoundization reaction conditions can be arbitrarily.

In order not make the dissolving of crystalline polymer long filament, contain during solgel reaction in the waterborne liquid of hydrophilic organic solvent, the existence of water is preferably more than 20%, more preferably more than 40%.

In the solgel reaction,, then can form suitable the silica nano fibrous of polymkeric substance that contain if excessive as the ethyleneimine of polymine monomeric unit relatively as the amount of the organoalkoxysilane of silica source.Excessive degree is preferably the scope of 2～1000 times of equivalent of ethyleneimine.

Polymer concentration in the aqueous medium when forming the crystalline polymer long filament preferably be decided to be contained polymine in this polymkeric substance amount 0.1～30%.The amount of polymine in the aqueous medium, by concentrating under the condition of the crystal habit that keeps the crystalline polymer long filament, the concentration that reaches above 30% also is possible.As the concentration method of this moment, can use hydrogel with the aqueous dispersions of above-mentioned crystalline polymer long filament or crystalline polymer long filament to carry out at normal temperatures that normal pressure filters or the method for filtration under diminished pressure etc.

The time of solgel reaction be 1 minute to a few days, have nothing in common with each other, under the situation of the high methoxy silane class of the reactive behavior of organoalkoxysilane, the reaction times can be 1 minute～24 hours, will be set at 30 minutes the reaction times for improving reaction efficiency～5 hours then be more suitably.And under the situation of the low Ethoxysilane class of reactive behavior, butoxy silane class, the solgel reaction time was preferably more than 24 hours, also preferably this reaction times was set at about a week.

By this operation gained contain polymkeric substance silica nano fibrous be to constitute by above-mentioned crystalline polymer long filament and the silicon-dioxide that covers the crystalline polymer long filament, its thickness is 10～1000nm, be preferably 15～100nm, length is more than 10 times of thickness, is preferably more than 100 times.

The silica nano fibrous dioxide-containing silica that contains polymkeric substance changes in certain amplitude according to reaction conditions etc., can be set at the scope of 30～90 quality % that contain the silica nano fibrous integral body of polymkeric substance.The content of silicon-dioxide during with solgel reaction the increase of used amount of polymers increase.Also the prolongation with the solgel reaction time increases.

Containing the silica nano fibrous of polymkeric substance, the crystalline polymer long filament with the polymkeric substance that contains straight chain type polymine skeleton is as core, is this crystalline polymer long filament by complex body that silicon-dioxide covered.Therefore this contains polymkeric substance silica nano fibrously can concentrate by being present in ethyleneimine cell height in this crystalline polymer long filament, adsorbing metal ions.

In addition, the silica nano fibrous structure that can form multiple shape by mutual association that contains polymkeric substance.Form the state of hydrogel or this hydrogel and be crosslinked under the crosslinked state of agent and contact by be crosslinked the crosslinked state of agent, crystalline polymer long filament at the crystalline polymer long filament, can obtain by the silica nano fibrous structure that constitutes that contains polymkeric substance with silica source.Therefore this structure has the shape of formed shapes such as the hydrogel that derives from above-mentioned crystalline polymer long filament or cross-linked hydrogel.

The silica nano fibrous structure that contains polymkeric substance is, behind the hydrogel that will form by the crystalline polymer long filament or the three grades of shape random moldings of cross-linked hydrogel, cover crystalline polymer long filament in this hydrogel with silicon-dioxide, be shaped to the structure of random appearance shape thus.In addition, because the secondary shape of the association body that forms in the above-mentioned hydrogel also is transferred, therefore derives from the formed association shape of the silica nano fibrous association body formed secondary shape of crystalline polymer long filament, that contain polymkeric substance and be present in this silica nano fibrous structure that contains polymkeric substance.

So, owing to can fix three grades of shapes that formed by above-mentioned crystalline polymer long filament, the profile that therefore any shaping contains the silica nano fibrous structure of polymkeric substance is possible.In addition, the silica nano fibrous structure that contains polymkeric substance, the association shape that its inside has, according to the non-ethyleneimine part in the geometrical shape of the polymer architecture of use polymkeric substance, molecular weight, the importing primary structure, the usage quantity of silica source etc., can become different shapes such as fibrous, brush shape, starlike, romaine lettuce shape, spongy, aster shape (aster), celestial being's palmate, taraxacum shape.The size of these association shapes can be set at about 3 μ m～1mm.So the shape of size is by as the silica nano fibrous association that contains polymkeric substance of elementary cell and the 3D shape that space layout constitutes.Become the core that contains the crystalline polymer long filament in polymkeric substance silica nano fibrous that contains of this elementary cell.That is to say, the silica nano fibrous structure that contains polymkeric substance may form by following process, promptly, in water, connect between the crystalline polymer long filament and be disposed in the space by the secondary or physical bond that forms by hydrogen bond, become the template of the 3D shape of different shape, be fixed along this template silicon-dioxide, formed the silica nano fibrous mutual association that contains polymkeric substance thus and be configured in the spatial form.

The silica nano fibrous structure that contains polymkeric substance is the product with the silica stationary hydrogel, described hydrogel is to form through associating the formation physical crosslinking again between the associating association body of crystalline polymer long filament, amount by adjusting used polymer architecture, polymer concentration or silica source etc., with silica stationary the time, cut off the physical crosslinking between this association body, with the association body of silica stationary crystalline polymer long filament or a plurality of aggregate that should the association body, also can take out the silica nano fibrous association body that contains polymkeric substance.

The silica nano fibrous association shape that contains polymkeric substance can make geometrical shape, the molecular weight of the polymer architecture when containing polymkeric substance silica nano fibrous by adjustment, the formation condition that can import the non-ethyleneimine part in the primary structure and contain the silica nano fibrous structure of polymkeric substance waits and adjusts.Molecular structure, the polymerization degree, composition and the modulation that this association shape depends on used polymkeric substance very much reduces method of temperature when containing the silica nano fibrous structure of polymkeric substance.

For example, by as the polymkeric substance use polymerization degree being the linear polyethylene imines more than 300 with straight chain type polymine skeleton, obtain using this hydrogel to carry out solgel reaction after the hydrogel from reducing to normal temperature naturally more than 80 ℃, can obtain having the silica nano fibrous complex structure body that contains polymkeric substance of romaine lettuce type association shape.The thickness that forms the leaf part in the association shape of romaine lettuce the type decline of polymer concentration and thickening in the polymers soln when making polymer crystallization, concentration is 2% when above, the thickness of leaf part is about 100nm, and concentration becomes about 500nm at 1% leaf when following thickness partly.

Use under the situation of star-like polymine, become the structure of the center residue of its nuclear, also can control the secondary shape of gained by change.For example, the center residue is for as the big π planar material of having of porphyrin and so on the time, and the association shape that gained contains in the silica nano fibrous structure of polymkeric substance is an aster shape, and the size of an aster shape is about 2～6 μ m.Concentration is 1% when above, and the handle number of aster is few, and each handle has the tendency of bunchy, the concentration below this, and the handle number is many, and each handle has tendency separately.When the center residue is a minor structure as phenyl ring and so in addition, the association shape that gained contains in the silica nano fibrous structure of polymkeric substance is the fibrous of many silk bunchys, its fiber twines mutually, has formed the spongiform silica nano fibrous structure that contains polymkeric substance as a whole.The thickness of a fiber shape is about 150nm.

By using between the crystalline polymer long filament, also can obtain the silica nano fibrous structure that contains polymkeric substance of various outer shape with the crosslinked cross-linked hydrogel of chemical bond.Size and shape that its shape and size can be decided to be the container that uses when modulating cross-linked hydrogel are identical, for example, can be modulated into discoid, cylindric, sheet, arbitrary shape such as spherical.Can also be configured as the shape that needs by cutting off, cutting cross-linked hydrogel.The cross-linked hydrogel that so is shaped is soaked in the solution of silica source, can obtains the silica nano fibrous structure that contains polymkeric substance of arbitrary shape simply.As the time of the solution that is soaked in silica source, being divided into according to the kind of used silica source and not waiting in 1 hour～1 week, so be necessary to carry out suitable modulation, is to get final product in 1～48 hour in the solution of methoxy silane class, in the solution of Ethoxysilane class, 1～7 day is suitable.

As mentioned above, the polymkeric substance that has straight chain type polymine skeleton by dissolving, in the presence of water, separate out, obtain behind the crystalline polymer long filament this crystalline polymer long filament being contacted with organoalkoxysilane, can easily make and contain the silica nano fibrous of polymkeric substance.In this manufacture method, enforcement obtains to contain the silica nano fibrous operation of polymkeric substance at short notice, the solgel reaction operation of silicon-dioxide is possible.In addition, the dispersion liquid of crystalline polymer long filament or the hydrogel of crystalline polymer long filament can be easily modulated,, the silica nano fibrous structure that contains polymkeric substance can be easily made by this dispersion liquid or hydrogel are contacted with organoalkoxysilane.

[obtaining the operation of composite nano fiber]

In the manufacture method of the present invention, by after the operation of above-mentioned (2), implementing operation (3), can obtain metal ion and be contained in silica nano fibrous composite nano fiber with polymkeric substance with straight chain type polymine skeleton, operation (3) makes metal ion be incorporated into the operation of the straight chain type polymine skeleton in the above-mentioned polymkeric substance by coordinate bond for containing the silica nano fibrous of polymkeric substance and contact with being dissolved with metal ion solution above-mentioned.

At this,, can use above-mentioned metal ion as used metal ion.Be dissolved with metal ion solution, the salt that contains this metal ion can be dissolved in the water and modulate.

Make in the operation as above-mentioned (3) and above-mentionedly contain the silica nano fibrous of polymkeric substance and be dissolved with the method that metal ion solution contacts, have no particular limits, can enumerate the silica nano fibrous method that impregnated in the aqueous solution of metal ion that contains polymkeric substance that for example will obtain by the operation of above-mentioned (2).By this method, metal ion can concentrate in simply silica nano fibrous in.Owing to concentrate in the crystalline polymer long filament formation coordinate bond of the metal ion that contains in polymkeric substance silica nano fibrous and silica nano fibrous inside, therefore the crystalline polymer long filament is disintegrated in silicon-dioxide, and polymkeric substance and metal ion that the formation that replaces has straight chain type polymine skeleton pass through coordinate bond bonded metal complex.Can easily obtain metal ion of the present invention thus and be contained in silica nano fibrous composite nano fiber with polymkeric substance with straight chain type polymine skeleton.

With metal ion concentrate in silica nano fibrous in the time, the polymkeric substance that contains in polymkeric substance silica nano fibrous is many more, and metal ion is high more to the ratio of mixture of this polymkeric substance, the amount that concentrates in the metal ion in the silicon-dioxide is big more.In the composite nano fiber of metal ion of the present invention, be that the metal ion of 0.1～0.5 times of amount can form coordination compound with respect to the mole number that contains the nitrogen-atoms of contained polymine skeleton in polymkeric substance silica nano fibrous.

Obtain under the situation of composite nano fiber of metal ion, when the silica nano fibrous aqueous solution that impregnated in metal ion that will contain polymkeric substance, the amount of its metal ion is that ethyleneimine is specially suitable for unitary about 0.1～10 times.

After introducing metal ion, take out resultant, clean, just can obtain metal ion of the present invention and be contained in silica nano fibrous composite nano fiber with polymkeric substance with straight chain type polymine skeleton with normal-temperature water or cold water.

After the operation of above-mentioned (3), make the transition metal ion reductive operation that is incorporated into the straight chain type polymine skeleton in the above-mentioned polymkeric substance by coordinate bond through (4), can obtain metal and be contained in silica nano fibrous composite nano fiber with polymkeric substance with straight chain type polymine skeleton.

In the above-mentioned operation (3), contain the silica nano fibrous of polymkeric substance and be dissolved with contacting of metal ion solution by above-mentioned, can in silica nano fibrous, form polymkeric substance and metal ion and pass through coordinate bond bonded metal complex with straight chain type polymine skeleton.By the spontaneous reduction of this metal ion or with the reductive agent reduction, obtain metal of the present invention and be contained in silica nano fibrous composite nano fiber with polymkeric substance with straight chain type polymine skeleton.

In the composite nano fiber that contains the reducing metal of the present invention,, can fix the atoms metal of 1～20 times of amount with respect to the nitrogen-atoms mole number that contains polymine skeleton contained in polymkeric substance silica nano fibrous.

Obtain under the situation of metallic composite nano fiber, silica nano fibrous when impregnated in metal ion solution what will contain polymkeric substance, the amount of this metal ion is excessive to the ethyleneimine unit to be ideal, is specially suitable about 30 times.

In the above-mentioned metal ion, the metallic ion coordination of Au, Ag, Pt, Pd is behind polymine, under room temperature or heated condition, can spontaneously reduce, therefore being transformed into the metal nanoparticle or the metal nano silk of nonionic, is particularly preferred when obtaining metallic composite nano fiber of the present invention.Heating temperature is getting final product below 100 ℃, is preferably 60～80 ℃ especially.If will reduce these metal ions, only will contain getting final product silica nano fibrous mixing of polymkeric substance with metal ion solution.That is, need not just can obtain metallic composite nano fiber of the present invention through being concentrated in the silicon-dioxide metal ion and this silicon-dioxide and reductant solution blended operation.If will keep these with the state of metal ion, can be by pH value being decided to be acidity etc., controlling reduction reaction and modulate coordination compound.

In addition, when reducing above-mentioned metal, will contain the silica nano fibrous of polymkeric substance and mix, different metal ions will be concentrated in after this complex body simultaneously with more than one metal ion, by reducing these different ions, just can obtain containing the composite nano fiber of dissimilar metals.

Use and not resemble spontaneous reductive metal these metal ions, or use under the situation of the inadequate metal of spontaneous reduction, by implementing to utilize reductive agent reduction coordination to be incorporated into the operation of the metal ion of straight chain type polymine skeleton, can form metallic crystal.In addition, even state in the use under the situation of spontaneous reductive metal ion, also can be as required by above-mentioned (4) operation and make its reduction with other reductive agent.

As the reductive agent that can use in this operation, can enumerate hydrogen, sodium borohydride, ammonium borohydride, aldehyde, hydrazine etc. as an example.When using reductive agent reducing metal ion, reaction can be carried out in aqueous medium, at this moment, with metal ion concentrate in contain polymkeric substance silica nano fibrous after, wash its silicon-dioxide, then it being mixed with reductant solution is ideal.That is, only the reduction metal ion that is contained in silicon-dioxide just can obtain composite nano fiber of the present invention.

When the metal ion that is incorporated into straight chain type polyethylene imonium skeleton by coordinate bond is reduced, owing to contain the silica nano fibrous shape of polymkeric substance or contain the not variation of shape of the silica nano fibrous association body that constitutes or the structure of polymkeric substance by this, inner polymkeric substance can be from silica nano fibrous outflow yet, therefore finally can obtain having the polymkeric substance of straight chain type polyethylene imonium skeleton and at least a metal ion and be contained in composite nano fiber in silica nano fibrous.

The metal that is reduced through metal beam, becomes metallics or wire in silica nano fibrous inside.Wire can be by being reduced into metal and forming along containing the spissated metal ion of crystalline polymer long filament in polymkeric substance silica nano fibrous.

The time of reduction reaction is different with species of metal ion, and about 24 hours is sufficient.To make reaction times lengthening at ambient temperature as far as possible, just be enough to reduction under the heating condition basically in 1 hour, but, also can be made as a few hours according to the kind of metal ion.

Temperature by suitable adjustment reduction reaction, the size of metal in the composite nano fiber of the present invention can be adjusted, when transition metal is thread, the product that thickness is 2～20nm left and right sides scope can be easily formed, when granular, can easily form the product that particle diameter is 2～20nm left and right sides scope.Thread thickness or granulous particle diameter are controlled at 10nm when following, preferably the temperature of reduction reaction are made as the temperature below 100 ℃.

As mentioned above, need complicated step and exacting terms etc. in the manufacture method of the present invention hardly, can easily obtain containing in the silicon-dioxide composite nano fiber of metal ion or metal.Also kept intact owing to the above-mentioned silica nano fibrous association shape of constructing or the structure shape that contain polymkeric substance, therefore can easily obtain by having composite nano fiber association body that the composite nano fiber of same shape constitutes or the complex structure body that is made of composite nano fiber with this association body or structure, its spatial form can easily be controlled.

[metallic silica nano fibrous manufacture method]

In addition, after obtaining the composite nano fiber of the above-mentioned polymkeric substance that contains metal and tool straight chain type polymine skeleton in silica nano fibrous, by the operation that (5) remove the component of polymer in the above-mentioned composite nano fiber, it is metallic silica nano fibrous that composite nano fiber is become.

As the method for from above-mentioned composite nano fiber, removing component of polymer, can enumerate to burn till and handle or method that solvent is cleaned, owing to can remove component of polymer fully, burn till facture in the preferred firing furnace.

Burn till in the processing, can be used in that high temperature under the existence of air, oxygen burns till and the high temperature in the presence of non-active gas such as nitrogen, helium burns till usually preferred aerial burning till.

As the temperature of burning till, because can thermolysis near 300 ℃ as the polymkeric substance with straight chain type polymine skeleton of component of polymer, therefore the above temperature of 300 degree just can suitably be removed, and 300～900 scopes of spending are specially suitable.

As concrete process for calcining, can be that benchmark carries out with known method during hole body silicon-dioxide in burning till (Diaz et al.J.Mater.Chem.2004,14 volumes, 48 pages).Can enumerate following method, in promptly heating up the complex body sample was placed 10～30 minutes about 100 degree, then with 10 degree/minute heat-up rate be warming up to 300 degree, placed 1 hour in this temperature, be warming up to 500 degree with same heat-up rate again, burnt till 1～6 hour in this temperature.When heating up again, can be warming up to 700 to 800 degree, burn till 1～6 hour in this temperature with same heat-up rate.After burning till, can make the temperature of firing furnace be cooled to room temperature naturally, also can be in firing furnace bubbling air, make it reduce to room temperature.

By removing component of polymer from composite nano fiber association body or complex structure body in the same manner therewith, can obtain metallic silica nano fibrous association body or metallic silica nano fibrous structure.

As above record, composite nano fiber of the present invention and metallic silica nano fibrous except having the silica nano fibrous big surface-area that has and the good molecular selectivity and the chemical stability that derive from the silicon-dioxide that is covered, metal or metal ion are also contained in inside.In addition, because its aspect ratio is very high, might make it become the shape of non-woven fabrics etc. by interfibrous gatheringization or stratification, be expected to be widely used as solid electrolyte, solid catalyst, nanometer additive, nano film material, metallic catalyst, nano metal electro-conductive material, nano metal look material, nano metal transmitter, light image material, photoelectron material, medical material.

And then, the composite nano fiber that except metal or metal ion, also contains the polymkeric substance of tool straight chain type polymine skeleton simultaneously, because the ethyleneimine unit in this polymkeric substance is cationization easily, therefore absorption or the immobilization to various ionic substances such as anionic property biochemical materials also is possible.In addition, because this has polymkeric substance easy and other polymer blocks or the grafting of straight chain type polymine skeleton, the structure control of polymer lateral chain or end structure etc. is also easy, therefore by with the blockization or the control end structure of various functional polymers, may give composite nano fiber various functions, so also be useful material in fields such as the corresponding goods of biological field or environment fields.

Complex structure body of the present invention or metallic silica nano fibrous structure are, be immobilized along the following template that connects by secondary or physical bond by silicon-dioxide, the composite nano fiber of nano level thickness or metallic silica nano fibrous mutual associating product, the secondary shape that described template is formed by the crystalline polymer long filament in the presence of water forms crosslinking structure through association again and obtains.Therefore, these structures are under the state that keeps above-mentioned composite nano fiber or metallic silica nano fibrous characteristic, form these nanofibers by the product of the tridimensional network of gatheringization highly, its profile can be shaped arbitrarily with the size more than the millimeter.Because these structure inside have tridimensional network, can be used for biofilter, the contour performance strainer of air filter or high-specific surface area catalyzer etc.In addition, these structures because its profile is controlled easily, can also be realized various fine association shapes in its structure, therefore be not limited to such use, are expected to use as the most advanced and sophisticated functional materials in various fields.

Therefore, above-mentioned composite nano fiber or complex structure body are a kind of brand-new complex bodys, and the difficulty of shape control is removed fully when making earth silicon material in the past, make also to be easy to, and industry is planted, the field so be regardless of, and it is used all express very big hope.In addition, because metal or metal ion are contained in the inside of composite nano fiber of the present invention and complex structure body etc., therefore much less be all Application Areass of silicon-dioxide, even also be useful material at the metal of applying nano shape or the field of metal complex.

Embodiment

With reference example the present invention is made more specific description by the following examples, but the present invention is not only limited to these.Short ofly forbid " % " expression " quality % " especially.

[with the analysis of X-ray diffraction method]

The exsiccant test portion of will emanating places measures test portion with on the anchor clamps, be fixed in リ ガ Network corporate system wide-angle x-ray diffraction instrument " Rint-Ultma ", under the condition of Cu/K α line, 40kV/30mA, 10 ℃/minute of sweep velocitys, 10～40 ° of sweep limits, measure.

[with the analysis of dsc]

With measuring fragment (patch) weighing segregation exsiccant test portion, be fixed on the Perkin Elmer corporate system apparatus for thermal analysis " DSC-7 ", heat-up rate is made as 10 ℃/minute, measures 20 ℃～90 ℃ temperature range.

[with the shape analysis of scanning electronic microscope]

The exsiccant test portion of will emanating is placed on the slide glass, observes with キ-エ Application ス corporate system surface observation device VE-7800.

[with the observation of transmission electron microscope]

Place evaporation to have on the copper mesh of carbon segregation exsiccant test portion, observe with (strain) ト プ コ Application, ノ-ラ Application イ Application ス Star Le メ Application ト corporate system EM-002B, VOYAGER M3055 very high resolution transmission electron microscope or NEC (strain) system transmission electron microscope " JEM-200CX ".

[UV-Vis absorption spectrum]

The SiO 2 powder of containing metal coordination compound is placed on the quartz glass plate, measure with the system U-3500UV-Vis of Hitachi's (strain) that is with integrating sphere.

(synthesis example 1)

[silica nano fibrous (SLP-1) synthetic that contains the linear polyethylene imines]

＜linear polyethylene imines (L's-PEI) is synthetic 〉

3g is dissolved in the aqueous hydrochloric acid 15mL of 5M with commercially available Ju ethyl oxazoline (number-average molecular weight 50000, mean polymerisation degree 5000, Aldrich corporate system).This solution is heated to 90 ℃ with oil bath, stirred 10 hours in this temperature.In reaction solution, add 50mL acetone, make polymkeric substance precipitate fully, filter, use methanol cleaning 3 times, obtain the polymine powder of white.The gained powder is identified with 1H-NMR (heavy water), confirms to derive from the peak 1.2ppm (CH of Ju ethyl oxazoline side chain ethyl ₃) and 2.3ppm (CH ₂) completely dissolve.That is, show that the Ju ethyl oxazoline by complete hydrolysis, has changed into polymine.

With this powder dissolution in 5mL distilled water, 15% of Dropwise 5 0mL ammoniacal liquor while stirring.After this mixed solution placed an evening, the polymer associate body powder of filtering-depositing was cleaned this polymer associate body powder 3 times with cold water.With the crystalline powder moisture eliminator drying at room temperature after cleaning, obtain the polymine (L-PEI) of line style.The receipts amount is 2.2g (containing crystal water).The polymine that the hydrolysis of You Ju oxazoline obtains has only side chain to react, and main chain does not change.Therefore preceding 5000 identical of the polymerization degree of L-PEI and hydrolysis.

＜contain the silica nano fibrous of linear polyethylene imines 〉

Weighing is a certain amount of to be scattered in it in distilled water by above-mentioned gained L-PEI powder, makes L-PEI dispersion liquid.With oil bath dispersion liquid is heated to 90 ℃, obtains concentration and be 1% complete transparent aqueous solution.Place this aqueous solution in room temperature, make it naturally cool to room temperature, obtain the hydrogel of opaque L-PEI association body.

Gained association body is carried out X ray measure, its results verification is at 20.7 °, 27.6 °, the 28.4 ° peaks that demonstrate scattering strength.In addition, the measurement result of the heat absorption change of state of being measured by the calorimetric analysis device can be confirmed, has endotherm(ic)peak at 64.7 °.Confirmed that by these measurement results L-PEI association body crystalline exists in the hydrogel.

In hydrogel 5mL, add tetramethoxy-silicane (TMSO) and alcoholic acid 1/1 (volume ratio) mixed solution 5mL, stir gently after one minute and placed 40 minutes by above-mentioned gained L-PEI association body.Clean with excessive acetone then, it is cleaned 3 times with centrifuge separator.Reclaim solid matter,, obtain containing the silica nano fibrous structure (SLP-1) of L-PEI in drying at room temperature.This contains in the X-ray diffraction measurement result of silica nano fibrous structure (SLP-1) of L-PEI, at 20.5 °, 27.2 °, the 28.2 ° peaks that scattering strength occurs.

Must contain the silica nano fibrous structure (SLP-1) of L-PEI with scan microscope observation post, found that the silica nano fibrous structure (SLP-1) that contains L-PEI is the association shape of shaped-like leaf.

(synthesis example 2)

[silica nano fibrous (SLP-2) synthetic that contains starlike polyethylene imonium]

＜be that the starlike polymine (P-PEI) at center is synthetic with the porphyrin

With Jin et al., J.Porphyrin﹠amp; Phthalocyanine, 3,60-64 (1999); Jin, Macromol.Chem.Phys., 204, the method shown in the 403-409 (2003) is carried out synthetic as the star-like poly-first oxazolin in porphyrin center of precursor polymer as described below.

Have two mouthfuls of flasks of 50mL of T-valve with argon replaces, add the N,N-dimethylacetamide of 0.0352g four (p-iodo-methyl phenyl) porphyrin (TIMPP), 8.0mL then, at room temperature stir, TIMPP is dissolved fully.After in this solution, adding the 2-methyl-2-oxazoline 3.4mL (3.27g) of 1280 times of mole numbers being equivalent to porphyrin, the temperature of reaction solution is risen to 100 ℃, stirred 24 hours.After reacting liquid temperature is reduced to room temperature, add 10mL methyl alcohol, then with the mixed solution concentrating under reduced pressure.Residue is dissolved in the methyl alcohol of 15mL, injects the 100mL tetrahydrofuran (THF), make polymer precipitation to this solution.After making polymkeric substance redeposition, suction filtration with Same Way, resulting polymers put into be placed with P ₂O ₅Moisture eliminator, with vent fan drying under reduced pressure 1 hour.With the vacuum pump decompression, drying is 24 hours under the vacuum, obtains precursor polymer (TPMO-P) again.The receipts amount is 3.05g, and yield is 92.3%.

The GPC number-average molecular weight of gained precursor polymer (TPMO-P) is 28000, and molecular weight distribution is 1.56.Calculate the integration ratio of the pyrrole ring proton of ethylidene proton in the polymer chain and polymkeric substance center porphyrin again by 1H-NMR, the mean polymerisation degree of each chain is 290.Therefore inferring by 1H-NMR gained number-average molecular weight is 99900.Surpass GPC number-average molecular weight value by 1H-NMR gained number-average molecular weight value, meet star-like high molecular general feature.

Use this precursor polymer, use the method same with above-mentioned synthesis example 1, hydrolysis Ju Jia oxazolin obtains the star-like polymine (P-PEI) that 4 polymines are incorporated into the porphyrin center.The result that 1H-NMR (in TMS external perimysium reference, the heavy water) measures derives from the peak completely dissolve of the 1.98ppm of the preceding precursor polymer pendant methyl of hydrolysis.

＜contain the silica nano fibrous complex body of star-like polymine 〉

Use above-mentioned synthetic P-PEI to replace the L-PEI powder that uses in the synthesis example 1, use the method same, obtain the gelationus P-PEI association of the water-setting body of 1% concentration with synthesis example 1.

Hydrogel to gained P-PEI association body carries out X-ray diffraction mensuration, and results verification is at 20.4 °, 27.8 °, the 28.1 ° peaks that scattering strength occurs.There is endotherm(ic)peak in the results verification of the heat absorption change of state of being measured by the calorimetric analysis device at 64.1 °.Confirmed that by these measurement results the P-PEI crystalline exists in the hydrogel.

In the hydrogel 1mL of gained P-PEI association body, add the mixed solution of 1mL tetramethoxy-silicane (TMSO) and alcoholic acid 1/1 (volume ratio), stir 1 minute gently after, former state placement 40 minutes.Clean with excessive acetone then, it is cleaned 3 times with centrifuge separator.Reclaim solids, dry under the room temperature, obtain containing the silica nano fibrous structure (SLP-2) of P-PEI.The X-ray diffraction that contains the silica nano fibrous structure (SLP-2) of P-PEI is measured, and the result is identical scattering peak before 20.5 °, 27.4 °, 28.1 ° appearance and silicon-dioxide covering.

Must contain the silica nano fibrous structure (SLP-2) of P-PEI with scan microscope observation post, the silica nano fibrous structure (SLP-2) that the result contains P-PEI is aster shape association shape.

(synthesis example 3)

[silica nano fibrous (SLP-3) synthetic that contains starlike polymine]

＜be starlike polymine (B-PEI) synthetic at center with the phenyl ring

According to Jin, J.Mater.Chem., 13, the method shown in the 672-675 (2003) is carried out 6 Ju Jia oxazolins chain combination synthetic in the starlike Ju Jia oxazolin precursor polymer at phenyl ring center as described below.

Add six (brooethyl) the benzene 0.021g (0.033mmol) as polymerization starter in the rub oral examination tube that is fixed with magnetic stir bar, after the test tube mouth was loaded onto T-valve, the state that is evacuated was replaced with nitrogen then.Under stream of nitrogen gas, add 2-methyl-2-oxazoline 2.0ml (24mmol), N,N-dimethylacetamide 4.0ml successively with syringe from the T-valve introducing port.Test tube is heated to 60 ℃ in oil bath, kept 30 minutes, mixed solution becomes transparent.With transparent mixed solution reheat to 100 ℃, stirred 20 hours in this temperature, obtain precursor polymer.1H-NMR mensuration by this mixed solution learns that monomeric transformation efficiency is 98%.By the mean polymerisation degree of this transformation efficiency estimation polymkeric substance, the mean polymerisation degree of each chain is 115 as a result.By the GPC determining molecular weight, the weight-average molecular weight of polymkeric substance is 22700 as a result, and molecular weight distribution is 1.6.

Use this precursor polymer, use the method hydrolysis Ju Jia oxazolin same, obtain the starlike polymine B-PEI that 6 polymines are incorporated into the phenyl ring center with above-mentioned synthesis example 1.The result that 1H-NMR (in TMS external perimysium reference/heavy water) measures derives from the peak completely dissolve of the 1.98ppm of the preceding precursor polymer pendant methyl of hydrolysis.

The starlike Ju Jia of method hydrolysis gained oxazolin with same with above-mentioned synthesis example 1 obtains the starlike polymine (B-PEI) that 6 polymines are incorporated into the phenyl ring center.

＜contain silica nano fibrous (SLP-3) of starlike polymine 〉

Use above-mentioned synthetic B-PEI to replace the L-PEI that uses in the synthesis example 1, use the method same, obtain the hydrogel of the B-PEI association body of 1% concentration with synthesis example 1.Hydrogel to gained B-PEI association body carries out X-ray diffraction mensuration, and results verification is at 20.3 °, 27.3 °, the 28.2 ° peaks that scattering strength occurs.The results verification of the heat absorption change of state of measuring according to the calorimetric analysis device in the existence of 55.3 ° endotherm(ic)peak.Confirmed that by these measurement results the B-PEI crystalline exists in the hydrogel.

Add the mixed solution of 1mL tetramethoxy-silicane (TMSO) and alcoholic acid 1/1 (volume ratio) in the hydrogel 1mL of gained B-PEI association body, stir ice cream shape thing gently after 1 minute, former state was placed 40 minutes.Clean with excessive acetone then, it is cleaned 3 times with centrifuge separator.Reclaim solids, dry under the room temperature, obtain containing the silica nano fibrous structure (SLP-3) of B-PEI.The X-ray diffraction that contains the silica nano fibrous structure (SLP-3) of B-PEI is measured, and the result is at 20.5 °.27.5 °, 28.3 ° of peaks that scattering strength occurs.

Must contain the silica nano fibrous structure (SLP-3) of B-PEI with scan microscope observation post, the silica nano fibrous structure (SLP-3) that the result contains B-PEI is the aggregative sponge structure of fibrous association shape.

(synthesis example 4)

[silica nano fibrous (SLP-4) synthetic that contains the linear polyethylene imines]

Synthesizing of＜linear polyethylene imines (L-PEI2) 〉

5g is dissolved among the aqueous hydrochloric acid 20mL of 5M with commercially available Ju ethyl oxazoline (number-average molecular weight 500000, mean polymerisation degree 5000, Aldrich corporate system).Heat this solution to 90 ℃ with oil bath, under this temperature, stirred 10 hours.In reaction solution, add 50mL acetone, polymkeric substance is precipitated fully, filter, use methanol cleaning 3 times, obtain the polymine powder of white.Identify the gained powder with 1H-NMR (heavy water), results verification derives from the peak 1.2ppm (CH of Ju ethyl oxazoline side chain ethyl ₃) and 2.3ppm (CH ₂) completely dissolve.Represent that promptly the Ju ethyl oxazoline by complete hydrolysis, is converted into polymine.

With the distilled water of this powder dissolution, in this solution, drip 15% ammoniacal liquor 50mL while stirring in 5mL.After this mixed solution was placed an evening, the polymer crystallization powder of filtering-depositing was cleaned this crystalline powder 3 times with cold water.Crystalline powder drying at room temperature in moisture eliminator with cleaning obtains linear polyethylene imines (L-PEI2).The receipts amount is 4.2g (containing crystal water).Polymine by Ju ethyl oxazoline hydrolysis gained has only side chain to participate in reaction, and main chain does not change.Therefore, 5000 identical before the polymerization degree of L-PEI2 and the hydrolysis.

＜contain the silica nano fibrous of linear polyethylene imines 〉

A certain amount of above-mentioned gained L-PEI2 powder of weighing is scattered in it in distilled water, makes the L-PEI2 dispersion liquid.With oil bath heating dispersion liquid to 90 ℃, obtain concentration and be 3% complete transparent aqueous solution.This aqueous solution is positioned over room temperature, naturally cools to room temperature, obtain the hydrogel of opaque L-PEI2 association body.

Gained association body is carried out X-ray diffraction measure, results verification is at 20.7 °, 27.6 °, the 28.4 ° peaks that scattering strength occurs.According to the results verification of the heat absorption change of state of measuring with the calorimetric analysis device in the existence of 64.7 ° endotherm(ic)peak.Confirmed that by these measurement results the L-PEI2 crystalline exists in the hydrogel.

The hydrogel 1mL of above-mentioned gained L-PEI2 association body is modulated into sheet, it is added in the aqueous solution (5%) of 10mL glutaraldehyde, at room temperature placed 24 hours, obtain cross-linked hydrogel.Hydrogel before crosslinked is the ice cream state, can change shape arbitrarily by shearing force, becomes one but handle the gained cross-linked hydrogel by chemically crosslinked, can not be caused the variation of shape by shearing force.The sheet of gained cross-linked hydrogel soaked 24 hours in the mixed solution 2mL of TMSO/EtOH (1/1) after, in acetone, soak repeatedly and clean, obtain containing the silica nano fibrous sheet-like structure (SLP-4) of L-PEI2.

(embodiment 1)

＜L-PEI/ gold/silicon-dioxide composite nano fiber 〉

The aqueous solution that will be immersed in (containing 3.4mg L-PEI approximately) the 1mL gold ion by silica nano fibrous structure (SLP-1) 0.01g that contains L-PEI of above-mentioned synthesis example 1 gained (contains 0.02gNaAuCl ₄) in, with this mixture in room temperature through 30 minutes, 80 ℃ after 30 minutes, clean with distilled water with centrifuge separator, obtained L-PEI/ gold/silicon-dioxide composite nano fiber.The silica nano fibrous structure (SLP-1) that contains L-PEI is white, and gained L-PEI/ gold/silicon-dioxide composite nano fiber structure is yellow.

Measure affirmation by the X-ray diffraction of this composite nano fiber structure and the sharp-pointed scattering peak that derives from Au is arranged at 38.1 °, 44.4 °, 64.5 °, 77.6 °.

The transmission electron microscope photo of gained composite nano fiber structure is shown in Fig. 1, and high degree of resolution transmission electron microscope photo is shown in Fig. 2.Can confirm the nano thread of gold of core shape and the existence that covers its silicon dioxide layer by Fig. 2.

(embodiment 2)

＜L-PEI/ platinum/silicon-dioxide composite nano fiber 〉

The aqueous solution that will be immersed in (containing 5.1mg PEI approximately) the 1.5mL platinum ion by silica nano fibrous structure (SLP-1) 0.015g that contains L-EPI of above-mentioned synthesis example 1 gained (contains 0.034gNa ₂PtCl ₄) in, with this mixture in room temperature through 30 minutes, 80 ℃ after 30 minutes, clean with distilled water with centrifuge separator, obtain L-PEI/ platinum/silicon-dioxide composite nano fiber.The silica nano fibrous structure (SLP-1) that contains L-PEI is white, and gained composite nano fiber structure is a grey.

Measure affirmation by the X-ray diffraction of this complex body and the sharp-pointed scattering peak that derives from Pt is arranged at 40.0 °, 46.4 °, 67.7 °.

The transmission electron microscope photo of gained composite nano fiber structure is shown in Fig. 3, and high degree of resolution transmission electron microscope photo is shown in Fig. 4.Can confirm the platinum nano thread of core shape and the existence that covers its silicon dioxide layer by Fig. 4.

(embodiment 3)

＜L-PEI/ palladium/silicon-dioxide composite nano fiber 〉

The aqueous solution that will be immersed in (containing 5.1mg PEI approximately) the 1.5mL palladium ion by silica nano fibrous structure (SLP-1) 0.015g that contains L-PEI of above-mentioned synthesis example 1 gained (contains 0.025gPd (NO ₃) ₂) in after 1.5 hours, wash the silica solid thing.Silica solid thing after cleaning is scattered in the water of 2mL, adds the NaBH of 1mL to this dispersion liquid ₄The aqueous solution (containing the 0.02g reductive agent) was placed 30 minutes in room temperature.Clean solids with centrifuge separator with distilled water, obtain L-PEI/ palladium/silicon-dioxide composite nano fiber structure.The silica nano fibrous structure (SLP-1) that contains L-PEI is white, and gained L-PEI/ palladium/silicon-dioxide composite nano fiber is a Dark grey.

Measure affirmation by the X-ray diffraction of this complex body and the sharp-pointed scattering peak that derives from Pd is arranged at 38.8 °, 45.6 °, 66.3 °.

(embodiment 4)

＜P-PEI/ gold/silicon-dioxide composite nano fiber 〉

Use is by the silica nano fibrous structure (SLP-2) that contains P-PEI of above-mentioned synthesis example 2 gained, and the method reduction gold ion aqueous solution with similarly to Example 1 obtains P-PEI/ gold/silicon-dioxide composite nano fiber structure.

Measure affirmation by the X-ray diffraction of gained composite nano fiber structure and the sharp-pointed scattering peak that derives from Au is arranged at 38.0 °, 44.6 °, 64.7 °, 77.7 °.

The transmission electron microscope photo of gained composite nano fiber structure is shown in Fig. 5.Can confirm the existence of the 3D shape of the association body in the composite nano fiber structure by Fig. 5.

(embodiment 5)

＜B-PEI/ gold/silicon-dioxide composite nano fiber 〉

Use is by the silica nano fibrous structure (SLP-3) that contains B-PEI of above-mentioned synthesis example 3 gained, and the method reduction gold ion aqueous solution with similarly to Example 1 obtains B-PEI/ gold/silicon-dioxide composite nano fiber structure.

Measure affirmation by the X-ray diffraction of gained composite nano fiber structure and the sharp-pointed scattering peak that derives from Au is arranged at 38.3 °, 44.6 °, 64.8 °, 77.7 °.

(embodiment 6)

＜L-PEI2/ silver/silicon dioxide composite nano fiber 〉

Will be by silica nano fibrous sheet-like structure (SLP-4) 0.03g that contains L-PEI2 of synthesis example 4 gained, in the silver nitrate aqueous solution (1M) of 4mL in soaking at room temperature 1 hour.Then clean this sheet, obtain green L-PEI2/ silver/silicon dioxide composite nano fiber structure with distilled water.Absorption spectrum by gained composite nano fiber structure sheet observes the プ ラ ズ モ Application absorption that there is the nanocrystal that derives from silver at the 420nm place.In addition, learn that by X-ray diffraction mensuration the scattering peak that derives from silver appears at 38.2 °, 44.4 °, 64.6 °, 77.5 ° and locates.

(embodiment 7)

＜L-PEI/ gold platinum/silicon-dioxide composite nano fiber 〉

The mixed aqueous solution that will be immersed in 2mL gold and platinum ion by silica nano fibrous structure (SLP-1) 0.02g (containing 6.8mg PEI approximately) that contains L-PEI of above-mentioned synthesis example 1 gained (contains 0.02g NaAuCl ₄, 0.023g Na ₂PtCl ₄) in, with this mixture in room temperature through 30 minutes, 80 ℃ after 30 minutes, clean with distilled water with centrifuge separator.Color is become faint yellow by white, obtain L-PEI/ gold platinum/silicon-dioxide composite nano fiber structure.X-ray diffraction mensuration by this composite nano fiber structure learns that the scattering peak that derives from Au and Pt appears at 38.1 °, 40.1 °, 44.2 °, 46.4 °, 64.6 °, 67.7 °, 77.6 ° and locates.

(embodiment 8)

＜L-PEI/ cupric ion/silicon-dioxide composite nano fiber 〉

Take by weighing silica nano fibrous structure (SLP-1) 50mg (nitrogen 0.319mmol) that contains L-PEI, it is added in the copper nitrate aqueous solution (2mM) of 5mL by above-mentioned synthesis example 1 gained.The structure of white becomes blueness in the aqueous solution.This mixture was placed 3 hours, filtered, clean 3 times with distilled water, dry then, obtain blue L-PEI/ cupric ion/silicon-dioxide composite nano fiber structure.

With absorption spectrometry gained composite nano fiber structure, the strong absorption peak of the coordination compound that formed by copper nitrogen (Cu-N) coordination has appearred in the result at 303nm, 630nm place.

(embodiment 9)

＜L-PEI/ sodium ion/silicon-dioxide composite nano fiber 〉

Take by weighing silica nano fibrous structure (SLP-1) 50mg (nitrogen 0.319mmol) that contains L-PEI, it is added the NaSO of 5mL by above-mentioned synthesis example 1 gained ₃CF ₃In (sodium triflate) aqueous solution (2mM).This mixture was placed 3 hours, filtered, clean 3 times with distilled water, dry then, obtain L-PEI/ sodium ion/silicon-dioxide composite nano fiber structure.

WAXS mensuration by dried L-PEI/ sodium ion/silicon-dioxide composite nano fiber structure is learnt, the diffraction image that derives from the L-PEI in the silica nano fibrous structure (SLP-1) that contains L-PEI disappears, replace, locate to occur diffraction image at 21 °, 32 °, 37 °.In addition, learn that by DSC observation fusing point appears at 169 ℃.These are illustrated in the coordination compound that has formed L-PEI and sodium ion in silica nano fibrous.

Claims (27)

1. a composite nano fiber is characterized in that, described fiber is, contains at least a metal or metal ion and by the fiber of the crystalline polymer long filament of the polymer formation with straight chain type polymine skeleton, wherein in silica nano fibrous

The ratio of the straight chain type polymine skeleton in the described polymkeric substance is 25 moles more than the %.

2. composite nano fiber as claimed in claim 1, wherein, described at least a metal or metal ion and polymkeric substance with straight chain type polymine skeleton are by the coordinate bond combination.

3. composite nano fiber as claimed in claim 1, wherein, described polymkeric substance with straight chain type polymine skeleton is chain, star-like or comb-shaped polymer.

4. composite nano fiber as claimed in claim 1, wherein, described polymkeric substance with straight chain type polymine skeleton is made of the segmented copolymer of straight chain type polymine block and other polymer blocks.

5. composite nano fiber as claimed in claim 1, wherein, the ratio of the polymine in the described polymkeric substance with straight chain type polymine skeleton is 40 moles more than the %.

6. composite nano fiber as claimed in claim 1, wherein, the content of silicon-dioxide is in the scope of 30～80 quality %.

7. composite nano fiber as claimed in claim 1, its thickness is in the scope of 15～100nm.

8. composite nano fiber as claimed in claim 1, wherein, described at least a metal or metal ion are at least a metal ion of selecting from alkalimetal ion, alkaline-earth metal ions, transition metal ion, metalloid ion, lanthanide metal ion, polyoxometallic acid salt.

9. composite nano fiber as claimed in claim 1, wherein, described at least a metal or metal ion are transition metal.

10. composite nano fiber as claimed in claim 9, wherein, at least a metallic crystal of described transition metal for from Au, Ag, Cu, Pt, Pd, Mn, Ni, Rh, Co, Ru, Re, Mo, selecting.

11. composite nano fiber as claimed in claim 9, wherein, described transition metal has nano thread or nanoparticle shape.

12. a composite nano fiber association body is characterized in that, it is that the composite nano fiber of any one record in the claim 1～11 associates mutually and forms.

13. composite nano fiber association body as claimed in claim 12, wherein, described association is netted association.

14. a complex structure body is characterized in that, its composite nano fiber association body that is claim 12 is put down in writing associates mutually and forms.

15. one kind metallic silica nano fibrous, it is that the polymkeric substance of removing in the composite nano fiber of any one record in the claim 9～11 forms.

16. a metallic silica nano fibrous association body, its silica nano fibrous mutual association that contains metal that is claim 15 is put down in writing forms.

17. a metallic silica nano fibrous structure, its silica nano fibrous association body that contains metal that is claim 16 is put down in writing associates mutually and forms.

18. the manufacture method of a composite nano fiber, comprising:

(1) polymer dissolution that will have straight chain type polymine skeleton separates out it in the presence of water in solvent then, obtains having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton;

(2) in the presence of water, contact with organoalkoxysilane by making described crystalline polymer long filament, cover described crystalline polymer long filament with silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance;

(3) contain the silica nano fibrous of polymkeric substance and contact described, make metal ion be incorporated into the operation of the straight chain type polymine skeleton in the described polymkeric substance by coordinate bond with being dissolved with metal ion solution.

19. the manufacture method of a composite nano fiber, comprising:

(1) polymer dissolution that will have straight chain type polymine skeleton separates out it in the presence of water in solvent then, obtains having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton;

(2) in the presence of water, contact with organoalkoxysilane by making described crystalline polymer long filament, cover described crystalline polymer long filament with silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance;

(3) contain the silica nano fibrous of polymkeric substance and contact described, make metal ion be incorporated into the operation of the straight chain type polymine skeleton in the described polymkeric substance by coordinate bond with being dissolved with metal ion solution;

(4) make the transition metal ion reductive operation that is incorporated into the straight chain type polymine skeleton in the described polymkeric substance by coordinate bond.

20. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, described organoalkoxysilane is the above organoalkoxysilanes of 3 valencys.

21. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, described organoalkoxysilane is one or both that select from tetraalkoxysilane class, tri-alkoxy alkyl silane class.

22. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, described polymkeric substance with straight chain type polymine skeleton is chain, star-like or comb-shaped polymer.

23. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, described polymkeric substance with straight chain type polymine skeleton is, the polymkeric substance that is made of the segmented copolymer of straight chain type polymine block and other polymer blocks.

24. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, the ratio of the polymine skeleton in the described polymkeric substance with straight chain type polymine skeleton is 40 moles more than the %.

25. as the manufacture method of claim 18 or 19 described composite nano fibers, wherein, described metal ion is a transition metal ion.

26. the manufacture method of composite nano fiber as claimed in claim 25, wherein, at least a transition metal ion of described transition metal ion for from Au, Ag, Cu, Pt, Pd, Mn, Ni, Rh, Co, Ru, Re, Mo, selecting.

27. a metallic silica nano fibrous manufacture method, comprising:

(1) polymer dissolution that will have straight chain type polymine skeleton separates out it in the presence of water in solvent then, obtains having the operation of crystalline polymer long filament of the polymkeric substance of straight chain type polymine skeleton;

(2) in the presence of water, contact with organoalkoxysilane by making described crystalline polymer long filament, cover described crystalline polymer long filament with silicon-dioxide, obtain containing the silica nano fibrous operation of polymkeric substance;

(3) contain the silica nano fibrous of polymkeric substance and contact described, make metal ion be incorporated into the operation of the straight chain type polymine skeleton in the described polymkeric substance by coordinate bond with being dissolved with metal ion solution;

(4) make the transition metal ion reduction that is incorporated into the straight chain type polymine skeleton in the described polymkeric substance by coordinate bond, obtain the operation of composite nano fiber;

(5) remove the operation of the component of polymer in the described composite nano fiber.

Images