CN105777934A - Water-soluble metal ion loaded hybrid material and method for preparing same - Google Patents
Water-soluble metal ion loaded hybrid material and method for preparing same Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
Abstract
The invention relates to a water-soluble metal ion loaded hybrid material and a method for preparing the same. The water-soluble metal ion loaded hybrid material comprises carrier molecules A, stabilizer molecules B and metal ions. The method includes steps of stirring and mixing aqueous solution of the carrier molecules A and aqueous solution of the stabilizer molecules B with each other to obtain mixed solution; regulating a pH (potential of hydrogen) value of the mixed solution; adding metal ion salt solution into the mixed solution drop by drop; continuously stirring the mixed solution and the metal ion salt solution; adding precipitants into the mixed solution and the metal ion salt solution; filtering the mixed solution and the metal ion salt solution to obtain precipitates; drying the precipitates by the aid of a vacuum drying oven to obtain the dry-state metal ion loaded hybrid material. The water-soluble metal ion loaded hybrid material and the method have the advantages that the metal ions in the metal ion loaded hybrid material are stably and effectively connected onto molecular chains of the carrier molecules in ionic bond and coordination bond forms, so that the water-soluble metal ion loaded hybrid material is good in water solubility, and the metal ion loading capacity of the water-soluble metal ion loaded hybrid material can be adjusted; the method for preparing the hybrid material is free of pollution and easy to implement, and products rarely contain impurities; the water-soluble metal ion loaded hybrid material prepared by the aid of the method can be widely applied to the aspects such as antibacterial finishing liquid, self-assembly stock solution and intermediates prepared from metal nano-materials.
Description
Technical field
The present invention relates to hybrid material of a kind of water soluble negative carrying metal ion and preparation method thereof, particularly relate to a kind of stable hybrid material of water soluble negative carrying metal ion and preparation method thereof.
Background technology
The hybrid material of loaded metal ion refers to that metal ion is keyed on carrier molecule by the effect by chemical bond or secondary or physical bond, and such hybrid material is widely applied to the aspects such as metal ion adsorption material, catalysis material, self assembly unit, anti-biotic material and fire proofing.
Metal ion is had good chelation by the groups such as hydroxyl in carrier molecule, amino and carboxyl, can effectively adsorb or metal ion in trapping solution.Based on this principle, researcheres have been prepared for the hybrid material of a lot of loaded metal ion.Propose slaine adds the chitosan preparation liquid preparing metallic print ion in chitosan-acetic acid solution in CN102430391A, obtaining metal ion imprinted chitosan crosslinked membrane eventually through the means of crosslinking after first film forming, this film mainly utilizes hydroxyl and amino in chitosan molecule to adsorb the metal ion in chelating waste water.CN104404760A utilizes modified by maleic acid anhydride graft cellulose fibre, generation ester is reacted with cellulosic molecule C6 position primary hydroxyl, thus introducing carboxyl on cellulose molecular chain to increase the binding site of metal ion, thus being prepared for the flame retardant cellulose fiber of a metal ion species graft modification.
A kind of Metal ion/starch aggregate and preparation method thereof disclosed in CN102964607A, Wen Zhongxian has prepared starch solution and metal ion solution respectively, under 50～90 DEG C of stirring conditions, in starch solution, add metal ion solution again, induce starch to assemble with metal ion and prepare Metal ion/starch aggregate；In addition, they are investigated the impact of the kind size on this aggregation of metal ion, shape and color.There are some researches show, metal ion directly contacts with polysaccharide material (including starch) can make metal ion generation reduction reaction, is directly changed metallic particles, and non-stable ionic state exists.As CN101450385A and CN103785854A reduced presoma silver nitrate using sodium carboxymethyl cellulose and sodium alginate as stabilizer and reducing agent respectively and chlorauric acid solution is prepared for nanometer silver and nanogold particle, metal ion is had certain reproducibility by hydroxyl to a certain extent that prove in polysaccharide, it is impossible to ensure that the metal ion in same system can stable existence.On the other hand, the poorly water-soluble of the hybrid material of the loaded metal ion of present research preparation, it is difficult to stable dispersion in the solution, many forms unstable with precipitation or suspension etc. exist, and the hybrid material of water solublity load metal nano ion is prepared intermediate etc. at antibiotic finishing solution, self assembly stock solution and metal nano material and needed the application aspect of solubilized stable liquid to have prospect widely.
Summary of the invention
It is an object of the invention to provide hybrid material of a kind of water soluble negative carrying metal ion and preparation method thereof, a kind of stable hybrid material of water soluble negative carrying metal ion and preparation method thereof is particularly provided.Loaded metal ion hybrid material prepared by the present invention is adopted to have good water solublity, its aqueous solution has again good stability, namely the dissolving that hybrid material is stable disperses in aqueous, and this aqueous solution is the transparent system not having obvious particulate matter to suspend or precipitate；Metal ion load capacity in hybrid material is adjustable, and metal ion is effectively connected on the strand of carrier molecule with the form stable of ionic bond and coordinate bond；Less input for the instrument and equipment that preparation process adopts, and operating process is simply easy to implement, and the raw material environmental friendliness and pollution-free used in course of reaction, impurity in products is few and is prone to post processing；Whole course of reaction is conducive to industrial amplification production.
The hybrid material of a kind of water soluble negative carrying metal ion of the present invention, in the hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between carboxyl, amino and metal ion；Described carboxyl and amino adhere to molecule A and the strand of molecule B separately；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are be more than or equal to the 160% of described molecule A and the mole sum of described molecule B, carboxyl in A and B Compound complex, amino and hydroxyl hydrophilic group are to ensure that the water miscible principal element of Compound complex, and 160% this numerical value is to ensure that Compound complex can have water miscible minimum numerical value；
The described carboxyl by ionic bond and coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing be more than or equal to the 30% of carboxyl in described molecule A and described molecule B and amino mole sum；
Relative molecular weight >=10000 of described molecule A, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
Relative molecular weight≤5000 of described molecule B, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
The general structure of the hybrid material of described water soluble negative carrying metal ion is:
Or
Wherein, strand repetitive number m >=0, n > 0；
The mechanism that triangle bonding scheme stable in general structure schematic diagram is formed is as follows :-the COO in molecule A and B-With-NH3 +Because the attraction of positive and negative charge, produce electrostatic attraction, namely form ionic bond；-COO-In hydroxyl oxygen on have lone pair electrons, therefore lone pair electrons enter metal ion unoccupied orbital be combined with metal ion generation covalent coordinate, formation coordinate bond；-NH3 +In atom N there is also lone pair electrons, lone pair electrons and metal ion can be provided equally to form coordinate bond and to be combined.Therefore the stable triangle bonding scheme in general structure schematic diagram is defined.
In the process, the pH value of reaction system is to-COO in system-、-NH3 +And Mx+The formation of bonding structure has a great impact.-NH in molecule A or molecule B2At pH value, < when 7, H proton that can be excessive in solution is in conjunction with formation-NH3 +；Along with the rising of pH value, to neutrality or alkali condition, H proton free in solution reduces, it is impossible to form-NH again3 +Structure.For-the COOH in molecule A and molecule B, at strong acid condition pH value, < when 2, the dissociation of-COOH is suppressed ,-COO in system-Content less, therefore the complexing power of metal ion is weakened significantly；Along with pH value increases, it is gradually increased with the complexing power of metal ion, when solution ph reaches 5～7 ,-COO-Tend to maximum with metal ion combination degree；But when the pH value of system improves again ,-NH can be destroyed again3 +Structure, thus destroying the three-legged structure relation of stable system of making.Therefore, in order to form the stable stable triangle bonding scheme as shown in schematic diagram, thus must the pH value of effective adjustment and control system, and ensure pH value range for 4～6.
R1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For metal ion, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+Or 3 valency rare earth ions, described 3 valency rare earth ions are: La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+。
As preferred technical scheme:
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecule B with amino also comprises hydroxyl or carboxyl；Molecule B with carboxyl also comprises hydroxyl or amino.
The hybrid material of a kind of water soluble negative carrying metal ion as above, described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecular backbone of described molecule A also includes element O, N or S common in Organic substance.
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecular backbone of described molecule B also includes element O, N or S common in Organic substance.
The hybrid material of a kind of water soluble negative carrying metal ion as above, R in described molecule A and molecule B1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；Preferably: anionic group, carboxylic acid group (-COO-)；Polar nonionic group, hydroxyl (-OH) and amino (-NH2)。
The hybrid material of a kind of water soluble negative carrying metal ion as above, the load capacity of described metal ion is 10～825mg/g.
The preparation method that present invention also offers the hybrid material of a kind of water soluble negative carrying metal ion, by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, regulate the pH value of reaction system to 4～6, then in mixed liquor, drip metal ion salt solution, stir after dropwising, obtain the aqueous solution of loaded metal ion hybrid material, continuously stirred and add precipitant, sucking filtration, obtain the precipitate of hygrometric state, after the drying precipitate of hygrometric state, namely obtain the hybrid material of water soluble negative carrying metal ion；
Intersect containing carboxyl and amino containing molecule A material and the B substance containing molecule, it may be assumed that when the A material containing molecule is containing carboxyl, the B substance containing molecule contains amino；Otherwise, when the A material containing molecule is containing amino, the B substance containing molecule contains carboxyl.
The preparation method of the hybrid material of a kind of water soluble negative carrying metal ion as above, by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, is under 20～60 DEG C of conditions；Stirring is accompanied by during mixing；The pH value regulating reaction system adopts the H of the HCl solution of 0.1～0.3mol/L, 0.05～0.15mol/L2SO4The HNO of solution or 0.1～0.3mol/L3Solution；Metal ion salt solution stirs after dropwising, and the persistent period is 1～2h；Repeatedly rinse precipitate with precipitant 2～3 times, fully remove the deionized water in precipitate；Mode that vacuum drying oven dries that what the drying precipitate of hygrometric state adopted is, baking temperature is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
The preparation method of the hybrid material of a kind of water soluble negative carrying metal ion as above, the described A material containing molecule be molecule A carboxylic containing molecule A material or molecule A containing amino containing molecule A material；Described molecule A carboxylic containing molecule A material selected from sodium alginate, potassium alginate, sodium carboxymethyl cellulose, potassium carboxymethylcellulose, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyetbyl chitosan sodium, carboxyetbyl chitosan potassium, 2, one in 3-bis-sodium carboxymethyl cellulose, 2,3-bis-potassium carboxymethylcellulose, sodium polyacrylate and polyacrylic acid potassium；Preferably sodium alginate, potassium alginate, sodium carboxymethyl cellulose, potassium carboxymethylcellulose, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, sodium polyacrylate and polyacrylic acid potassium, optimum is sodium carboxymethyl cellulose and potassium carboxymethylcellulose；
The described molecule A A material containing molecule containing amino is chitosan, carboxymethyl chitosan or polyacrylamide；Preferably chitosan；
Described containing molecule B substance be molecule B carboxylic containing molecule B substance or molecule B containing amino containing molecule B substance；
Described molecule B is carboxylic sour less than the alkyl chain of 6 carbon selected from chain length containing molecule B substance, is specially n-butyric acie, positive valeric acid or n-caproic acid；
Described molecule B containing amino containing molecule B substance selected from chain length less than the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, one in aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；The preferably one in polyetheramine D230, aliphatic amine polyoxyethylene ether AC-1810, polyetheramine T403 and aliphatic amine polyoxyethylene ether AC-1205, is polyetheramine D230 best；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
Described metal ion salt solution is selected from AgNO3、FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2、CdCl2Aqueous solution or rare earth ion saline solution, described metal ion salt solution preferably AgNO3、CuSO4、PtCl2Or PdCl2Aqueous solution；Described rare earth ion saline solution is selected from LaCl3、Ce2(SO4)3、Eu(NO3)3、ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO3)3Aqueous solution；
Described precipitant is ethanol or acetone, it is preferred that for ethanol；The volume ratio of the aqueous solution of the hybrid material of described precipitant and loaded metal ion is 2～4:1；
When the preparation method of the hybrid material of a kind of water soluble negative carrying metal ion as above, the described aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, it is 1:0.3～1 containing molecule A material and the mol ratio containing molecule B substance；
The described mass percent concentration containing the aqueous solution of molecule A material is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing molecule B substance is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio containing molecule A material；
The mass percent concentration of the aqueous solution of described loaded metal ion hybrid material is 0.5%～10.5%；
The volume ratio of the aqueous solution of the hybrid material of described precipitant and loaded metal ion is 2～4:1.
Beneficial effect:
The invention provides a kind of technique simple, the easy-operating preparation method preparing loaded metal ion hybrid material, the loaded metal ion hybrid material that the method prepares has good water solublity, and metal ion load capacity on carrier molecule is adjustable.
The hybrid material of water soluble negative carrying metal ion prepared by the present invention, has good water solublity, i.e. this hybrid material stable being dispersed in water of energy, and its aqueous solution is the transparent system not having obvious particulate matter to suspend or precipitate.Compared with the aqueous solution without molecule B class material stabilizer, its aqueous solution has good stability, by the pH value of regulation system, form metal ion to be bonded with the ionic bond between molecule A and molecule B and coordinate bond, metal ion can always with ionic state load on carrier molecule A class material, and disperse in aqueous, and during without molecule B class material stabilizer, the metal ion in aqueous solution is easily reduced；The amount of portative metal ion on carrier molecule A class material can be regulated and controled by the amount of the molecule B class material stabilizer that regulation and control are added；The hybrid material obtained can be purified to the fibrous solids of dry state by dehydrated alcohol or acetone, it is simple to storing, the solid matter after purification can be re-dissolved in again in water, is configured to aqueous solution；This material can use after being re-dubbed solution with water, has good antibacterial functional effect such as grade；Or after being re-dubbed aqueous solution, carry out the preparation of next step load simple metal nano particle hybridization material or loaded metal sulfide nano particle hybridization material.This course of reaction is adopted and uses water as reaction dissolvent, nontoxic, environmental protection；Less input for the instrument and equipment that preparation technology itself adopts, and operating process is simply easy to implement, and experiment condition is gentle, it is simple to realize large-scale industrial production.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than restriction the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
The hybrid material of a kind of water soluble negative carrying metal ion of the present invention, in the hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between carboxyl, amino and metal ion；Described carboxyl and amino adhere to molecule A and the strand of molecule B separately；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are be more than or equal to the 160% of described molecule A and the mole sum of described molecule B；
The described carboxyl by ionic bond and coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing be more than or equal to the 30% of carboxyl in described molecule A and described molecule B and amino mole sum；
Relative molecular weight >=10000 of described molecule A, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
Relative molecular weight≤5000 of described molecule B, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
The general structure of the hybrid material of described water soluble negative carrying metal ion is:
Or
Wherein, strand repetitive number m >=0, n > 0；
R1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For metal ion, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+Or it is 3 valency rare earth ions；Described 3 valency rare earth ions are La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+。
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecule B with amino also comprises hydroxyl or carboxyl；Molecule B with carboxyl also comprises hydroxyl or amino.
The hybrid material of a kind of water soluble negative carrying metal ion as above, described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecular backbone of described molecule A also includes element O, N or S common in Organic substance.
The hybrid material of a kind of water soluble negative carrying metal ion as above, the molecular backbone of described molecule B also includes element O, N or S common in Organic substance.
The hybrid material of a kind of water soluble negative carrying metal ion as above, the load capacity of described metal ion is 10～825mg/g.
Embodiment 1
A kind of water solublity loaded Ag+The preparation method of hybrid material, under 20 DEG C of conditions, by the aqueous solution of n-amylamine that the aqueous solution of sodium alginate that mass percent concentration is 0.5% and mass percent concentration are 3%, the mol ratio of sodium alginate and n-amylamine is 1:0.3, the relative molecular weight of sodium alginate and n-amylamine respectively 25000 and 87.16, accompanying by stirring during mixing, with the HCl solution of 0.1mol/L, the pH value of system is adjusted to 4, then dripping concentration in mixed liquor is the AgNO of 0.005g/mL3Aqueous solution, AgNO3Being 0.1:1 with the mol ratio of sodium alginate, stir after dropwising, the persistent period is 1h, namely obtains loaded Ag+The aqueous solution of hybrid material, its mass percent concentration is 0.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Ag+The volume ratio of the aqueous solution of hybrid material is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 2 times, and precipitate is 25 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity loaded Ag after drying+Hybrid material, Ag in this hybrid material+Load capacity be 42mg/g.
Embodiment 2
A kind of water solublity load Fe2+The preparation method of hybrid material, under 60 DEG C of conditions, by the aqueous solution of n-butylamine that the aqueous solution of potassium alginate that mass percent concentration is 0.6% and mass percent concentration are 6%, the mol ratio of potassium alginate and n-butylamine is 1:0.7, the relative molecular weight of potassium alginate and n-butylamine respectively 15000 and 73.14, accompanying by stirring during mixing, with the HCl solution of 0.15mol/L, the pH value of system is adjusted to 6, then dripping concentration in mixed liquor is the FeCl of 0.2g/mL2Aqueous solution, FeCl2Being 2.5:1 with the mol ratio of potassium alginate, stir after dropwising, the persistent period is 2h, namely obtains load Fe2+The aqueous solution of hybrid material, its mass percent concentration is 1.2%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe2+The volume ratio of the aqueous solution of hybrid material is 4:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 3 times, and precipitate is 30 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity load Fe after drying2+Hybrid material, Fe in this hybrid material2+Load capacity be 263mg/g.
Embodiment 3
A kind of water solublity load Fe3+The preparation method of hybrid material, under 25 DEG C of conditions, by the aqueous solution of polyetheramine D400 that the aqueous solution of sodium carboxymethyl cellulose that mass percent concentration is 1% and mass percent concentration are 4%, the mol ratio of sodium carboxymethyl cellulose and polyetheramine D400 is 1:0.5, the relative molecular weight of sodium carboxymethyl cellulose and polyetheramine D400 respectively 19000 and 400, stirring is accompanied by during mixing, with the HCl solution of 0.2mol/L, the pH value of system being adjusted to 6, then dripping concentration in mixed liquor is the FeCl of 0.1g/mL3Aqueous solution, FeCl3Being 0.5:1 with the mol ratio of sodium carboxymethyl cellulose, stir after dropwising, the persistent period is 1.5h, namely obtains load Fe3+The aqueous solution of hybrid material, its mass percent concentration is 1.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe3+The volume ratio of the aqueous solution of hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, and precipitate is 26 DEG C in temperature, and when vacuum is 0.08MPa, namely vacuum drying oven obtains water solublity load Fe after drying3+Hybrid material, Fe in this hybrid material3+Load capacity be 10mg/g.
Embodiment 4
A kind of water solublity load Au3+The preparation method of hybrid material, under 30 DEG C of conditions, by the aqueous solution of polyetheramine D2000 that the aqueous solution of potassium carboxymethylcellulose that mass percent concentration is 1% and mass percent concentration are 5%, the mol ratio of potassium carboxymethylcellulose and polyetheramine D2000 is 1:0.5, the relative molecular weight of potassium carboxymethylcellulose and polyetheramine D2000 respectively 26000 and 2000, stirring is accompanied by during mixing, with the HCl solution of 0.25mol/L, the pH value of system being adjusted to 5, then dripping concentration in mixed liquor is the HAuCl of 1g/mL4Aqueous solution, HAuCl4Being 0.5:1 with the mol ratio of potassium carboxymethylcellulose, stir after dropwising, the persistent period is 1h, namely obtains load Au3+The aqueous solution of hybrid material, its mass percent concentration is 2.9%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Au3+The volume ratio of aqueous solution of hybrid material be 4:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 27 DEG C in temperature, and when vacuum is 0.07MPa, namely vacuum drying oven obtains water solublity load Au after drying3+Hybrid material, Au in this hybrid material3+Load capacity be 73mg/g.
Embodiment 5
A kind of water solublity load Cr3+The preparation method of hybrid material, under 50 DEG C of conditions, by the aqueous solution of polyetheramine D4000 that the aqueous solution of sodium hydroxyethlcellulose that mass percent concentration is 1.5% and mass percent concentration are 8%, the mol ratio of sodium hydroxyethlcellulose and polyetheramine D4000 is 1:0.8, the relative molecular weight of sodium hydroxyethlcellulose and polyetheramine D4000 respectively 310000 and 4000, stirring is accompanied by during mixing, with the HCl solution of 0.3mol/L, the pH value of system being adjusted to 4, then dripping concentration in mixed liquor is the Cr of 0.5g/mL2(SO4)3Aqueous solution, Cr2(SO4)3Being 5:1 with the mol ratio of sodium hydroxyethlcellulose, stir after dropwising, the persistent period is 2h, namely obtains load C r3+The aqueous solution of hybrid material, its mass percent concentration is 6.3%, continuously stirred and add precipitant acetone, precipitant acetone and load C r3+The volume ratio of aqueous solution of hybrid material be 3:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 28 DEG C in temperature, and when vacuum is 0.06MPa, namely vacuum drying oven obtains water solublity load Cr after drying3+Hybrid material, Cr in this hybrid material3+Load capacity be 70mg/g.
Embodiment 6
A kind of water solublity load Zn2+The preparation method of hybrid material, under 60 DEG C of conditions, by the aqueous solution of polyetheramine T403 that the aqueous solution of carboxyethyl cellulose potassium that mass percent concentration is 2% and mass percent concentration are 6%, the mol ratio of carboxyethyl cellulose potassium and polyetheramine T403 is 1:0.8, the relative molecular weight of carboxyethyl cellulose potassium and polyetheramine T403 respectively 35200 and 400, stirring is accompanied by, with the H of 0.05mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the ZnCl of 0.03g/mL2Aqueous solution, ZnCl2Being 8:1 with the mol ratio of carboxyethyl cellulose potassium, stir after dropwising, the persistent period is 2h, namely obtains load Zn2+The aqueous solution of hybrid material, its mass percent concentration is 2.0%, continuously stirred and add precipitant acetone, precipitant acetone and load Zn2+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 30 DEG C in temperature, and when vacuum is 0.05MPa, namely vacuum drying oven obtains water solublity load Zn after drying2+Hybrid material, Zn in this hybrid material2+Load capacity be 408mg/g.
Embodiment 7
A kind of water solublity supporting Pt2+The preparation method of hybrid material, under 28 DEG C of conditions, by the aqueous solution of polyetheramine T3000 that the aqueous solution of carboxymethyl chitosan sodium that mass percent concentration is 1.7% and mass percent concentration are 9%, the mol ratio of carboxymethyl chitosan sodium and polyetheramine T3000 is 1:0.7, the relative molecular weight of carboxymethyl chitosan sodium and polyetheramine T3000 respectively 340000 and 3000, stirring is accompanied by, with the H of 0.07mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the PtCl of 1.6g/mL2Aqueous solution, PtCl2Being 0.5:1 with the mol ratio of carboxymethyl chitosan sodium, stir after dropwising, the persistent period is 1h, namely obtains supporting Pt2+The aqueous solution of hybrid material, its mass percent concentration is 5.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and supporting Pt2+The volume ratio of the aqueous solution of hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 2 times, and precipitate is 30 DEG C in temperature, and when vacuum is 0.04MPa, namely vacuum drying oven obtains water solublity supporting Pt after drying2+Hybrid material, Pt in this hybrid material2+Load capacity be 40mg/g.
Embodiment 8
A kind of water solublity load Pd2+The preparation method of hybrid material, under 40 DEG C of conditions, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1210 that the aqueous solution of carboxymethyl chitosan potassium that mass percent concentration is 1.5% and mass percent concentration are 7%, the mol ratio of carboxymethyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1210 is 1:0.6, the relative molecular weight of carboxymethyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1210 respectively 200000 and 1200, stirring is accompanied by, with the H of 0.1mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the PdCl of 0.01g/mL2Aqueous solution, PdCl2Being 3:1 with the mol ratio of carboxymethyl chitosan potassium, stir after dropwising, the persistent period is 2h, namely obtains load P d2+The aqueous solution of hybrid material, its mass percent concentration is 3.1%, continuously stirred and add precipitant acetone, precipitant acetone and load P d2+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 26 DEG C in temperature, and when vacuum is 0.03MPa, namely vacuum drying oven obtains water solublity load Pd after drying2+Hybrid material, Pd in this hybrid material2+Load capacity be 180mg/g.
Embodiment 9
A kind of water solublity loaded Cu2+The preparation method of hybrid material, under 50 DEG C of conditions, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1810 that the aqueous solution of carboxyetbyl chitosan sodium that mass percent concentration is 0.5% and mass percent concentration are 5%, the mol ratio of carboxyetbyl chitosan sodium and aliphatic amine polyoxyethylene ether AC-1810 is 1:0.8, the relative molecular weight of carboxyetbyl chitosan sodium and aliphatic amine polyoxyethylene ether AC-1810 respectively 21000 and 1800, stirring is accompanied by, with the H of 0.12mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the CuSO of 0.05g/mL4Aqueous solution, CuSO4Being 0.8:1 with the mol ratio of carboxyetbyl chitosan sodium, stir after dropwising, the persistent period is 1h, namely obtains loaded Cu2+The aqueous solution of hybrid material, its mass percent concentration is 2.2%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Cu2+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 29 DEG C in temperature, and when vacuum is 0.02MPa, namely vacuum drying oven obtains water solublity loaded Cu after drying2+Hybrid material, Cu in this hybrid material2+Load capacity be 27mg/g.
Embodiment 10
A kind of water solublity load Ni2+The preparation method of hybrid material, under 20 DEG C of conditions, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1812 that the aqueous solution of carboxyetbyl chitosan potassium that mass percent concentration is 2.5% and mass percent concentration are 5%, the mol ratio of carboxyetbyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1812 is 1:0.6, the relative molecular weight of carboxyetbyl chitosan potassium and aliphatic amine polyoxyethylene ether AC-1812 respectively 165000 and 1900, stirring is accompanied by, with the H of 0.15mol/L during mixing2SO4The pH value of system is adjusted to 4 by solution, then drips the Ni (NO that concentration is 0.16g/mL in mixed liquor3)2Aqueous solution, Ni (NO3)2Being 0.6:1 with the mol ratio of carboxyetbyl chitosan potassium, stir after dropwising, the persistent period is 1.5h, namely obtains load Ni2+The aqueous solution of hybrid material, its mass percent concentration is 4.2%, continuously stirred and add precipitant acetone, precipitant acetone and load Ni2+The volume ratio of the aqueous solution of hybrid material is 2:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, and precipitate is 30 DEG C in temperature, and when vacuum is 0.01MPa, namely vacuum drying oven obtains water solublity load Ni after drying2+Hybrid material, Ni in this hybrid material2+Load capacity be 23mg/g.
Embodiment 11
A kind of water solublity load Cd2+The preparation method of hybrid material, under 40 DEG C of conditions, it is the 2 of 2.8% by mass percent concentration, the aqueous solution of 3-bis-sodium carboxymethyl cellulose and mass percent concentration are the aqueous solution of the aliphatic amine polyoxyethylene ether AC-1815 of 6%, 2, the mol ratio of 3-bis-sodium carboxymethyl cellulose and aliphatic amine polyoxyethylene ether AC-1815 is 1:0.8,2, the relative molecular weight of 3-bis-sodium carboxymethyl cellulose and aliphatic amine polyoxyethylene ether AC-1815 respectively 40000 and 900, stirring is accompanied by, with the HNO of 0.1mol/L during mixing3The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the CdCl of 0.18g/mL2Aqueous solution, CdCl2Being 3:1 with the mol ratio of 2,3-bis-sodium carboxymethyl cellulose, stir after dropwising, the persistent period is 2h, namely obtains load C d2+The aqueous solution of hybrid material, its mass percent concentration is 3%, continuously stirred and add precipitant ethanol, precipitant ethanol and load C d2+The volume ratio of the aqueous solution of hybrid material is 4:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 2 times, and precipitate is 26 DEG C in temperature, and namely vacuum obtain water solublity load Cd after drying for vacuum drying oven under-0.1MPa condition2+Hybrid material, Cd in this hybrid material2+Load capacity be 148mg/g.
Embodiment 12
A kind of water solublity load La3+The preparation method of hybrid material, under 30 DEG C of conditions, it is the 2 of 0.9% by mass percent concentration, the aqueous solution of 3-bis-potassium carboxymethylcellulose and mass percent concentration are the aqueous solution of the aliphatic amine polyoxyethylene ether AC-1205 of 8%, 2, the mol ratio of 3-bis-potassium carboxymethylcellulose and aliphatic amine polyoxyethylene ether AC-1205 is 1:1,2, the relative molecular weight of 3-bis-potassium carboxymethylcellulose and aliphatic amine polyoxyethylene ether AC-1205 respectively 250000 and 1200, stirring is accompanied by, with the HNO of 0.15mol/L during mixing3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the LaCl of 0.006g/mL3Aqueous solution, LaCl3Being 0.6:1 with the mol ratio of 2,3-bis-potassium carboxymethylcelluloses, stir after dropwising, the persistent period is 1h, namely obtains load La3+The aqueous solution of hybrid material, its mass percent concentration is 2.8%, continuously stirred and add precipitant ethanol, precipitant ethanol and load La3+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 25 DEG C in temperature, and namely vacuum obtain water solublity load La after drying for vacuum drying oven under-0.09MPa condition3+Hybrid material, La in this hybrid material3+Load capacity be 34mg/g.
Embodiment 13
A kind of water solublity load Ce3+The preparation method of hybrid material, under 60 DEG C of conditions, by the aqueous solution of polyetheramine T5000 that the aqueous solution of carboxymethyl chitosan sodium that mass percent concentration is 3% and mass percent concentration are 10%, the mol ratio of carboxymethyl chitosan sodium and polyetheramine T5000 is 1:1, the relative molecular weight of carboxymethyl chitosan sodium and polyetheramine T5000 respectively 340000 and 5000, stirring is accompanied by, with the HNO of 0.2mol/L during mixing3The pH value of system is adjusted to 4 by solution, and then dripping concentration in mixed liquor is the Ce of 2g/mL2(SO4)3Aqueous solution, Ce2(SO4)3Being 10:1 with the mol ratio of carboxymethyl chitosan sodium, stir after dropwising, the persistent period is 2h, namely obtains load C e3+The aqueous solution of hybrid material, its mass percent concentration is 8.3%, continuously stirred and add precipitant ethanol, precipitant ethanol and load C e3+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 30 DEG C in temperature, and namely vacuum obtain water solublity load Ce after drying for vacuum drying oven under-0.1MPa condition3+Hybrid material, Ce in this hybrid material3+Load capacity be 49mg/g.
Embodiment 14
A kind of water solublity load Eu3+The preparation method of hybrid material, under 40 DEG C of conditions, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1215 that the aqueous solution of polyacrylic acid potassium that mass percent concentration is 1.2% and mass percent concentration are 3%, the mol ratio of polyacrylic acid potassium and aliphatic amine polyoxyethylene ether AC-1215 is 1:0.5, the relative molecular weight of polyacrylic acid potassium and aliphatic amine polyoxyethylene ether AC-1215 respectively 20000 and 800, stirring is accompanied by, with the HNO of 0.25mol/L during mixing3The pH value of system is adjusted to 5 by solution, then drips the Eu (NO that concentration is 0.12g/mL in mixed liquor3)3Aqueous solution, Eu (NO3)3Being 2:1 with the mol ratio of polyacrylic acid potassium, stir after dropwising, the persistent period is 1h, namely obtains load Eu3+The aqueous solution of hybrid material, its mass percent concentration is 2.9%, continuously stirred and add precipitant acetone, precipitant acetone and load Eu3+The volume ratio of the aqueous solution of hybrid material is 2:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, and precipitate is 26 DEG C in temperature, and namely vacuum obtain water solublity load Eu after drying for vacuum drying oven under-0.1MPa condition3+Hybrid material, Eu in this hybrid material3+Load capacity be 215mg/g.
Embodiment 15
A kind of water solublity load Er3+The preparation method of hybrid material, under 30 DEG C of conditions, by the aqueous solution of n-butyric acie that the aqueous solution of chitosan that mass percent concentration is 1.6% and mass percent concentration are 7%, the mol ratio of chitosan and n-butyric acie is 1:0.9, the relative molecular weight of chitosan and n-butyric acie respectively 240000 and 88.1, stirring is accompanied by, with the HNO of 0.3mol/L during mixing3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the ErCl of 0.8g/mL3Aqueous solution, ErCl3Being 6:1 with the mol ratio of chitosan, stir after dropwising, the persistent period is 1h, namely obtains load Er3+The aqueous solution of hybrid material, its mass percent concentration is 10.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Er3+The volume ratio of the aqueous solution of hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times, and precipitate is 28 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity load Er after drying3+Hybrid material, Er in this hybrid material3+Load capacity be 825mg/g.
Embodiment 16
A kind of water solublity load Yb3+The preparation method of hybrid material, under 20 DEG C of conditions, by the aqueous solution of positive valeric acid that the aqueous solution of carboxymethyl chitosan that mass percent concentration is 2.4% and mass percent concentration are 6%, the mol ratio of carboxymethyl chitosan and positive valeric acid is 1:0.4, the relative molecular weight of carboxymethyl chitosan and positive valeric acid respectively 10000 and 102.13, stirring is accompanied by during mixing, with the HCl solution of 0.1mol/L, the pH value of system being adjusted to 6, then dripping concentration in mixed liquor is the YbCl of 0.06g/mL3Aqueous solution, YbCl3Being 0.8:1 with the mol ratio of carboxymethyl chitosan, stir after dropwising, the persistent period is 2h, namely obtains load Yb3+The aqueous solution of hybrid material, its mass percent concentration is 2.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Yb3+The volume ratio of the aqueous solution of hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 2 times, and precipitate is 29 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity load Yb after drying3+Hybrid material, Yb in this hybrid material3+Load capacity be 119mg/g.
Embodiment 17
A kind of water solublity load Tm3+The preparation method of hybrid material, under 25 DEG C of conditions, by the aqueous solution of n-caproic acid that the aqueous solution of polyacrylamide that mass percent concentration is 0.8% and mass percent concentration are 5%, the relative molecular weight that mol ratio is 1:0.7, polyacrylamide and n-caproic acid of polyacrylamide and n-caproic acid respectively 1 × 106With 115.15, during mixing, accompany by stirring, with the HCl solution of 0.3mol/L, the pH value of system is adjusted to 4, in mixed liquor, then drip the Tm (NO that concentration is 0.08g/mL3)3Aqueous solution, Tm (NO3)3Being 3.5:1 with the mol ratio of polyacrylamide, stir after dropwising, the persistent period is 2h, namely obtains load Tm3+The aqueous solution of hybrid material, its mass percent concentration is 0.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Tm3+The volume ratio of the aqueous solution of hybrid material is 3:1, collected by suction precipitate, repeatedly rinses precipitate with acetone 3 times, and precipitate is 29 DEG C in temperature, and namely vacuum obtain water solublity load Tm after drying for vacuum drying oven under-0.1MPa condition3+Hybrid material, Tm in this hybrid material3+Load capacity be 795mg/g.
Embodiment 18
A kind of water solublity loaded Ag+The preparation method of hybrid material, under 50 DEG C of conditions, by the aqueous solution of n-hexylamine that the aqueous solution of sodium alginate that mass percent concentration is 2.6% and mass percent concentration are 5%, the mol ratio of sodium alginate and n-hexylamine is 1:0.5, the relative molecular weight of sodium alginate and n-hexylamine respectively 25000 and 101.19, stirring is accompanied by, with the H of 0.05mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the AgNO of 0.5g/mL3Aqueous solution, AgNO3Being 5:1 with the mol ratio containing sodium alginate, stir after dropwising, the persistent period is 1h, namely obtains loaded Ag+The aqueous solution of hybrid material, its mass percent concentration is 7.3%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Ag+The volume ratio of the aqueous solution of hybrid material is 2:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 2 times, and precipitate is 27 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity loaded Ag after drying+Hybrid material, Ag in this hybrid material+Load capacity be 669mg/g.
Embodiment 19
A kind of water solublity load Ho3+The preparation method of hybrid material, under 60 DEG C of conditions, by the aqueous solution of n-propylamine that the aqueous solution of potassium alginate that mass percent concentration is 1.4% and mass percent concentration are 3%, the mol ratio of potassium alginate and n-propylamine is 1:0.3, the relative molecular weight of potassium alginate and n-propylamine respectively 15000 and 59.11, stirring is accompanied by, with the H of 0.15mol/L during mixing2SO4The pH value of system is adjusted to 5 by solution, then drips the Ho (NO that concentration is 0.15g/mL in mixed liquor3)3Aqueous solution, Ho (NO3)3The mol ratio of aqueous solution and potassium alginate is 0.6:1, stirs after dropwising, and the persistent period is 1h, namely obtains load Ho3+The aqueous solution of hybrid material, its mass percent concentration is 2.1%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Ho3+The volume ratio of aqueous solution of hybrid material be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 26 DEG C in temperature, and namely vacuum obtain water solublity load Ho after drying for vacuum drying oven under-0.1MPa condition3+Hybrid material, Ho in this hybrid material3+Load capacity be 246mg/g.
Embodiment 20
A kind of water solublity load Pr3+The preparation method of hybrid material, under 20 DEG C of conditions, by the aqueous solution of polyetheramine D230 that the aqueous solution of sodium polyacrylate that mass percent concentration is 2.9% and mass percent concentration are 4%, the mol ratio of sodium polyacrylate and polyetheramine D230 is 1:0.6, the relative molecular weight of sodium polyacrylate and polyetheramine D230 respectively 30000 and 230, stirring is accompanied by, with the HNO of 0.3mol/L during mixing3The pH value of system is adjusted to 6 by solution, then drips the Pr (NO that concentration is 0.5g/mL in mixed liquor3)3Aqueous solution, Pr (NO3)3Being 3:1 with the mol ratio of sodium polyacrylate, stir after dropwising, the persistent period is 2h, namely obtains load P r3+The aqueous solution of hybrid material, its mass percent concentration is 10.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and load P r3+The volume ratio of the aqueous solution of hybrid material is 4:1, collected by suction precipitate, repeatedly rinses precipitate with ethanol 3 times, and precipitate is 25 DEG C in temperature, and when vacuum is 0.09MPa, namely vacuum drying oven obtains water solublity load Pr after drying3+Hybrid material, Pr in this hybrid material3+Load capacity be 544mg/g.
Claims (10)
1. a hybrid material for water soluble negative carrying metal ion, is characterized in that: in the hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between carboxyl, amino and metal ion；Described carboxyl and amino adhere to molecule A and the strand of molecule B separately；
In described molecule A and described molecule B, carboxyl-content, amino content and hydroxy radical content sum are be more than or equal to the 160% of described molecule A and the mole sum of described molecule B；
The described carboxyl by ionic bond and coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing be more than or equal to the 30% of carboxyl in described molecule A and described molecule B and amino mole sum；
Relative molecular weight >=10000 of described molecule A, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
Relative molecular weight≤5000 of described molecule B, except the O of carboxyl or the N of amino, molecular backbone is mainly made up of C and H；
The general structure of the hybrid material of described water soluble negative carrying metal ion is:
Or
Wherein, strand repetitive number m >=0, n > 0；
R1、R2And R3One in respectively following functional group of functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For metal ion, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Au3+、Cr3+、Zn2+、Pt2+、Pd2+、Cu2+、Ni2+、Cd2+Or it is 3 valency rare earth ions；Described 3 valency rare earth ions are La3+、Ce3+、Eu3+、Er3+、Yb3+、Tm3+、Ho3+Or Pr3+。
2. the hybrid material of a kind of water soluble negative carrying metal ion according to claim 1, it is characterised in that the molecule B with amino also comprises hydroxyl or carboxyl；Molecule B with carboxyl also comprises hydroxyl or amino.
3. the hybrid material of a kind of water soluble negative carrying metal ion according to claim 1, it is characterised in that described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
4. the hybrid material of a kind of water soluble negative carrying metal ion according to claim 1, it is characterised in that the molecular backbone of described molecule A also includes element O, N or S.
5. the hybrid material of a kind of water soluble negative carrying metal ion according to claim 1, it is characterised in that the molecular backbone of described molecule B also includes element O, N or S.
6. the hybrid material of a kind of water soluble negative carrying metal ion according to claim 1, it is characterised in that the load capacity of described metal ion is 10～825mg/g.
7. the preparation method of the hybrid material of a kind of water soluble negative carrying metal ion as according to any one of claim 1～6, it is characterized in that: by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, regulate the pH value of reaction system to 4～6, then in mixed liquor, drip metal ion salt solution, stir after dropwising, obtain the aqueous solution of loaded metal ion hybrid material, continuously stirred and add precipitant, collect by filtration precipitate, after drying precipitate, namely obtain the hybrid material of water soluble negative carrying metal ion；
Intersect containing carboxyl and amino containing molecule A material and the B substance containing molecule, it may be assumed that when the A material containing molecule is containing carboxyl, the B substance containing molecule contains amino；Otherwise, when the A material containing molecule is containing amino, the B substance containing molecule contains carboxyl.
8. the preparation method of the hybrid material of a kind of water soluble negative carrying metal ion according to claim 7, it is characterised in that by the aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, be under 20～60 DEG C of conditions；Stirring is accompanied by during mixing；The pH value regulating reaction system adopts the H of the HCl solution of 0.1～0.3mol/L, 0.05～0.15mol/L2SO4The HNO of solution or 0.1～0.3mol/L3Solution；Metal ion salt solution stirs after dropwising, and the persistent period is 1～2h；Drying precipitate adopts vacuum drying oven to dry.
9. the preparation method of the hybrid material of a kind of water soluble negative carrying metal ion according to claim 7, it is characterised in that the described A material containing molecule be molecule A carboxylic containing molecule A material or molecule A containing amino containing molecule A material；Described molecule A carboxylic containing molecule A material selected from sodium alginate, potassium alginate, sodium carboxymethyl cellulose, potassium carboxymethylcellulose, sodium hydroxyethlcellulose, carboxyethyl cellulose potassium, carboxymethyl chitosan sodium, carboxymethyl chitosan potassium, carboxyetbyl chitosan sodium, carboxyetbyl chitosan potassium, 2, one in 3-bis-sodium carboxymethyl cellulose, 2,3-bis-potassium carboxymethylcellulose, sodium polyacrylate and polyacrylic acid potassium；
The described molecule A A material containing molecule containing amino is chitosan, carboxymethyl chitosan or polyacrylamide；
Described containing molecule B substance be molecule B carboxylic containing molecule B substance or molecule B containing amino containing molecule B substance；
Described molecule B is carboxylic sour less than the alkyl chain of 6 carbon selected from chain length containing molecule B substance, is specially n-butyric acie, positive valeric acid or n-caproic acid；
Described molecule B containing amino containing molecule B substance selected from chain length less than the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, one in aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
Described metal ion salt solution is AgNO3、FeCl2、FeCl3、HAuCl4、Cr2(SO4)3、ZnCl2、PtCl2、PdCl2、CuSO4、Ni(NO3)2、CdCl2Aqueous solution or rare earth ion saline solution；Described rare earth ion saline solution is LaCl3、Ce2(SO4)3、Eu(NO3)3、ErCl3、YbCl3、Tm(NO3)3、Ho(NO3)3Or Pr (NO3)3Aqueous solution；
Described precipitant is ethanol or acetone.
10. the preparation method of the hybrid material of a kind of water soluble negative carrying metal ion according to claim 7, it is characterized in that, when the described aqueous solution containing molecule A material and the aqueous solution containing molecule B substance, it is 1:0.3～1 containing molecule A material and the mol ratio containing molecule B substance；
The described mass percent concentration containing the aqueous solution of molecule A material is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing molecule B substance is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio containing molecule A material；
The mass percent concentration of the aqueous solution of described loaded metal ion hybrid material is 0.5%～10.5%；
The volume ratio of the aqueous solution of the hybrid material of described precipitant and loaded metal ion is 2～4:1；
The temperature of described drying precipitate is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
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| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
| CN109400960A (en) * | 2018-08-28 | 2019-03-01 | 江苏理工学院 | A kind of graphene/nano silver polymer composites and preparation method thereof |
| CN109594144A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | The fused mass directly spinning method of PLA fiber containing metal-modified cross carboxylate |
| CN109629038A (en) * | 2018-12-13 | 2019-04-16 | 上海德福伦化纤有限公司 | Flame-proof polylactic acid fiber and preparation method thereof containing metal-modified cross carboxylate |
| CN109721968A (en) * | 2018-12-13 | 2019-05-07 | 东华大学 | The functional agglomerate and preparation method thereof of the hybridization porous material containing hyperbranched type |
| CN109735062A (en) * | 2018-12-13 | 2019-05-10 | 上海东华镜月资产经营有限公司 | Master batch and preparation method thereof containing cross hybridization porous material |
| CN109749073A (en) * | 2018-12-13 | 2019-05-14 | 东华大学 | The dissaving polymer and preparation method thereof of the easily distributed loaded metal ion of water phase |
| CN109762195A (en) * | 2018-12-13 | 2019-05-17 | 东华大学 | A kind of hybridization porous material of hyperbranched type of metal ion and preparation method thereof |
| CN109810277A (en) * | 2018-12-13 | 2019-05-28 | 上海东华镜月资产经营有限公司 | A kind of cross hybridization porous material of metal ion and preparation method thereof |
| CN109852008A (en) * | 2018-12-13 | 2019-06-07 | 上海东华镜月资产经营有限公司 | Antibacterial fresh-keeping film and preparation method thereof containing cross hybridization porous material |
| CN109912952A (en) * | 2018-12-13 | 2019-06-21 | 东华大学 | The unsaturated polyester resin and preparation method thereof of the hybridization porous material containing hyperbranched type |
| CN110016729A (en) * | 2018-12-13 | 2019-07-16 | 上海德福伦化纤有限公司 | Hollow PLA fiber and preparation method thereof containing metal-modified cross carboxylate |
| CN112979974A (en) * | 2021-02-01 | 2021-06-18 | 攀枝花学院 | ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and preparation method thereof |
-
2016
- 2016-04-28 CN CN201610278050.5A patent/CN105777934B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 花蓓蓓: ""有机/无机杂化可溶型纳米银及其功能材料的构筑与应用开拓"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107855133A (en) * | 2016-09-22 | 2018-03-30 | 中国科学院大连化学物理研究所 | A kind of method for preparing support type little particle Au catalyst |
| CN107855133B (en) * | 2016-09-22 | 2020-09-11 | 中国科学院大连化学物理研究所 | Method for preparing supported small-particle gold catalyst |
| CN109400960A (en) * | 2018-08-28 | 2019-03-01 | 江苏理工学院 | A kind of graphene/nano silver polymer composites and preparation method thereof |
| CN109400960B (en) * | 2018-08-28 | 2020-12-04 | 江苏理工学院 | Graphene/nano-silver polymer composite material and preparation method thereof |
| CN109810277A (en) * | 2018-12-13 | 2019-05-28 | 上海东华镜月资产经营有限公司 | A kind of cross hybridization porous material of metal ion and preparation method thereof |
| CN110016729A (en) * | 2018-12-13 | 2019-07-16 | 上海德福伦化纤有限公司 | Hollow PLA fiber and preparation method thereof containing metal-modified cross carboxylate |
| CN109749073A (en) * | 2018-12-13 | 2019-05-14 | 东华大学 | The dissaving polymer and preparation method thereof of the easily distributed loaded metal ion of water phase |
| CN109762195A (en) * | 2018-12-13 | 2019-05-17 | 东华大学 | A kind of hybridization porous material of hyperbranched type of metal ion and preparation method thereof |
| CN109721968A (en) * | 2018-12-13 | 2019-05-07 | 东华大学 | The functional agglomerate and preparation method thereof of the hybridization porous material containing hyperbranched type |
| CN109852008A (en) * | 2018-12-13 | 2019-06-07 | 上海东华镜月资产经营有限公司 | Antibacterial fresh-keeping film and preparation method thereof containing cross hybridization porous material |
| CN109912952A (en) * | 2018-12-13 | 2019-06-21 | 东华大学 | The unsaturated polyester resin and preparation method thereof of the hybridization porous material containing hyperbranched type |
| CN109735062A (en) * | 2018-12-13 | 2019-05-10 | 上海东华镜月资产经营有限公司 | Master batch and preparation method thereof containing cross hybridization porous material |
| CN109721968B (en) * | 2018-12-13 | 2020-06-12 | 东华大学 | Functional master batch containing hyperbranched hybrid porous material and preparation method thereof |
| CN109629038A (en) * | 2018-12-13 | 2019-04-16 | 上海德福伦化纤有限公司 | Flame-proof polylactic acid fiber and preparation method thereof containing metal-modified cross carboxylate |
| CN109594144A (en) * | 2018-12-13 | 2019-04-09 | 上海德福伦化纤有限公司 | The fused mass directly spinning method of PLA fiber containing metal-modified cross carboxylate |
| CN109735062B (en) * | 2018-12-13 | 2021-01-01 | 上海东华镜月资产经营有限公司 | Master batch containing cross hybrid porous material and preparation method thereof |
| CN110016729B (en) * | 2018-12-13 | 2021-03-23 | 上海德福伦化纤有限公司 | Hollow PLA fiber containing metal modified cross-shaped esterified substance and preparation method thereof |
| CN109810277B (en) * | 2018-12-13 | 2021-07-06 | 上海东华镜月资产经营有限公司 | Cross hybrid porous material containing metal ions and preparation method thereof |
| CN112979974A (en) * | 2021-02-01 | 2021-06-18 | 攀枝花学院 | ZnAl two-dimensional metal hydroxide-chitosan supramolecular hybrid material and preparation method thereof |
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