CN101220154A - Crosslinked polyalcohol membrana body material, method for producing the same and process of using - Google Patents
Crosslinked polyalcohol membrana body material, method for producing the same and process of using Download PDFInfo
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Abstract
The invention relates to a main material of a crosslinking polymer film in the technical field of high molecular material and a preparation method and a using method thereof. Through Michael addition polymerization, the invention obtains hyper branched polyamide containing an end double bond. By the protonation of a tertiary amine unit, the introducing of anion ligand and thermal initiation and self crosslinking of the end double bond, the main material of the crosslinking polymer film can be prepared. The components of the material the contents of the weight percentage are as follows: 12 to 19wt percent of amide group, 17 to 29wt percent of methylene, 2 to 3wt percent of protonated tertiary amine and 52 to 66wt percent of fluoroform sulfonate radical. The material of the invention can not only efficiently enrich object dye molecules from an aqueous solution, but also can efficiently enrich precious metal ions from the aqueous solution and restore the metal ions to be internally embedded metal nanoparticles in position. The invention has simple operation and is environment friendly; therefore, the invention can be applied to the treatment of waste water containing dye, the recycling of precious metal or metal-catalyzing and other fields.
Description
Technical field
The present invention relates to a kind of material and preparation method thereof and using method of technical field of polymer materials, be specifically related to a kind of crosslinked polyalcohol membrana body material based on hyperbranched polymer and preparation method thereof and using method.
Background technology
In the last few years, because the host-guest material shows application prospects at aspects such as molecular recognition, self assembling process, chemical sensors, people grew with each passing day to its research interest.Up to now, obtained the further investigation of academia in a large number based on the host-guest system of cyclodextrin, crown ether, Amphipathilic block polymer and branch-shape polymer.Recently, the host-guest system based on hyperbranched polymer has also caused people's attention.Hyperbranched polymer molecule not only has three-dimensional branched structure, and contains many functional groups and intramolecule hole, and these particular structure features help hyperbranched polymer molecule efficiently in conjunction with the object small molecules; In addition, hyperbranched polymer is synthetic easy.Therefore, research and development are based on the novel host-guest functionalization material of hyperbranched polymer, and meaning is very great.
Find through literature search prior art, people such as Chen are at " Macromolecules " (macromole 2005, V38, P227) delivered " Role of Topology and Amphiphilicity for GuestEncapsulation in Functionalized Hyperbranched Poly (ethylenimine) s " (functional hyperbranched polyethyleneimine is by its topological framework and amphipathic characteristic encapsulation guest molecule) on, propose hyperbranched polymer in this article and sealed the method for water-soluble dye molecule, concrete grammar is: adopt the amphiphilic hyper-branched polymine of palmityl chloride modification, with yellowish eosin, uranine, tropeolin-D or dye molecule such as Congo red are transferred to the polymer molecule internal layer of chloroform phase from water.Its deficiency is: dye molecule needs to enter in the polymkeric substance of organic phase through phase transition, and the use of a large amount of poisonous organic solvents easily causes environmental pollution, and the later separation difficulty of host-guest molecule.P é rignon etc. are at " Chemistry of Materials " (materials chemistry 2004, V16, P4856) delivered " Formation and Stabilization in Water of MetalNanoparticles by a Hyperbranched Polymer Chemically Analogous to PAMAMDendrimers " (in water, generating and the stable metal nanoparticle) on by the hyperbranched polymer of a kind of similar in the PAMAM branch-shape polymer, propose hyperbranched polymer in this article and sealed the method for nano metal, concrete grammar is: adopt a kind of aqueous solution of over-branched polyamidoamine to mix with hydrochloro-auric acid, form polymkeric substance/Au
3+Complex system, then under the effect of sodium borohydride, Au
3+By in-situ reducing and obtain the nanometer gold aqueous dispersions.Its deficiency is: at the package metals ion and prepare in the process of metal nanoparticle, need add and go back original reagent, be unfavorable for environmental protection and energy saving.In addition, the over-expense polymkeric substance generally is difficult to make stable mould material and is used owing to lack intensity, and in the process of realization to the encapsulation of guest molecule, the solution that need be made into polymkeric substance is used, and the product separation difficulty, brings inconvenience to practical application.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of crosslinked polyalcohol membrana body material and preparation method thereof and using method are provided.The present invention is directed to hyperbranched polymer distinctive molecular structure feature, it is applied to the advantage and the deficiencies in the prior art part of object encapsulation, by molecular designing and chemical modification, prepared a kind of stable crosslinked polyalcohol membrana body material based on hyperbranched polymer, this polyalcohol membrana body material can not only be from the aqueous solution efficiently concentrating object dye molecule, can also be from the aqueous solution effective enriching precious metal ion and its in-situ reducing generated embedded metal nanoparticle.
The present invention is achieved by the following technical solutions:
Crosslinked polyalcohol membrana body material involved in the present invention is based on the crosslinked polyalcohol membrana body material of hyperbranched polymer.At first by the Michael addition polyreaction, a synthetic class contains the terminal double bond over-branched polyamidoamine, introduce and terminal double link thermal initiation self-crosslinking by, anion ligand protonated then, prepare a kind of stable crosslinked polyalcohol membrana body material tertiary amine unit in this base polymer.This polymeric film possesses three-dimensional cross-linked network structure, contains a large amount of inner cavities and branching microstructure, and by many amide groups, methylene radical, protonated tertiary amine and trifluoromethanesulfonic acid root (Tf
2N
-) form, the weight percent content of each component is: amide group 12%-19%, methylene radical 17%-29%, protonated tertiary amine 2%-3%, trifluoromethanesulfonic acid root 52%-66%.
Crosslinked polyalcohol membrana body material of the present invention is uniform faint yellow transparent film, and its concrete parameter is: thickness 100 μ m-500 μ m, water-intake rate 5%-15%, tensile strength 10MP-50MP, storage modulus 0.8GPa-2.0GPa.
The preparation method of crosslinked polyalcohol membrana body material involved in the present invention may further comprise the steps:
Step a: with vinyl monomer and amine monomer in molar ratio 1.8: 1-2.2: 1 feeds intake, in polar solvent, carry out polyaddition reaction, afterwards reaction system is revolved that inspissation contracts, washing of precipitate, drying, obtain containing the terminal double bond over-branched polyamidoamine, productive rate 92-97%.
Described vinyl monomer is N,N methylene bis acrylamide or N, N '-two (third rare acyl) cystamine;
Described amine monomer is 1-(2-amine ethyl) piperazine, 4-amine methyl piperidine, N-methyl ethylenediamine, N-ethylethylenediamine, N-hexyl quadrol or N-methyl isophthalic acid, a kind of in the 3-propylene diamine;
Described polar solvent is meant water, methyl alcohol, ethanol, N, a kind of in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the N-Methyl pyrrolidone;
Described polyreaction, temperature of reaction are 0 ℃-60 ℃, and the reaction times is 24 hours-120 hours;
Described washing of precipitate is meant with acetone, ether or both mixed solvent washings of precipitate.
Step b: gained is contained the terminal double bond over-branched polyamidoamine be made into the aqueous solution, nitric acid is dropwise added solution to acid, dropwise add trifluoromethanesulfonic acid lithium (LiTf
2N) aqueous solution, stirring reaction, standing over night is collected bottom settlings, and washing, drying get the white powder shaped polymer, productive rate 87-94% repeatedly.
The described terminal double bond over-branched polyamidoamine aqueous solution that contains, its weight percent concentration is 5%-15%;
Described nitric acid is dropwise added solution to acid, be meant that pH value of solution reaches 2.0-3.0;
Described nitric acid, its concentration are 10mol/L-15.9mol/L;
The described trifluoromethanesulfonic acid lithium aqueous solution, its weight percent concentration is 15%-25%, add-on is 10 times-50 times of nitric acid volume;
Described reaction was meant normal-temperature reaction 1 hour-5 hours.
Step c: white powder shaped polymer among the step b is made into acetone soln, it slowly is poured on the clean glass plate of level, treats that solvent evaporates finishes, it is carried out crosslinking reaction under vacuum state, naturally cooling, the demoulding obtain stable crosslinking polymer film.
The acetone soln of described white powder shaped polymer, its volume percent are 3%-8%;
Described crosslinking reaction, temperature of reaction are 120 ℃-180 ℃, and the reaction times is 3 hours-10 hours.
The using method of crosslinked polyalcohol membrana body material involved in the present invention is meant application and the application in the precious metal ion enrichment in the dye molecule enrichment.
The using method of described crosslinked polyalcohol membrana body material in the dye molecule enrichment may further comprise the steps:
Step a: described polymeric film is immersed aqueous dye solutions, and room temperature leaves standstill, and dyestuff is aggregated the enrichment gradually of thing film in this process, and final bioaccumulation efficiency all reaches more than 98%, and dye liquor becomes colorless.
Described polymeric film immerses aqueous dye solutions, and the film consumption is 0.5g film/L dye liquor-2g film/L dye liquor;
Described room temperature leaves standstill, and is meant that room temperature left standstill 48 hours-72 hours;
Described dyestuff comprises water-soluble dyes such as C.I. weak acid dye, Congo red, tropeolin-D, Methylene blue, tetrabromophenol sulfonphthalein, tiger are red, phloxine, tetrabromofluorescein, uranine, and concentration is 0.1g/L-0.3g/L;
Described C.I. weak acid dye, be meant according to the red A-2BF of Neil, active emerald green blue KN-G, according to the yellow A-3G of Neil, orchid receive free and easy green B, according to the black AM-R of Neil, according to the purple A-B of Neil, according to pake purpke etc.
Step b: with enrichment the polymeric film of dyestuff take out, behind deionized water rinsing, immerse concentrated ammonia solution, room temperature leaves standstill, dyestuff is discharged into from polymeric film in the ammonia soln gradually, faint yellow uniformly transparent regeneration membrane.
Described concentrated ammonia solution, its consumption are 200mL/g film-300mL/g film;
Described room temperature leaves standstill, and its time is 12 hours-24 hours.
Step c: with the a-b repetitive operation set by step of this regeneration membrane, its dyestuff bioaccumulation efficiency is still greater than 98%.
Crosslinked polyalcohol membrana body material involved in the present invention using method in the precious metal ion enrichment may further comprise the steps:
Described polymeric film immersion is contained in the aqueous solution of precious metal ion compound, leave standstill, metal ion quilt enrichment gradually enters the inner and even embedded metal nanoparticle of in-situ reducing generation of film.
Described polymeric film consumption is 5g/L-10g/L;
The described compound that contains precious metal ion comprises Silver Nitrate, hydrochloro-auric acid, Palladous chloride, potassium palladichloride, Platinic chloride, potassium platinichloride etc., and concentration is 0.1mol/L-3.0mol/L;
Described leaving standstill is meant and left standstill under 20 ℃-60 ℃ 12 hours-72 hours.
Effect of the present invention and benefit are: introduce and terminal double link thermal initiation self-crosslinking by, anion ligand protonated to the tertiary amine unit in the over-branched polyamidoamine, prepare uniform and stable crosslinked polyalcohol membrana body material, its novel structure, and can prepare in a large number.This crosslinked polyalcohol membrana body material can be from the aqueous solution of dyestuff the efficiently concentrating dye molecule, bioaccumulation efficiency is up to more than 98%; Behind the enrichment dyestuff, the renewable and repeated use of this polymeric film.This crosslinked polyalcohol membrana body material can also be from the aqueous solution that contains precious metal ion effective enriching precious metal ion, and its in-situ reducing generated evenly embedded metal nanoparticle, the metal nanoparticle size is several nanometers to tens nanometer.This polyalcohol membrana body material is used easy, only can make object dye molecule or the effective enrichment of precious metal ion by " immersion " method, and need not to use highly toxic organic solvent in the use or add and go back original reagent, possesses eco-friendly characteristics.Therefore, this class crosslinking polymer mould material can be applicable to fields such as the recovery of processing, noble metal of waste water containing dye or metal catalytic.
Description of drawings
The schematic arrangement of the crosslinked polyalcohol membrana body material of Fig. 1: embodiment 1 preparation.
The crosslinked polyalcohol membrana body material (a) of Fig. 2: embodiment 1 preparation and the infrared spectrum of crosslinked preceding hyperbranched polymer (b).
The crosslinked polyalcohol membrana body material (a) of Fig. 3: embodiment 1 preparation and the differential heat scan spectrogram of crosslinked preceding hyperbranched polymer (b).
Tensile stress-the strain figure of the crosslinked polyalcohol membrana body material of Fig. 4: embodiment 1 preparation.
The thermogravimetric analysis and the cross-sectional scans Electronic Speculum figure of (b) after the crosslinked polyalcohol membrana body material (a) of Fig. 5: embodiment 1 preparation and the enrichment nanometer silver thereof.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, and the case study on implementation that describes in detail below is to further specify of the present invention, rather than limits the scope of the invention.
Preparation based on the crosslinked polyalcohol membrana body material of hyperbranched polymer, realize by following examples:
Embodiment 1:
Is to feed intake at 2: 1 N,N methylene bis acrylamide and 1-(2-amine ethyl) piperazine according to mol ratio, under 50 ℃ in deionized water polyreaction 150 hours, the acetone precipitation washing, 40 ℃ of following vacuum-dryings obtain containing the terminal double bond over-branched polyamidoamine.Take by weighing gained and contain terminal double bond over-branched polyamidoamine 2.0g, be made into the aqueous solution of 10wt%, (15.9mol/L) dropwise is added to pH value of solution=3.0 with nitric acid, dropwise add the 20mL mass percent concentration and be 20% the trifluoromethanesulfonic acid lithium aqueous solution, stirring at normal temperature reaction 2 hours, standing over night is collected bottom settlings, washing, drying get the white powder shaped polymer repeatedly.It is 5% acetone soln that this white powder shaped polymer is made into concentration of volume percent, get on the clean glass plate of level that 4mL slowly is poured into 10 * 10cm, treat that solvent evaporates finishes, with it in 160 ℃ of following vacuum crosslinking reactions 6 hours, naturally cooling, the demoulding obtain crosslinked polyalcohol membrana body material then.
The schematic arrangement of gained crosslinking polymer film is seen accompanying drawing 1, and it possesses three-dimensional cross-linked network structure, contains a large amount of inner cavities and branching microstructure, and by many amide groups, methylene radical, protonated tertiary amine unit and trifluoromethanesulfonic acid root (Tf
2N
-) form, its weight percent content is respectively 14%, 17%, 4%, 65%.This crosslinking polymer film proves its structure and character through infrared spectra, differential heat scan and stretching experiment, and embodiment the results are shown in accompanying drawing 2-4.From Fig. 2 (a) infrared spectrum of cross-linked polymer film as can be seen, this film is 1350,1196,1134 and 1056cm
-1The absorption peak at place corresponds respectively to v
aSO
2, v
aCF
3, v
sSO
2And v
aNS; In addition, from Fig. 2 (b) as can be seen, crosslinked preceding hyperbranched polymer is at 1615cm
-1There is the absorption peak (v that obviously belongs to vinyl at the place
aC=C), and among Fig. 2 (a) in the cross-linked polymer film this peak disappear, show in this crosslinking polymer film the two keys of noresidue.Differential heat scan spectrogram from Fig. 3 as can be seen, hyperbranched polymer before crosslinked has a tangible glass transition peak at 47 ℃, locate an exothermic peak that significantly causes at 135 ℃ because of thermal initiation is crosslinked, and the no obvious neither endothermic nor exothermic peak in whole Range of measuring temp of the polymeric film after crosslinked illustrates that this polymeric film possesses good thermostability.Stress-strain curve from Fig. 4 as can be seen, the tensile strength of this polymeric film is 9.2MPa, shows that it possesses favorable mechanical stability.
Based on the application of crosslinked polyalcohol membrana body material in the dyestuff enrichment of hyperbranched polymer, realize among the present invention by following examples:
Embodiment 2:
With the described crosslinking polymer film based on N,N methylene bis acrylamide and 1-(2-amine ethyl) piperazine gained of 0.2g immerse 0.3g/L according in the red A-2BF aqueous dye solutions of Neil, the polymeric film consumption is 1g film/L dye liquor.Under the room temperature this system is left standstill, dyestuff is aggregated the enrichment of thing film gradually, and the dyestuff bioaccumulation efficiency reaches 99.3% after 48 hours, and dye liquor becomes colorless.With enrichment the polymeric film of dyestuff take out, the water flushing is immersed in the 50mL strong aqua, room temperature was placed 12 hours, dyestuff is discharged into from polymeric film in the solution gradually, obtains regeneration membrane.This regeneration membrane is reused 4 times, and it still is 98.5% to the bioaccumulation efficiency according to the red A-2BF of Neil.
Embodiment 3:
0.2g is described based on N, N-methylene-bisacrylamide and N-methyl isophthalic acid, 3-propylene diamine gained crosslinking polymer film (weight percent content of amide group, methylene radical, protonated tertiary amine and trifluoromethanesulfonic acid root is respectively 19%, 18%, 3%, 60%) immerses in the methyl orange aqueous solution of 0.2g/L, film consumption 1g film/L dye liquor.Under the room temperature this system is left standstill, tropeolin-D is aggregated the enrichment of thing film gradually, and the bioaccumulation efficiency of tropeolin-D reaches 99.2% after 48 hours, and solution becomes colorless.With enrichment the polymeric film of tropeolin-D take out, the 50mL strong aqua is immersed in the water flushing, room temperature was placed 12 hours, tropeolin-D is discharged into from polymeric film in the solution gradually, obtains regeneration membrane.This regeneration membrane is reused 4 times, and its bioaccumulation efficiency to methyl orange dye still is 98.3%.
Based on the application of crosslinking polymer mould material in the enriching precious metal ion of hyperbranched polymer, realize among the present invention by following examples:
Embodiment 4:
Take by weighing the crosslinking polymer film of 0.1g based on N,N methylene bis acrylamide and 1-(2-amine ethyl) piperazine, immersing 10mL concentration is in the silver nitrate aqueous solution of 3.0mol/L, at room temperature leaves standstill 48 hours.In the process of leaving standstill, silver ions quilt enrichment gradually enters the inner and in-situ reducing generation simple substance silver of film.
The polymeric film of gained enrichment silver reflects its microscopic appearance and character through scanning electron microscope and thermogravimetric analysis, and embodiment the results are shown in accompanying drawing 5.Sem photograph from Fig. 5 as can be seen, polymeric film is after enrichment silver, many silver nano-grains evenly are embedded in polymeric film inside, size of particles is several nanometers to tens nanometer.By comparing the enrichment silver thermal weight loss test result of polymeric film under 800 ℃ before, the enriching quantity that draws silver in this polymeric film is about 16wt%.
Embodiment 5:
Take by weighing 0.1g based on N, the crosslinking polymer film (weight percent content of amide group, methylene radical, protonated tertiary amine and trifluoromethanesulfonic acid root is respectively 16%, 29%, 3%, 52%) of N '-two (third rare acyl) cystamine and N-hexyl quadrol, immersing 10mL concentration is in the aqueous solution of chloraurate of 0.5mol/L, at room temperature places 48 hours.In the process of leaving standstill, gold ion quilt enrichment gradually enters the inner and in-situ reducing generation simple substance gold of film.Scanning electron microscope observation is several nanometers to tens nanometer to the gold nano grain diameter, and evenly is embedded in film inside.The thermal weight loss test result shows that the enriching quantity of gold in this polymeric film is about 13wt%.
Embodiment 6:
Take by weighing 0.1g based on N, the crosslinking polymer film of N-methylene-bisacrylamide and N-methyl ethylenediamine (weight percent content of amide group, methylene radical, protonated tertiary amine and trifluoromethanesulfonic acid root is respectively 18%, 22%, 3%, 57%), immersing 10mL concentration is in the Palladous chloride aqueous dispersions of 0.1mol/L, at room temperature leaves standstill 48 hours.In the process of leaving standstill, palladium ion quilt enrichment gradually enters the inner and in-situ reducing generation simple substance palladium of film.Scanning electron microscope observation is several nanometers to tens nanometer to the palladium nano-particles diameter, and evenly is embedded in film inside.The thermal weight loss test result shows that the enriching quantity of palladium in this polymeric film is about 8wt%.
Claims (10)
1. a crosslinked polyalcohol membrana body material is characterized in that, the component and the weight percent content that are comprised are respectively: amide group 12%-19%, methylene radical 17%-29%, protonated tertiary amine 2%-3%, trifluoromethanesulfonic acid root 52%-66%.
2. crosslinked polyalcohol membrana body material according to claim 1, it is characterized in that, possesses three-dimensional cross-linked network structure, contain a large amount of inner cavities and branching microstructure, be uniform faint yellow transparent film, the concrete parameter of polymeric film is: thickness 100 μ m-500 μ m, water-intake rate 5%-15%, tensile strength 10MP-50MP, storage modulus 0.8GPa-2.0GPa.
3. the preparation method of a crosslinked polyalcohol membrana body material as claimed in claim 1 is characterized in that, may further comprise the steps:
Step a: with vinyl monomer and amine monomer in molar ratio 1.8: 1-2.2: 1 feeds intake, and carries out polyaddition reaction in polar solvent, revolves that inspissation contracts, washing of precipitate, drying, must contain the terminal double bond over-branched polyamidoamine;
Step b: gained is contained the terminal double bond over-branched polyamidoamine be made into the aqueous solution, dropwise add nitric acid, dropwise add the trifluoromethanesulfonic acid lithium aqueous solution then to acid, stirring reaction, standing over night is collected bottom settlings, washing, drying get the white powder shaped polymer repeatedly;
Step c: gained white powder shaped polymer is made into acetone soln, it slowly is poured on the clean glass plate of level, treats that solvent evaporates finishes, it is carried out crosslinking reaction under vacuum state, naturally cooling, the demoulding obtain stable crosslinking polymer film.
4. the preparation method of crosslinked polyalcohol membrana body material according to claim 3 is characterized in that, among the step a, described vinyl monomer is N,N methylene bis acrylamide or N, N '-two (third rare acyl) cystamine;
Described amine monomer is 1-(2-amine ethyl) piperazine, 4-amine methyl piperidine, N-methyl ethylenediamine, N-ethylethylenediamine, N-hexyl quadrol or N-methyl isophthalic acid, a kind of in the 3-propylene diamine;
Described polar solvent is meant water, methyl alcohol, ethanol, N, a kind of in dinethylformamide, N,N-dimethylacetamide, methyl-sulphoxide or the N-Methyl pyrrolidone;
Described polyreaction, its temperature of reaction are 0 ℃-60 ℃, and the reaction times is 24 hours-120 hours;
Described washing of precipitate is meant with acetone, ether or both mixed solvent washings of precipitate.
5. the preparation method of crosslinked polyalcohol membrana body material according to claim 3 is characterized in that, among the step b, and the described terminal double bond over-branched polyamidoamine aqueous solution that contains, its weight percent concentration is 5%-15%;
The described nitric acid that dropwise adds is meant that to acid the pH value of solution value reaches 2.0-3.0;
Described nitric acid, its concentration are 10mol/L-15.9mol/L;
The described trifluoromethanesulfonic acid lithium aqueous solution, its weight percent concentration is 15%-25%, add-on is 10 times-50 times of nitric acid volume;
Described stirring reaction was meant normal-temperature reaction 1 hour-5 hours.
6. the preparation method of crosslinked polyalcohol membrana body material according to claim 3 is characterized in that, described white powder shaped polymer is made into acetone soln, and its volume percent content is 3%-8%;
Described crosslinking reaction, its temperature of reaction are 120 ℃-180 ℃, and the reaction times is 3 hours-10 hours.
7. the using method of a crosslinked polyalcohol membrana body material as claimed in claim 1 in the dye molecule enrichment is characterized in that, the application of described crosslinked polyalcohol membrana body material in the dye molecule enrichment may further comprise the steps:
Step a: described polymeric film is immersed in the aqueous solution of dyestuff, room temperature leaves standstill, and dyestuff is aggregated the enrichment gradually of thing film in this process, and final bioaccumulation efficiency all reaches more than 98%, and dye liquor becomes colorless;
Step b: with enrichment the polymeric film of dyestuff take out, behind deionized water rinsing, immerse concentrated ammonia solution, room temperature leaves standstill, dyestuff is discharged into from polymeric film in the ammonia soln gradually, obtains regeneration membrane;
Step c: with the a-b repetitive operation set by step of this regeneration membrane, its dyestuff bioaccumulation efficiency is still greater than 98%.
8. the using method of crosslinked polyalcohol membrana body material according to claim 7 in the dye molecule enrichment is characterized in that, among the step a, described polymeric film consumption is 0.5g film/L dye liquor-2g film/L dye liquor;
Described room temperature leaves standstill, and is meant that room temperature left standstill 48 hours-72 hours;
Described dyestuff is meant a kind of in the water-soluble dyes such as C.I. weak acid dye, Congo red, tropeolin-D, Methylene blue, tetrabromophenol sulfonphthalein, tiger are red, phloxine, tetrabromofluorescein, uranine, and dye strength is 0.1g/L-0.3g/L;
Described C.I. weak acid dye, be meant according to the red A-2BF of Neil, active emerald green blue KN-G, according to the yellow A-3G of Neil, orchid receive free and easy green B, according to the black AM-R of Neil, according to the purple A-B of Neil, a kind of according in pake purpke;
Among the step b, described room temperature leaves standstill, and its time is 48 hours-72 hours;
Described concentrated ammonia solution, its consumption are 200mL/g film-300mL/g film;
Described room temperature leaves standstill, and its time is 12 hours-24 hours.
9. the using method of a crosslinked polyalcohol membrana body material as claimed in claim 1 in the precious metal ion enrichment, it is characterized in that, be specially: described polymeric film immersion is contained in the aqueous solution of precious metal ion compound, leave standstill, metal ion quilt enrichment gradually enters the inner and in-situ reducing generation even metal nano particle of film.
10. the using method of crosslinked polyalcohol membrana body material according to claim 9 in the precious metal ion enrichment is characterized in that described polymeric film consumption is 5g/L-10g/L;
The described compound that contains precious metal ion is meant in Silver Nitrate, hydrochloro-auric acid, Palladous chloride, potassium palladichloride, Platinic chloride, the potassium platinichloride a kind ofly, and concentration is 0.1mol/L-3.0mol/L;
Described leaving standstill is meant at 20 ℃-60 ℃ and placed 12 hours-72 hours down.
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