CN102430435A - Multifunctional chelating ion-exchange fibers, and preparation method and application thereof - Google Patents
Multifunctional chelating ion-exchange fibers, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides multifunctional chelating ion-exchange fibers. According to the invention, natural cotton fibers, fibrilia, natural wood fibers, natural bamboo fibers or natural grass fibers, or blend fibers of one selected from the group consisting of atural cotton fibers, fibrilia, natural wood fibers, natural bamboo fibers or natural grass fibers and one selected from the group consisting of polypropylene fibers, acrylic fibers, vinylon, terylene and spandex are used as a fiber based material; the fiber based material is dipped in amino-containing resin emulsion so as to prepare functional fibers whose surface is coated with tertiary amino-containing resin; the tertiary amine functional fibers sequentially react with 5-chloromethyl salicylaldehyde and thiosemicarbazide, and therefore, quaternary ammonium groups and salicylaldehyde thiosemicarbazone are introduced onto the functional fibers which become the multifunctional chelating ion-exchange fibers.
Description
Technical field
The present invention relates to a kind of chelating ion exchange fiber, particularly the ion-exchange fibre that forms of chelating resin coated fiber has detection, analysis, separation, enrichment and function of exchange to various water system ions, belongs to field of functional materials.
Technical background
Ion-exchange fibre be on the fiber reinforcement with cation or anionic group through anion or cation sites in Coulomb attraction and the medium, produce respectively and adsorb and separation function.Chelate fibre is to form coordinate bond by the chelating function group of N that substrate fiber has, O, S, P coordination atom and metal ion, constitutes complex, thereby produces detection, analysis, separation, enrichment function to metal ion.Chelate fibre has more rich functions group and more single-minded selectivity than ion-exchange fibre.Some chelate fibres also have abundant ion-exchange group, and anion or cationic absorption are also had high selectivity, are referred to as the chelating ion exchange fiber.The chelating ion exchange fiber grows up on ion exchange resin or chelating resin; Compare with conventional particles shape ion exchange resin or chelating resin; The chelating ion exchange fiber has particular performances and characteristics: the diameter of (1) fiber is much smaller than particulate resin, therefore specific area is obviously greater than particulate resin; The adsorption rate of chelating ion exchange fiber is than fast several times of corresponding granular resin, and elution speed is also significantly greater than resin.(2) use the form free degree big, the chelating ion exchange fiber has various ways, and like yarn, fabric, non-weaving cloth etc., but machine-shaping is variforms such as bunchy, paper, felt, and applying flexible is applicable to the ionic adsorption process of various different modes.(3) the chelating ion exchange fiber also has fabulous osmotic stability, can repeatedly use under the dried repeatedly wet condition.And ion exchange resin must be kept in the water in use repeatedly, does repeatedly wetly can cause subsiding of pore structure.(4) the chelating ion exchange fiber can both use at liquid and gas, fluid resistance is little.
The preparation method of chelating ion exchange fiber mainly contains two kinds; At first through the functional group on the substrate fiber; Carry out chemical modification like cyanic acid, hydroxyl, amino etc. and be converted into oxime, carboxyl, sulfydryl, polyamino or schiff bases etc., make substrate fiber have ion adsorption capacity.Existing common chelating ion exchange fiber mainly is to be the chemical modification functional fibre of base material with polyacrylonitrile fibre and string cellulose fiber.But natural fiber or synthetic fibers are through after the chemical modification, and some mechanical performances have obvious degradation phenomena, influence the processing characteristics and the serviceability of chelating ion exchange fiber.Next is the copolymerization of the functional monomer and second monomer, and functional monomer obtains the chelating ion exchange fiber through spinning again to the graft copolymerization of base material, or functional monomer is to the graft copolymerization of substrate fiber.But functional monomer mostly is the synthetic technology complicacy or costs an arm and a leg that the functional group part of the chelating ion exchange fiber that spinning obtains is hidden at fibrous inside or skewness, causes the waste of functional monomer.
The technology of preparation chelating ion exchange fiber also has the mixed fiber method, and a kind of is that functional mass is distributed in the fine spinning solution, makes the chelating ion exchange fiber through operations such as coating, curing; Another kind is that functional resin and general polymer blend spinning are made the chelating ion exchange fiber.The functional mass that the mixed fiber technology can be used is rare, and functional resin is difficult to bear the condition technology of spinning, causes mixed fiber technology preparation chelating ion exchange fiber rare.Function singleness, hydrophily is little, technology of preparing is complicated, cost of material is high, to recycle loaded down with trivial details etc. also be the defective of existing chelating ion exchange fiber to desorption and regeneration.
In view of above problem; The present invention designs a kind of multi-functional chelating ion exchange fiber; Described multi-functional chelating ion exchange fiber is that the blend fibre that forms with string, protein fibre, aftergrowth fiber or string and protein fibre and synthetic fibers blending is a substrate fiber; Described substrate fiber floods in the amine resin emulsion, makes the tertiary amine functional fibre of surface-coated amine resin; Then described tertiary amine functional fibre reacts with 5-chloromethyl salicylide and amino-compound successively, thereby on functional fibre, introduces quaternary ammonium group and two kinds of construction units of salicylidene amino-compound, becomes multi-functional chelating ion exchange fiber.
Summary of the invention
The present invention provides a kind of multi-functional chelating ion exchange fiber, it is characterized in that: fiber surface coating functions resin, and two kinds of functional groups of said functional resin bonding quaternary ammonium group and salicylidene amino-compound have the chelating ion function of exchange; Said multi-functional chelating ion exchange fiber is through substrate fiber surface-coated amido functional resin; Obtain the tertiary amine functional fibre; After this, the tertiary amine functional fibre is processed with the necleophilic reaction of 5-chloromethyl salicylide and with the condensation reaction of amino-compound successively.
The concrete preparation method of multi-functional chelating ion exchange fiber provided by the invention comprises the steps:
The preparation of step 1, tertiary amine functional fibre
Under the room temperature, substrate fiber pads in the amine resin emulsion, after the coating evenly, extracts fiber out, and drying makes the tertiary amine functional fibre; Also available natural fiber is immersed in the amine resin emulsion, applies evenly, extracts fiber out, after the drying, makes the tertiary amine functional fibre with the synthetic fibers blending.
Wherein said substrate fiber is selected from one or more union twist yarn yarns in cotton fiber, flaxen fiber, bamboo fibre, wood-fibred, grass fiber, polypropylene fibre, polyvinyl chloride fibre, acrylic fibers, polyamide fibre, vinylon, terylene or the spandex.Described natural fiber is selected from one or more union twist yarn yarns in cotton fiber, flaxen fiber, bamboo fibre, wood-fibred or the grass fiber.With cotton, bast yarn and thread, cotton/hemp blended yarn, cotton or fiber crops and synthetic fibers scribbled optimum as the substrate fiber raw material.
Described amine resin emulsion is carried out emulsion polymerisation by function monomer and second olefinic monomer and crosslinking agent and is made.
Described function monomer is selected from one or more in dimethylaminoethyl acrylate, acrylic acid lignocaine ethyl ester, acrylic acid dipropyl amino ethyl ester, acrylic acid dibutylamino ethyl ester, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid dipropyl amino ethyl ester, methacrylic acid dibutylamino ethyl ester, N-(2-dimethylamino) ethyl-2-Methacrylamide or N-(2-dimethylamino) ethyl acrylamide.
Described second olefinic monomer is selected from one or more in styrene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, EMA, butyl methacrylate, maleic anhydride or the vinylacetate.
Described crosslinking agent is selected from one or more in divinylbenzene, two acrylic acid glycol ester, methacrylate glycol ester, isocyanuric acid three propylene esters or the dimethyl diallyl ammonium chloride.
The quality proportioning of said function monomer/second olefinic monomer/crosslinking agent is 3～300: 100: 2～50.
Described amine resin emulsion preparation method is selected from Xu Zhongping's " the emulsion copolymers study on the synthesis that contains amine functional monomer " Master's thesis (University Of Tianjin, 2003).
The preparation of step 2, quaternary ammonium group functional fibre
The tertiary amine functional fibre that step 1 is made is immersed in the solvent that contains 5-chloromethyl salicylide, reacts under the room temperature 4～48 hours, leaches fiber, and solvent wash makes quaternary amine base functional fibre.
Wherein said solvent refers to toluene, chlorobenzene, methyl phenyl ethers anisole, xylenes, benzinum, cyclohexane, hexahydrotoluene or decahydronaphthalene; The consumption of solvent is 2～10 times of said tertiary amine functional fibre quality, and described 5-chloromethyl salicylide consumption is 0.5～5 times of said tertiary amine functional fibre quality.
The preparation of step 3, multi-functional chelating ion exchange fiber
The quaternary ammonium group functional fibre that step 2 is made is immersed in the solvent that contains amino-compound, and 20～90 ℃ of temperature controls reacted 2～200 hours, leached fiber, solvent wash, and drying makes multi-functional chelating ion exchange fiber.
Wherein said amino-compound refers to one or more in azanol, hydrazine, 2-pyridine formylhydrazine, 3-cumarin formylhydrazine, 7-lignocaine 3-cumarin formylhydrazine, ethylenediamine, diethylenetriamine, o-phenylenediamine, p-phenylenediamine (PPD), o-aminophenol, ortho-aminobenzoic acid, thiosemicarbazides, 2-aminopyridine, 2-amido benzothiazole, 2-aminooimidazole, glycine, alanine or the cysteine, and the consumption of said amino-compound is 0.25～2.5 times of said quaternary ammonium group functional fibre quality.
Described solvent refers to water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, acetate or formic acid, and the consumption of solvent is 2～10 times of said quaternary ammonium group functional fibre quality.
The beneficial effect of multi-functional chelating ion exchange fiber provided by the invention is:
The mechanical performance of multi-functional chelating ion exchange fiber 1. provided by the invention (fracture strength, fatigue strength, the intensity that circumnutates, hot strength) is compared former base material fiber and is improved significantly.
2. the substrate fiber for preparing multi-functional chelating ion exchange fiber according to the invention is not limited by looks, comprises that circular fiber, doughnut, heterotypic fibre, superfine fibre all can be used as the substrate fiber raw material.
The ion-exchange sites of multi-functional chelating ion exchange fiber 3. according to the invention and chelating center evenly distribute on the fiber base material surface, and are exposed to the top layer of multi-functional chelating ion exchange fiber all, and be fast to the absorption and the desorption rate of ion thus.
4. the salicylidene amino-compound construction unit in the multi-functional chelating ion exchange fiber according to the invention is a kind of three tooth chelands, can form that color and luster is different with multiple metal ion, fluorescent emission or the totally different complex supramolecular system of fluorescent quenching character.It is qualitative detection species of metal ion and valence state that the professional knows such as salicylidene thiosemicarbazides, salicylidene ortho-aminobenzoic acid etc., the fluorescence analysis reagent of concentration of metal ions in the quantitative analysis aqueous solution.The present invention will be such as salicylidene thiosemicarbazides, salicylidene ortho-aminobenzoic acid analytical reagent producing high-molecular, and purpose is to introduce analytical reagent at fiber surface, as the real-time in-situ monitoring material of metal ion in the water body.
5. the quaternary ammonium group in the multi-functional chelating ion exchange fiber according to the invention is a kind of anion exchange groups, so multi-functional chelating ion exchange fiber according to the invention has the anion exchange function.
6. multi-functional chelating ion exchange fiber according to the invention is in alkaline aqueous solution (comprising sodium hydrate aqueous solution, potassium hydroxide aqueous solution, ammonium hydroxide aqueous solution, aqueous sodium carbonate, wet chemical); Can be converted into the inner salt structure; Can with alkaline-earth metal ions or transition metal ions bonding; Use nitric acid, hydrochloric acid, vulcanized sodium, NaHS etc. can wash desorption; Said alkaline-earth metal ions or transition metal ions enriching and recovering, multi-functional chelating ion exchange fiber of the present invention also are able to regeneration, so multi-functional chelating ion exchange fiber according to the invention has the cation exchange function.
The heat endurance of multi-functional chelating ion exchange fiber 7. according to the invention is high, mechanical stability is high, reuses not receive to store and does wet condition restriction, recycles convenient and safe.
8. the substrate fiber raw material source for preparing multi-functional chelating ion exchange fiber according to the invention is wide, and the amine resin emulsion preparation is convenient, technical maturity, and 5-chloromethyl salicylide and thiosemicarbazides are the commercial goods, production technology is easy, and is nontoxic, pollution-free.
9. multi-functional chelating ion exchange fiber provided by the invention is totally different with the complex colour developing of different heavy metal ion, can conclude said multifunction ion exchange fiber adsorption and enrichment heavy metal ion saturation state in view of the above.Convenient absorption or the desorption manipulation implemented.
Specific embodiment
Through following embodiment multi-functional chelating ion exchange fiber provided by the invention and preparation method thereof is further specified, its purpose is to understand better content of the present invention.Therefore, unlisted multi-functional chelating ion exchange fiber and preparation method thereof should not be regarded as the restriction to protection domain of the present invention among the embodiment.Any improvement to multi-functional chelating ion exchange fiber provided by the invention all belongs to the intellectual property aggressive behavior.
The preparation of embodiment 1 multi-functional chelating ion exchange cotton thread (1)
The preparation of step 1, tertiary amine function cotton thread
Commercially available 18S true qualities slubbing cotton single-yarn 100 grams were soaked the amine resin emulsion of being processed in ratio emulsion copolymerization in 50: 40: 10 by butyl methacrylate/dimethylaminoethyl methacrylate/methacrylate glycol ester; Extract the cotton thread that evenly applies emulsion out; Oven dry; Weightening finish 113 grams make tertiary amine groups function cotton thread.
The preparation of step 2, quaternary ammonium group function cotton thread
Tertiary amine groups function cotton thread 100 grams that step 1 is made immerse in 300 milliliters of toluene that contain 5-chloromethyl salicylide 56 grams, and reaction is 24 hours under the room temperature, extracts cotton thread out, toluene wash 3 times, and drying, weightening finish 47 grams make quaternary ammonium group function cotton thread.Learn that through chemical analysis quaternary ammonium group function cotton thread contains bigcatkin willow aldehyde radical 1.881mmol/g.
The preparation of step 3, multi-functional chelating ion exchange cotton thread (1)
Quaternary ammonium group function cotton thread 100 grams that step 2 is made immerse in 300 ml methanol that contain thiosemicarbazides 40 grams; 2 milliliters of glacial acetic acid are as catalyst, and cotton thread is extracted in 35～40 ℃ of reactions of temperature control 12 hours out; Water washing; Air blow drying, weightening finish 22.5 grams make faint yellow multi-functional chelating ion exchange cotton thread (1).
The preparation of embodiment 2 multi-functional chelating ion exchange polyester cotton blending lines (2)
Method and operating procedure according to embodiment 1; It is that commercially available 18S true qualities 55/45 cotton is washed bag core single thread that commercially available 18S true qualities slubbing cotton single-yarn in embodiment 1 step 1 is changed; Thiosemicarbazides in embodiment 1 step 3 changes and is ortho-aminobenzoic acid, promptly makes orange red multi-functional chelating ion exchange cotton-polyester blend line (2).
The preparation of embodiment 3 multi-functional chelating ion exchange polyester cotton blending lines (3)
Method and operating procedure according to embodiment 1; It is that commercially available 18S true qualities 55/45 cotton is washed bag core single thread that commercially available 18S true qualities slubbing cotton single-yarn in embodiment 1 step 1 is changed; Thiosemicarbazides in embodiment 1 step 3 changes and is 3-cumarin formylhydrazine, promptly makes bright faint yellow multi-functional chelating ion exchange cotton-polyester blend line (3).
The preparation of embodiment 4 multi-functional chelating ion exchange fiber flax/viscose fiber blending lines (4)
According to method and the operating procedure of embodiment 1, it is commercially available 18S flax/viscose rayon 55/45 mixed yarn that the commercially available 18S true qualities slubbing cotton single-yarn in embodiment 1 step 1 is changed, and promptly makes multi-functional chelating ion exchange flax/viscose fiber blending line (4).
The preparation of embodiment 5 multi-functional chelating ion exchange cotton threads (5)
Method and operating procedure according to embodiment 1; With the amine resin emulsion change of being processed in ratio emulsion copolymerization in 50: 40: 10 by butyl methacrylate/dimethylaminoethyl methacrylate/methacrylate glycol ester in embodiment 1 step 1 is the amine resin emulsion of being processed in ratio emulsion copolymerization in 50: 40: 10 by methyl methacrylate/dimethylaminoethyl methacrylate/methacrylate glycol ester, promptly makes multi-functional chelating ion exchange cotton thread (5).
The preparation of embodiment 6 multi-functional chelating ion exchange cotton thread/blend polyester lines (6)
The multi-functional chelating ion exchange cotton thread (1) that embodiment 1 is made spins with commercially available 18S polyester filament ply twist, promptly makes multi-functional chelating ion exchange cotton thread/blend polyester line (6).
The preparation of embodiment 7 multi-functional chelating ion exchange cotton threads (7)
Method and operating procedure according to embodiment 1; With the amine resin emulsion change of being processed in ratio emulsion copolymerization in 50: 40: 10 by methyl methacrylate/dimethylaminoethyl methacrylate/methacrylate glycol ester in embodiment 1 step 1 is the amine resin emulsion of being processed in ratio emulsion copolymerization in 50: 40: 10 by diethylaminoethyl methacrylate/methyl methacrylate/methacrylate glycol ester, promptly makes multi-functional chelating ion exchange cotton thread (7).
Assay method according to GB/T 4743 yarn linear densities; The multi-functional chelating ion exchange fiber (1) among mensuration embodiment 1 and the embodiment 7 and the line density of (7); Calculate line density increment (%) with the substrate fiber contrast; According to determination of test method embodiment 1 and the multi-functional chelating ion exchange fiber (1) among the embodiment 7 and the fracture strength of (7) of GB/T 3916 single yarn ultimate strengths, calculate ultimate strength increment (%) with the substrate fiber contrast, the result sees table 1.
The characteristic and the application of embodiment 8 multi-functional chelating ion exchange fibers (1) and (2)
Take by weighing multi-functional chelating ion exchange fiber (1) and (2) 10.00 grams among the dry embodiment 1～2 respectively; Immerse respectively in the 0.2mol/L solder(ing)acid of 200 milliliters of pH=6; After 30 minutes; All variable colors of the multi-functional chelating ion exchange fiber (1) of embodiment 1 and embodiment 2 and (2) separate and remove solder(ing)acid.Use deionized water washing embodiment 1 extremely neutral respectively with multi-functional chelating ion exchange fiber (1) and (2) among the embodiment 2; Oven dry; Weigh respectively, calculate weightening finish, calculate that the multi-functional chelating ion exchange fiber (1) that draws among 10.00 gram embodiment 1 and the embodiment 2 and (2) are to ZnCl
2Possess adsorbance, see table 1.
Employing is with quadrat method and operation, and the result shows multi-functional chelating ion exchange fiber (1) and (2) dipping CuCl among embodiment 1 and the embodiment 2
2Behind the aqueous solution, the multi-functional chelating ion exchange fiber (1) of embodiment 1 and embodiment 2 and (2) all variable colors.Embodiment 1 and embodiment 2 multi-functional chelating ion exchange fibers (1) and (2) are to CuCl
2The adsorbance of possessing see table 1.
The characteristic and the function of the multi-functional chelating ion exchange fiber of table 1 (1) and (2)
Claims (8)
1. multi-functional chelating ion exchange fiber is characterized in that: the fiber of surface-coated functional resin, and two kinds of functional groups of said functional resin bonding quaternary ammonium group and salicylidene amino-compound have the chelating ion function of exchange; Said multi-functional chelating ion exchange fiber is through substrate fiber surface-coated amido functional resin; Obtain the tertiary amine functional fibre; After this, the tertiary amine functional fibre is processed with the necleophilic reaction of 5-chloromethyl salicylide and with the condensation reaction of amino-compound successively.
2. according to the described multi-functional chelating ion exchange fiber of claim 1, it is characterized in that described substrate fiber is selected from one or more union twist yarn yarns in cotton fiber, flaxen fiber, bamboo fibre, wood-fibred, grass fiber, polypropylene fibre, polyvinyl chloride fibre, acrylic fibers, polyamide fibre, vinylon, terylene or the spandex.
3. according to the described multi-functional chelating ion exchange fiber of claim 1, it is characterized in that described amido functional resin refers to the copolymer of function monomer and second olefinic monomer and crosslinking agent.
4. according to the described multi-functional chelating ion exchange fiber of claim 1, it is characterized in that described amino-compound refers to one or more in azanol, hydrazine, 2-pyridine formylhydrazine, 3-cumarin formylhydrazine, 7-lignocaine 3-cumarin formylhydrazine, ethylenediamine, diethylenetriamine, triethylene tetramine, o-phenylenediamine, p-phenylenediamine (PPD), o-aminophenol, ortho-aminobenzoic acid, thiosemicarbazides, 2-aminopyridine, 2-amido benzothiazole, 2-aminooimidazole, glycine, alanine or the cysteine.
5. according to the described multi-functional chelating ion exchange fiber of claim 3, it is characterized in that described function monomer is selected from one or more in dimethylaminoethyl acrylate, acrylic acid lignocaine ethyl ester, acrylic acid dipropyl amino ethyl ester, acrylic acid dibutylamino ethyl ester, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid dipropyl amino ethyl ester, methacrylic acid dibutylamino ethyl ester, N-(2-dimethylamino) ethyl-2-Methacrylamide or N-(2-dimethylamino) ethyl acrylamide.
6. according to the described multi-functional chelating ion exchange fiber of claim 3, it is characterized in that described second olefinic monomer is selected from one or more in styrene, acrylonitrile, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, EMA, butyl methacrylate, maleic anhydride or the vinylacetate.
7. according to the described multi-functional chelating ion exchange fiber of claim 3, it is characterized in that described crosslinking agent is selected from one or more in divinylbenzene, two acrylic acid glycol ester, methacrylate glycol ester, isocyanuric acid three propylene esters or the dimethyl diallyl ammonium chloride.
8. according to the preparation method of the described multi-functional chelating ion exchange fiber of claim 1, it is characterized in that realizing through following steps:
The preparation of step 1, tertiary amine functional fibre
Under the room temperature, substrate fiber pads in the amine resin emulsion, after the coating evenly, extracts fiber out, and drying makes the tertiary amine functional fibre; Or in the amine resin emulsion, pad under the natural fiber room temperature, apply evenly, extract fiber out, after the drying,, make the tertiary amine functional fibre with polypropylene fibre, polyvinyl chloride fibre, acrylic fibers, polyamide fibre, vinylon, terylene or spandex blending;
Wherein the amine resin emulsion is carried out emulsion polymerisation by function monomer and second olefinic monomer and crosslinking agent and is made; The quality proportioning of said function monomer/second olefinic monomer/crosslinking agent is 3～300: 100: 2～50; Said amine resin emulsion preparation method is selected from Xu Zhongping's " the emulsion copolymers study on the synthesis that contains amine functional monomer " Master's thesis (University Of Tianjin, 2003);
Said substrate fiber such as claim 2 are said, and described natural fiber is selected from one or more union twist yarn yarns in cotton fiber, flaxen fiber, bamboo fibre, wood-fibred or the grass fiber;
Described function monomer such as claim 5 are said, and described second olefinic monomer such as claim 6 are said, and described crosslinking agent such as claim 7 are said;
The preparation of step 2, quaternary ammonium group functional fibre
The tertiary amine functional fibre that step 1 is made is immersed in the solvent that contains 5-chloromethyl salicylide, reacts under the room temperature 4～48 hours, leaches fiber, and solvent wash is dry, make the quaternary ammonium group functional fibre;
Wherein said solvent refers to toluene, chlorobenzene, methyl phenyl ethers anisole, xylenes, benzinum, cyclohexane, hexahydrotoluene or decahydronaphthalene; The consumption of said solvent is 2～10 times of said tertiary amine functional fibre quality, and described 5-chloromethyl salicylide consumption is 0.5～5 times of said tertiary amine functional fibre quality;
The preparation of step 3, multi-functional chelating ion exchange fiber
The quaternary amine base functional fibre that step 2 is made is immersed in the solvent that contains amino-compound, and 20～90 ℃ of temperature controls reacted 2～200 hours, leached fiber, solvent wash, and drying makes multi-functional chelating ion exchange fiber;
Wherein said amino-compound such as claim 4 are said;
Described solvent refers to water, methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, acetate or formic acid, and the consumption of said solvent is 2～10 times of said quaternary ammonium group functional fibre quality.
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| CN103709279A (en) * | 2013-12-11 | 2014-04-09 | 淮海工学院 | Salicylic acid chelating ion exchange resin modified by quaternary ammonium cation |
| CN110665476A (en) * | 2019-11-04 | 2020-01-10 | 桂林理工大学 | Melamine-thiourea modified soybean protein microsphere, preparation method and application thereof in cadmium adsorption and detection |
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| CN111074560A (en) * | 2019-12-16 | 2020-04-28 | 浙江工商大学 | Polyacrylonitrile-2-aminopyridine chelate fiber and synthetic method and application thereof |
| CN111074560B (en) * | 2019-12-16 | 2022-07-26 | 浙江工商大学 | Polyacrylonitrile-2-aminopyridine chelate fiber and synthetic method and application thereof |
| CN111302427A (en) * | 2020-02-26 | 2020-06-19 | 新昌县以琳环保科技有限公司 | Preparation method of antibacterial and deodorant modified fiber for water purification |
| CN111302427B (en) * | 2020-02-26 | 2021-11-02 | 新昌县以琳环保科技有限公司 | Preparation method of antibacterial and deodorant modified fiber for water purification |
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