CN105350285A - Manufacturing method of fiber for catalytic oxidation decomposition of cationic dye - Google Patents

Manufacturing method of fiber for catalytic oxidation decomposition of cationic dye Download PDF

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CN105350285A
CN105350285A CN201510615551.3A CN201510615551A CN105350285A CN 105350285 A CN105350285 A CN 105350285A CN 201510615551 A CN201510615551 A CN 201510615551A CN 105350285 A CN105350285 A CN 105350285A
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fiber
acrylate
monomer
solution
take
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CN105350285B (en
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徐乃库
马艳
封严
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Tianjin Polytechnic University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/48—Oxides or hydroxides of chromium, molybdenum or tungsten; Chromates; Dichromates; Molybdates; Tungstates
    • D06M11/485—Oxides or hydroxides of manganese; Manganates
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/36—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated carboxylic acids or unsaturated organic esters as the major constituent
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention discloses a manufacturing method of fiber for catalytic oxidation decomposition of a cationic dye by an oxidizing agent, and relates to the technical field of functional fiber manufacturing, according to the method, solution polymerization method is used for synthesis of poly (methyl) acrylate, poly (methyl) acrylate fiber with rich hydroxyl groups on the surface is spun by wet spinning technology, and finally under alkaline conditions, by oxidation-reduction reaction between the hydroxyl groups on the fiber surface and potassium permanganate, the potassium permanganate is reduced to produce a manganese oxide, the hydroxyl groups are oxidized to generate carboxylic acid groups, on the basis of the complexation between the manganese oxide and the carboxylic acid groups, the manganese oxide is firmly bonded to the fiber surface to produce composite fiber with the poly (methyl) acrylate as a skeleton and the manganese oxide as a coating, and the characteristic of catalytic oxidation decomposition of the cationic dye by the oxidizing agent is given to the composite fiber. Compared with a powdered or granular manganese oxide material, a variety of forms of products can be processed by weaving or no weaving of the fiber, and the requirements of industrial applicability can be better met.

Description

A kind of catalytic oxidation decomposes the manufacture method of cationic dyes fiber
Technical field
The present invention relates to a kind of manufacturing technology of fiber, be specially a kind of can the manufacture method of catalytic oxidant oxidation Decomposition cationic dyes fiber, this manufacture method make use of the technology such as potassium permanganate process under polymerisation in solution, wet spinning and alkali condition.
Background technology
In view of the trend that China population increases, to the year two thousand thirty China's water resources ownership per capita by from present 2200m 3reduce to 1700m 3-1800m 3(Zhang Lili, Lee's pollen, Su Dechun, Distribution Characteristics of Heavy Metals and Changing Pattern in China's sludge from wastewater treatment plant, Research of Environmental Sciences, 2013, 26 (3): 313-319), gross water requirement can develop total amount close to water resource especially, water shortage problem will be more outstanding, and day by day serious water pollutions will make water shortage problem more highlight (WangCY, ZhouB, HuangB, Acontinuing30-yeardeclineinwaterqualityofJiaojiangEstuar y, China, WaterScienceandEngineering, 2015, 8:20-29).Along with the stable development of China's dye industry, dyeing has become the discharge rich and influential family of industrial wastewater, and cation type dye waste water is the Typical Representative in dyeing waste water.The composition kind of cation type dye waste water is complicated, COD is high, concentration is high, salt content is high, pH value is low, biodegradability is poor.China is cationic dyes big producing country, along with contaminating the constantly perfect of type acrylic fibers manufacturing technology, cationic dyes also constantly expands (Li Guangchao in the application of dyeing with popularization, the absorption of organically-modified sepiolite to unit and polynary cation dyes system is studied, 2014, Hunan University's Engineering Master academic dissertation), cation type dye wastewater flow rate sharply increases, if such direct discharging of waste water is in water body, water transparency can be reduced, affect aquatile and growth of microorganism, be unfavorable for the self-purification of water, easily cause visual pollution (Zhu Hongfei simultaneously, Li Dinglong, Zhu Chuanwei, the harm of dyeing waste water and watershed management behave, environmental science and management, 2007, 32 (11): 89-92), thus directly or indirectly high risks (KhanS is caused to human survival, MalikA, EnvironmentalandHealthEffectsofTextileIndustryWastewater, EnvironmentalDeterioration & HumanHealth, 2014:55-71, TerinteN, MandaB, TaylorJ, Environmentalassessmentofcolouredfabricsandopportunities forValuecreation:spin-dyeingversusconventionaldyeingofmo dalfabrics, JournalofCleanerProduction, 2014,72 (6): 127-138), therefore, how effectively the cationic dyes pollutant removed in waste water becomes particularly important.At present, (Wu Jie, the fiber-loaded phthalocyanine activation H such as Coagulation Method, absorption method, photochemical oxidation method and catalytic oxidation decomposition method are mainly contained to the processing method of cation type dye waste water both at home and abroad 2o 2the research of degradation of dye, 2013, Institutes Of Technology Of Zhejiang's master thesis).Coagulation Method has good decolorizing effect, clearance advantages of higher, but Coagulation Method can produce a large amount of mud in flocculation sediment process, need further lignin-sludge, otherwise easily cause secondary pollution, and the pH of solution and ion component are larger on coagulation effect impact, thus, the range of application of Coagulation Method is restricted; Absorption method have easy and simple to handle, invest the advantages such as little, but due to adsorbent reactivation costly, and to exist shortcomings such as hydrophobic particle adsorptivity differences, therefore be only applicable to the process of on a small scale specific waste water; Photochemical oxidation method has the advantages such as reaction condition gentleness, oxidability be strong, applied widely, but because reactor designing requirement is high, the problem such as UV lamp source service life is short, further developing of photochemical oxidation method is restricted; Catalytic oxidation decomposition method can make up the defect existing for above-mentioned additive method, process the comparatively ideal method of cation type dye waste water ratio at present, therefore, the novel material with catalytic oxidation decomposition cationic dyes of Study and Development has important practical significance in improvement cationic dyes contaminated wastewater.
There is the material that can be used for catalytic decomposition cationic dyes at present, such as, 1. nano titanium oxide, it is a kind of material of desirable photocatalysis Decomposition cationic dyes, but its Solar use efficiency is low, practical application is restricted (Jiang Yinhua, Zhao Chenxuan, Liu Hui, nano-TiO 2the photodissociation decolouring of-ZnO composite photo-catalyst to cationic blue X-GRL is studied, solar energy journal, 2008,29 (3): 299-305); 2. titanium oxide/multi-wall carbon nano thin-film material, this material can significantly improve photocatalytic activity, but exist and the shortcoming such as matrix load is uneven, insecure, application is restricted (Li Aichang, Lu Yanhong, Chen Rongying etc., electrophoresis prepares the performance of titanium oxide/multi-wall carbon nano film and photocatalytic degradation rhodamine B thereof, silicate journal, 2014); 3. nano zinc oxide material, as photochemical catalyst, it has high luminous sensitivity, good can, with character, cheap price, have good photocatalytic activity, but its quantum yield be low when decomposing some dyestuff, significantly reduce photocatalysis efficiency, and be separated and reclaim difficulty, easy inactivation, therefore, its application is restricted (WANG Xiaohong, the application study of lignin in nano ZnO photocatalyst preparation and dye wastewater treatment, 2014, Jiangsu University Ph.D. Dissertation); 4. tungstic acid catalysis material, this material has less energy gap, the visible light part in sunshine can be absorbed, but its conduction band electron is not easily carried by oxygen, therefore, its application in photocatalysis Decomposition cationic dyes less (Bi Dongqin, the bulk phase-doped and finishing of iron oxide is on the impact of tungsten oxide photocatalysis performance, 2012, Zhejiang University Ph.D. Dissertation); 5. Mn oxide (Wang Xue, the research of nano-structure manganese oxide catalyst oxidation processes dye well paper waste, 2013, Institutes Of Technology Of Zhejiang's master thesis; Liu Wei, Zhao Tao, Huaihe River road maple, nascent state MnO 2preparation and the research of process alizarin red dyestuff, Wuhan University of Technology's journal, 2008,27 (2): 41-44; Pay military strength, the preparation of manganese oxide catalyst and catalytic performance research thereof, 2014, Nanchang University of aviation's master thesis; Cai Dongming, Ren Nanqi, sour modification δ-MnO 2remove characteristic and the mechanism of dyestuff in water, Environmental Chemistry, 2007,26 (2): 171-174), Mn oxide is compared with other oxide materials above-mentioned, have with low cost, the advantage such as easily manufactured, and decompose in cationic dyes process at catalytic oxidation, there is Catalysis Rate fast, catalytic efficiency high, therefore, causes scholars to pay close attention to widely.However, Mn oxide obtained mostly at present is Powdered or graininess, form is single, rear being difficult to is used directly to be separated with water, need by filtration or the means such as centrifugal, substantially increase its application cost, its application is restricted, therefore, research and develop and polymorphicly have and can decompose the Mn oxide sill of cationic dyes there is important practical usage by catalytic oxidation.
For the problems referred to above, the present invention with (methyl) esters of acrylic acid material for monomer, adopt poly-(methyl) acrylate of solution polymerization process synthesis, wet spinning technology preparation surface is adopted to be rich in poly-(methyl) acrylate fiber of hydroxyl, subsequently in the basic conditions, utilize the redox reaction between fiber surface hydroxyl and potassium permanganate, potassium permanganate is reduced and generates Mn oxide, hydroxyl oxidize generates carboxylic acid group, based on the complexing between Mn oxide and carboxylic acid group, the Mn oxide of generation is made to be combined in fiber surface securely, obtained to gather (methyl) acrylate for skeleton, Mn oxide is the composite fibre of coating, thus give the characteristic of composite fibre catalytic oxidant oxidation Decomposition cationic dyes.Compared with this fiber or graininess Mn oxide material Powdered with above-mentioned, can weave or non-wovenly be processed into variform product, can meet the requirement of different application field to product form, the Application Areas of this fibrous material is expected to widen further.
Summary of the invention
Not yet done for prior art, the technical problem that quasi-solution of the present invention is determined is, provides a kind of manufacture method having catalytic oxidation and decompose cationic dyes fiber.First, select suitable (methyl) acrylate monomer, by controlling polymerization technique, what adopt solution polymerization process synthesis to be rich in hydroxyl can poly-(methyl) acrylate of wet spinning, subsequently, wet spinning technology is adopted synthesized polymer solution to be spun into poly-(methyl) acrylate fiber of rich surface hydroxyl, finally, in the basic conditions, utilize the redox reaction between fiber surface hydroxyl and potassium permanganate, potassium permanganate is reduced and generates Mn oxide, hydroxyl oxidize generates carboxylic acid group, based on the complexing between Mn oxide and carboxylic acid group, Mn oxide is made to be combined in fiber surface securely, obtained to gather (methyl) acrylate for skeleton, Mn oxide is the composite fibre of coating, thus give the characteristic of composite fibre catalytic oxidant oxidation Decomposition cationic dyes.Gained can decompose compared with cationic dyes fiber or graininess Mn oxide material Powdered with existing by catalytic oxidation, there is low, easy to use, the easy recovery of cost, not easily cause the advantages such as secondary pollution, the more important thing is, gained can decompose cationic dyes fibre spinnable and knits or be non-wovenly processed into variform product by catalytic oxidation, more meets industrial applicibility requirement.
The technical scheme that the present invention solve the technical problem is: design a kind of manufacture method having catalytic oxidation and decompose cationic dyes fiber, its technical process is as follows:
(1) solution polymerization process: take monomer 1, be placed in suitable beaker, take monomer 2, monomer 2 is made to be 0: 10 ~ 4: 6 with the mass ratio of monomer 1, and monomer 2 is poured in above-mentioned beaker, take the initator accounting for monomer 1 and monomer 2 gross mass 0.2 ~ 2%, and initator is joined in above-mentioned beaker, open magnetic agitation, until initator is dissolved in monomer completely, after this, take solvent, solvent is made to be 1: 1 ~ 5: 1 with the ratio of monomer 1 and monomer 2 gross mass, and solvent is joined in above-mentioned beaker, open magnetic agitation, make solvent, monomer, mix between initator three, subsequently by monomer, the solution that initator and solvent are formed is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 70 ~ 90 DEG C, reaction 2 ~ 6h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use,
Described monomer 1 is the one in hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate;
Described monomer 2 is methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, EHMA, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, one in octadecyl acrylate,
Described initator is the one in benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide;
Described solvent is the one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene;
(2) wet spinning technology: resulting polymers solution in above-mentioned beaker is poured into wet spinning and contain in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulating bath is by water and solvent composition, the mass ratio of water and solvent is 10: 0 ~ 2.5: 7.5, subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, form as-spun fibre, as-spun fibre is washed in deionized water once, be placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained as-spun fibre,
Described solvent is the one in dimethyl formamide, dimethylacetylamide, dimethyl alum, toluene, dimethylbenzene, tetrachloro-ethylene;
(3) potassium permanganate treatment process under alkali condition: the potassium permanganate taking certain mass, be placed in volumetric flask, subsequently, the deionized water of certain volume is joined in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1 ~ 2.0mol/L, measure the above-mentioned potassium permanganate solution of certain volume, be placed in suitable beaker, take the water soluble alkali of certain mass, the quality of water soluble alkali is made to be 1: 5 ~ 1: 20 with the ratio of the volume of potassium permanganate solution in beaker, and water soluble alkali is joined in above-mentioned beaker, open magnetic agitation, water soluble alkali is dissolved in potassium permanganate solution completely, obtained by potassium permanganate, deionized water, the mixed solution of water soluble alkali composition, take the above-mentioned mixed solution of certain mass, be placed in treatment trough, take the fiber of certain mass, fiber and above-mentioned mixed solution mass ratio is made to be 1: 5 ~ 1: 20, and fiber is placed in treatment trough, it is made to be immersed in mixed solution, treatment trough temperature is increased to 70 ~ 90 DEG C, start timing, fiber is processed, processing time is 0.5 ~ 6h, after reaching the processing time, fiber is taken out immediately from treatment trough, spend deionized water, until no longer including till black granule takes off, subsequently fiber is placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation,
Described water soluble alkali is the one in NaOH, lithium hydroxide, potassium hydroxide, barium hydroxide.
Compared with prior art products, first, gained fiber of the present invention morphologically has outstanding advantage, existing Mn oxide material mostly is Powdered or graininess, form is single, rear extremely difficulty is used directly to be separated with water, need by filtration or the means such as centrifugal, application cost is high, and gained fiber of the present invention can make the product of variform by weaving or non-woven manufacturing process for the requirement of Application Areas, separation directly can be salvaged after application, drying process, fiber can continue repeatedly to use, and application cost significantly reduces, secondly, gained fiber of the present invention also has outstanding advantage in cost of material, existing can catalytic decomposition cationic dyes inorganic material be many is made up of single inorganic matter or multiple inorganic matter, needed raw material price is all higher, the price of shaping rear catalysis material is more expensive, and gained fiber of the present invention with general inorganic thing and organic matter for raw material obtains, body material is cheap poly-(methyl) acrylate, the few auxiliary material of consumption is potassium permanganate, cost of material is lower, after being shaped, the price of fiber is also lower, for its sizable application is provided convenience, again, gained fiber of the present invention also has outstanding advantage in preparation method, existing Powdered or graininess Mn oxide material is usually by hydro-thermal method, sol-gal process, the preparation methods such as solid phase method obtain, hydro-thermal method is pyroreaction, energy consumption is large, output is little, reaction condition requires harsh, therefore be difficult to meet large-scale industrial production requirement, there is reaction condition complexity in sol-gel process, the defects such as productive rate is low, solid phase method is prepared in Mn oxide process and then be there is the uneven and reaction problem such as insufficient of powder contact, limit a large amount of preparations of Mn oxide, and the present invention's step in treatment trough realizes Mn oxide generation, the reactions such as carboxylic acid group is formed, realized the strong bonded of Mn oxide thin layer and matrix polymer by the complexing between carboxylate anion and Mn oxide simultaneously, preparation process is simplified, flow process shortens greatly, finally, in the scope of applicant's retrieval, there is not yet the pertinent literature report adopting manufacture technics of the present invention to have the fiber of catalytic oxidation decomposition cationic dyes performance.
Detailed description of the invention
The present invention is described further: the manufacture method (hereinafter referred to as manufacture method) of the catalytic oxidation decomposition cationic dyes fiber of the present invention's design relates to polymerisation in solution below in conjunction with embodiment, the integrated application of the technology such as potassium permanganate process under wet spinning and alkali condition, be intended to solve the form single (Powdered or graininess) that existing Powdered or graininess Mn oxide exists in process cationic dyes waste water, because of need by filtration during recovery, the technological means such as centrifugal and the problem such as cost is high, for cationic dyes waste water treatment creates a kind of new material, its technical process or step as follows:
(1) solution polymerization process: take monomer 1, be placed in suitable beaker, take monomer 2, monomer 2 is made to be 0: 10 ~ 4: 6 with the mass ratio of monomer 1, and monomer 2 is poured in above-mentioned beaker, take the initator accounting for monomer 1 and monomer 2 gross mass 0.2 ~ 2%, and initator is joined in above-mentioned beaker, open magnetic agitation, until initator is dissolved in monomer completely, after this, take solvent, solvent is made to be 1: 1 ~ 5: 1 with the ratio of monomer 1 and monomer 2 gross mass, and solvent is joined in above-mentioned beaker, open magnetic agitation, make solvent, monomer, mix between initator three, subsequently by monomer, the solution that initator and solvent are formed is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 70 ~ 90 DEG C, reaction 2 ~ 6h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use,
(2) wet spinning technology: resulting polymers solution in above-mentioned beaker is poured into wet spinning and contain in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulating bath is by water and solvent composition, the mass ratio of water and solvent is 10: 0 ~ 2.5: 7.5, subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, form as-spun fibre, as-spun fibre is washed in deionized water once, be placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained as-spun fibre,
(3) potassium permanganate treatment process under alkali condition: the potassium permanganate taking certain mass, be placed in volumetric flask, subsequently, the deionized water of certain volume is joined in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1 ~ 2.0mol/L, measure the above-mentioned potassium permanganate solution of certain volume, be placed in suitable beaker, take the water soluble alkali of certain mass, the quality of water soluble alkali is made to be 1: 5 ~ 1: 20 with the ratio of the volume of potassium permanganate solution in beaker, and water soluble alkali is joined in above-mentioned beaker, open magnetic agitation, water soluble alkali is dissolved in potassium permanganate solution completely, obtained by potassium permanganate, deionized water, the mixed solution of water soluble alkali composition, take the above-mentioned mixed solution of certain mass, be placed in treatment trough, take the fiber of certain mass, fiber and above-mentioned mixed solution mass ratio is made to be 1: 5 ~ 1: 20, and fiber is placed in treatment trough, it is made to be immersed in mixed solution, treatment trough temperature is increased to 70 ~ 90 DEG C, start timing, fiber is processed, processing time is 0.5 ~ 6h, after reaching the processing time, fiber is taken out immediately from treatment trough, spend deionized water, until no longer including till black granule takes off, subsequently fiber is placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation.
Monomer 1 described in manufacture method of the present invention is the one in hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate.The effect of monomer 1 is as follows: 1. introduce in polymer by specific functional groups hydroxyl, for it provides convenient in the basic conditions with potassium permanganate generation redox reaction; 2. the hydrophily of fiber after being shaped is improved, for its process cation type dye waste water provides convenient; 3. improve the reactivity of polymerization system, improve the molecular weight of polymerizate, the polymer molecular weight that narrows distributes, and is convenient to polymer spinning technique.
Monomer 1 preferable methyl hydroxy-ethyl acrylate described in manufacture method of the present invention, reason is as follows: compared with hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, and hydroxyethyl methylacrylate is nonpoisonous chemicla, can not produce harm to human body.
Monomer 2 described in manufacture method of the present invention is methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, EHMA, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, one in octadecyl acrylate.The effect of monomer 2 is as follows: 1. the homopolymers solution of monomer 2 has splendid wet spinning spinnability, therefore wet spinning spinnability can be given the polymer solution generated by the introducing of monomer 2, makes it can wet method spinning technique; 2. destroy the hydrogen bond action between monomer 1 and solvent, suppress the homopolymerization of monomer 1, make polymerization system generate copolymer.
Monomer 2 preferable methyl n-butyl acrylate described in manufacture method of the present invention, reason is as follows: 1. compared with methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA is easier to, with monomer 2, copolymerization occurs, and reaction condition is gentleer, be easy to control polymerization process; 2. compared with ester just own with Tert-butyl Methacrylate, methacrylic acid, n octyl methacrylate, EHMA, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, the polymer generated after its polymerization has better wet spinning spinnability, is easy to obtained fibrous material; 3. compared with ester just own with methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate, after its polymer spinning technique, there is better intensity, be more conducive to practical application.
Initator described in manufacture method of the present invention is the one in benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide.The principle of initator is selected to comprise: 1. according to the initator that polymerization temperature selects the half-life suitable, to make polymerization time moderate, select highly active initator, namely the initator that the half-life is shorter, to improve rate of polymerization, shorten polymerization time, polymerization temperature can be reduced simultaneously and reduce initiator amount, 2. initator should also be considered on polymer quality with or without impact, initator has avirulence, use and whether security problems in storage process, as everyone knows, the half-life of di-t-butyl peroxide 100 DEG C time is 218h, the half-life of cumyl peroxide 115 DEG C time is 12.3h, the half-life of tert-butyl hydroperoxide 154.5 time is 44.8h, the half-life of isopropyl benzene hydroperoxide 125 DEG C time is 21h, the half-life of azodiisobutyronitrile 100 DEG C time is 0.1h, the half-life of benzoyl peroxide 125 DEG C time is 0.42h, and temperature reduces Increased Plasma Half-life, temperature raises half life.The range of reaction temperature that solution polymerization process of the present invention relates to is 70 ~ 90 DEG C, time is 2 ~ 6h, compared to other initators, the half-life of benzoyl peroxide is comparatively suitable, can ensure to reach desirable extent of polymerization in the polymerization time related to, and belong to low toxicity chemicals due to benzoyl peroxide, use and store comparatively safe, therefore the preferred benzoyl peroxide of initator described in manufacture method of the present invention.
Solvent described in manufacture method of the present invention is the one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene.Dimethyl formamide price is relatively low, for organic solvent conventional during spinning, also be easy to especially at ambient temperature be separated with poly-(methyl) acrylate, and wet spinning carries out at ambient temperature, therefore be more conducive to dynamic analysis of spinning solidified forming; Compared with dimethylacetylamide, dimethyl sulfoxide (DMSO), the boiling point of dimethyl formamide is minimum, and relative evaporation rate is faster, therefore can accelerate dynamic analysis of spinning solidified forming further; Compared with other solvents except dimethylacetylamide, dimethyl sulfoxide (DMSO), the toxicity of dimethyl formamide is minimum, be lower toxicity product, and other solvents is middle high toxicity product, for these reasons, the preferred dimethyl formamide of the solvent described in manufacture method of the present invention
Water soluble alkali described in manufacture method of the present invention is the one in NaOH, lithium hydroxide, potassium hydroxide, barium hydroxide.Compared with lithium hydroxide, potassium hydroxide, NaOH is cheap, be easy to get, and is more conducive to industrial implementation; Compared with barium hydroxide, in process fiber process, though NaOH and the carbon dioxide reaction in air, but product is water miscible, not easily remains on fiber, and the product that barium hydroxide and Carbon Dioxide in Air are reacted is water-fast, very easily remain on fiber, its subsequent applications is impacted, based on above-mentioned two reasons, the preferred NaOH of the water soluble alkali described in manufacture method of the present invention.
Provide specific embodiment below, so that the present invention to be described in further detail, but the application's claims is not by the restriction of specific embodiment.
Embodiment 1
Take 1.25g hydroxyethyl methylacrylate, be placed in suitable beaker, take 11.25g n-BMA, and be poured in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, deionized water is added subsequently in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, fiber is processed, processing time is 1h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation.
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 90%.
Embodiment 2
Take 1.25g hydroxyethyl methylacrylate, be placed in suitable beaker, take 11.25g n-BMA, and be poured in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, deionized water is added subsequently in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, fiber is processed, processing time is 2h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation.
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 93%.
Embodiment 3
Take 1.25g hydroxyethyl methylacrylate, be placed in suitable beaker, take 11.25g n-BMA, and be poured in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, deionized water is added subsequently in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, fiber is processed, processing time is 3h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation.
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 94%.
Embodiment 4
Take 12.5g n-BMA, and be poured in suitable beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, deionized water is added subsequently in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, fiber is processed, processing time is 3h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation,
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 53%.
Embodiment 5
Take 2.5g hydroxyethyl methylacrylate, and be poured in suitable beaker, take 10g n-BMA, join in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, subsequently, deionized water is added in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, the temperature for the treatment of trough is increased to 80 DEG C, start timing, fiber is processed, processing time is 3h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation,
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 74%.
Embodiment 6
Take 3.75g hydroxyethyl methylacrylate, and be poured in suitable beaker, take 8.75g n-BMA, join in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, subsequently, deionized water is added in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, the temperature for the treatment of trough is increased to 80 DEG C, start timing, fiber is processed, processing time is 3h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation,
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 76%.
Embodiment 7
Take 5g hydroxyethyl methylacrylate, and be poured in suitable beaker, take 7.5g n-BMA, join in above-mentioned beaker, take 0.0625g benzoyl peroxide, and joined in above-mentioned beaker, open magnetic agitation, until benzoyl peroxide dissolves completely, after this, take 12.5g dimethyl formamide, join in above-mentioned beaker, open magnetic agitation, above-mentioned substance is mixed, above-mentioned gained solution is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 85 DEG C, reaction 2h, after cessation reaction, resulting polymers solution is moved in suitable beaker, seal for subsequent use, resulting polymers solution in above-mentioned beaker being poured into wet spinning contains in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulation bath composition is the water of 100%, and subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, obtained as-spun fibre, washs as-spun fibre in deionized water once, is then placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained as-spun fibre, take 3.95g potassium permanganate, being placed on specification is in the volumetric flask of 500ml, subsequently, deionized water is added in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1mol/L, measure the above-mentioned potassium permanganate solution of 90ml, be placed in suitable beaker, take 10g NaOH, and joined in above-mentioned beaker, open magnetic agitation, NaOH is dissolved completely, obtained by potassium permanganate, deionized water, the mixed solution of NaOH composition, take the above-mentioned mixed solution of 80g, be placed in treatment trough, take 10g fiber, and fiber is put into treatment trough, be immersed in mixed solution, the temperature for the treatment of trough is increased to 80 DEG C, start timing, fiber is processed, processing time is 3h, after reaching the processing time, fiber is taken out immediately from treatment trough, use deionized water cyclic washing, take off until no longer include black granule, then fiber is placed in air dry oven, dry 1h under 30 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation,
Get the cationic blue aqueous solution that 10ml concentration is 20mg/L, add 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the removal efficiency of cationic blue dyestuff is 39%; 0.1g fiber is placed in the cationic blue aqueous solution that 10ml concentration is 20mg/L, adds 0.5ml hydrogen peroxide, pass into 1min ozone, under magnetic agitation condition, after 200 minutes, the clearance of cationic blue can reach 84%.

Claims (5)

1. catalytic oxidation decomposes a manufacture method for cationic dyes fiber, it is characterized in that technical process is as follows:
(1) solution polymerization process: take monomer 1, be placed in suitable beaker, take monomer 2, monomer 2 is made to be 0: 10 ~ 4: 6 with the mass ratio of monomer 1, and monomer 2 is poured in above-mentioned beaker, take the initator accounting for monomer 1 and monomer 2 gross mass 0.2 ~ 2%, and initator is joined in above-mentioned beaker, open magnetic agitation, until initator is dissolved in monomer completely, after this, take solvent, make solvent be 1: 1 ~ 5: 1 with the ratio of monomer 1 and monomer 2 gross mass, and solvent is joined in above-mentioned beaker, open magnetic agitation, make solvent, monomer, mix between initator three, subsequently by monomer, the solution that initator and solvent are formed is poured in polymeric kettle, pass into nitrogen with air residual in emptying polymeric kettle, open polymeric kettle heating system, be warming up to 70 ~ 90 DEG C, reaction 2 ~ 6h, after cessation reaction, moves to resulting polymers solution in suitable beaker, seal for subsequent use, described monomer 1 is hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, one in hydroxypropyl acrylate, described monomer 2 is methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-BMA, isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, EHMA, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, one in octadecyl acrylate,
(2) wet spinning technology: resulting polymers solution in above-mentioned beaker is poured into wet spinning and contain in liquid device, by peristaltic pump, the polymer solution contained in liquid device is transported in the spinning pack be immersed in coagulating bath, coagulating bath is by water and solvent composition, the mass ratio of water and solvent is 10: 0 ~ 2.5: 7.5, subsequently, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning solidifies in coagulating bath, form as-spun fibre, as-spun fibre is washed in deionized water once, be placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained as-spun fibre,
(3) potassium permanganate treatment process under alkali condition: the potassium permanganate taking certain mass, be placed in volumetric flask, subsequently, the deionized water of certain volume is joined in above-mentioned volumetric flask, configuration concentration is the potassium permanganate solution of 0.1 ~ 2.0mol/L, measure the above-mentioned potassium permanganate solution of certain volume, be placed in suitable beaker, take the water soluble alkali of certain mass, the quality of water soluble alkali is made to be 1: 5 ~ 1: 20 with the ratio of the volume of potassium permanganate solution in beaker, and water soluble alkali is joined in above-mentioned beaker, open magnetic agitation, water soluble alkali is dissolved in potassium permanganate solution completely, obtained by potassium permanganate, deionized water, the mixed solution of water soluble alkali composition, take the above-mentioned mixed solution of certain mass, be placed in treatment trough, take the fiber of certain mass, fiber and above-mentioned mixed solution mass ratio is made to be 1: 5 ~ 1: 20, and fiber is placed in treatment trough, it is made to be immersed in mixed solution, treatment trough temperature is increased to 70 ~ 90 DEG C, start timing, fiber is processed, processing time is 0.5 ~ 6h, after reaching the processing time, fiber is taken out immediately from treatment trough, spend deionized water, until no longer including till black granule takes off, subsequently fiber is placed in air dry oven, dry 1 ~ 6h under 25 ~ 60 DEG C of conditions, obtained can decompose the fiber of cationic dyes by catalytic oxidation.
2. catalytic oxidation according to claim 1 decomposes the manufacture method of cationic dyes fiber, it is characterized in that described initator is the one in benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, cumyl peroxide, di-t-butyl peroxide.
3. catalytic oxidation according to claim 1 decomposes the manufacture method of cationic dyes fiber, it is characterized in that described solvent is the one in dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene.
4. catalytic oxidation according to claim 1 decomposes the manufacture method of cationic dyes fiber, it is characterized in that described water soluble alkali is the one in NaOH, lithium hydroxide, potassium hydroxide, barium hydroxide.
5. the catalytic oxidation according to any one of Claims 1 to 4 decomposes the manufacture method of cationic dyes fiber, it is characterized in that described monomer 1 is hydroxyethyl methylacrylate; Described monomer 2 is n-BMA; Described initator is benzoyl peroxide; Described solvent is dimethyl formamide; Described water soluble alkali is NaOH.
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CN107245771A (en) * 2017-06-29 2017-10-13 天津工业大学 A kind of manufacture method of hollow fiber out-phase embryonic stem-like cells catalyst
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CN107308988B (en) * 2017-06-29 2019-11-05 天津工业大学 A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst
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