CN105350285B - A kind of catalysis oxidation decomposes the manufacture method of cationic dyes fiber - Google Patents
A kind of catalysis oxidation decomposes the manufacture method of cationic dyes fiber Download PDFInfo
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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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
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- 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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Abstract
The invention discloses functional fibre manufacturing technology field can catalytic oxidant oxidation Decomposition cationic dyes fiber manufacture method, the manufacture method synthesizes poly- (methyl) acrylate using solution polymerization process, poly- (methyl) acrylate fiber of hydroxyl is then rich in using wet spinning technology spinning surface, in the basic conditions finally, utilize the redox reaction between fiber surface hydroxyl and potassium permanganate, make potassium permanganate reduction generation Mn oxide, hydroxyl oxygen metaplasia is into carboxylic acid group, based on the complexing between Mn oxide and carboxylic acid group, Mn oxide is set to be firmly bonded to fiber surface, it is made using poly- (methyl) acrylate as skeleton, Mn oxide is the composite fibre of coating, so as to assign the characteristic of composite fibre catalytic oxidant oxidation Decomposition cationic dyes.Gained fiber compared with powdered or graininess Mn oxide material, can weave or it is non-woven be processed into variform product, more meet industrial applicibility requirement.
Description
Technical field
The present invention relates to a kind of manufacturing technology of fiber, specially one kind can catalytic oxidant oxidation Decomposition cationic dye
Expect the manufacture method of fiber, the manufacture method make use of potassium permanganate under polymerisation in solution, wet spinning and alkalescence condition to handle
Etc. technology.
Background technology
In view of the trend that China human mortality increases, to the year two thousand thirty China's water resources ownership per capita by from present 2200m3Drop
For 1700m3-1800m3(in Zhang Lili, Lee's pollen, Su Dechun, China's sludge from wastewater treatment plant Distribution Characteristics of Heavy Metals and
Changing rule, Research of Environmental Sciences, 2013,26 (3)：313-319), gross water requirement is even more and can developed always close to water resource
Amount, water shortage problem will protrude more, and increasingly serious water pollution will make water shortage problem more highlight (Wang C Y, Zhou
B, Huang B, A continuing 30-year decline in water quality of Jiaojiang Estuary,
China, Water Science and Engineering, 2015,8：20-29).With the stable development of China's dye industry,
Dyeing turns into the discharge rich and influential family of industrial wastewater, and cation type dye waste water is the Typical Representative in dyeing waste water.Contain
The composition species of cationic dyes waste water is complicated, COD is high, concentration is high, salt content is high, pH value is low, biodegradability
Difference.China is cationic dyes big producer, and with that can contaminate the constantly improve of type acrylic fibers manufacturing technology, cationic dyes exist
(Li Guangchao, organically-modified sepiolite is to unit and polynary dye of positive ion body with promoting also constantly expansion for the application of dyeing
The absorption research of system, 2014, Hunan University's Engineering Master academic dissertation), cation type dye wastewater flow rate drastically increases, if should
Class direct discharging of waste water can reduce water transparency, influence aquatile and microorganism growth, be unfavorable for water body certainly into water body
Only, at the same easily cause it is visual pollution (Zhu Hongfei, Li Dinglong, Zhu Chuanwei, the harm and watershed management behave of dyeing waste water,
Environmental science and management, 2007,32 (11)：89-92), so as to directly or indirectly cause high risks (Khan to human survival
S, Malik A, Environmental and Health Effects of Textile Industry Wastewater,
Environmental Deterioration＆Human Health, 2014：55-71；Terinte N, Manda B, Taylor
J, Environmental assessment of coloured fabrics and opportunities for Value
creation：Spin-dyeing versus conventional dyeing of modal fabrics, Journal of
Cleaner Production, 2014,72 (6)：127-138), therefore, the cationic dye in waste water how is effectively removed
Material pollutant becomes particularly important.At present, the processing method both at home and abroad to cation type dye waste water mainly has Coagulation Method, suction
(Wu Jie, fiber-loaded phthalocyanine activates H for attached method, photochemical oxidation method and catalysis oxidation decomposition method etc.2O2The research of degradation of dye,
2013, Institutes Of Technology Of Zhejiang's master thesis).Coagulation Method has the advantages that good decolorizing effect, clearance are high, but Coagulation Method exists
Flocculation sediment process can produce a large amount of sludge, need to further handle sludge, otherwise easily cause secondary pollution, and the pH of solution and
Ion component influences larger to coagulation effect, and thus, the application of Coagulation Method is restricted；Absorption method have it is easy to operate,
The advantages of investing small, but because adsorbent reactivation is costly, and the shortcomings of have poor to hydrophobic particle adsorptivity, therefore be only applicable
In the processing of small-scale specific waste water；Photochemical oxidation method has that reaction condition is gentle, oxidability is strong, applied widely etc. excellent
Point, but due to the problems such as reactor design requirement is high, UV lamp source service life is short, the further development of photochemical oxidation method by
Limitation；Catalysis oxidation decomposition method can make up the defect present in above-mentioned other method, be current processing cation type dye
The comparatively ideal method of waste water ratio, therefore, develops and develops the new material for decomposing cationic dyes with catalysis oxidation and controlling
Had important practical significance in terms of reason cationic dyes contaminated wastewater.
Occurs the material that can be used for catalytic decomposition cationic dyes at present, for example, 1. nano titanium oxide, it is one
The material of preferable photocatalysis Decomposition cationic dyes is planted, but its Solar use efficiency is low, and practical application is restricted (Jiang
Honeysuckle flower, Zhao Chenxuan, Liu Hui, nano-TiO2Photodissociation of-ZnO the composite photo-catalysts to cationic blue X-GRL decolourizes to study, solar energy
Journal, 2008,29 (3)：299-305)；2. titanium oxide/multi-wall carbon nano thin-film material, this material is remarkably improved light
Catalytic activity, but exist and the shortcomings of matrix load is uneven, insecure, using being restricted (Li Aichang, Lu Yanhong, Chen Rong
English etc., electrophoresis prepares the performance of titanium oxide/multi-wall carbon nano film and its photocatalytic degradation rhodamine B, silicate
Report, 2014)；3. nano zinc oxide material, as photochemical catalyst, it has high luminous sensitivity, it is good can band property, cheap
Price, there is good photocatalytic activity when decomposing some dyestuffs, but its quantum yield is low, significantly reduces photocatalysis
Efficiency, and separate and reclaim difficult, easily inactivate, therefore, using being restricted, (WANG Xiaohong, lignin is urged in nano-ZnO light for it
Application study in agent preparation and dye wastewater treatment, 2014, Jiangsu University Ph.D. Dissertation)；4. tungstic acid light is urged
Change material, this material has less energy gap, can absorb the visible light part in sunshine, but its conduction band electron is not
Easily carried by oxygen, therefore, its application less (Bi Dongqin, iron oxide body phase in terms of photocatalysis Decomposition cationic dyes
Doping and influence of the surface modification to 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 dyestuff and paper waste, 2013, Institutes Of Technology Of Zhejiang master
Academic dissertation；Liu Wei, Zhao Tao, Huaihe River road maple, nascent state MnO2Preparation and handle alizarin red research, Wuhan industry learn
Institute's journal, 2008,27 (2)：41-44；Pay military strength, the preparation of manganese oxide catalyst and its catalytic performance research, 2014, Nanchang
Aviation university master thesis；Cai Dongming, Ren Nanqi, the modified δ-MnO of acid2Go the characteristic and mechanism of dyestuff in water removal, environment
Chemistry, 2007,26 (2)：171-174), Mn oxide is compared with other above-mentioned oxide materials, with low cost, manufacturer
Just the advantages of, and during catalysis oxidation decomposes cationic dyes, the spy such as catalytic efficiency height fast with Catalysis Rate
Point, therefore, causes scholars' widely concern.Nevertheless, obtained Mn oxide is generally powdered or graininess at present, shape
State is single, is difficult to be directly separated with water after use, need to substantially increase its application cost by the means such as filtering or centrifugation,
Its application be restricted, therefore, research and develop it is polymorphic have can catalysis oxidation decompose cationic dyes manganese oxidation
Thing sill has important practical usage.
In view of the above-mentioned problems, the present invention is using (methyl) esters of acrylic acid material as monomer, synthesize poly- using solution polymerization process
(methyl) acrylate, prepares poly- (methyl) acrylate fiber that surface is rich in hydroxyl using wet spinning technology, then exists
Under alkalescence condition, using the redox reaction between fiber surface hydroxyl and potassium permanganate, make potassium permanganate reduction generation manganese
Oxide, hydroxyl oxygen metaplasia, based on the complexing between Mn oxide and carboxylic acid group, makes the Mn oxide of generation into carboxylic acid group
Fiber surface is firmly bonded to, is made using poly- (methyl) acrylate as skeleton, Mn oxide is the composite fibre of coating, from
And assign the characteristic of composite fibre catalytic oxidant oxidation Decomposition cationic dyes.This fiber and above-mentioned powdered or particle
Shape Mn oxide material is compared, can weave or it is non-woven be processed into variform product, can meet different application field to production
The requirement of product form, the application field of this fibrous material is expected further to widen.
The content of the invention
For the not yet done of prior art, the technical problem that the present invention is intended to solve is to provide a kind of with catalysis oxidation decomposition
The manufacture method of cationic dyes fiber.First, suitable (methyl) acrylate monomer is selected, by controlling polymerization work
Skill, using solution polymerization process synthesize rich in hydroxyl can wet spinning poly- (methyl) acrylate, then, using wet spinning
Synthesized polymer solution is spun into poly- (methyl) acrylate fiber that surface is rich in hydroxyl by technology, finally, in alkaline bar
Under part, using the redox reaction between fiber surface hydroxyl and potassium permanganate, make potassium permanganate reduction generation Mn oxide,
Hydroxyl oxygen metaplasia, based on the complexing between Mn oxide and carboxylic acid group, is firmly bonded to Mn oxide into carboxylic acid group
Fiber surface, is made using poly- (methyl) acrylate as skeleton, and Mn oxide is the composite fibre of coating, so as to assign compound fibre
Tie up the characteristic of catalytic oxidant oxidation Decomposition cationic dyes.Gained can catalysis oxidation decompose cationic dyes fiber with it is existing
There is powdered or graininess Mn oxide material to compare, with cost it is low, easy to use, it is easy reclaim, do not easily cause secondary pollution
The advantages of, it is often more important that, gained can catalysis oxidation decompose cationic dyes fibre spinnable knit or it is non-woven be processed into it is many
Form product is planted, industrial applicibility requirement is more met.
The technical scheme that the present invention solves the technical problem is：Design is a kind of, and there is catalysis oxidation to decompose cationic dye
Expect the manufacture method of fiber, its technical process is as follows：
(1) solution polymerization process：Monomer 1 is weighed, is placed in suitable beaker, monomer 2 is weighed, makes monomer 2 and list
The mass ratio of body 1 is 0: 10~4: 6, and monomer 2 is poured into above-mentioned beaker, weigh account for monomer 1 and the gross mass 0.2 of monomer 2~
2% initiator, and initiator is added in above-mentioned beaker, magnetic agitation is opened, until initiator is dissolved completely in monomer
In, hereafter, solvent is weighed, it is 1: 1~5: 1 to make solvent and the ratio between monomer 1 and the gross mass of monomer 2, and solvent is added to above-mentioned
In beaker, magnetic agitation is opened, makes to be well mixed between solvent, monomer, initiator three, then by monomer, initiator and solvent
The solution of formation is poured into polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, opens polymeric kettle heating system, is risen
Temperature is reacted after 2~6h, terminating reaction, resulting polymers solution moved in suitable beaker to 70~90 DEG C, is sealed standby；
The monomer 1 is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl
One kind in fat；
The monomer 2 be methyl methacrylate, EMA, propyl methacrylate, methacrylic acid just
Butyl ester, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methyl
Isooctyl acrylate monomer, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, methacrylic acid ten
Six esters, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, acrylic acid are different
Butyl ester, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, acrylic acid
One kind in ten diester, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate；
The initiator be benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP,
One kind in cumyl peroxide, di-t-butyl peroxide；
The solvent is in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
One kind；
(2) wet spinning technology：Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, passed through
The polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, and coagulating bath is by water and molten
Agent is constituted, and the mass ratio of water and solvent is 10: 0~2.5: 7.5, and then, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning
Solidify in coagulating bath, form as-spun fibre, as-spun fibre be washed once into the above in deionized water, be placed on air blast and do
In dry case, 1~6h is dried under the conditions of 25~60 DEG C, as-spun fibre is made；
The solvent is in dimethylformamide, dimethyl acetamide, dimethyl alum, toluene, dimethylbenzene, tetrachloro-ethylene
One kind；
(3) potassium permanganate handling process under alkalescence condition：The potassium permanganate of certain mass is weighed, volumetric flask is placed on
In, then, the deionized water of certain volume is added in above-mentioned volumetric flask, configuration concentration is 0.1~2.0mol/L Gao Meng
Sour aqueous solutions of potassium, measures the above-mentioned potassium permanganate solution of certain volume, is placed in suitable beaker, and weigh certain mass can
Dissolubility alkali, it is 1: 5~1: 20 to make in the quality and beaker of water soluble alkali the ratio between volume of potassium permanganate solution, and by solubility
Alkali is added in above-mentioned beaker, is opened magnetic agitation, water soluble alkali is dissolved completely in potassium permanganate solution, is made by height
Potassium manganate, deionized water, the mixed solution of water soluble alkali composition, weigh the above-mentioned mixed solution of certain mass, are placed on place
Manage in groove, weigh the fiber of certain mass, it is 1: 5~1: 20 with above-mentioned mixed solution mass ratio to make fiber, and fiber is put
In treatment trough, it is immersed in mixed solution, treatment trough temperature is increased to 70~90 DEG C, start timing, fiber is entered
Row processing, processing time is 0.5~6h, up to after processing time, and fiber is taken out from treatment trough immediately, is washed with deionized water
Wash, untill being taken off there is no little particle of black, then fiber is placed in air dry oven, done under the conditions of 25~60 DEG C
Dry 1~6h, be made can catalysis oxidation decompose cationic dyes fiber；
The water soluble alkali is one kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide.
Compared with prior art products, first, present invention gained fiber morphologically has outstanding advantage, existing manganese oxidation
Thing material is generally powdered or graininess, and form is single, using it is rear it is extremely difficult be directly separated with water, need to by filtering or centrifugation etc. hand
Section, application cost is high, and present invention gained fiber can pass through weaving or non-woven manufacturing process for the requirement of application field
The product of variform is made, separation can be directly salvaged after, through drying process, fiber can continue to be used for multiple times, applies
Cost is significantly reduced；Secondly, present invention gained fiber also has outstanding advantage in terms of cost of material, existing to be catalytically decomposed
Cationic dyes inorganic material is made up of single inorganic matter or a variety of inorganic matters more, and required cost of material is higher, after shaping
The price of catalysis material is more expensive, and present invention gained fiber is made using conventional inorganic matter and organic matter as raw material, and main body is former
Expect for cheap poly- (methyl) acrylate, the few auxiliary material of consumption is potassium permanganate, cost of material is relatively low, shaping
The price of fiber is relatively low afterwards, is that its sizable application is provided convenience；Again, present invention gained fiber is in terms of preparation method
With outstanding advantage, existing powdered or graininess Mn oxide material is generally by hydro-thermal method, sol-gal process, solid phase method etc.
Preparation method is made, and hydro-thermal method is pyroreaction, and energy consumption is big, and yield is small, and reaction condition requires harsh, therefore is difficult to meet extensive
There is reaction condition complexity, the low defect of yield in industrialization production requirements, sol-gel process, and solid phase method prepares Mn oxide
During then there are problems that powder contact is uneven and reacts, limit a large amount of preparations of Mn oxide, and this hair
A bright step in treatment trough realizes the reactions such as Mn oxide generation, carboxylic acid group's formation, while passing through carboxylate anion and manganese oxidation
Complexing between thing realizes the strong bonded of Mn oxide thin layer and matrix polymer, and preparation process is simplified, and flow is significantly
Shorten；Finally, in the range of applicant retrieves, there is not yet using technique of the present invention manufacture there is catalysis oxidation to decompose
The pertinent literature report of the fiber of cationic dyes performance.
Embodiment
The present invention is further discussed below with reference to embodiment：It is fine that the catalysis oxidation that the present invention is designed decomposes cationic dyes
The manufacture method (hereinafter referred to as manufacture method) of dimension is related to potassium permanganate under polymerisation in solution, wet spinning and alkalescence condition and handled
Etc. the integrated application of technology, it is intended to solve existing powdered or graininess Mn oxide and deposited in processing cationic dyes waste water
Form single (powdered or graininess), reclaim when because need to by technological means such as filtering, centrifugations, cost be high etc. asks
Topic, is that cationic dyes waste water treatment creates a kind of new material, its technical process or step are as follows：
(1) solution polymerization process：Monomer 1 is weighed, is placed in suitable beaker, monomer 2 is weighed, makes monomer 2 and list
The mass ratio of body 1 is 0: 10~4: 6, and monomer 2 is poured into above-mentioned beaker, weigh account for monomer 1 and the gross mass 0.2 of monomer 2~
2% initiator, and initiator is added in above-mentioned beaker, magnetic agitation is opened, until initiator is dissolved completely in monomer
In, hereafter, solvent is weighed, it is 1: 1~5: 1 to make solvent and the ratio between monomer 1 and the gross mass of monomer 2, and solvent is added to above-mentioned
In beaker, magnetic agitation is opened, makes to be well mixed between solvent, monomer, initiator three, then by monomer, initiator and solvent
The solution of formation is poured into polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, opens polymeric kettle heating system, is risen
Temperature is reacted after 2~6h, terminating reaction, resulting polymers solution moved in suitable beaker to 70~90 DEG C, is sealed standby；
(2) wet spinning technology：Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, passed through
The polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, and coagulating bath is by water and molten
Agent is constituted, and the mass ratio of water and solvent is 10: 0~2.5: 7.5, and then, polymer solution changes into dynamic analysis of spinning, dynamic analysis of spinning
Solidify in coagulating bath, form as-spun fibre, as-spun fibre be washed once into the above in deionized water, be placed on air blast and do
In dry case, 1~6h is dried under the conditions of 25~60 DEG C, as-spun fibre is made；
(3) potassium permanganate handling process under alkalescence condition：The potassium permanganate of certain mass is weighed, volumetric flask is placed on
In, then, the deionized water of certain volume is added in above-mentioned volumetric flask, configuration concentration is 0.1~2.0mol/L Gao Meng
Sour aqueous solutions of potassium, measures the above-mentioned potassium permanganate solution of certain volume, is placed in suitable beaker, and weigh certain mass can
Dissolubility alkali, it is 1: 5~1: 20 to make in the quality and beaker of water soluble alkali the ratio between volume of potassium permanganate solution, and by solubility
Alkali is added in above-mentioned beaker, is opened magnetic agitation, water soluble alkali is dissolved completely in potassium permanganate solution, is made by height
Potassium manganate, deionized water, the mixed solution of water soluble alkali composition, weigh the above-mentioned mixed solution of certain mass, are placed on place
Manage in groove, weigh the fiber of certain mass, it is 1: 5~1: 20 with above-mentioned mixed solution mass ratio to make fiber, and fiber is put
In treatment trough, it is immersed in mixed solution, treatment trough temperature is increased to 70~90 DEG C, start timing, fiber is entered
Row processing, processing time is 0.5~6h, up to after processing time, and fiber is taken out from treatment trough immediately, is washed with deionized water
Wash, untill being taken off there is no little particle of black, then fiber is placed in air dry oven, done under the conditions of 25~60 DEG C
Dry 1~6h, be made can catalysis oxidation decompose cationic dyes fiber.
Monomer 1 described in manufacture method of the present invention is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxyethyl methacrylate
One kind in propyl ester, hydroxypropyl acrylate.The effect of monomer 1 is as follows：1. specific functional groups hydroxyl is introduced into polymer, is it
Occur redox reaction with potassium permanganate in the basic conditions and facility is provided；2. improve the hydrophily of fiber after shaping, be it
Handle cation type dye waste water and facility is provided；3. improve the reactivity of polymerization system, improve the molecular weight of polymerizate,
The polymer molecular weight that narrows is distributed, and is easy to polymer spinning technique.
The preferred hydroxyethyl methacrylate of monomer 1 described in manufacture method of the present invention, reason is as follows：With acrylic acid hydroxyl second
Ester, hydroxy propyl methacrylate, hydroxypropyl acrylate are compared, and hydroxyethyl methacrylate is nonpoisonous chemicla, will not be to human body
Produce harm.
Monomer 2 described in manufacture method of the present invention is methyl methacrylate, EMA, methacrylic acid third
Ester, n-BMA, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, methyl-prop
Olefin(e) acid n-octyl, EHMA, isodecyl methacrylate, lauryl methacrylate, methacrylic acid 14
Ester, hexadecyl metrhacrylate, octadecyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid
N-butyl, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, propylene
One kind in sour isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate.Monomer 2
Effect is as follows：1. the homopolymer solution of monomer 2 has splendid wet spinning spinnability, therefore the introducing of monomer 2 can be by Wet-spinning
Silk spinnability assigns generated polymer solution, makes it can wet method spinning technique；2. the hydrogen bond between destruction monomer 1 and solvent is made
With the homopolymerization of suppression monomer 1 makes polymerization system generate copolymer.
The preferred n-BMA of monomer 2 described in manufacture method of the present invention, reason is as follows：1. with methacrylic acid
Methyl esters, EMA, propyl methacrylate are compared, and n-BMA is easier to be copolymerized with monomer 2,
And reaction condition is gentleer, it is easy to control polymerization process；2. with Tert-butyl Methacrylate, the just own ester of methacrylic acid, methyl
N-octyl, EHMA, isodecyl methacrylate, lauryl methacrylate, methacrylic acid ten
Four esters, hexadecyl metrhacrylate, octadecyl methacrylate are compared, and its polymer generated after polymerizeing has more preferable wet method
Spinning spinnability, it is easy to fibrous material is made；3. with methyl acrylate, ethyl acrylate, propyl acrylate, the positive fourth of acrylic acid
Ester, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, acrylic acid are different
Last of the ten Heavenly stems ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate are compared, its polymer spinning technique
There is more preferable intensity afterwards, practical application is more beneficial for.
Initiator described in manufacture method of the present invention is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide,
One kind in TBHP, cumyl peroxide, di-t-butyl peroxide.The principle of selection initiator includes：①
Half-life period appropriate initiator is selected according to polymerization temperature, makes polymerization time moderate, from the initiator of high activity, i.e. half-life period
Shorter initiator, to improve rate of polymerization, shortens polymerization time, while can reduce polymerization temperature and reduce initiator amount；
2. it should also be taken into account that initiator polymer quality is whether there is influence, initiator have it is non-toxic, using and storage process in whether pacify
Congruent problem, it is well known that half-life period of the di-t-butyl peroxide at 100 DEG C is 218h, and cumyl peroxide is at 115 DEG C
When half-life period be 12.3h, half-life period of the TBHP at 154.5 be 44.8h, isopropyl benzene hydroperoxide is 125
DEG C when half-life period be 21h, half-life period of the azodiisobutyronitrile at 100 DEG C is 0.1h, and benzoyl peroxide is at 125 DEG C
Half-life period is 0.42h, and temperature reduces Increased Plasma Half-life, temperature rise half life.Solution polymerization process of the present invention is related to
Range of reaction temperature be 70~90 DEG C, the time is 2~6h, compared to other initiators, half-life period of benzoyl peroxide compared with
To be suitable, it is ensured that reach preferable extent of polymerization in the polymerization time being related to, and because benzoyl peroxide belongs to low toxicity
Product, use and store comparatively safe, therefore the preferred benzoyl peroxide of initiator described in manufacture method of the present invention.
Solvent described in manufacture method of the present invention is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene,
One kind in dimethylbenzene, tetrachloro-ethylene.Dimethylformamide price is relatively low, the organic solvent commonly used when being spinning, in room
Also it is especially susceptible to be separated with poly- (methyl) acrylate under the conditions of temperature, and wet spinning is to carry out at ambient temperature
, therefore it is more beneficial for dynamic analysis of spinning solidified forming；Compared with dimethyl acetamide, dimethyl sulfoxide (DMSO), the boiling of dimethylformamide
Point is minimum, and relatively volatile speed faster, therefore can further speed up dynamic analysis of spinning solidified forming；With except dimethyl acetamide, diformazan
Other solvents outside base sulfoxide are compared, and the toxicity of dimethylformamide is minimum, is lower toxicity product, and other solvents are middle height
Toxic product, for these reasons, the preferred dimethylformamide of solvent described in manufacture method of the present invention
Water soluble alkali described in manufacture method of the present invention is in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide
It is a kind of.Compared with lithium hydroxide, potassium hydroxide, sodium hydroxide is cheap, be easy to get, more conducively industrial implementation；With barium hydroxide
Compare, processing fiber during, though sodium hydroxide and the carbon dioxide reaction in air, product be it is water miscible, no
Easily remain on fiber, and the product that barium hydroxide reacts with Carbon Dioxide in Air is water insoluble, is easily remained
On fiber, its subsequent applications is impacted, based on above-mentioned two aspects reason, the water soluble alkali described in manufacture method of the present invention
It is preferred that sodium hydroxide.
Specific embodiment is given below, so that the present invention to be described in further detail, but the application claims are not
Limited by specific embodiment.
Embodiment 1
1.25g hydroxyethyl methacrylates are weighed, are placed in suitable beaker, 11.25g methacrylic acids are being weighed just
Butyl ester, and be poured into above-mentioned beaker, 0.0625g benzoyl peroxides are weighed, and add it in above-mentioned beaker, open
Magnetic agitation, until benzoyl peroxide is completely dissolved, hereafter, weighs 12.5g dimethylformamides, is added to above-mentioned beaker
In, magnetic agitation is opened, above-mentioned substance is well mixed, above-mentioned resulting solution is poured into polymeric kettle, nitrogen is passed through with emptying
The air remained in polymeric kettle, opens polymeric kettle heating system, is warming up to 85 DEG C, reacts after 2h, terminating reaction, gained is polymerize
Thing solution is moved in suitable beaker, is sealed standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning and contains liquid
In device, the polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, solidified
Bath composition is 100% water, and then, polymer solution changes into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, is made just
Raw fiber, as-spun fibre washed once in deionized water, be subsequently placed in air dry oven, be dried under the conditions of 30 DEG C
1h, is made as-spun fibre；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then to above-mentioned appearance
Deionized water is added in measuring bottle, configuration concentration is 0.1mol/L potassium permanganate solution, measures the above-mentioned potassium permanganate waters of 90ml
Solution, is placed in suitable beaker, weighs 10g sodium hydroxides, and adds it in above-mentioned beaker, opens magnetic agitation,
Sodium hydroxide is completely dissolved, the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide is made, 80g is weighed above-mentioned
Mixed solution, is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, is immersed in mixed solution,
Treatment trough temperature is increased to 80 DEG C, starts timing, fiber is handled, processing time is 1h, up to after processing time, by fibre
Dimension is taken out from treatment trough immediately, uses deionized water cyclic washing, until being taken off there is no little particle of black, then puts fiber
In air dry oven, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 90% after clock.
Embodiment 2
1.25g hydroxyethyl methacrylates are weighed, are placed in suitable beaker, 11.25g methacrylic acids are being weighed just
Butyl ester, and be poured into above-mentioned beaker, 0.0625g benzoyl peroxides are weighed, and add it in above-mentioned beaker, open
Magnetic agitation, until benzoyl peroxide is completely dissolved, hereafter, weighs 12.5g dimethylformamides, is added to above-mentioned beaker
In, magnetic agitation is opened, above-mentioned substance is well mixed, above-mentioned resulting solution is poured into polymeric kettle, nitrogen is passed through with emptying
The air remained in polymeric kettle, opens polymeric kettle heating system, is warming up to 85 DEG C, reacts after 2h, terminating reaction, gained is polymerize
Thing solution is moved in suitable beaker, is sealed standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning and contains liquid
In device, the polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, solidified
Bath composition is 100% water, and then, polymer solution changes into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, is made just
Raw fiber, as-spun fibre washed once in deionized water, be subsequently placed in air dry oven, be dried under the conditions of 30 DEG C
1h, is made as-spun fibre；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then to above-mentioned appearance
Deionized water is added in measuring bottle, configuration concentration is 0.1mol/L potassium permanganate solution, measures the above-mentioned potassium permanganate waters of 90ml
Solution, is placed in suitable beaker, weighs 10g sodium hydroxides, and adds it in above-mentioned beaker, opens magnetic agitation,
Sodium hydroxide is completely dissolved, the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide is made, 80g is weighed above-mentioned
Mixed solution, is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, is immersed in mixed solution,
Treatment trough temperature is increased to 80 DEG C, starts timing, fiber is handled, processing time is 2h, up to after processing time, by fibre
Dimension is taken out from treatment trough immediately, uses deionized water cyclic washing, until being taken off there is no little particle of black, then puts fiber
In air dry oven, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 93% after clock.
Embodiment 3
1.25g hydroxyethyl methacrylates are weighed, are placed in suitable beaker, 11.25g methacrylic acids are being weighed just
Butyl ester, and be poured into above-mentioned beaker, 0.0625g benzoyl peroxides are weighed, and add it in above-mentioned beaker, open
Magnetic agitation, until benzoyl peroxide is completely dissolved, hereafter, weighs 12.5g dimethylformamides, is added to above-mentioned beaker
In, magnetic agitation is opened, above-mentioned substance is well mixed, above-mentioned resulting solution is poured into polymeric kettle, nitrogen is passed through with emptying
The air remained in polymeric kettle, opens polymeric kettle heating system, is warming up to 85 DEG C, reacts after 2h, terminating reaction, gained is polymerize
Thing solution is moved in suitable beaker, is sealed standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning and contains liquid
In device, the polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, solidified
Bath composition is 100% water, and then, polymer solution changes into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, is made just
Raw fiber, as-spun fibre washed once in deionized water, be subsequently placed in air dry oven, be dried under the conditions of 30 DEG C
1h, is made as-spun fibre；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then to above-mentioned appearance
Deionized water is added in measuring bottle, configuration concentration is 0.1mol/L potassium permanganate solution, measures the above-mentioned potassium permanganate waters of 90ml
Solution, is placed in suitable beaker, weighs 10g sodium hydroxides, and adds it in above-mentioned beaker, opens magnetic agitation,
Sodium hydroxide is completely dissolved, the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide is made, 80g is weighed above-mentioned
Mixed solution, is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, is immersed in mixed solution,
Treatment trough temperature is increased to 80 DEG C, starts timing, fiber is handled, processing time is 3h, up to after processing time, by fibre
Dimension is taken out from treatment trough immediately, uses deionized water cyclic washing, until being taken off there is no little particle of black, then puts fiber
In air dry oven, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber.
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 94% after clock.
Embodiment 4
12.5g n-BMAs are weighed, and are poured into suitable beaker, 0.0625g benzoyl peroxide first is weighed
Acyl, and add it in above-mentioned beaker, magnetic agitation is opened, until benzoyl peroxide is completely dissolved, hereafter, is weighed
12.5g dimethylformamides, are added in above-mentioned beaker, open magnetic agitation, are well mixed above-mentioned substance, by above-mentioned gained
Solution is poured into polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, is opened polymeric kettle heating system, is warming up to 85
DEG C, react after 2h, terminating reaction, resulting polymers solution is moved in suitable beaker, sealed standby；By institute in above-mentioned beaker
Obtain polymer solution to pour into wet spinning Sheng liquid device, the polymer solution contained in liquid device is transported to by peristaltic pump and soaked
In spinning pack not in coagulating bath, coagulation bath composition is 100% water, and then, polymer solution changes into dynamic analysis of spinning,
Dynamic analysis of spinning solidifies in coagulating bath, and as-spun fibre is made, as-spun fibre washed once in deionized water, drum is subsequently placed in
In wind drying box, 1h is dried under the conditions of 30 DEG C, as-spun fibre is made；3.95g potassium permanganate is weighed, being placed on specification is
In 500ml volumetric flask, then to deionized water is added in above-mentioned volumetric flask, configuration concentration is 0.1mol/L potassium permanganate water
Solution, measures the above-mentioned potassium permanganate solutions of 90ml, is placed in suitable beaker, weigh 10g sodium hydroxides, and be added into
Into above-mentioned beaker, magnetic agitation is opened, sodium hydroxide is completely dissolved, be made by potassium permanganate, deionized water, sodium hydroxide
The mixed solution of composition, weighs the above-mentioned mixed solutions of 80g, is placed in treatment trough, weighs 10g fibers, and fiber is put into
In treatment trough, it is immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, start timing, fiber is handled, handles
Time is 3h, up to after processing time, and fiber is taken out from treatment trough immediately, deionized water cyclic washing is used, until there is no
Little particle of black is taken off, and then fiber is placed in air dry oven, and 1h is dried under the conditions of 30 DEG C, and being made can catalysis oxidation point
Solve the fiber of cationic dyes；
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 53% after clock.
Embodiment 5
2.5g hydroxyethyl methacrylates are weighed, and are poured into suitable beaker, the positive fourth of 10g methacrylic acids is weighed
Ester, is added in above-mentioned beaker, weighs 0.0625g benzoyl peroxides, and adds it in above-mentioned beaker, opens magnetic force and stirs
Mix, until benzoyl peroxide is completely dissolved, hereafter, weighs 12.5g dimethylformamides, be added in above-mentioned beaker, open
Magnetic agitation, is well mixed above-mentioned substance, above-mentioned resulting solution is poured into polymeric kettle, nitrogen is passed through with emptying polymeric kettle
The air of residual, opens polymeric kettle heating system, is warming up to 85 DEG C, reacts after 2h, terminating reaction, resulting polymers solution is moved
Into suitable beaker, seal standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, passed through
The polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by peristaltic pump, and coagulation bath composition is
100% water, then, polymer solution change into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, and as-spun fibre is made,
As-spun fibre washed once in deionized water, be subsequently placed in air dry oven, 1h is dried under the conditions of 30 DEG C, be made just
Raw fiber；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then, is added into above-mentioned volumetric flask
Enter deionized water, configuration concentration is 0.1mol/L potassium permanganate solution, the above-mentioned potassium permanganate solutions of 90ml is measured, by it
It is placed in suitable beaker, weighs 10g sodium hydroxides, and add it in above-mentioned beaker, opens magnetic agitation, make sodium hydroxide
It is completely dissolved, the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide is made, the above-mentioned mixed solutions of 80g are weighed,
It is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, is immersed in mixed solution, by treatment trough
Temperature is increased to 80 DEG C, starts timing, fiber is handled, processing time is 3h, up to after processing time, by fiber immediately from
Taken out in treatment trough, use deionized water cyclic washing, until being taken off there is no little particle of black, fiber then is placed in into air blast does
In dry case, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber；
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 74% after clock.
Embodiment 6
3.75g hydroxyethyl methacrylates are weighed, and are poured into suitable beaker, 8.75g methacrylic acids are being weighed just
Butyl ester, is added in above-mentioned beaker, weighs 0.0625g benzoyl peroxides, and adds it in above-mentioned beaker, opens magnetic force
Stirring, until benzoyl peroxide is completely dissolved, hereafter, weighs 12.5g dimethylformamides, is added in above-mentioned beaker, opens
Magnetic agitation is opened, above-mentioned substance is well mixed, above-mentioned resulting solution is poured into polymeric kettle, nitrogen is passed through with emptying polymeric kettle
The air of middle residual, opens polymeric kettle heating system, is warming up to 85 DEG C, reacts after 2h, terminating reaction, by resulting polymers solution
Move in suitable beaker, seal standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, led to
Cross peristaltic pump the polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath, coagulation bath composition is
100% water, then, polymer solution change into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, and as-spun fibre is made,
As-spun fibre washed once in deionized water, be subsequently placed in air dry oven, 1h is dried under the conditions of 30 DEG C, be made just
Raw fiber；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then, is added into above-mentioned volumetric flask
Enter deionized water, configuration concentration is 0.1mol/L potassium permanganate solution, the above-mentioned potassium permanganate solutions of 90ml is measured, by it
It is placed in suitable beaker, weighs 10g sodium hydroxides, and add it in above-mentioned beaker, opens magnetic agitation, make sodium hydroxide
It is completely dissolved, the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide is made, the above-mentioned mixed solutions of 80g are weighed,
It is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, is immersed in mixed solution, by treatment trough
Temperature is increased to 80 DEG C, starts timing, fiber is handled, processing time is 3h, up to after processing time, by fiber immediately from
Taken out in treatment trough, use deionized water cyclic washing, until being taken off there is no little particle of black, fiber then is placed in into air blast does
In dry case, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber；
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 76% after clock.
Embodiment 7
5g hydroxyethyl methacrylates are weighed, and are poured into suitable beaker, 7.5g n-BMAs are weighed,
It is added in above-mentioned beaker, weighs 0.0625g benzoyl peroxides, and add it in above-mentioned beaker, opens magnetic agitation,
Until benzoyl peroxide is completely dissolved, hereafter, 12.5g dimethylformamides is weighed, be added in above-mentioned beaker, open magnetic force
Stirring, is well mixed above-mentioned substance, above-mentioned resulting solution is poured into polymeric kettle, is passed through nitrogen to remain in emptying polymeric kettle
Air, open polymeric kettle heating system, be warming up to 85 DEG C, react after 2h, terminating reaction, resulting polymers solution is moved to suitable
In suitable beaker, seal standby；Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, by wriggling
The polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by pump, and coagulation bath composition is 100%
Water, then, polymer solution changes into dynamic analysis of spinning, and dynamic analysis of spinning solidifies in coagulating bath, and as-spun fibre is made, will be nascent
Fiber be washed once in deionized water, be subsequently placed in air dry oven, and 1h is dried under the conditions of 30 DEG C, and nascent fibre is made
Dimension；3.95g potassium permanganate is weighed, is placed in the volumetric flask that specification is 500ml, then, is added and go into above-mentioned volumetric flask
Ionized water, configuration concentration is 0.1mol/L potassium permanganate solution, measures the above-mentioned potassium permanganate solutions of 90ml, is placed on
In suitable beaker, 10g sodium hydroxides are weighed, and are added it in above-mentioned beaker, magnetic agitation is opened, makes sodium hydroxide complete
Dissolving, is made the mixed solution being made up of potassium permanganate, deionized water, sodium hydroxide, the above-mentioned mixed solutions of 80g is weighed, by it
It is placed in treatment trough, weighs 10g fibers, and fiber is put into treatment trough, be immersed in mixed solution, by the temperature for the treatment of trough
80 DEG C are increased to, starts timing, fiber is handled, processing time is 3h, up to after processing time, by fiber immediately from processing
Taken out in groove, use deionized water cyclic washing, until being taken off there is no little particle of black, fiber is then placed in air dry oven
In, under the conditions of 30 DEG C dry 1h, be made can catalysis oxidation decompose cationic dyes fiber；
The cationic blue aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic
Under power stirring condition, the removal efficiency of cationic blue dyestuff is 39% after 200 minutes；0.1g fibers are placed in into 10ml concentration is
In the 20mg/L cationic blue aqueous solution, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, under the conditions of magnetic agitation, 200 points
The clearance of cationic blue is up to 84% after clock.
Claims (4)
1. a kind of catalysis oxidation decomposes the manufacture method of cationic dyes fiber, it is characterised in that technical process is as follows：
(1) solution polymerization process：Monomer 1 is weighed, is placed in suitable beaker, monomer 2 is weighed, makes monomer 2 and monomer 1
Mass ratio is 0: 10~4: 6, and monomer 2 is poured into above-mentioned beaker, weighs and accounts for monomer 1 and the gross mass 0.2~2% of monomer 2
Initiator, and initiator is added in above-mentioned beaker, magnetic agitation is opened, until initiator is dissolved completely in monomer, this
Afterwards, solvent is weighed, it is 1: 1~5: 1 with the ratio between monomer 1 and the gross mass of monomer 2 to make solvent, and solvent is added into above-mentioned beaker
In, magnetic agitation is opened, makes to be well mixed between solvent, monomer, initiator three, then forms monomer, initiator and solvent
Solution pour into polymeric kettle, the air for being passed through nitrogen to be remained in emptying polymeric kettle, open polymeric kettle heating system, be warming up to
70~90 DEG C, react after 2~6h, terminating reaction, resulting polymers solution is moved in suitable beaker, seal standby, it is described
Monomer 1 is one kind in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, institute
Monomer 2 is stated for methyl methacrylate, EMA, propyl methacrylate, n-BMA, methyl-prop
Olefin(e) acid isobutyl ester, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methacrylic acid are different pungent
Ester, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, hexadecyl metrhacrylate, methyl-prop
Olefin(e) acid octadecyl ester, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid
The tert-butyl ester, the just own ester of acrylic acid, n-octyl, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, propylene
One kind in sour 14 esters, Process Conditions of Cetane Acrylate, octadecyl acrylate, the solvent is dimethylformamide, dimethylacetamide
One kind in amine, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene；
(2) wet spinning technology：Resulting polymers solution in above-mentioned beaker is poured into wet spinning to contain in liquid device, by wriggling
The polymer solution contained in liquid device is transported in the spinning pack being immersed in coagulating bath by pump, and coagulating bath is by water and solvent group
Into the mass ratio of water and solvent is 10: 0~2.5: 7.5, then, and polymer solution changes into dynamic analysis of spinning, and dynamic analysis of spinning is solidifying
Gu solidifying in bath, as-spun fibre is formed, as-spun fibre be washed once into the above in deionized water, air dry oven is placed on
In, 1~6h is dried under the conditions of 25~60 DEG C, as-spun fibre is made, the solvent is dimethylformamide, dimethylacetamide
One kind in amine, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene；
(3) potassium permanganate handling process under alkalescence condition：The potassium permanganate of certain mass is weighed, is placed in volumetric flask, with
Afterwards, the deionized water of certain volume is added in above-mentioned volumetric flask, configuration concentration is 0.1~2.0mol/L potassium permanganate water
Solution, measures the above-mentioned potassium permanganate solution of certain volume, is placed in suitable beaker, weigh the solubility of certain mass
Alkali, it is 1: 5~1: 20 to make the ratio between volume of potassium permanganate solution in the quality and beaker of water soluble alkali, and water soluble alkali is added
Enter into above-mentioned beaker, open magnetic agitation, water soluble alkali is dissolved completely in potassium permanganate solution, be made by permanganic acid
Potassium, deionized water, the mixed solution of water soluble alkali composition, weigh the above-mentioned mixed solution of certain mass, are placed on treatment trough
In, the fiber of certain mass is weighed, it is 1: 5~1: 20 with above-mentioned mixed solution mass ratio to make fiber, and fiber is placed in into place
Manage in groove, it is immersed in mixed solution, treatment trough temperature is increased to 70~90 DEG C, start timing, at fiber
Reason, processing time is 0.5~6h, up to after processing time, and fiber is taken out from treatment trough immediately, is washed with deionized, directly
Untill being taken off there is no little particle of black, then fiber is placed in air dry oven, dry 1 under the conditions of 25~60 DEG C~
6h, be made can catalysis oxidation decompose cationic dyes fiber.
2. catalysis oxidation according to claim 1 decomposes the manufacture method of cationic dyes fiber, it is characterised in that institute
The initiator stated is benzoyl peroxide, azodiisobutyronitrile, isopropyl benzene hydroperoxide, TBHP, peroxidating two
One kind in isopropylbenzene, di-t-butyl peroxide.
3. catalysis oxidation according to claim 1 decomposes the manufacture method of cationic dyes fiber, it is characterised in that institute
The water soluble alkali stated is one kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide.
4. the manufacture method of cationic dyes fiber is decomposed according to catalysis oxidation according to any one of claims 1 to 3, its
It is hydroxyethyl methacrylate to be characterised by described monomer 1；Described monomer 2 is n-BMA；Described draws
Hair agent is benzoyl peroxide；Described solvent is dimethylformamide；Described water soluble alkali is sodium hydroxide.
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| CN107245771B (en) * | 2017-06-29 | 2019-09-13 | 天津工业大学 | A kind of manufacturing method of hollow fiber out-phase embryonic stem-like cells catalyst |
| 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 |
| CN110767883B (en) * | 2019-07-02 | 2023-07-04 | 罗宝林 | Modified fiber, preparation method and application |
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| CN100408492C (en) * | 2006-09-15 | 2008-08-06 | 合肥工业大学 | Method of processing organic contaminant waste-water difficult to biochemical degradation using tetravalent manganese compounds |
| CN100436346C (en) * | 2006-11-16 | 2008-11-26 | 五邑大学 | Multiple phase catalytic oxidation-coagulation precipitation method for processing active dye printing waste water |
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