CN105970353B - A kind of manufacture method of catalysis oxidation disperse dyes doughnut - Google Patents
A kind of manufacture method of catalysis oxidation disperse dyes doughnut Download PDFInfo
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- CN105970353B CN105970353B CN201610343408.8A CN201610343408A CN105970353B CN 105970353 B CN105970353 B CN 105970353B CN 201610343408 A CN201610343408 A CN 201610343408A CN 105970353 B CN105970353 B CN 105970353B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as 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
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
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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
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- 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
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- 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
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/06—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention discloses fibre manufacturing technology field can catalytic oxidant rapidly and efficiently a variety of dyestuff doughnuts of oxidation Decomposition manufacture method,The manufacture method synthesizes poly- (methyl) acrylate solution using solution polymerization process first,Surfaces externally and internally poly- (methyl) the acrylate doughnut rich in hydroxyl is then prepared using wet spinning technology,Then in the basic conditions,Etching based on alkali lye from outward appearance to inner essence,The strong complexing between redox reaction and generation carboxylic acid group and Mn oxide between hydroxyl and potassium permanganate,It is made using poly- (methyl) acrylate as skeleton,Mn oxide is the composite hollow fibre of loaded article,Composite hollow fibre not only has the characteristic of catalytic oxidant oxidation Decomposition dyestuff,And directly it can be separated when applying with water body,Its specific surface area is also very big,Therefore,Have catalytic activity high again,Processing speed is fast,The advantages that dyestuff clearance is high,Administering field in waste water from dyestuff has more wide application prospect.
Description
Technical field
The present invention relates to a kind of manufacturing technology of doughnut, specially one kind can catalytic oxidant rapidly and efficiently aoxidize point
The manufacture method of a variety of dyestuff doughnuts is solved, the manufacture method make use of under polymerisation in solution, wet spinning and alkalescence condition
The technologies such as potassium permanganate processing.
Background technology
Water is the indispensable natural resources of the mankind, and water resource is the basis of social development, and the indispensability of economic development
Resource.One of strategic issue that water pollution control and fwaater resources protection have become China at present or even the whole world is paid close attention to jointly.
The tcm of China's gross amount of water resources 2.8, the 4th, the world is occupied, accounts for the 7% of world water resources total amount.But water provides per capita in China
Source measures only 2300 cubic metres, and only the 1/4 of world average level, China's water resource of per capita counts in recent years in the World Bank
The 82nd is occupied in 132 countries, belongs to water scarcity country, moreover, our distribution of water resources are also extremely uneven, the north
Only 995 cubic metres of water resource of per capita, belongs to areas of serious, although and southwestern and southern each province water resource of per capita exceedes
3000 cubic metres, but the problems such as water resource still suffers from skewness, and some areas water pollution is serious, generates water quality and lacks
Water (Tian Lili, Jiang Bo, Fu Yi, national Water Pollution Problem analysis, Heilungkiang scientific and technological information, 2012 (25)：61-61).Population
The geometric growth of amount, the random row of modern industry waste water leave about, municipal refuse, rural area pesticide spraying etc., cause to be originally pole
Few freshwater resources aggravation shortage, can not be that China's contaminant water 70%~80% is directly discharged, and annual blowdown flow rate is about used in people
30000000000 tons, and the disposal ability of sewage only account for 20% or so (Xu Jianing, Chen Yan, China's Water Pollution Problem, Guangdong chemical industry,
2014,41 (3)：143-144).Textile and dyeing industry, as one of advantageous conventional column industry in China, from 20th century
Fast development is obtained since the nineties, its water requirement and displacement also increase substantially, and according to statistics, China produces printing and dyeing every year
Waste water is about 1,600,000,000 tons, occupies the whole discharged volume of industrial waste water in China the 6th, with the development of processing technology and new dye, helps
Application is continually developed in agent, and the intractability of dyeing waste water is also increasing, and dyeing is become increasingly conspicuous with water and drainage problem
(Dong Jianwei, dyeing waste water advanced treating and reuse technology research, Guangdong chemical industry, 2014,41 (1)：106-107).Dyeing waste water
Have the characteristics that water is big, organic pollution content is high, colourity is deep, alkalescence is big, change of water quality is big, belong to intractable industrial wastewater
(Yang Q, Wang J, Wang H, et al, Evolution ofthe microbial community in a full-
Scale printing and dyeing wastewater treatment system, Bioresource Technology,
2012,117 (4)：155-163；Lu Hongyu, Marvin's is into, beam etc., catalytic ozonation technique advanced treatment of dyeing wastewater, ring
Border engineering journal, 2013,7 (8)：2873-2876).Dyestuff in dyeing waste water can absorb light, reduce water transparency, shadow
Aquatile and microorganism growth are rung, is unfavorable for the self-purification of water, while easily causes visual pollution, the water body meeting seriously polluted
The health of the mankind is had influence on, has carried out great potential safety hazard (Papa M, Alfons í n C, Moreira M for mankind's living zone
T, et al, Ranking wastewater treatment trains based on their impacts and
benefits on human health：A " Biological Assay and Disease " approach, Journal of
Cleaner Production, 2016,113：311-317；Sze-Mun Lam, Jin-Chung Sin, Abdul Rahman
Mohamed, A review on photocatalytic application of g-C3N4/semiconductor (CNS)
Nanocomposites towards the erasure of dyeing wastewater, Materials Science in
Semiconductor Processing, 2016,47：62-84；Zhu Hongfei, Li Dinglong, Zhu Chuanwei, the harm of dyeing waste water and
Watershed management behave, environmental science and management, 2007,32 (11)：89-92), therefore, how quickly and efficiently to remove in waste water
Various dyestuffs be the primary problem faced at present.
At present, industrially generally using physical chemistry (such as adsorb, flocculate) and it is biological the methods of the processing organic dirt of dyestuff
Thing is contaminated, wherein physico-chemical process has the advantages that equipment is simple, easy to operate, but such method is generally only to have dyestuff etc.
Machine thing is transferred to solid phase (such as active carbon adsorption) from liquid phase, and organic pollution is not completely eliminated, and can bring substantial amounts of
Solid waste and regenerative wastewater, therefore, removal effect and secondary pollution etc. exist the defects of certain (Ali I,
Asim M, Khan T A, Low cost adsorbents for the removal of organic pollutants
From wastewater, Journal of Environmental Management, 2012,113 (1)：170-183).Biology
The method advantage such as have operating cost low, but have that long processing period, hold facility area are big, and the organic pollution such as dyestuff is to biology
Toxic action the problems such as removal effect being caused bad, be also possible to generate carcinogenic aromatic amine chemical combination under conditions of anaerobism
Thing (Fan J, Li H, Shuang C, et al, Dissolved organic matter removal using magnetic
anion exchange resin treatment on biological effluent of textile dyeing
Wastewater, Journal of Environmental Sciences, 2014,26 (8)：1567-1574；Lv Wangyang, catalysis
The research of the organic pollutions such as functional fibre degradation of dye, Institutes Of Technology Of Zhejiang, 2010).It is compared to the above, catalysis oxidation
Decomposition technique is by caused strong oxidizing property living radical (such as hydroxyl radical free radical, superoxide radical) by various dyestuff oxygen
Change, and then dye molecule is resolved into the mankind and environmentally friendly small-molecule substance (such as water and carbon dioxide), and have
The advantages that reaction time is short, and treatment effeciency is high, and product will not cause secondary pollution, therefore, catalysis oxidation decomposition technique increasingly draws
Play the concern of people.
Titanium dioxide (TiO2), as the photochemical catalyst of function admirable, have nontoxic, catalytic activity is high, oxidability is strong,
The features such as stability is good, corrosion-resistant, easily prepared and use, therefore, with TiO2Based on material catalysis oxidation decomposition technique
Attract attention, it is administered field in used water difficult to degradate such as dyestuff, papermaking, coking, process hides, pharmacy and is applied.Nevertheless,
TiO2The application of photochemical catalyst still suffers from two big key technical barriers：①TiO2Greater band gap, can only utilize few in sunshine
The ultraviolet portion of amount, photoresponse scope are narrower；After 2. photochemical catalyst light excites, caused electron-hole pair stability is poor,
The compound of phase inside and outside easily occurs, photon utilization rate reduces (Zhao Huan, mesoporous TiO2The preparation and photocatalysis of composite photo-catalyst
The research of degradation of dye waste water, Chang An University, 2013).Zinc oxide (ZnO) has and TiO2Similar energy gap, while again
The advantages that cheap with cost, preparation technology is simple, nontoxic, pollution-free, and degradation efficiency is higher, turns at extensive organic wastewater
That manages is appropriately selected, but ZnO only absorbs ultraviolet light, and under ultraviolet light, photoetch can occur for ZnO, in extreme pH
Value is lower and dissolvable, its photocatalysis performance largely by material this body structure, particle size, pattern, defect kind and
The influence of the factors such as concentration, and these factors are further influenceed (Li Meng, different-shape ZnO material by material preparation method
Preparation and Photocatalytic Performance Study, He'nan Normal University, 2013；Zhou Mojiao, the controllable conjunction of zinc oxide base nano composite
Into and its Photocatalytic Performance Study, Zhejiang Normal University, 2013), therefore, ZnO application is also restrained.Tried using Fenton
Agent can effectively handle various waste water from dyestuff (Shi Penghui, heterogeneous Co3O4/GO/PMS systems catalyzing oxidizing degrading waste water from dyestuff
Research, Donghua University, 2013), but there is also it is various the shortcomings that and limitation：1. Fenton reagent method and application at present
Widest biological treatment, flocculence etc. compare, and processing cost is higher, this is because, Fenton reagent cost is higher,
The limitation (such as influence of pH value, temperature, inorganic ions) of Fenton reaction conditions also increases the processing cost of waste water；It is 2. single
The H added needed for the waste water permineralization processing of position2O2Amount is far above calculated value, illustrates hydroxyl radical free radical (OH) life
It is not high into rate and utilization rate；3. the high efficiency of Fenton reagent method processing waste water from dyestuff is in strict reaction system acid-base value
(pH value), H2O2With Fe2+Dosage and the reaction condition such as ratio under realize, because containing Fe in the water outlet after processing3+Ion
And color is carried, that (Li Hong, Fenton high-level oxidation technology oxidative degradation multiring aromatic hydrocarbon contaminate for serious secondary pollution be present
The research of material waste water, University Of Chongqing, 2007), these shortcomings limit the large-scale application of Fenton reagent method.Mn oxide,
With excellent catalytic activity, and there is the advantages such as raw material sources are wide, processing technology is simple, production cost is low, it gives up in dyestuff
Water harnessing field can play more positive effect, can not only handle a variety of dye wastewater with high concentration, and processing method has
It is standby without that can implement under illumination, non-secondary pollution, normal temperature, cheap, mineral origin is extensive, percent of decolourization is high, COD clearances
Many advantages, such as high, therefore, handling waste water from dyestuff using Mn oxide, (Wang Zheng, Mn oxide is to secondary first by extensive concern
The absorption of base indigo plant dyestuff and oxidative decoloration research, Chinese Marine University, 2007；Li Hongyan, the oxidation of mesoporous and hollow-core construction manganese
The preparation of thing and its catalytic performance research, HeFei University of Technology, 2010).Although Mn oxide is led in catalysis oxidation disperse dyes
Domain has price advantage the most prominent, but obtained Mn oxide is mostly powdered at present or graininess, catalysis oxidation are decomposed
After dyestuff, easily residue in water body, need to be separated by means such as filtering, centrifugations, improve application cost, limiting it should
With therefore, the Mn oxide base catalysis material that research and develop directly to separate with water body has important practical significance.
To obtain the Mn oxide base catalysis material that directly can be separated with water body, while assign catalysis material bigger ratio table
Area, the present invention are molten using poly- (methyl) acrylate of solution polymerization process synthesis using (methyl) esters of acrylic acid material as monomer
Liquid, then using the solution as spinning solution, by the filament spinning component of designed, designed, surfaces externally and internally is prepared using wet spinning technology
It is rich in poly- (methyl) the acrylate doughnut of hydroxyl, then in the basic conditions, the etching based on alkali lye from outward appearance to inner essence
And the redox reaction between hydroxyl and potassium permanganate, potassium permanganate are reduced and generate Mn oxide, hydroxyl is oxidized
And carboxylic acid group is generated, strong complexing between Mn oxide and carboxylic acid group be present, as a result make the Mn oxide of generation not only firm
Ground is incorporated into fiber surfaces externally and internally, but also in the hole being carried between surfaces externally and internally, is made with poly- (methyl) acrylate
For skeleton, Mn oxide is the composite hollow fibre of loaded article, and composite hollow fibre not only has catalytic oxidant oxidation Decomposition
The characteristic of dyestuff, and directly can be separated during application with water body, its specific surface area is also very big, therefore, has catalytic activity height again,
The advantages that processing speed is fast, dyestuff clearance is high, administering field in waste water from dyestuff has more wide application prospect.
The content of the invention
In view of the shortcomings of the prior art, the technical problem that intends to solve of the present invention be to provide one kind can catalytic oxidant it is quick
Efficient oxidation decomposes the manufacture method of a variety of dyestuff doughnuts.The manufacture method selects suitable (methyl) acrylate first
Monomer, by controlling polymerization technique, using solution polymerization process synthesis rich in hydroxyl can wet method spinning poly (methyl) acrylate
Solution, then using the solution as spinning solution, by the filament spinning component of designed, designed, using wet spinning technology prepare in appearance
Face is rich in poly- (methyl) the acrylate doughnut of hydroxyl, then in the basic conditions, the quarter based on alkali lye from outward appearance to inner essence
Erosion and the redox reaction between hydroxyl and potassium permanganate, potassium permanganate are reduced and generate Mn oxide, and hydroxyl is by oxygen
Change and generate carboxylic acid group, strong complexing between Mn oxide and carboxylic acid group be present, as a result make the Mn oxide of generation not only firm
Admittedly be incorporated into fiber surfaces externally and internally, but also in the hole being carried between surfaces externally and internally, be made with poly- (methyl) acrylic acid
Ester is skeleton, and Mn oxide is the composite hollow fibre of loaded article.Gained composite hollow fibre and existing powdered or graininess
Mn oxide material is compared, have cost it is low, easy to use, easy recovery, do not easily cause secondary pollution, can fabricate into it is a variety of
The advantages that form product；Compared with same type wet spinning process solid fibre, gained composite hollow fibre has bigger ratio table
Area, more Mn oxides can be loaded, the efficiency of catalytic oxidant oxidation Decomposition dyestuff significantly improves, and application cost significantly drops
It is low, therefore, more meet industrial applicibility requirement.
The present invention solve the technical problem technical scheme be：Design one kind can catalytic oxidant rapidly and efficiently aoxidize point
The manufacture method of a variety of dyestuff doughnuts is solved, its technical process is as follows：
(1) solution polymerization process：The quality monomers 1 such as two parts are weighed, is placed in suitable beaker a, b, weighs respectively
Monomer 2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned a
In beaker, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and will trigger
Agent adds beaker a, weighs initiator again, current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and is added
Beaker b, open magnetic agitation, until beaker a, b in initiator be completely dissolved, weigh solvent, make solvent and two parts of monomers 1 and
The ratio between gross mass of monomer 2 is 1: 5~5: 1, and solvent is added in above-mentioned beaker a, opens magnetic agitation, makes thing in beaker a
Matter is well mixed, and then pours into solution in beaker a in polymeric kettle, is passed through nitrogen with residual air in emptying polymeric kettle, is opened
Polymeric kettle heating system, 50~100 DEG C are warming up to, the monomer 1 containing initiator in beaker b is progressively now added drop-wise to polymeric kettle
In, time for adding is controlled within 10~60min, after completion of dropwise addition, is continued 2~6h of reaction, is obtained polymer solution A, by gained
Polymer solution A is moved in suitable beaker, and sealing is standby, changes above-mentioned monomer 2 into monomer 3, obtains polymer solution B, and close
Seal standby；
The monomer 1 is hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, acrylic acid hydroxypropyl
One kind in ester；
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
One kind in six esters, octadecyl methacrylate；
The monomer 3 is methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl
Ester, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, Isooctyl acrylate monomer, propylene
One kind in sour isodecyl ester, dodecyl acrylate, 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：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~
Mixed at 0.01: 99.99, and by mixture 1~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into wet
Method spinning will then be contained liquid device and be placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa conditions with containing in liquid device
Lower deaeration, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, and quantitative transporting velocity is
0.2~2ml/min, hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface and coagulating in coagulating bath are formed after spinneret orifice is extruded
Gu agent contacts, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump, make itself and table in hollow dynamic analysis of spinning
Face contacts, and the speed for conveying coagulator is 0.5~5ml/min, and coagulator is made up of deionized water and solvent, deionized water and molten
The mass ratio of agent is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut, by doughnut
The above is washed once in deionized water, is placed in air dry oven, 1~6h is dried under the conditions of 25~50 DEG C, is made just
Raw doughnut；
The solvent is in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
One kind；
(3) aftertreatment technology：The potassium permanganate of certain mass is weighed, is placed in volumetric flask, certain volume is added and goes
Ionized water, configuration concentration are 0.01~10mol/L potassium permanganate solution, and it is water-soluble to measure the above-mentioned potassium permanganate of certain volume
Liquid, it is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes the quality and potassium permanganate solution of water soluble alkali
The ratio between volume be 1: 5~1: 20, and water soluble alkali is added in above-mentioned beaker, opens magnetic agitation, make water soluble alkali complete
Fully dissolved, the mixed solution being made up of potassium permanganate, deionized water, water soluble alkali is made, weighs the above-mentioned mixing of certain mass
Solution, it is placed in treatment trough, weighs the nascent doughnut of certain mass, makes nascent doughnut and above-mentioned mixed solution
Mass ratio is 1: 5~1: 50, and nascent doughnut is placed in treatment trough, it is immersed in mixed solution, will be handled
Bath temperature degree is increased to 25~95 DEG C, starts timing, and nascent doughnut is post-processed, and finishing time is 5min~6h,
After post processing terminates, nascent doughnut is taken out, washed repeatedly with deionized water, fallen until there is no black particle thing,
Then nascent doughnut is placed in air dry oven, 1~6h is dried under the conditions of 25~50 DEG C, being made can catalytic oxidant
The rapidly and efficiently doughnut of a variety of dyestuffs of oxidation Decomposition；
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 doughnut morphologically has outstanding advantage, at present system
The Mn oxide obtained is mostly powdered or graininess, and after catalytic oxidant oxidation Decomposition dyestuff, these Mn oxides easily residue in
In water body, it need to be separated by means such as filtering, centrifugations, application cost is obviously improved, and after present invention gained doughnut use
It can directly take out from water, through drying process, can repeatedly utilize, reduce use cost, and variform product can be processed into,
Can meet the needs of different application field is to form；Compared with same type wet spinning process solid fibre, present invention gained is hollow
Fiber has bigger specific surface area, can load more Mn oxides, and the efficiency of catalytic oxidant oxidation Decomposition dyestuff is notable
Improve, application cost significantly reduces, in addition, present invention gained doughnut can directly carry the circulation of waste water from dyestuff, dyestuff gives up
Water when inside hollow fibre flows, can a step complete dyestuff catalysis oxidation decompose, exit directly collection processing after
Water purification；Secondly, in preparation method novel aspects, the present invention also has outstanding advantage, the oxidation of existing powdered or graininess manganese
Thing material is generally made by hydro-thermal method, sol-gal process, solid phase method etc., the low yield generally having, and severe reaction conditions etc. are asked
Topic limits powdered or graininess Mn oxide material large-scale production, and present invention step in treatment trough realizes manganese
The reactions such as oxide, carboxylic acid group's generation, while manganese oxygen is realized based on the strong complexing between carboxylate anion and Mn oxide
The strong bonded of compound thin layer and matrix polymer, there is the advantages that reaction condition is gentle, low for equipment requirements, yield is high；Most
Afterwards, in the range of applicant retrieves, there is not yet can catalytic oxidant rapidly and efficiently oxygen using technique of the present invention manufacture
Change the pertinent literature report for decomposing a variety of dyestuff doughnuts.
Embodiment
The present invention is further discussed below with reference to embodiment：The present invention design can catalytic oxidant rapidly and efficiently aoxidize point
The manufacture method (hereinafter referred to as manufacture method) for solving a variety of dyestuff doughnuts is related to polymerisation in solution, wet spinning and alkaline bar
The integrated application of the technology such as potassium permanganate processing under part, it is intended to solve existing powdered or graininess Mn oxide in processing dyestuff
Form present in waste water is single, recovery when because need to by technological means such as filtering, centrifugations and cost is high, is difficult to be used for multiple times
The problems such as, at the same solve specific surface area existing for same type wet spinning process solid fibre it is small, complexing Mn oxide it is few, catalysis effect
The low problem of rate, a kind of new material is provided for dye wastewater treatment, its technical process or step are as follows：
(1) solution polymerization process：The quality monomers 1 such as two parts are weighed, is placed in suitable beaker a, b, weighs respectively
Monomer 2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned a
In beaker, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and will trigger
Agent adds beaker a, weighs initiator again, current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and is added
Beaker b, open magnetic agitation, until beaker a, b in initiator be completely dissolved, weigh solvent, make solvent and two parts of monomers 1 and
The ratio between gross mass of monomer 2 is 1: 5~5: 1, and solvent is added in above-mentioned beaker a, opens magnetic agitation, makes thing in beaker a
Matter is well mixed, and then pours into solution in beaker a in polymeric kettle, is passed through nitrogen with residual air in emptying polymeric kettle, is opened
Polymeric kettle heating system, 50~100 DEG C are warming up to, the monomer 1 containing initiator in beaker b is progressively now added drop-wise to polymeric kettle
In, time for adding is controlled within 10~60min, after completion of dropwise addition, is continued 2~6h of reaction, is obtained polymer solution A, by gained
Polymer solution A is moved in suitable beaker, and sealing is standby, changes above-mentioned monomer 2 into monomer 3, obtains polymer solution B, and close
Seal standby；
(2) wet spinning technology：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~
Mixed at 0.01: 99.99, and by mixture 1~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into wet
Method spinning will then be contained liquid device and be placed in vacuum drier in 25~95 DEG C and -0.07~-0.1MPa conditions with containing in liquid device
Lower deaeration, time are 0~60min, quantify mixed solution by peristaltic pump and are transported in spinning pack, and quantitative transporting velocity is
0.2~2ml/min, hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface and coagulating in coagulating bath are formed after spinneret orifice is extruded
Gu agent contacts, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump, make itself and table in hollow dynamic analysis of spinning
Face contacts, and the speed for conveying coagulator is 0.5~5ml/min, and coagulator is made up of deionized water and solvent, deionized water and molten
The mass ratio of agent is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut, by doughnut
The above is washed once in deionized water, is placed in air dry oven, 1~6h is dried under the conditions of 25~50 DEG C, is made just
Raw doughnut；
(3) aftertreatment technology：The potassium permanganate of certain mass is weighed, is placed in volumetric flask, certain volume is added and goes
Ionized water, configuration concentration are 0.01~10mol/L potassium permanganate solution, and it is water-soluble to measure the above-mentioned potassium permanganate of certain volume
Liquid, it is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes the quality and potassium permanganate solution of water soluble alkali
The ratio between volume be 1: 5~1: 20, and water soluble alkali is added in above-mentioned beaker, opens magnetic agitation, make water soluble alkali complete
Fully dissolved, the mixed solution being made up of potassium permanganate, deionized water, water soluble alkali is made, weighs the above-mentioned mixing of certain mass
Solution, it is placed in treatment trough, weighs the nascent doughnut of certain mass, makes nascent doughnut and above-mentioned mixed solution
Mass ratio is 1: 5~1: 50, and nascent doughnut is placed in treatment trough, it is immersed in mixed solution, will be handled
Bath temperature degree is increased to 25~95 DEG C, starts timing, and nascent doughnut is post-processed, and finishing time is 5min~6h,
After post processing terminates, nascent doughnut is taken out, washed repeatedly with deionized water, fallen until there is no black particle thing,
Then nascent doughnut is placed in air dry oven, 1~6h is dried under the conditions of 25~50 DEG C, being made can catalytic oxidant
The rapidly and efficiently doughnut of a variety of dyestuffs of oxidation Decomposition.
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. introducing hydroxyl, hydroxyl is as reducing agent, with permanganic acid
Redox reaction occurs for potassium, realizes the in-situ preparation of Mn oxide, and hydroxyl is oxidized to carboxyl, carboxylic under potassium permanganate effect
Base is complexed with generated in-situ Mn oxide, realizes load of the doughnut to Mn oxide；2. improve the hydrophilic of doughnut
Performance, it is easy to the processing of waste water from dyestuff；3. monomer conversion during polymerisation in solution is improved, the polymer molecular weight that narrows distribution,
Improve the spinning spinnability of polymer.1 preferred hydroxyethyl methacrylate of monomer described in manufacture method of the present invention, reason is such as
Under：Compared with hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate is Non-toxic
Reagent is learned, harm will not be produced to human body.
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
One kind in ester, hexadecyl metrhacrylate, octadecyl methacrylate.The effect of monomer 2 is as follows：1. the homopolymer of monomer 2
Solution has preferable spinning spinnability, therefore the introducing of monomer 2 can improve the spinning spinnability of polymer solution, be advantageous to wet method
Spinning technique；2. destroying the hydrogen bond action between monomer 1 and solvent, rate of polymerization is improved, suppresses the homopolymerization of monomer 1, makes condensate
System's generation copolymer.2 preferred n-BMA of monomer described in manufacture method of the present invention, reason are as follows：1. with methyl
Methyl acrylate, EMA, propyl methacrylate are compared, and n-BMA is easier to send out with monomer 2
Raw copolymerization, and smell is smaller, reaction condition is gentleer, easily controllable polymerization process, in the absence of implode, it is highly exothermic phenomena such as；
2. with 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 ester are compared, and n-BMA side chain lengths are suitable, and polymer can be assigned after polymerization and is fitted
In glass transition temperature, make it have excellent pliability, suitable elastic, more prominent intensity.
Monomer 3 described in manufacture method of the present invention is methyl acrylate, ethyl acrylate, and propyl acrylate, acrylic acid are just
Butyl ester, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, third
In the different monooctyl ester of olefin(e) acid, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate
One kind.The effect of monomer 3 is as follows：1. the homopolymer of monomer 3 has a fabulous pliability, prominent elasticity, therefore monomer 3 draws
Enter to substantially improve the pliability and elasticity of doughnut, be advantageous to the progress of post processing, there is final doughnut
More practical mechanical property；2. destroying the hydrogen bond action between monomer 1 and solvent, rate of polymerization is improved, suppresses the equal of monomer 1
It is poly-, polymerization system is generated copolymer, in last handling process, accelerate the etching of alkali lye from outward appearance to inner essence, while occur hydrolysis and
More hydroxy-acid groups are introduced, doughnut is loaded more Mn oxides.Monomer 3 described in manufacture method of the present invention is preferred
N-butyl acrylate, reason are as follows：1. compared with methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate life
Into polymer there is preferable pliability and lower temperature resistance, be more beneficial for improving the mechanical property of doughnut and low temperature resistant
Performance；2. compared with isobutyl acrylate, tert-butyl acrylate, the polymer strands of n-butyl acrylate generation are best, have
Beneficial to spinning technique；3. with the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, n-octyl, Isooctyl acrylate monomer, third
Olefin(e) acid isodecyl ester, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, octadecyl acrylate long alkyl chain ester are compared,
N-butyl acrylate is short alkyl chain ester, during long alkyl chain polyisocyanate polyaddition, because glass transition temperature is extremely low, and the polymer of generation
Especially soft viscous, the later stage easily glues and into bulk each other in the reaction, or even causes the failure of polymerization implode is agglomerating because of moment,
And above mentioned problem is then not present during the polymerization of short alkyl chain ester n-butyl acrylate polymerization.
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, shorten polymerization time, while polymerization temperature can be reduced and reduce initiator amount；
2. it should also be taken into account that initiator whether there is influence on polymer quality, whether initiator has in non-toxic, use and storage process and 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 DEG C is 44.8h, and isopropyl benzene hydroperoxide exists
Half-life period at 125 DEG C is 21h, and half-life period of the azodiisobutyronitrile at 100 DEG C is 0.1h, and benzoyl peroxide is at 125 DEG C
When half-life period be 0.42h, and temperature reduces Increased Plasma Half-life, temperature rise half life.Solution polymerization process of the present invention
The range of reaction temperature being related to is 50~100 DEG C, and polymerization time is within 7h, compared to other initiators, benzoyl peroxide
Half-life period it is more suitable, it is ensured that reach preferable extent of polymerization in the polymerization time being related to, and due to benzoyl peroxide first
Acyl belongs to less toxic chemicals, uses and store comparatively safe, therefore the preferred benzoyl peroxide first of initiator described in manufacture method of the present invention
Acyl.
Solvent described in manufacture method of the present invention is dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene,
One kind in dimethylbenzene, tetrachloro-ethylene.Compared with dimethyl acetamide, dimethyl sulfoxide (DMSO), the dimethylformamide dissolving present invention
The ability of synthesized polymer is the most prominent, and when obtained polymer solution contacts with water, dimethylformamide enters water body
Speed is also relatively fast, therefore is more beneficial for dynamic analysis of spinning solidified forming；Compared with toluene, dimethylbenzene, tetrachloro-ethylene, dimethyl methyl
The toxicity of acid amides is minimum, is lower toxicity product, and other solvents are middle high toxicity product, for these reasons, present invention manufacture
The preferred dimethylformamide of solvent described in method.
Water soluble alkali described in manufacture method of the present invention is sodium hydroxide, in lithium hydroxide, potassium hydroxide, barium hydroxide
It is a kind of.Compared with lithium hydroxide, potassium hydroxide, sodium hydroxide is cheap, is easy to get, more conducively industrial implementation；With barium hydroxide
Compare, in doughnut last handling process, though sodium hydroxide and the carbon dioxide reaction in air, product is water-soluble
, be not easy residual on the hollow fibers, and the product of barium hydroxide and Carbon Dioxide in Air reaction be it is not soluble in water,
Easily remain on the hollow fibers, its subsequent applications is impacted, based on above-mentioned two aspects reason, manufacture method institute of the present invention
The preferred sodium hydroxide of water soluble alkali stated.
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
Two parts of 10g hydroxyethyl methacrylates are weighed, is respectively placed in beaker a, b, is weighing 30g methacrylic acids just
Butyl ester, and be poured into above-mentioned beaker a, 0.2g benzoyl peroxides are weighed, and add it in above-mentioned beaker a, weigh
0.05g benzoyl peroxides, add it in above-mentioned beaker b, open magnetic agitation, until the benzoyl peroxide in beaker a, b
Formyl is completely dissolved, and hereafter, weighs 50g dimethylformamides, is added in above-mentioned beaker a, is opened magnetic agitation, is made beaker a
In material mixing it is uniform, then solution in beaker a is poured into polymeric kettle, the sky for being passed through nitrogen to be remained in emptying polymeric kettle
Gas, polymeric kettle heating system is opened, is warming up to 85 DEG C, by the hydroxyethyl methacrylate containing initiator in beaker b progressively now
It is added drop-wise in polymeric kettle, time for adding 0.5h, after completion of dropwise addition, continues to react 2h, it is after reaction terminates, resulting polymers are molten
Liquid A is moved in suitable beaker, and sealing is standby；Above-mentioned n-BMA is replaced with n-butyl acrylate, is repeated above-mentioned
Experiment, after reaction terminates, polymer solution B is obtained, is placed in suitable beaker, sealing is standby；The above-mentioned gained of 34ml is taken to gather
Polymer solution A, it is placed in suitable beaker, takes the above-mentioned polymer solution B of 6ml, be also added in above-mentioned beaker, magnetic agitation
1h, to be well mixed, pours into wet spinning by well mixed solution and contains in liquid device, and Sheng liquid device then is placed in into vacuum does
The deaeration under the conditions of 40 DEG C and -0.1MPa in dry machine, mixed solution time 30min, quantified by peristaltic pump and be transported to
In spinning pack, quantitative transporting velocity is 0.6ml/min, hollow dynamic analysis of spinning is formed after spinneret orifice is extruded, hollow spinning is thin
Stream outer surface contacts with the coagulator in coagulating bath, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump,
It is set to be contacted with hollow dynamic analysis of spinning inner surface, the speed for conveying coagulator is 0.9ml/min, and coagulator is by deionized water group
Into, double diffusion effect under, hollow dynamic analysis of spinning is cured as doughnut, doughnut washed once in deionized water with
On, it is placed in air dry oven, 1h is dried under the conditions of 50 DEG C, nascent doughnut is made；3.95g potassium permanganate is weighed,
It is placed in the volumetric flask that specification is 250ml, then to deionized water is added in above-mentioned volumetric flask, configuration concentration is
0.1mol/L potassium permanganate solution, the above-mentioned potassium permanganate solutions of 90ml are measured, is placed in suitable beaker, weighs
10g sodium hydroxides, and add it in above-mentioned beaker, magnetic agitation is opened, is completely dissolved sodium hydroxide, is made by Gao Meng
Sour potassium, deionized water, the mixed solution of sodium hydroxide composition, weigh the above-mentioned mixed solutions of 100g, are placed in treatment trough, claim
Take 10g to come into being doughnut, put it into treatment trough, be immersed in mixed solution, treatment trough temperature is increased to 80 DEG C, opened
Beginning timing, nascent doughnut is post-processed, processing time 30min, after post processing terminates, nascent doughnut taken
Go out, washed repeatedly with deionized water, to be fallen until there is no black particle thing, nascent doughnut is then placed in forced air drying
In case, 1h is dried under the conditions of 30 DEG C, be made can catalytic oxidant rapidly and efficiently a variety of dyestuffs of oxidation Decomposition doughnut.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 97.36% after 90min.
The alkaline gorgeous 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 clearance of the gorgeous blue dyestuff of alkalescence is 4.26% after 90min；It is dense that the above-mentioned doughnuts of 0.1g are placed in 10ml
Spend in the alkaline gorgeous blue aqueous solution for 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min ozone, under the conditions of magnetic agitation,
The gorgeous blue clearance of alkalescence is up to 85.43% after 90min.
The aqueous solution of methylene blue 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 clearance of methylene blue dye is 0.12% after 90min；It is dense that the above-mentioned doughnuts of 0.1g are placed in 10ml
Spend in the aqueous solution of methylene blue for 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of methylene blue is up to 83.29% after 90min.
The Titration orchid aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, is passed through 1min ozone,
Under the conditions of magnetic agitation, the clearance of Titration orchid dyestuff is 3.33% after 90min；The above-mentioned doughnuts of 0.1g are placed in
10ml concentration is in the 20mg/L Titration orchid aqueous solution, adds 0.5ml hydrogen peroxide, 1min ozone is passed through, in magnetic agitation
Under the conditions of, the blue clearance of Titration is up to 78.91% after 90min.
The cationic brilliant red aqueous solution that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, is passed through 1min ozone,
Under the conditions of magnetic agitation, the clearance of Titration red is 3.07% after 90min；The above-mentioned doughnuts of 0.1g are placed in
10ml concentration is in the 20mg/L cationic brilliant red aqueous solution, adds 0.5ml hydrogen peroxide, 1min ozone is passed through, in magnetic agitation
Under the conditions of, the clearance of cationic brilliant red is up to 83.92% after 90min.
The emerald green blue aqueous solution of cation that 10ml concentration is 20mg/L is taken, 0.5ml hydrogen peroxide is added, is passed through 1min ozone,
Under the conditions of magnetic agitation, the clearance of the emerald green blue dyestuff of cation is 1.36% after 90min；The above-mentioned doughnuts of 0.1g are placed in
In the emerald green blue aqueous solution of cation that 10ml concentration is 20mg/L, 0.5ml hydrogen peroxide is added, 1min ozone is passed through, in magnetic agitation
Under the conditions of, the emerald green blue clearance of cation is up to 61.24% after 90min.
The gorgeous blue aqueous solution of weak acid 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 clearance of the gorgeous blue dyestuff of weak acid is 20.89% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L gorgeous blue aqueous solution of weak acid, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The gorgeous blue clearance of weak acid is up to 46.89% after 90min.
The acid lake 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 clearance of acid lake blue dyestuff is 2.09% after 90min；It is dense that the above-mentioned doughnuts of 0.1g are placed in 10ml
Spend in the acid lake blue aqueous solution for 20mg/L, add 0.5ml hydrogen peroxide, be passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of acid lake blue is up to 31.73% after 90min.
Embodiment 2
The volume that polymer solution A is measured only is adjusted to 36ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 4ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
Learnt by the test result of embodiment 1, under doughnut catalysis, hydrogen peroxide and ozone oxidation decompose cationic blue
Ability is most strong, and therefore, the present embodiment and subsequent embodiment carry out catalytic performance sign by model dyestuff of cationic blue.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 82.37% after 90min.
Embodiment 3
The volume that polymer solution A is measured only is adjusted to 32ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 8ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 94.23% after 90min.
Embodiment 4
The volume that polymer solution A is measured only is adjusted to 30ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 10ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 95.44% after 90min.
Embodiment 5
The volume that polymer solution A is measured only is adjusted to 28ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 12ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 97.58% after 90min.
Embodiment 6
The volume that polymer solution A is measured only is adjusted to 20ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 20ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 95.69% after 90min.
Embodiment 7
The volume that polymer solution A is measured only is adjusted to 40ml by the 34ml in embodiment 1, polymer solution B is measured
Volume by being adjusted to 0ml by the 6ml in embodiment 1, other technical process and parameter are same as Example 1.
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 clearance of cationic blue dyestuff is 23.28% after 90min；The above-mentioned doughnuts of 0.1g are placed in 10ml
Concentration is in the 20mg/L cationic blue aqueous solution, adds 0.5ml hydrogen peroxide, is passed through 1min ozone, under the conditions of magnetic agitation,
The clearance of cationic blue is up to 84.44% after 90min.
Claims (4)
1. a kind of manufacture method of catalysis oxidation disperse dyes doughnut, it is characterised in that technical process is as follows：
(1) solution polymerization process：The quality monomers 1 such as two parts are weighed, is placed on respectively in suitable beaker a, b, weighs monomer
2, it is 0.01: 9.99~9.99: 0.01 to make the ratio between gross mass of monomer 2 and two parts of monomers 1, and monomer 2 is poured into above-mentioned a beakers
In, initiator is weighed, make that initiator quality is monomer 1 and the gross mass of monomer 2 in beaker a 0.2~2%, and initiator is added
Enter beaker a, weigh initiator again, current initiator quality is 0.2~2% of the mass of monomer 1 in beaker b, and adds beaker
B, magnetic agitation is opened, until initiator is completely dissolved in beaker a, b, weighs solvent, make solvent and two parts of monomers 1 and monomer
The ratio between 2 gross masses are 1: 5~5: 1, and solvent is added in above-mentioned beaker a, open magnetic agitation, mix material in beaker a
Close uniformly, then pour into solution in beaker a in polymeric kettle, be passed through nitrogen with residual air in emptying polymeric kettle, open polymerization
Kettle heating system, 50~100 DEG C are warming up to, are now progressively added drop-wise to the monomer 1 containing initiator in beaker b in polymeric kettle, dripped
Add time control within 10~60min, after completion of dropwise addition, continue 2~6h of reaction, obtain polymer solution A, by resulting polymers
Solution A is moved in suitable beaker, and sealing is standby, changes above-mentioned monomer 2 into monomer 3, obtains polymer solution B, and seal standby；
The monomer 1 is in hydroxyethyl methacrylate, hydroxy-ethyl acrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate
One kind, the monomer 2 be methyl methacrylate, EMA, propyl methacrylate, the positive fourth of methacrylic acid
Ester, Isobutyl methacrylate, Tert-butyl Methacrylate, the just own ester of methacrylic acid, n octyl methacrylate, methyl-prop
The different monooctyl ester of olefin(e) acid, isodecyl methacrylate, lauryl methacrylate, tetradecyl methylacrylate, methacrylic acid 16
One kind in ester, octadecyl methacrylate, the monomer 3 is methyl acrylate, ethyl acrylate, propyl acrylate, propylene
Sour N-butyl, isobutyl acrylate, tert-butyl acrylate, the just own ester of acrylic acid, acrylic acid-2-ethyl caproite, acrylic acid are just pungent
Ester, Isooctyl acrylate monomer, isodecyl acrylate, dodecyl acrylate, tetradecyl acrylate, Process Conditions of Cetane Acrylate, acrylic acid ten
One kind in octaester；
The solvent is one in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
Kind；
(2) wet spinning technology：By above-mentioned steps (1) resulting polymers solution A, B using volume ratio as 99.99: 0.01~0.01:
99.99 are mixed, and by mixture 1~3h of magnetic agitation, to be well mixed, gained mixed solution is poured into wet spinning
With containing in liquid device, then Sheng liquid device is placed in vacuum drier and taken off under the conditions of 25~95 DEG C and -0.07~-0.1MPa
Bubble, the time is 0~60min, quantifies mixed solution by peristaltic pump and is transported in spinning pack, and quantitative transporting velocity is 0.2
~2ml/min, hollow dynamic analysis of spinning, hollow dynamic analysis of spinning outer surface and the coagulator in coagulating bath are formed after spinneret orifice is extruded
Contact, in addition, coagulator is transported to inside hollow dynamic analysis of spinning by peristaltic pump, makes it be connect with hollow dynamic analysis of spinning inner surface
Touch, the speed for conveying coagulator is 0.5~5ml/min, and coagulator is made up of deionized water and solvent, deionized water and solvent
Mass ratio is 10: 0~5: 5, and under double diffusion effect, hollow dynamic analysis of spinning is cured as doughnut, and doughnut is being gone
The above is washed once in ionized water, is placed in air dry oven, 1~6h is dried under the conditions of 25~50 DEG C, in being made nascent
Hollow fiber；
The solvent is one in dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO), toluene, dimethylbenzene, tetrachloro-ethylene
Kind；
(3) aftertreatment technology：The potassium permanganate of certain mass is weighed, is placed in volumetric flask, adds certain volume deionization
Water, configuration concentration are 0.01~10mol/L potassium permanganate solution, measure the above-mentioned potassium permanganate solution of certain volume, will
It is placed in suitable beaker, weighs the water soluble alkali of certain mass, makes the quality of water soluble alkali and the body of potassium permanganate solution
The ratio between product is 1: 5~1: 20, and water soluble alkali is added in above-mentioned beaker, opens magnetic agitation, makes water soluble alkali completely molten
Solution, the mixed solution being made up of potassium permanganate, deionized water, water soluble alkali is made, weighs the above-mentioned mixed solution of certain mass,
It is placed in treatment trough, weighs the nascent doughnut of certain mass, makes nascent doughnut and above-mentioned mixed solution quality
The ratio between be 1: 5~1: 50, and nascent doughnut is placed in treatment trough, it is immersed in mixed solution, bath temperature will be handled
Degree is increased to 25~95 DEG C, starts timing, and nascent doughnut is post-processed, and finishing time is 5min~6h, rear place
After reason terminates, nascent doughnut is taken out, washed repeatedly with deionized water, fallen until there is no black particle thing, then
Nascent doughnut is placed in air dry oven, under the conditions of 25~50 DEG C dry 1~6h, be made can catalytic oxidant it is quick
Efficient oxidation decomposes the doughnut of a variety of dyestuffs.
A kind of 2. manufacture method of catalysis oxidation disperse dyes doughnut according to claim 1, 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.
A kind of 3. manufacture method of catalysis oxidation disperse dyes doughnut according to claim 1, it is characterised in that institute
The water soluble alkali stated is one kind in sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide.
4. according to a kind of manufacture method of catalysis oxidation disperse dyes doughnut according to any one of claims 1 to 3, its
It is characterised by that described monomer 1 is hydroxyethyl methacrylate, described monomer 2 is n-BMA, described list
Body 3 is n-butyl acrylate, and described initiator is benzoyl peroxide, and described solvent is dimethylformamide, described
Water soluble alkali is sodium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610343408.8A CN105970353B (en) | 2016-05-20 | 2016-05-20 | A kind of manufacture method of catalysis oxidation disperse dyes doughnut |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610343408.8A CN105970353B (en) | 2016-05-20 | 2016-05-20 | A kind of manufacture method of catalysis oxidation disperse dyes doughnut |
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| Publication Number | Publication Date |
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