CN101864034A - Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment - Google Patents
Application of acrylic acid cyclodextrin polymer in dyeing industrial waste water treatment Download PDFInfo
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Abstract
The invention discloses an acrylic acid cyclodextrin polymer represented in a structure formula (I) and a preparation method thereof. In the preparation method, in the presence of an oxidation-reduction system initiator of ammonium persulfate-sodium hydrogensulfite, bulk polymerization and suspension polymerization are carried out on maleic anhydride beta- cyclodextrin and acrylic acid in a water and cyclohexane system to respectively obtain a cyclodextrin polymer which is hydrogel sensitive to pH, wherein the synthesis reaction conditions are mild and simple and easy to control. An adsorption experiment result shows that after a dye solution is subjected to adsorption, the absorbance is obviously reduced, and the invention is particularly suitable for basic dye wastewater treatment.
Description
Technical field
The present invention relates to a kind of acrylic acid cyclodextrin polymer with inclusion function and preparation method thereof, this cyclodextrin can be used for dying industrial wastewater to be handled, and belongs to technical field of polymer chemistry.
Background technology
It is hydrophobic to have an inner chamber as the cyclodextrin of s-generation super molecular compound, the hydrophilic special construction of outer rim, make it become chemistry and the interested research object of chemical research person according to Van der Waals force, hydrophobic interaction power, the intermolecular matching effect of Subjective and Objective etc. and many organic and inorganic molecule formation inclusion compound and molecular assembly systems.The effect of this optionally envelope is that usually said molecular recognition function is used widely in fields such as chemical separation, organic synthesis and catalysis, medicine control, food-processing, environment protection and nano materials.The solubleness of β-CD only is 1.85g in 100ml water, in order to overcome the defective of the solubleness of cyclodextrin own, in recent years natural cyclodextrin is carried out modification and causes very big attention.Cyclodextrin has the ability of catching organic molecule and complexation of metal ions from gas, liquid, the polymer materials that contains cyclodextrin is having important application aspect the environmental protection such as environmental monitoring and wastewater treatment, thereby utilizes cyclodextrin derivative to prepare polymkeric substance to be expected to obtain the higher type material of stability.
Vinylformic acid is mainly used to produce esters of acrylic acid industrial, accounts for about 62% of vinylformic acid aggregate consumption, is applied to fields such as building, papermaking, leather, weaving, plastic working, wrapping material, daily-use chemical industry, metallurgy, oil recovery, water treatment.Polypropylene and acrylic copolymer with vinylformic acid is produced are used as dispersion agent, flocculation agent and thickening material etc. traditionally.The multipolymer that vinylformic acid and maleic anhydride form can be used as copolymer antisludging agent and is applied to water treatment field.Acrylic copolymer also can be used as the seawater dirt dispersion agent.
At present, the method that is used for conventional water treatment has throw out filtration method, water softening, active carbon adsorption, deionization method, reverse osmosis, ultra-filtration method, distillation method and ultraviolet sterilization etc.In the production of dyestuff and use, can produce a large amount of waste water serious harm environment, because waste water from dyestuff complicated component, colourity are good, and contain hazardous substance, the biochemical treatment difficulty, conventional water technology does not reach promising result.Therefore, decolorization of dyeing and be degraded into the problem that water pollution presses for solution in administering.
Summary of the invention
One of purpose of the present invention is to provide a kind of acrylic acid cyclodextrin polymer with favourable absorption function.
Another object of the present invention is to provide the preparation method of above-mentioned polymkeric substance.
Three of purpose of the present invention is to provide the application of acrylic acid cyclodextrin polymer in dying industrial wastewater is handled.
Implementation procedure of the present invention is as follows:
Acrylic acid cyclodextrin polymer shown in the structural formula (I),
N is 20～100.
The preparation method of acrylic acid cyclodextrin polymer of the present invention comprises:
1, the preparation of cyclodextrin derivative MAH-β-CD
2, the preparation of cyclodextrin
In aqueous systems, concrete steps are as follows:
(1) with N, N '-dimethyl formamide is a reaction solvent, and beta-cyclodextrin and maleic anhydride mol ratio are (1: 5)～(1: 20), 40-90 ℃ of reaction 2-10h, synthon cyclodextrin maleic acid derivatives MAH-β-CD;
(2) MAH-β-CD is water-soluble, add initiator ammonium persulfate and monomer vinylformic acid, the monomer total mol concentration is 20-30%, cyclosiloxane monomer dextrin derivative MAH-β-CD and acrylic acid mol ratio are (1: 1)～(1: 10), initiator concentration is 30-90mg/L, 30-80 ℃ of polyreaction 2-10h.
In organic solvent system, concrete steps are as follows:
(1) with N, N '-dimethyl formamide is a reaction solvent, and beta-cyclodextrin and maleic anhydride mol ratio are (1: 5)～(1: 20), 40-90 ℃ of reaction 2-10h, synthon cyclodextrin maleic acid derivatives MAH-β-CD;
(2) with mol ratio be the cyclosiloxane monomer dextrin derivative MAH-β-CD and the vinylformic acid of (1: 1)～(1: 10), and initiator ammonium persulfate and sodium bisulfite are soluble in water, the monomer total mol concentration is 20-30%, initiator concentration is 30-90mg/L, in hexanaphthene, slowly drip above-mentioned mixing solutions, 30-80 ℃ of polyreaction 2-10h, suspension polymerization obtains pulverous cyclodextrin.
Advantage of the present invention and positively effect:
(MAH-β-CD) and vinylformic acid (AA) are at oxidation-reducting system initiator ammonium persulphate (APS)-sodium bisulfite (NaHSO with cyclodextrin derivative maleic anhydride beta-cyclodextrin
3) effect under, obtain novel cyclodextrin-a kind of hydrogel respectively by mass polymerization and suspension polymerization in water and organic solvent system (hexanaphthene) to the pH sensitivity, the synthetic reaction condition gentleness, simple and easy to control.The preparation dye solution is as simulated sewage, and with novel cyclodextrin absorbing dye solution, after the adsorption experiment result showed that dye solution is through absorption, absorbancy obviously reduced, and the present invention is particularly useful for the basic dyestuff wastewater treatment.Compare with traditional method, this novel cyclodextrin compound has good chemical stability, when absorbing dye waste water, reach capacity absorption time short, adsorptive capacity is big, effect is obvious, simple to operate, can directly from dye solution, separate after the absorption, free of a burden to environment, have practical application and promotional value aspect the processing dying industrial wastewater.
Description of drawings
Fig. 1 is the infrared spectra of MAH-β-CD (a) and hydrogel (b);
Fig. 2 is the flight time mass spectrum of MAH-β-CD;
Fig. 3 is the influence (pH=10) of temperature to the swelling row;
Fig. 4 is the influence (T=30 ℃) of pH to swelling behavior.
Embodiment
Mass polymerization in embodiment 1 aqueous systems
Take by weighing 5.68g β-CD and place three-necked bottle, add 30ml exsiccant DMF and make it dissolving, add the 2.45g maleic anhydride then.Stopped reaction behind 40-90 ℃ of stirred in water bath reaction 10h adds excessive trichloromethane and separates out a large amount of white precipitates, and suction filtration gets white precipitate, uses a large amount of washing with acetones, and sealing is preserved.
Take by weighing 2.5gMAH-β-CD and place reaction flask, put into after 50 ℃ of waters bath with thermostatic control make it to dissolve fully, measuring vinylformic acid (mol ratio of vinylformic acid and MAH-β-CD is 1: 5) again adds in the above-mentioned solution, treat that it dissolves fully, behind the logical about 20min of nitrogen, add the aqueous solution of initiator, making initiator concentration is 60mg/L, after continuing logical nitrogen 10min, 60 ℃ of reactions of sealed thermostat 8h, 50 ℃ of following vacuum-dryings promptly get cyclodextrin.
The synthetic polymkeric substance that obtains characterizes by infrared spectra and thermogravimetric.
As shown in Figure 1, by infrared spectra as can be seen, there is following peak: 3389cm in the infrared spectra of MAH-β-CD
-1The place for β-CD-the OH peak, the C-H peak is at 2929cm
-1The place, 1728cm
-1The place is the C=O vibration peak, and the C=C vibration peak is at 1653cm
-1Place and 1027cm
-1The C-O-C vibration peak at place.The infrared figure of final product is 3389,2929 and 1027cm
-1There are strong absorption peak, 2300cm in the place
-1The peak at place disappears and to show and make aquogel polymer.
As shown in Figure 2, in the flight time mass spectrum of MAH-β-CD, nearly all MAH-β-CD connects 1 or 2 maleic anhydride on the position of 21-OH of cyclodextrin.Introduce two keys to cyclodextrin molecular, when improving its solubleness, reaction provides the foundation with polymerizing acrylic acid for next step.
Suspension polymerization in embodiment 2 organic systems
Take by weighing 5.68g β-CD and place three-necked bottle, add 30ml exsiccant DMF and make it dissolving, add the 2.45g maleic anhydride then.Stopped reaction behind 40-90 ℃ of stirred in water bath reaction 10h adds excessive trichloromethane and separates out a large amount of white precipitates, and suction filtration gets white precipitate, uses a large amount of washing with acetones, and sealing is preserved.
With 2.5g cyclosiloxane monomer dextrin derivative MAH-β-CD and vinylformic acid (mol ratio is 1: 5), and initiator ammonium persulfate and sodium bisulfite (APS and NaHSO
3Mol ratio be 1: 1) soluble in water, initiator concentration is 50mg/L, slowly drips above-mentioned mixing solutions in the hexanaphthene behind letting nitrogen in and deoxidizing, 30-80 ℃ of polyreaction 2-10h, suspension polymerization obtains pulverous cyclodextrin.
In the present invention, (MAH-β-CD) is because beta-cyclodextrin and maleic anhydride all are dissolved in DMF, so employing DMF is as reaction solvent at first to prepare cyclodextrin derivative monomer maleic anhydride beta-cyclodextrin.Temperature of reaction is at 40-90 ℃, and yield is the highest in the time of 80 ℃.Reaction times 2-10h, yield is the highest during 10h.After reaction stops, adding excessive trichloromethane and separate out a large amount of white precipitates, suction filtration, white precipitate extracts 12h with acetone as the solvent Soxhlet, and calculating productive rate after the vacuum-drying is 78.5%.
The swelling experiment of embodiment 3 hydrogels
The xerogel that accurately takes by weighing certain mass places the buffered soln of the different pH of 10ml (3～10), investigates it in differing temps, the swelling ratio of different swelling times.Before weighing, the water of hydrogel surface must be dried with filter paper.Swelling ratio (SR) calculation formula is as follows:
SR＝(w
t-w
d)/w
d
W in the formula
dBe the quality (g) of xerogel, w
tQuality (g) for hydrogel after the certain hour swelling.
As shown in Figure 3 and Figure 4, the swelling ratio of hydrogel increases along with the increase of pH value.Under acidic conditions ,-COO
-Form with-COOH exists, simultaneously hydrogel-OH and-can form hydrogen bond between the COOH, these all can cause the swelling ratio of hydrogel less; When the pH value increased to alkaline range, most-COOH can become-COO
-,-OH and-hydrogen bond rupture between the COOH, cause the swelling ratio of hydrogel to increase.
The adsorption experiment of example 4 dyestuffs
Take by weighing the cyclodextrin 0.1g of preparation, place the 25ml Erlenmeyer flask, the pH buffered soln that adds certain density dye solution of 10ml and 10ml mixes, and Erlenmeyer flask is placed the thermostatic water-circulator bath vibrator.In certain temperature, carry out adsorption experiment under the oscillation frequency 130rpm.Absorption back centrifuging and taking supernatant liquor under the maximum absorption wavelength of dye solution, is measured its absorbancy with ultraviolet-visible spectrophotometer.
Dye adsorption result of experiment shows: the absorbancy of dye solution after handling with cyclodextrin of the present invention obviously reduces, and the adsorptive capacity of dyestuff methylene blue and magenta is respectively 22.7mg/g and 19.9mg/g.
Table 1 methylene blue dyestuff adsorption time is to the influence of percent of decolourization
| Adsorption time/min | ??5 | ??10 | ??15 | ??20 | ??25 | ??30 |
| Percent of decolourization/% | ??17.5 | ??28.4 | ??42.3 | ??59.8 | ??78.0 | ??94.5 |
The adsorption time of methylene blue dyestuff is to the influence of percent of decolourization as can be seen from the above table, adsorbs to reach capacity when 30min, and percent of decolourization reaches 94.5%.Adsorption time surpasses 30min, and percent of decolourization does not have considerable change.
Table 2 alkaline fuchsin dye adsorption time is to the influence of percent of decolourization
| Adsorption time/min | ??15 | ??30 | ??60 | ??90 | ??120 | ??150 |
| Percent of decolourization/% | ??12.7 | ??19.4 | ??37.6 | ??54.2 | ??76.5 | ??81.3 |
Alkaline fuchsin dye is in the absorption absorption that reaches capacity during 150min as can be seen from the above table, and percent of decolourization reaches 81.3%.Prolong adsorption time again, to not influence of percent of decolourization.
Take by weighing the cyclodextrin 0.1g of preparation, place the 25ml Erlenmeyer flask, add the certain density dye solution of 10ml, Erlenmeyer flask is placed the thermostatic water-circulator bath vibrator.In certain temperature, carry out adsorption experiment under the oscillation frequency 130rpm.Absorption back centrifuging and taking supernatant liquor under the maximum absorption wavelength of dye solution, is measured its absorbancy with ultraviolet-visible spectrophotometer.
It is that the absorption of representative and basic dyestuff contrasts that the Congo red and eosin B of matching stain is selected in experiment for use:
The Congo red dye adsorption time of table 1 is to the influence of percent of decolourization
| Adsorption time/min | ??15 | ??30 | ??60 | ??90 | ??120 | ??150 |
| Percent of decolourization/% | ??4.3 | ??7.8 | ??9.6 | ??12.5 | ??14.9 | ??16.3 |
The dye adsorption time of table 2 eosin B is to the influence of percent of decolourization
| Adsorption time/min | ??15 | ??30 | ??60 | ??90 | ??120 | ??150 |
| Percent of decolourization/% | ??2.7 | ??4.8 | ??6.4 | ??7.9 | ??9.2 | ??11.5 |
By the Congo red and absorbancy numerical value change of eosin B in 150min of record matching stain, the percent of decolourization that calculates dyestuff is listed in table 1 and the table 2 respectively.After comparing with the percent of decolourization of basic dyestuff methylene blue and magenta, cyclodextrin obviously is better than absorption to matching stain to the absorption of basic dyestuff as can be seen.
Claims (5)
1. the acrylic acid cyclodextrin polymer shown in the structural formula (I),
2. the preparation method of the described acrylic acid cyclodextrin polymer of claim 1 may further comprise the steps:
(1) with N, N '-dimethyl formamide is a reaction solvent, and beta-cyclodextrin and maleic anhydride mol ratio are (1: 5)～(1: 20), 40-90 ℃ of reaction 2-10h, synthon cyclodextrin maleic acid derivatives MAH-β-CD;
(2) MAH-β-CD is water-soluble, add monomer vinylformic acid and initiator ammonium persulfate, the monomer total mol concentration is 20-30%, cyclosiloxane monomer dextrin derivative MAH-β-CD and acrylic acid mol ratio are (1: 1)～(1: 10), initiator concentration is 30-90mg/L, 30-80 ℃ of polyreaction 2-10h.
3. the preparation method of the described acrylic acid cyclodextrin polymer of claim 1 may further comprise the steps:
(1) with N, N '-dimethyl formamide is a reaction solvent, and beta-cyclodextrin and maleic anhydride mol ratio are (1: 5)～(1: 20), 40-90 ℃ of reaction 2-10h, synthon cyclodextrin maleic acid derivatives;
(2) with mol ratio be the cyclosiloxane monomer dextrin derivative MAH-β-CD and the vinylformic acid of (1: 1)～(1: 10), and initiator ammonium persulfate and sodium bisulfite are soluble in water, the monomer total mol concentration is 20-30%, initiator concentration is 30-90mg/L, in hexanaphthene, slowly drip above-mentioned mixing solutions, 30-80 ℃ of polyreaction 2-10h, suspension polymerization obtains pulverous cyclodextrin.
4. the application of the described acrylic acid cyclodextrin polymer of claim 1 in dying industrial wastewater is handled.
5. the described acrylic acid cyclodextrin polymer of claim 1 is in the basic dyestuff Application in Industrial Wastewater Treatment.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102634992A (en) * | 2012-05-02 | 2012-08-15 | 江南大学 | Method for dyeing cyclodextrin cross-linked modified polyester, cotton and blended fabric by cationic dyes |
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN103145256A (en) * | 2013-03-18 | 2013-06-12 | 武汉理工大学 | Preparation method and application of ternary high polymer copolymer scale inhibitor |
| CN103303998A (en) * | 2013-06-28 | 2013-09-18 | 山东大学 | Method for purifying cationic dye wastewater based on lithocholic acid salt gel adsorption |
| CN104120607A (en) * | 2014-07-16 | 2014-10-29 | 陕西科技大学 | Preparation method of grafting modified beta-cyclodextrin aromatic finishing agent |
| CN104327198A (en) * | 2014-05-15 | 2015-02-04 | 中国农业科学院原子能利用研究所 | Maleic acid [beta]-cyclodextrin ester and preparation method thereof |
| CN107162747A (en) * | 2017-07-11 | 2017-09-15 | 河南工业大学 | A kind of preparation method of multi-functional composite aquogel slow release fertilizer |
| EP3176221A4 (en) * | 2014-08-02 | 2018-04-18 | LG Chem, Ltd. | Dye complex, photoconversion film and electronic element including same |
| CN109054844A (en) * | 2018-07-16 | 2018-12-21 | 四川省兰月科技有限公司 | Multifunctional protective aqua and preparation method |
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| CN102634992A (en) * | 2012-05-02 | 2012-08-15 | 江南大学 | Method for dyeing cyclodextrin cross-linked modified polyester, cotton and blended fabric by cationic dyes |
| CN102872836A (en) * | 2012-09-11 | 2013-01-16 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN102872836B (en) * | 2012-09-11 | 2014-01-29 | 安徽理工大学 | Cyclodextrin immobilized macromolecular polymer and preparation method and application thereof |
| CN103145256A (en) * | 2013-03-18 | 2013-06-12 | 武汉理工大学 | Preparation method and application of ternary high polymer copolymer scale inhibitor |
| CN103145256B (en) * | 2013-03-18 | 2014-04-09 | 武汉理工大学 | Preparation method and application of ternary high polymer copolymer scale inhibitor |
| CN103303998A (en) * | 2013-06-28 | 2013-09-18 | 山东大学 | Method for purifying cationic dye wastewater based on lithocholic acid salt gel adsorption |
| CN103303998B (en) * | 2013-06-28 | 2014-07-23 | 山东大学 | Method for purifying cationic dye wastewater based on lithocholic acid salt gel adsorption |
| CN104327198B (en) * | 2014-05-15 | 2016-11-02 | 中国农业科学院原子能利用研究所 | Maleic acid beta-schardinger dextrin-ester and preparation method thereof |
| CN104327198A (en) * | 2014-05-15 | 2015-02-04 | 中国农业科学院原子能利用研究所 | Maleic acid [beta]-cyclodextrin ester and preparation method thereof |
| CN104120607B (en) * | 2014-07-16 | 2016-07-13 | 陕西科技大学 | A kind of preparation method of graft modification beta-schardinger dextrin-Aroma finishing agent |
| CN104120607A (en) * | 2014-07-16 | 2014-10-29 | 陕西科技大学 | Preparation method of grafting modified beta-cyclodextrin aromatic finishing agent |
| EP3176221A4 (en) * | 2014-08-02 | 2018-04-18 | LG Chem, Ltd. | Dye complex, photoconversion film and electronic element including same |
| CN107162747A (en) * | 2017-07-11 | 2017-09-15 | 河南工业大学 | A kind of preparation method of multi-functional composite aquogel slow release fertilizer |
| CN107162747B (en) * | 2017-07-11 | 2021-03-12 | 河南工业大学 | Preparation method of multifunctional composite water-retention slow-release fertilizer |
| CN109054844B (en) * | 2018-07-16 | 2020-09-22 | 四川省兰月科技有限公司 | Multifunctional water-retaining agent and preparation method thereof |
| CN109054844A (en) * | 2018-07-16 | 2018-12-21 | 四川省兰月科技有限公司 | Multifunctional protective aqua and preparation method |
| CN109456422B (en) * | 2018-11-14 | 2020-04-14 | 河北科技大学 | Hyperbranched hemicellulose polymer and preparation method and application thereof |
| CN109456422A (en) * | 2018-11-14 | 2019-03-12 | 河北科技大学 | A kind of hyperbranched hemicellulose polymer and its preparation method and application |
| CN109722187A (en) * | 2018-12-26 | 2019-05-07 | 肖彬 | Automobile sun blind Aqueous Adhesives and its production technology |
| CN115318345A (en) * | 2022-08-29 | 2022-11-11 | 顾泓刚 | Manufacturing device and application of hypochlorous acid |
| CN115318345B (en) * | 2022-08-29 | 2024-04-05 | 顾泓刚 | Hypochlorous acid manufacturing device and application thereof |
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