CN111154027A - Preparation method and application of temperature-sensitive composite hydrogel utilizing photocatalysis and temperature-sensitive synergistic effect - Google Patents
Preparation method and application of temperature-sensitive composite hydrogel utilizing photocatalysis and temperature-sensitive synergistic effect Download PDFInfo
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Abstract
The invention relates to the technical field of printing and dyeing wastewater treatment, and discloses a preparation method and application of a temperature-sensitive composite hydrogel utilizing photocatalysis and temperature-sensitive synergistic effects. The photocatalyst embedded in the hydrogel can be used for degrading the adsorption dye and recycling the composite hydrogel, and can be applied to the fields of printing and dyeing sewage treatment and the like.
Description
Technical Field
The invention relates to the technical field of printing and dyeing wastewater treatment, in particular to a preparation method and application of a temperature-sensitive composite hydrogel with a good removal function on organic dyes such as methylene blue and malachite green.
Background
Up to now, the removal of dyes from printing and dyeing wastewater has remained a problem in industry. At present, the treatment method aiming at organic dye pollution mainly comprises a physical-chemical method, a chemical method and a biological method. Physical methods usually remove large-particle impurities by precipitation, centrifugation, adsorption, filtration (screening), air flotation and other methods without changing the properties of sewage and impurities. The chemical method is that some chemical substances are added into the water body to react with the pollutants in the water, such as water-insoluble salt or decomposed into non-toxic and harmless micromolecules, thereby achieving the purpose of water treatment and purification. The biological method is to create an environment suitable for mass propagation of anaerobic microorganisms or aerobic microorganisms in a water body through manual intervention, and purify sewage through microbial oxidation, decomposition of organic pollutants and conversion of the organic pollutants into harmless substances.
The photocatalytic degradation method, which is a novel technique, is widely used for photocatalysis due to its excellent thermal and chemical stability and photocatalytic propertiesDecomposition of water (H)2Decomposition and water decomposition) and photocatalytic degradation of pollutants. The photocatalyst can oxidize and decompose organic pollutants adsorbed on the surface of the photocatalyst into CO under the condition of light irradiation2，H2O and some simple small molecules.
However, the photocatalyst mostly exists in the form of nano-scale or micron-scale powder or flake, so that the generated high specific surface energy and strong agglomeration tendency greatly reduce the catalytic activity and selectivity when the photocatalyst is used as a catalyst, and the photocatalyst is not easy to separate after the reaction is finished to cause the loss of the catalyst, thereby causing environmental pollution. To solve this problem, it is critical to select a good carrier to load it.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method and application of a temperature-sensitive composite hydrogel utilizing photocatalysis and temperature sensitivity synergistic effects. The temperature-sensitive composite hydrogel is prepared by introducing a temperature-sensitive copolymer and a photocatalyst into alginate hydrogel, wherein the porosity of the hydrogel is adjustable in the temperature change process, and the hydrogel can adsorb and degrade dyes under the illumination condition. The photocatalyst embedded in the hydrogel can be used for degrading the adsorption dye and recycling the composite hydrogel, and can be applied to the fields of printing and dyeing sewage treatment and the like.
The technical scheme of the invention is as follows: a preparation method of temperature-sensitive composite hydrogel doped with photocatalyst and having an interpenetrating network structure is characterized in that the hydrogel is prepared by free radical polymerization of temperature-sensitive monomer M1, temperature-sensitive monomer M2, chemical cross-linking agent M3, photocatalyst M4 and alginate M5 which are used as reaction raw materials according to the mass ratio of (5-70) to (15-99) to (0-25) to (0-50) to (0-99).
Preferably, the preparation method specifically comprises the following steps:
1) sequentially adding a temperature-sensitive monomer M1, a temperature-sensitive monomer M2, a chemical cross-linking agent M3, a photocatalyst M4 and alginate M5 into deionized water to prepare an aqueous solution with the mass concentration of 5-20%, introducing inert gas into a sealed container at 15-25 ℃, and stirring for 30-70min until the mixture is completely dispersed to form a uniform mixed solution.
2) Adding an initiator into the mixed solution, injecting a stabilizer after 5-15min, and continuing to react for 25-35min under the protection of inert gas until the mixed solution begins to be in a gel state.
3) Standing the mixed solution in gel state at 20-30 deg.C, sealing for 10-36h, and placing the reaction product in divalent cation solution to replace cation in alginate; taking out, soaking in deionized water for 1-3 days, and freeze drying to obtain the temperature-sensitive composite hydrogel.
The preparation raw materials of the temperature-sensitive composite hydrogel mainly comprise a photocatalyst, alginate and two temperature monomers, the hydrogel is used as a carrier of the photocatalyst, and the high adsorption and degradation performance is realized through the synergistic effect of the photocatalyst and the hydrogel. The introduction of the photocatalyst increases the porosity of the hydrogel. By means of the temperature-sensitive characteristic of the introduced temperature-sensitive copolymer, when the temperature of the solution rises to be higher than the hydrogel transition temperature, the temperature-sensitive polymer in the interpenetrating network structure collapses in the composite hydrogel to cause larger porosity, and the dye adsorption performance is further enhanced. The photocatalyst embedded in the hydrogel can be used for degrading the adsorbed dye and recycling the composite hydrogel. The composite hydrogel material is simple to prepare, wide in application range, high in efficiency and strong in reusability. And TT is adjusted to the required temperature by simply adjusting the type and the molar ratio of the temperature-sensitive monomers in the composite hydrogel, so that the aim of adapting to practical application to a greater extent is fulfilled.
Specifically, in the invention, temperature-sensitive monomers M1 and M2 and a cross-linking agent M3 are copolymerized in an aqueous solution through free radical polymerization to serve as a first phase in an interpenetrating network structure, alginate M5 is used as a second phase in the interpenetrating network structure, and a photocatalyst M4 is uniformly dispersed in hydrogel to prepare the temperature-sensitive composite hydrogel with high adsorption and rapid degradation characteristics, excellent mechanical properties and self-cleaning performance. The photocatalyst embedded in the hydrogel can be used for degrading the adsorbed dye and recycling the temperature-sensitive composite hydrogel.
The temperature-sensitive composite hydrogel can adsorb pollutants below the transition temperature and discharge water above the transition temperature to form a porous structure, so that the adsorption rate is further improved. Furthermore, in order to improve the defects of compact structure, low adsorption rate, poor recycling performance and the like of the temperature-sensitive hydrogel, in the research of the inventor, the photocatalyst is introduced into the interpenetrating network temperature-sensitive hydrogel, and on one hand, doped photocatalyst nanoparticles can be uniformly dispersed in the hydrogel, so that the catalyst agglomeration is prevented, and the catalytic activity is reduced; on the other hand, the key point is that the catalyst can induce holes in the hydrogel to provide a channel for catalytic reaction, so that pollutant molecules are more fully contacted with the photocatalyst, and the photodegradation rate is improved. After the dye is adsorbed by the hydrogel, the photocatalyst synergistically degrades the dye. Meanwhile, the temperature of the aqueous solution is expected to be increased, the temperature-sensitive polymer network in the interpenetrating network structure is contracted, and the porosity of the hydrogel is increased, so that the adsorption performance with higher efficiency can be realized.
Preferably, the mass percentages of the temperature-sensitive monomer M1, the temperature-sensitive monomer M2, the chemical cross-linking agent M3, the photocatalyst M4 and the alginate M5 are (5-50) to (15-70) to (0-20) to (0-40) to (0-50).
The temperature-sensitive composite hydrogel prepared by the above proportion has a uniform pore structure, the transition temperature of the temperature-sensitive composite hydrogel is 0-90 ℃, and an interpenetrating network structure formed by the alginate phase and the temperature-sensitive polymer phase is stable, and the pores are kept to be proper in size and uniform in distribution. The photocatalyst catalyzes and degrades the dye and the temperature-sensitive polymer to shrink so as to increase the porosity and improve the adsorption rate of the hydrogel, the synergistic effect of the photocatalyst and the temperature-sensitive polymer can play the maximum efficiency, and the synergistic adsorption and degradation of the dye can be realized. When the content of the photocatalyst is too high, the photocatalyst can be aggregated and even block holes formed by an interpenetrating network structure; when the content of the photocatalyst is too low, the degradation efficiency is slow, the time consumption is too long, and the wastewater treatment cost is increased. The hydrogel hole structure formed by the low proportion of the temperature-sensitive monomer and the alginate is less or even has no holes; the proportion of the temperature-sensitive monomer and the alginate is too high, and the hole structure in the interpenetrating network structure is gradually irregular, so that the performance of the hydrogel is influenced. The dosage of the cross-linking agent has obvious influence on the pore structure of the hydrogel, the hydrogel is changed into hard gel from irregular gel with nasal discharge along with the gradual increase of the dosage of the cross-linking agent, and the pore structure in the hydrogel is also changed into shallow and dense pore structure from loose and large pores.
Preferably, the structural general formulas of the temperature-sensitive monomer M1 and the temperature-sensitive monomer M2 are as follows:
wherein:
R1is-CH3or-H or
R2Is composed of
X is 1-10 and Y is 1-12.
The acrylic ester and acrylamide temperature-sensitive monomers are selected, and contain more water-absorbing groups, such as: hydroxyl, carboxyl, and amino groups, and the like. The acrylic ester temperature-sensitive monomer can adjust the transition temperature of the temperature-sensitive polymer by adjusting the number of side chain ethoxy groups, and in addition, the transition temperature can be controlled by the proportion of the acrylic ester and the acrylamide temperature-sensitive monomer.
The molar ratio of the temperature-sensitive monomer M1 to the temperature-sensitive monomer M2 is (1-99) to (1-200), and the transition temperature of the temperature-sensitive composite hydrogel is 0-150 ℃.
Further preferably, X is 2 to 6; y is 1 to 8; the molar ratio of the temperature-sensitive monomer M2 is (1-50) to (1-75), and the transition temperature of the temperature-sensitive composite hydrogel is 0-90 ℃.
Preferably, the alginate M5 is sodium alginate or calcium alginate.
Preferably, the chemical crosslinking agent M3 is N, N ' -methylene bisacrylamide, the initiator is ammonium persulfate or potassium persulfate, and the accelerator is N, N, N ', N ' -tetramethyl ethylenediamine.
Preferably, the dosage of the initiator is 0.1-20% of the total mass of the five reaction raw materials, and the stabilizer is 0.1-10% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-50 w/v%; the replacement time with the divalent cation solution is 1-24 h.
More preferably, the dosage of the initiator is 0.1-15% of the total mass of the five reaction raw materials, and the stabilizer is 0.1-5% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-20 w/v%; the replacement time with the divalent cation solution is 1-12 h.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) the photocatalyst-doped alginate-temperature-sensitive copolymer interpenetrating network structure temperature-sensitive composite hydrogel disclosed by the invention has an interpenetrating polymer network structure, takes a temperature-sensitive polymer system as a first network, takes sodium alginate and calcium ion crosslinking as a second network, is used for enhancing the mechanical strength of the hydrogel, maintains the temperature-sensitive characteristic of the hydrogel, enables the hydrogel to be gelled in a shorter time, has higher mechanical strength, and can be better applied to the application of adsorbing and degrading pollutants.
(2) The temperature-sensitive composite hydrogel is prepared by adopting a free radical polymerization method, controllable operation on the porosity, the mechanical strength and the like of the hydrogel can be realized by changing the using amount of the photocatalyst and the proportion of the temperature-sensitive monomers, and the hydrogel with any required shape can be prepared by adjusting a hydrogel preparation mold, namely controllable appearance size of the hydrogel. The photocatalyst is doped in the hydrogel prepared by the invention, so that pollutants such as dye and the like absorbed in the hydrogel can be completely degraded under the condition of light irradiation environment, and the temperature-sensitive composite hydrogel has good reusability. In addition, the temperature-sensitive composite hydrogel has hydrophilicity below TT, and the surface can be easily cleaned by flushing with cold water. Based on the characteristics of synergistic adsorption and easy cleaning, the temperature-sensitive composite hydrogel has wide application prospect and potential commercial value.
Drawings
FIG. 1 is a schematic view showing the preparation of a temperature-sensitive composite hydrogel in example 1 of the present invention;
FIG. 2 is a graph of the ultraviolet-visible spectrum of the aqueous solution of the dye before and after the temperature-sensitive composite hydrogel is adsorbed and degraded under simulated illumination conditions in example 2 of the present invention;
FIG. 3 is a graph showing the K/S value change before and after the temperature-sensitive hydrogel is adsorbed and degraded under simulated illumination conditions in example 3 of the present invention;
FIG. 4 is a graph showing the time-dependent change of the adsorption degradation rate of the temperature-sensitive composite hydrogel under simulated illumination conditions in example 3 of the present invention;
FIG. 5 is a graph showing the influence of temperature on the adsorption degradation rate of temperature-sensitive composite hydrogel under simulated illumination in example 3 of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
A method for preparing temperature-sensitive composite hydrogel by utilizing photocatalysis and temperature-sensitive synergistic effect is characterized in that the hydrogel is prepared by taking a temperature-sensitive monomer M1, a temperature-sensitive monomer M2, a chemical cross-linking agent M3, a photocatalyst M4 and alginate M5 as reaction raw materials in a mass ratio of (5-70) to (15-99) to (0-25) to (0-50) to (0-99) and carrying out free radical polymerization in an aqueous solution.
Preferably, the preparation method specifically comprises the following steps:
1) sequentially adding a temperature-sensitive monomer M1, a temperature-sensitive monomer M2, a chemical cross-linking agent M3, a photocatalyst M4 and alginate M5 into deionized water to prepare an aqueous solution with the mass concentration of 5-20%, introducing inert gas into a sealed container at 15-25 ℃, and stirring for 30-70min until the mixture is completely dispersed to form a uniform mixed solution.
2) Adding an initiator into the mixed solution, injecting a stabilizer after 5-15min, and continuing to react for 25-35min under the protection of inert gas until the mixed solution begins to be in a gel state.
3) Standing the mixed solution in gel state at 20-30 deg.C, sealing for 10-36h, and placing the reaction product in divalent cation solution to replace cation in alginate; taking out, soaking in deionized water for 1-3 days, and freeze drying to obtain the temperature-sensitive composite hydrogel.
Preferably, the mass percentages of the temperature-sensitive monomer M1, the temperature-sensitive monomer M2, the chemical cross-linking agent M3, the photocatalyst M4 and the alginate M5 are (5-50) to (15-70) to (0-20) to (0-40) to (0-50).
Preferably, the structural general formulas of the temperature-sensitive monomer M1 and the temperature-sensitive monomer M2 are as follows:
wherein:
R1is-CH3or-H or
R2Is composed of
X is 1-10 and Y is 1-12;
the molar ratio of the temperature-sensitive monomer M1 to the temperature-sensitive monomer M2 is (1-99) to (1-200), and the transition temperature of the temperature-sensitive composite hydrogel is 0-150 ℃. Further preferably, X is 2 to 6; y is 1 to 8; the molar ratio of the temperature-sensitive monomer M2 is (1-50) to (1-75), and the transition temperature of the temperature-sensitive composite hydrogel is 0-90 ℃.
Preferably, the alginate M5 is sodium alginate or calcium alginate. The chemical cross-linking agent M3 is N, N ' -methylene bisacrylamide, the initiator is ammonium persulfate or potassium persulfate, and the accelerator is N, N, N ', N ' -tetramethyl ethylenediamine.
Preferably, the dosage of the initiator is 0.1-20% of the total mass of the five reaction raw materials, and the stabilizer is 0.1-10% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-50 w/v%; the replacement time with the divalent cation solution is 1-24 h. More preferably, the dosage of the initiator is 0.1-15% of the total mass of the five reaction raw materials, and the stabilizer is 0.1-5% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-20 w/v%; the replacement time with the divalent cation solution is 1-12 h.
Example 1
1) 929. mu.L (5mmol) of MEO was added to the sample vial2MA monomer (molecular formula
Purchased from SigmaAldrich), 2857. mu.L (10mmol) of OEGMA300(molecular formula Sound)
Purchased from sigma aldrich), 0.2g of sodium alginate was dissolved in 10mL of deionized water to obtain a mixed solution a;
2) 5mg of cross-linking agents MBAA and 1gg-C are added into the mixed solution A3N4Carrying out ultrasonic dispersion on the photocatalyst uniformly to obtain a mixed solution B;
3) blowing nitrogen into the mixed solution B for 20min, adding 0.02g (0.088mmol) of initiator APS and 10 mu L (0.067mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, 5% (w/v) calcium chloride (CaCl) is used2) Soaking the solution for 5h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
Calcium alginate/P (MEO)2MA-co-OEGMA300)/g-C3N4The reaction system of the IPN temperature-sensitive composite hydrogel comprises a temperature-sensitive monomer MEO2MA、OEGMA300Photocatalyst g-C3N4And a sodium alginate solution. Wherein the monomer MEO2MA、OEGMA300And a crosslinking agent MBAA to form a chemically crosslinked network, g-C3N4Uniformly mixed in an interpenetrating network structure, calcium alginate penetrates through P (MEO) in a physical entanglement mode2MA-co-OEGMA300) In the crosslinked network, by Ca2+The ion exchange effect of the sodium alginate and calcium alginate form an egg box structure. Calcium alginate/P (MEO)2MA-co-OEGMA300)/g-C3N4The schematic diagram of the formation of the IPN temperature-sensitive composite hydrogel is shown in fig. 1. In the whole system, P (MEO)2MA-co-OEGMA300) The polymer network and the calcium alginate network system are mutually interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively maintain the unique property of the two networks, g-C3N4The photocatalyst is uniformly dispersed in the hydrogel.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (MEO)2MA-co-OEGMA300) And photocatalyst g-C3N4Introduced into calcium alginate hydrogel to successfully prepare g-C3N4IPN temperature-sensitive composite hydrogel. The temperature-sensitive composite hydrogel can realize the adjustability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (MEO)2MA-co-OEGMA300) The polymer network and the calcium alginate network system are interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively keep the unique properties of the two networks. P (MEO) during temperature rise2MA-co-OEGMA300) Collapse of the polymer network at g-C3N4Greater porosity is caused in the IPN temperature-sensitive composite hydrogel, and the additional holes can be used as methylene blue to diffuse to g-C3N4And (3) a channel of the IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. g-C obtained3N4The IPN temperature-sensitive composite hydrogel has good recyclability and can simulate the visible light irradiation environmentUnder the condition, the synchronous proceeding of the adsorption and the photodegradation can be realized. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily cleaned by washing with cold water, which is particularly suitable for industrial application. Calcium alginate/P (MEO)2MA-co-OEGMA300)/g-C3N4The synergistic adsorption degradation and easy-to-clean performance of the IPN temperature-sensitive composite hydrogel make the IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed by means of sunlight in the daytime. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to be widely developed in the field of printing and dyeing wastewater treatment.
Example 2
1) 566mg (5mmol) of NIPAM monomer (molecular formula
From Macklin), 2857. mu.L (10mmol) of OEGMA300(the formula is
Purchased from Sigma Aldrich), 0.1g of calcium alginate was dissolved in 10mL of deionized water to obtain a mixed solution a;
2) 10mg of a crosslinking agent MBAA and 0.2g of TiO were added to the mixed solution A2Carrying out ultrasonic dispersion on the photocatalyst uniformly to obtain a mixed solution B;
3) bubbling nitrogen into the mixed solution B for 20min, adding 0.03g (0.132mmol) of initiator APS and 15 mu L (0.1005mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, barium chloride (CaCl) with the concentration of 2% (w/v) is used2) Soaking the solution for 5h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
And measuring the absorbance of the simulated waste water solution at different time intervals by using an ultraviolet spectrophotometer, and representing that the composite hydrogel has an adsorption degradation effect on the dye. NIPAM and OEGMA in composite hydrogel300TiO with the molar ratio of 5: 102The amount of the photocatalyst used was 0.2 g. According to the time-varying graph of absorbance, as shown in fig. 2, the particle size of the methylene blue dye with the original concentration of 10mg/mL continuously decreases under the synergistic effect of adsorption and degradation of the composite hydrogel. The composite hydrogel is proved to have the functions of adsorbing and degrading methylene blue in a simulated waste water solution, has better effect and can be used as a water treatment adsorbent material.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (NIPAM-co-OEGMA)300) And photocatalyst TiO2The barium alginate hydrogel is introduced to successfully prepare the TiO2IPN temperature-sensitive composite hydrogel. The temperature-sensitive composite hydrogel can realize the adjustability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (NIPAM-co-OEGMA)300) The polymer network and the barium alginate network system are interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively keep the unique properties of the two networks. P (NIPAM-co-OEGMA) during temperature rise300) Collapse of polymer network in TiO2Greater porosity is caused in the IPN temperature-sensitive composite hydrogel, and the additional holes can be used as methylene blue to diffuse into TiO2And (3) a channel of the IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. Obtained TiO2The IPN temperature-sensitive composite hydrogel has good recyclability, and can realize synchronous adsorption and photodegradation under the environment condition of simulating ultraviolet irradiation. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily cleaned by washing with cold water, which is particularly suitable for industrial application. Barium alginate/P (NIPAM-co-OEGMA)300)/TiO2The synergistic adsorption degradation and easy-to-clean performance of the IPN temperature-sensitive composite hydrogel make the IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed under the environment condition of ultraviolet irradiation. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to be widely developed in the field of printing and dyeing wastewater treatment.
Example 3
1) 1190mg (10mmol) of NDEAm monomer (formula
Purchased from Sigma Aldrich), 2857. mu.L (10mmol) of OEGMA300(the formula is
Purchased from Sigma Aldrich), 0.15g of sodium alginate was dissolved in 10mL of deionized water to obtain a mixed solution a;
2) adding 15mg of cross-linking agent and 0.5g of ZnO photocatalyst into the mixed solution A, and uniformly dispersing by ultrasonic to obtain a mixed solution B;
3) blowing nitrogen into the mixed solution B for 20min, adding 0.02g (0.088mmol) of initiator APS and 10 mu L (0.067mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, calcium chloride (CaCl) with the concentration of 3% (w/v) is used2) Soaking the solution for 5h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
And measuring the absorbance of the simulated waste water solution at different time intervals by using an ultraviolet spectrophotometer, and calculating to obtain the adsorption degradation rate of the composite hydrogel to the dye. NDEAm and OEGMA in composite hydrogel300The molar ratio is 10: 10, and the amount of ZnO photocatalyst is 0.5 g. The adsorption degradation rate is calculated through absorbance, as shown in fig. 3, the adsorption degradation rate of the hydrogel with different specific surface knots on methylene blue dye reaches 99.9% after 12 hours in a simulated solar illumination environment, and the adsorption degradation effect is better when the specific surface area is larger. The composite hydrogel is proved to have the functions of adsorbing and degrading methylene blue in a simulated waste water solution, has better effect and can be used as a water treatment adsorbent material.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (NDEAm-co-OEGMA)300) Introducing calcium alginate water into photocatalyst ZnOIn the glue, the ZnO IPN temperature-sensitive composite hydrogel is successfully prepared. The temperature-sensitive composite hydrogel can realize the adjustability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (NDEAm-co-OEGMA)300) The polymer network and the calcium alginate network system are interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively keep the unique properties of the two networks. P (NDEAm-co-OEGMA) during the temperature rise300) The polymer network collapses, greater porosity is caused in the ZnO IPN temperature-sensitive composite hydrogel, and the additional holes can serve as channels for methylene blue to diffuse into the ZnO IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. The obtained ZnO IPN temperature-sensitive composite hydrogel has good recoverability, and can realize synchronous adsorption and photodegradation under the environment condition of simulated light irradiation. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily cleaned by washing with cold water, which is particularly suitable for industrial application. Calcium alginate/P (NDEAm-co-OEGMA)300) The synergistic adsorption degradation and easy-to-clean performance of the ZnO IPN temperature-sensitive composite hydrogel make the ZnO IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the ZnO IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed under the environment condition of light irradiation. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to be widely developed in the field of printing and dyeing wastewater treatment.
Example 4
1) 545mg (5mmol) of NEAm monomer (molecular formula
Purchased from SigmaAldrich), 1838. mu.L (10mmol) of MEO2MA monomer (molecular formula
Purchased from sigma aldrich), 0.1g of sodium alginate was dissolved in 10mL of deionized water to obtain a mixed solution a;
2) 5mg of a crosslinking agent and 0.1g g-C were added to the mixed solution A3N4Carrying out ultrasonic dispersion on the photocatalyst uniformly to obtain a mixed solution B;
3) blowing nitrogen into the mixed solution B for 20min, adding 0.02g (0.088mmol) of initiator APS and 10 mu L (0.067mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, 5% (w/v) calcium chloride (CaCl) is used2) Soaking the solution for 5h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
The color depth before and after the temperature-sensitive composite hydrogel adsorbs the dye is simply represented by the K/S value. The K/S values of the three samples before adsorption were 3.18, 8.89, 8.49, respectively. After adsorption, calcium alginate/P (NEAm-co-MEO) can be seen from the optical photograph in FIG. 42MA) IPN temperature-sensitive hydrogel, calcium alginate/P (NEAm-co-MEO)2MA)/g-C3N4IPN temperature-sensitive composite hydrogel and calcium alginate/P (NEAm-co-MEO) with larger specific surface area2MA)/g-C3N4The hydrogel is darker in color, and methylene blue dye molecules enter the hydrogel. Calcium alginate/P (NEAm-co-MEO) after degradation by simulated solar radiation2MA) the K/S value of the IPN temperature-sensitive hydrogel is slightly reduced to 12.45. This is mainly because methylene blue causes partial degradation of the methylene blue dye upon illumination. Calcium alginate/P (NEAm-co-MEO)2MA)/g-C3N4The IPN temperature-sensitive hydrogel contains photocatalyst g-C3N4In the presence of g-C under light3N4Catalyzing and degrading methylene blue dye adsorbed in the hydrogel to restore the hydrogel to an initial state, wherein K/S values are 8.48 and 8.26 respectively. The composite hydrogel is proved to have the functions of adsorbing and degrading methylene blue in a simulated waste water solution, has better effect and can be used as an adsorbent material for waste water treatment.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (NEAm-co-MEO)2MA) and photocatalysts g-C3N4Introduced into calcium alginate hydrogel to successfully prepare g-C3N4IPN temperature-sensitive composite hydrogel. Similar temperatureThe sensitive composite hydrogel can realize the controllability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (NEAm-co-MEO)2MA) the polymer network and the calcium alginate network system are interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively maintain the unique properties of the two networks. P (NEAm-co-MEO) during temperature rise2MA) collapse of the polymer network at g-C3N4Greater porosity is caused in the IPN temperature-sensitive composite hydrogel, and the additional holes can be used as methylene blue to diffuse to g-C3N4And (3) a channel of the IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. g-C obtained3N4The IPN temperature-sensitive composite hydrogel has good recoverability, and can realize synchronous absorption and photodegradation under the environment condition of simulating visible light irradiation. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily removed by washing with cold water, so that the hydrogel is suitable for industrial application. Calcium alginate/P (NEAm-co-MEO)2MA)/g-C3N4The synergistic adsorption degradation and easy-to-clean performance of the IPN temperature-sensitive composite hydrogel make the IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed by means of sunlight in the daytime. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to be widely developed in the field of printing and dyeing wastewater treatment.
Example 5
1) 1838. mu.L (10mmol) of MEO was added to the sample vial2MA monomer (molecular formula
Purchased from SigmaAldrich), 2857. mu.L (10mmol) of OEGMA300(the formula is
Purchased from Sigma Aldrich), 0.1g of sodium alginate was dissolved in 10mL of deionized water to obtain a mixed solution a;
2) 10mg of a crosslinking agent and0.3g g-C3N4carrying out ultrasonic dispersion on the photocatalyst uniformly to obtain a mixed solution B;
3) blowing nitrogen into the mixed solution B for 20min, adding 0.015g (0.066mmol) of initiator APS and 10 mu L (0.067mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, 5% (w/v) calcium chloride (CaCl) is used2) Soaking the solution for 10h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
Measuring absorbance of the simulated waste water solution at different time intervals by using an ultraviolet spectrophotometer, and calculating to obtain the temperature-sensitive IPN (isopropyl-p-phenylene terephthalamide) composite hydrogel and pure g-C3N4The influence of the absorption and degradation of methylene blue by the nano powder. As is clear from FIG. 5, when the temperature of the solution was raised from 30 ℃ to 45 ℃, pure g-C was present3N4The removal rate of the nanometer powder to methylene blue is almost unchanged. Due to pure g-C3N4The removal of methylene blue by the nanopowder is due to g-C3N4Is caused by photocatalytic degradation, it can be concluded that photodegradation is independent of temperature. However, the removal rate of the composite IPN temperature-sensitive hydrogel is significantly dependent on the solution temperature. It is evident that the removal rate in the first 0.5h increases significantly to 81.82% when the solution temperature is further increased to 45 ℃. This value is even twice that at 40 ℃. Furthermore, complete removal of methylene blue at 45 ℃ only took 2h, 3 times faster than at 40 ℃. This is because g-C3N4The Transition Temperature (TT) of the composite IPN hydrogel is 45 ℃, and when the temperature of the solution is 45 ℃, the temperature of the solution is P (MEO)2MA-co-OEGMA300) The network begins to collapse. P (MEO) because the second network calcium alginate has no temperature responsiveness2MA-co-OEGMA300) Collapse of the network will be at g-C3N4New porosity is induced in the composite IPN hydrogel. These tiny pores serve as the diffusion of methylene blue to g-C3N4Additional channels in the composite IPN hydrogel. Therefore, when the solution temperature is higher than TT, the adsorption effect is significantly enhanced. Thus g-C may be preceded3N4Composite IPN hydrogelsAfter immersion in the solution at 45 ℃ for 2h, g-C is added3N4The composite hydrogel is moved to ambient conditions under visible light irradiation to pass through g-C3N4The temperature-sensitive composite hydrogel has wide application prospect and potential commercial value in the fields of printing and dyeing wastewater treatment and the like by carrying out photodegradation on dyes.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (MEO)2MA-co-OEGMA300) And photocatalyst g-C3N4Introduced into calcium alginate hydrogel to successfully prepare g-C3N4IPN temperature-sensitive composite hydrogel. The temperature-sensitive composite hydrogel can realize the adjustability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (MEO)2MA-co-OEGMA300) The polymer network and the calcium alginate network system are interwoven, and the two networks do not have the function of chemical bond crosslinking and respectively keep the unique properties of the two networks. P (NIPAM-co-OEGMA) during temperature rise300) Collapse of the polymer network at g-C3N4Greater porosity is caused in the IPN temperature-sensitive composite hydrogel, and the additional holes can be used as methylene blue to diffuse to g-C3N4And (3) a channel of the IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. g-C obtained3N4The IPN temperature-sensitive composite hydrogel has good recoverability, and can realize synchronous absorption and photodegradation under the environment condition of simulating visible light irradiation. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily cleaned by washing with cold water, which is particularly suitable for industrial application. Calcium alginate/P (MEO)2MA-co-OEGMA300)/g-C3N4The synergistic adsorption degradation and easy-to-clean performance of the IPN temperature-sensitive composite hydrogel make the IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed by means of sunlight in the daytime. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to beThe method can be used for developing the body in the field of printing and dyeing wastewater treatment.
Example 6
1) To the sample bottle was added 464. mu.L (5mmol) of MEO2MA monomer (molecular formula
Purchased from SigmaAldrich), 1260mg (10mmol) of NnPAm (formula
Purchased from Aladdin) monomer, dissolved in 10mL deionized water to obtain a mixed solution a;
2) 30mg of a crosslinking agent and 0.5mg of TiO were added to the mixed solution A2Carrying out ultrasonic dispersion on the photocatalyst uniformly to obtain a mixed solution B;
3) blowing nitrogen into the mixed solution B for 20min, adding 0.02g (0.088mmol) of initiator APS and 15 mu L (0.1005mmol) of accelerator TEMED, introducing nitrogen for 30min, sealing, and reacting for 12 h;
4) after the reaction is finished, calcium chloride (CaCl) with the concentration of 10% (w/v) is used2) Soaking the solution for 10h to form the hydrogel with the interpenetrating network structure, soaking the hydrogel with deionized water, and changing water at intervals to remove unreacted monomers and crosslinking agents.
The temperature-sensitive composite hydrogel is used for adsorbing and degrading dye molecules in printing and dyeing wastewater. The temperature-sensitive composite hydrogel material is prepared by mixing a temperature-sensitive polymer P (MEO)2MA-co-NnPam) and photocatalyst TiO2Introducing into calcium alginate hydrogel to successfully prepare TiO2IPN temperature-sensitive composite hydrogel. The temperature-sensitive composite hydrogel can realize the adjustability of Transition Temperature (TT) according to specific use environment and requirements; and in the whole system, P (MEO)2MA-co-NnPam) polymer network and a calcium alginate network system are interwoven, and no chemical bond crosslinking effect exists between the two networks, so that the unique properties of the two networks are maintained. P (MEO) during temperature rise2MA-co-NnPam) polymer network collapse in TiO2Greater porosity is caused in the IPN temperature-sensitive composite hydrogel, and the additional holes can be used as methylene blue to diffuse into TiO2And (3) a channel of the IPN temperature-sensitive composite hydrogel. Therefore, the dye adsorption performance can be further enhanced above TT. Obtained TiO2The IPN temperature-sensitive composite hydrogel has good recyclability, and can realize synchronous adsorption and photodegradation under the environment condition of simulating ultraviolet irradiation. In addition, when the temperature is lower than TT, the hydrogel surface keeps hydrophilic, and stains on the hydrogel surface can be easily cleaned by washing with cold water, which is particularly suitable for industrial application. Calcium alginate/P (MEO)2MA-co-NnPAm)/TiO2The synergistic adsorption degradation and easy-to-clean performance of the IPN temperature-sensitive composite hydrogel make the IPN temperature-sensitive composite hydrogel suitable for treatment of printing and dyeing wastewater, and the adsorption-degradation characteristics of the IPN temperature-sensitive composite hydrogel can realize that pollutants are loaded firstly (adsorbed at night) and then are removed under the environment condition of ultraviolet irradiation. Therefore, the IPN temperature-sensitive composite hydrogel system is expected to be widely developed in the field of printing and dyeing wastewater treatment.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. A preparation method of temperature-sensitive composite hydrogel by utilizing photocatalysis and temperature-sensitive synergistic effect is characterized by comprising the following steps: the temperature-sensitive composite hydrogel is prepared by taking a temperature-sensitive monomer M1, a temperature-sensitive monomer M2, a chemical cross-linking agent M3, a photocatalyst M4 and alginate M5 as reaction raw materials in a mass ratio of (5-70) to (15-99) to (0-25) to (0-50) to (0-99) and carrying out free radical polymerization in an aqueous solution.
2. The method according to claim 1, comprising the steps of:
1) sequentially adding a temperature-sensitive monomer M1, a temperature-sensitive monomer M2, a chemical cross-linking agent M3, a photocatalyst M4 and alginate M5 into deionized water to prepare an aqueous solution with the mass concentration of 5-20%, introducing inert gas into a sealed container at 15-25 ℃, and stirring for 30-70min until the mixture is completely dispersed to form a uniform mixed solution;
2) adding an initiator into the mixed solution, injecting a stabilizer after 5-15min, and continuing to react for 25-35min under the protection of inert gas until the mixed solution begins to be in a gel state;
3) standing the mixed solution in gel state at 20-30 deg.C, sealing for 10-36h, and placing the reaction product in divalent cation solution to replace cation in alginate; taking out, soaking in deionized water for 1-3 days, and freeze drying to obtain the temperature-sensitive composite hydrogel.
3. The preparation method according to claim 1 or 2, wherein the mass percentages of the temperature-sensitive monomer M1, the temperature-sensitive monomer M2, the chemical cross-linking agent M3, the photocatalyst M4 and the alginate M5 are (5-50) to (15-70) to (0-20) to (0-40) to (0-50).
4. The preparation method according to claim 1 or 2, wherein the structural formulas of the temperature-sensitive monomer M1 and the temperature-sensitive monomer M2 are as follows:
wherein:
R1is composed of
R2Is composed of
X is 1-10 and Y is 1-12;
the molar ratio of the temperature-sensitive monomer M1 to the temperature-sensitive monomer M2 is (1-99) to (1-200), and the transition temperature of the temperature-sensitive composite hydrogel is 0-150 ℃.
5. The method of claim 4, wherein X is 2-6; y is 1 to 8; the molar ratio of the temperature-sensitive monomer M2 is (1-50) to (1-75), and the transition temperature of the temperature-sensitive composite hydrogel is 0-90 ℃.
6. The method of claim 1 or 2, wherein the alginate M5 is sodium alginate or calcium alginate.
7. The method according to claim 2, wherein the chemical crosslinking agent M3 is N, N ' -methylenebisacrylamide, the initiator is ammonium persulfate or potassium persulfate, and the accelerator is N, N, N ', N ' -tetramethylethylenediamine.
8. The preparation method according to claim 2 or 7, wherein the amount of the initiator is 0.1 to 20% of the total mass of the five reaction raw materials, and the amount of the stabilizer is 0.1 to 10% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-50 w/v%; the replacement time with the divalent cation solution is 1-24 h.
9. The preparation method according to claim 8, wherein the amount of the initiator is 0.1 to 15% of the total mass of the five reaction raw materials, and the amount of the stabilizer is 0.1 to 5% of the total mass of the five reaction raw materials; the concentration of the divalent cation solution is 0.1-20 w/v%; the replacement time with the divalent cation solution is 1-12 h.
10. The use of the temperature-sensitive composite hydrogel prepared by the preparation method according to any one of claims 1 to 9 as a dye adsorbent in the process of treating printing and dyeing wastewater.
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