CN113694903B - Phosphorus-containing polymer hydrogel and preparation method and application thereof - Google Patents

Phosphorus-containing polymer hydrogel and preparation method and application thereof Download PDF

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CN113694903B
CN113694903B CN202111003303.5A CN202111003303A CN113694903B CN 113694903 B CN113694903 B CN 113694903B CN 202111003303 A CN202111003303 A CN 202111003303A CN 113694903 B CN113694903 B CN 113694903B
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CN113694903A (en
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段彩均
向英
付登林
陈若楠
罗旋
颜邦民
兰剑平
张丹
蒋小琴
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Chongqing Chemical Research Institute Materials Technology Co ltd
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    • B01J20/26—Synthetic macromolecular compounds
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Abstract

A phosphorus-containing polymer hydrogel prepared by the steps of: 1) mixing a phosphonic acid olefin compound with an acrylate compound or an acrylamide compound or a vinyl azole compound as a comonomer, dissolving the comonomer in a first solvent, and adding a cross-linking agent to obtain a monomer solution for later use; 2) dissolving an initiator in a second solvent to obtain an initiator solution for later use; 3) and (3) heating the monomer solution to 60-80 ℃, dropwise adding an initiator solution, and copolymerizing to obtain a hydrogel product. The phosphorus-containing polymer hydrogel prepared by the invention has high adsorption efficiency on pollutants in wastewater, can be regenerated and recycled, and is a green and renewable wastewater adsorption material.

Description

Phosphorus-containing polymer hydrogel and preparation method and application thereof
Technical Field
The invention relates to the field of high polymer materials, in particular to a phosphorus-containing polymer hydrogel and a preparation method and application thereof.
Background
The environmental effect caused by the rapid advance of industrialization gradually draws wide attention, and especially, the discharge of industrial wastewater has great influence on the daily life of people, and the characteristics of easy loss and easy diffusion make the treatment of industrial wastewater particularly difficult.
The types of industrial wastewater are many, and the industrial wastewater can be divided into inorganic wastewater (such as electroplating wastewater) and organic wastewater (such as food processing wastewater) according to the chemical properties of main pollutants contained in the industrial wastewater; according to products and processing objects of industrial enterprises, the waste water can be divided into paper-making waste water, textile waste water, tanning waste water, pesticide waste water, metallurgical waste water, oil refining waste water and the like; according to the main components of the pollutants, the pollutants can be divided into acidic wastewater, alkaline wastewater, phenol-containing wastewater, chromium-containing wastewater, radioactive wastewater and the like.
At present, the treatment methods for different waste water are very different, for example, the inorganic waste water is treated mainly by technologies of chemical precipitation and then step-by-step separation, and the organic waste water is treated by a Fenton oxidation method. Aiming at different types of wastewater, the treatment methods are different and have certain limitations, such as higher operation cost, longer treatment time limit, high requirement on wastewater treatment equipment and high maintenance cost in the wastewater treatment process.
Therefore, in order to meet the requirement of green sustainable development, a wastewater treatment method with simple process and low cost needs to be developed. The absorption treatment of the waste water becomes a more common treatment technology at present, and the simple operation process and the low cost investment thereof make the waste water more than two choices of the current waste water treatment technology. The adsorption treatment by activated carbon is common, but the activated carbon is a solid hazardous waste due to toxic and harmful substances contained in the wastewater after the adsorption treatment, so that the possibility of regeneration and use of the activated carbon is low, and the activated carbon is an irrecoverable method to some extent. Therefore, the development of new green and renewable wastewater adsorbing materials is also an urgent need.
Vinylphosphonic acid polymers, because of their hydrophilic and lipophilic properties, are useful as mediators of cell adhesion and proliferation, as described in CN110693724B, which describes the use of polyvinylphosphonic acid in a dental mineralization fluid. In addition, the vinylphosphonic acid polymer has great development prospect in proton exchange membrane fuel cells due to the excellent proton conductivity of the vinylphosphonic acid polymer. For example, patent No. CN103346341A describes the use of polyvinylphosphonic acid to prepare an acid-base composite high-temperature proton exchange membrane. Polyvinyl phosphonic acid polymers are described in patent publication No. CN100350664C as being particularly suitable for use in PEM fuel cells as polymer electrolyte membranes. Patent publication No. CN100448086C describes the use of graft polymers based on vinylphosphonic acid for fuel cell separators. In addition, patent No. CN101770187A describes that polyvinylphosphonic acid can be used as a plate finishing agent for lithography, and patent No. CN102186892A describes that polyvinylphosphonic acid can be used for exploration and production of oil and gas. Although there are many reports on the application of polyvinylphosphonic acid, vinylphosphonic acid copolymers and their application in the field of water treatment have been reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a phosphorus-containing polymer hydrogel which has high adsorption efficiency on pollutants in wastewater, can be recycled and is a green and renewable wastewater adsorption material.
The invention also aims to provide the preparation method of the phosphorus-containing polymer hydrogel, which has simple preparation process and mild reaction conditions and is suitable for large-scale industrial production.
The technical scheme for realizing one purpose of the invention is as follows: a phosphorus-containing polymer hydrogel prepared by the steps of:
1) mixing a phosphonic acid olefin compound with an acrylate compound or an acrylamide compound or a vinyl azole compound as a comonomer, dissolving the comonomer in a first solvent, and adding a cross-linking agent to obtain a monomer solution for later use;
2) dissolving an initiator in a second solvent to obtain an initiator solution for later use;
3) and (3) heating the monomer solution to 60-80 ℃, dropwise adding an initiator solution, and copolymerizing to obtain a hydrogel product.
Further, the molar ratio of the phosphonic acid olefin compound to the acrylate compound or the acrylamide compound or the vinyl azole compound in the step 1) is 1-10: 1-10, preferably 1: 1.
further, in the step 1), the phosphonic acid olefin compound is any one or a mixture of several of 1-propenyl phosphonic acid, vinyl phosphonic acid and (1E) -1-butene-1-yl phosphonic acid, the acrylate compound is any one or a mixture of several of acrylic acid, methacrylic acid, 2-ethyl acrylic acid, methyl acrylate, ethyl acrylate, glycidyl methacrylate, triethylene glycol dimethacrylate and acrylonitrile, the acrylamide compound is methacrylamide and/or acrylamide, and the vinyl azole compound is any one or a mixture of several of N-vinyl imidazole, 1-vinyl 1,2, 4-triazole, N-1,2, 3-triazole, 5-vinyl tetrazole and vinyl indazole.
Further, the first solvent in step 1) is deionized water, and the second solvent in step 2) is deionized water or a water-soluble solvent, preferably methanol or ethanol.
Further, the crosslinking agent in the step 1) is polyethylene glycol diacrylate and N-maleimide chitosan, and the addition amount of the crosslinking agent is 1-3% of the mass of the comonomer, preferably 1%.
Further, in the step 2), the initiator is any one or a mixture of N, N-azobisisobutyronitrile, ammonium persulfate, 2', 2-azobisisobutylamidine dihydrochloride and benzoyl peroxide, and the addition amount of the initiator is 0.01-3% of the mass of the comonomer, and is preferably 1%.
Further, the dripping time in the step 3) is 0.5-8h, preferably 0.5-6h, and the obtained hydrogel product is soaked in deionized water and/or ethanol to remove impurities and dried to obtain the phosphorus-containing polymer hydrogel product.
The invention also provides the application of any one of the phosphorus-containing polymer hydrogel in wastewater treatment, preferably, the wastewater is dye wastewater or heavy metal wastewater.
Specifically, the wastewater treatment comprises the following steps:
1) taking the wastewater, adjusting the temperature to room temperature, and adjusting the pH to 4-8 for later use;
2) adding the phosphorus-containing polymer hydrogel, and uniformly stirring;
3) and (5) finishing the wastewater treatment until the adsorption balance is achieved.
Further, in the step 1), the pH is adjusted by using dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate, the concentrations of the dilute hydrochloric acid, the dilute nitric acid, the dilute sulfuric acid, the sodium hydroxide, the sodium carbonate and the sodium bicarbonate are 0.1mol/L, in the step 3), the added phosphorus-containing polymer hydrogel is taken out after adsorption balance, and the hydrogel is soaked in ethanol or EDTA disodium to realize regeneration.
Further, the phosphorus-containing polymer hydrogel adsorbs metal ions and is soaked into EDTA disodium to realize regeneration; the phosphorus-containing polymer hydrogel adsorbs organic pollutants, and is soaked in ethanol to realize regeneration.
Adopt above-mentioned technical scheme to have following beneficial effect:
1. the phosphorus-containing polymer hydrogel prepared by the invention contains a large amount of-COOH, -NH2And functional groups such as-OH and the like form chemical adsorption with metal ions or organic molecules through chelation, and the high moisture retention and high water absorption of the functional groups are also beneficial to improving the capability of the phosphorus-containing polymer hydrogel for adsorbing heavy metal ions and organic pollutants. The excellent solubility of ethanol and the generation of free H when ethanol is used to treat the phosphorus-containing polymer hydrogel adsorbed with organic pollutants during desorption+Can carry out ion exchange with organic pollutants adsorbed on the phosphorus-containing polymer hydrogel, thereby further promoting the desorption reaction and realizing the regeneration and the use of the phosphorus-containing polymer hydrogel; when the disodium EDTA is used for treating the phosphorus-containing polymer hydrogel adsorbed with the metal ions, the disodium EDTA is a typical chelating agent and has stronger coordination capacity with the metal ions, so that the disodium EDTA can be easily replaced with the heavy metal ions on the phosphorus-containing polymer hydrogel, and the regeneration and the use of the phosphorus-containing polymer hydrogel are realized.
2. According to the preparation method of the phosphorus-containing polymer hydrogel, the phosphonic acid olefin compound and other acrylate compounds or acrylamide compounds or vinyl azole compounds are added and can be directly mixed for polymerization reaction, and sodium hydroxide is not needed for neutralizing acidic monomers to adjust the pH value. The polymerization can be carried out in a stepwise manner by the stepwise addition of the initiator.
3. The preparation method of the phosphorus-containing polymer hydrogel controls the temperature of the monomer solution to be 60-80 ℃, and adds the initiator solution in a dropwise manner. Under the temperature condition, the initiator can be stably and gradually decomposed to generate active free radicals, and if the temperature is too low, the activity of the initiator is reduced, and the rate of initiating polymerization reaction is slowed down; if the temperature is too high, the activity of the initiator is increased, and the polymerization rate is easily increased during the initiation of polymerization reaction, thereby causing implosion. The initiator solution is dripped into the polymerization system in a dripping mode, so that the stable cracking of initiator molecules can be further ensured, the stable proceeding of polymerization reaction is ensured, the phenomena of implosion and agglomeration in the polymerization process are avoided, and the uniformity of a polymer network structure can also be ensured.
4. The phosphorus-containing polymer hydrogel needs to adjust the temperature of the wastewater to 20-30 ℃ (room temperature) and the pH to 4-8 in the process of treating the wastewater. The temperature of the treated wastewater is adjusted to be 20-30 ℃, namely the cost burden caused by temperature rise or temperature reduction in the wastewater treatment process is favorably reduced under the normal temperature condition, the adsorption activity of the polymer hydrogel is best at the normal temperature, if the temperature is too low, the pollutant adsorption rate is slowed down, and if the temperature is too high, partial analysis of adsorbed pollutant molecules is caused, so that the effective adsorption rate of the polymer hydrogel is reduced. Under neutral or off-neutral conditions, the cost input and further environmental pollution caused by pH adjustment can also be reduced. More importantly, in a strong acid environment, excessive H is contained in the solution+Protonating the functional groups such as carboxyl, amino and the like in the polymer hydrogel, thereby weakening the electrostatic attraction and the chelating capacity between the functional groups and metal ions or pollutant molecules, and excessive H+Hydronium ions can be formed, and competitive adsorption can be easily formed between the hydronium ions and pollutant molecules in the adsorption process, so that the adsorption effect of the polymer hydrogel is reduced; in strong alkaline environment, metal ions are easy to be in contact with OH in solution—Hydrolysis occursIn use, hydroxide is formed, thereby reducing the effective adsorption of metal ions by the polymer hydrogel.
The test of the applicant proves that the phosphorus-containing polymer hydrogel prepared by the invention has rich network structure and excellent swelling property, and the swelling rate can reach more than 80%; the thermal stability is good, and the thermal stability is good at the high temperature of 200 ℃; in addition, the polymer hydrogels have strong ion exchange capacity.
The following is a further description with reference to specific examples.
Detailed Description
In the invention, the used vinylphosphonic acid is self-made in a laboratory, the purity is 93 percent, and unsaturated olefin compounds such as acrylamide, acrylic acid and the like are mainly in AR grade and are purchased from Duokeron chemical Co. The initiators used were all of AR grade and were purchased from Allantin.
Example 1
In a 500mL round-bottom three-necked flask equipped with a thermometer, a dropping funnel and mechanical stirring, 75 parts by mass of vinylphosphonic acid and 25 parts by mass of methacrylic acid were added, 30 wt% of polyethylene glycol diacrylate crosslinking agent and 0.01 wt% of polyvinyl alcohol were added, and the three substances were fully dissolved in 200mL of deionized water at a constant temperature of 65 ℃ with vigorous mechanical stirring and mixed uniformly. Dissolving initiator benzoyl peroxide in proper amount of toluene to prepare initiator solution with concentration of 0.01 wt%, dropping the initiator solution into the polymerization reaction system after polymerization starts, and maintaining constant temperature at 65 deg.c for crosslinking polymerization for 2 hr. And repeatedly washing the synthesized gel microspheres in secondary deionized water, and drying the gel microspheres at 50 ℃ under a vacuum condition until the quality of the gel microspheres is unchanged.
An adsorption test step of the copolymer hydrogel to indium ions; firstly, the pH value of the indium-containing waste water is adjusted to 8, the experimental temperature is kept at 25 ℃, 0.1g of dried hydrogel product is put into the indium-containing waste water with the concentration of 100mg/L, and the indium-containing waste water is kept for 4 hours under the condition of fully stirring at 200rpm so as to achieve the adsorption balance of indium ions. Testing the adsorption quantity of the hydrogel; measuring the concentration of indium ions in the waste liquid after adsorption by using an EDTA titration method, taking 1- (2-pyridylazo) -2-naphthol (PAN) as an indicator, and calculating the adsorption capacity of the hydrogel polymer on the indium ions by using the following formula;
Figure BDA0003236348840000061
under the condition, the adsorption capacity of the hydrogel product to indium can reach 0.7 mmol/g.
Example 2
Adding 120 parts by mass of vinylphosphonic acid and 186 parts by mass of acrylic acid into a 500mL three-necked bottle, then adding 3 parts by mass of N-maleimide chitosan, finally adding 200mL of deionized water, fully stirring to fully and uniformly mix the three substances, introducing nitrogen into a polymerization device, keeping the nitrogen for 30min, heating to 80 ℃, and keeping the constant temperature state. 1.6 parts by mass of initiator 2', 2-azobisisobutylamidine dihydrochloride is dissolved in a proper amount of deionized water, and the initiator is dropped into a polymerization system at a constant temperature of 80 ℃. And after the crosslinking polymerization reaction is carried out for 0.5h, taking out the prepared hydrogel product, soaking the hydrogel product in deionized water for 48h to remove monomers which do not participate in the polymerization reaction in the hydrogel, and periodically replacing the deionized water until the deionized water is neutral. Finally, the hydrogel product was dried under vacuum at 60 ℃ to constant weight.
200mL of dye wastewater was taken, and the pH of the wastewater was adjusted to 8 with 0.1M hydrochloric acid and 0.1M sodium hydroxide. At room temperature, adding 100mg of copolymer hydrogel product to ensure that the concentration of the copolymer hydrogel product in the solution is 0.05g/L, violently stirring the waste liquid to ensure that the polymer adsorbing material fully absorbs harmful substances in the waste liquid, continuously stirring for 24 hours, determining the concentration of the pollutants in the waste liquid, and calculating the dye removal rate according to the following formula;
Figure BDA0003236348840000071
wherein, C0As initial dye contaminant concentration, CtThe concentration of the residual pollutants in the dye wastewater treated by the hydrogel polymer is high, and the removal rate of the dye in the treated waste liquid in the embodiment can reach 80%.
Example 3
Synthesizing polyvinyl phosphonic acid nanogel: 67 mL of vinylphosphonic acid were dispersed together with 10 mol% ethylene glycol dimethacrylate (14.4mL) relative to the total monomer amount in 0.01M 3000mL of cetyltrimethylammonium bromide solution. The mixture was stirred for 3 minutes using magnetic stirring to obtain a clear isotropic solution, which was then placed in a temperature controlled oil bath at 75 ℃. The stirring rate was adjusted to 600rpm and maintained for 20 minutes to equilibrate the system temperature to 75 ℃, and polymerization was initiated by adding 100mL of an aqueous ammonium persulfate solution having a concentration of 0.01734 g/mL. The polymerization was carried out for 8 hours, the nanogel was purified by centrifugation at 11000rpm for 20 minutes at 20 ℃, and then the supernatant was removed and re-dispersed in deionized water and re-centrifuged at least 5 times. The product was dried overnight using a lyophilizer and stored in closed vials for further use.
To demonstrate the application of polyvinylphosphonic acid nanogels in the environment, 4-nitrophenol (4-NP), 1 '-dimethyl-4, 4' -bipyridine dichloride (PQ), Methylene Blue (MB), and rhodamine 6G (R-6G) were used as model organic contaminants. Prior to adsorption studies, gel particles (0.25g) were treated with 0.2M NaOH solution (30mL) overnight. The particles were then centrifuged and washed twice with deionized water and dried in a lyophilizer. Adsorption studies were performed at ambient temperature using 0.05g of polyvinylphosphonic acid nanogel particles in 35mL of aqueous solution at a rate of 700rpm for 5 min. In the 5min rapid adsorption process, the adsorption capacity of the polyvinyl phosphonic acid nano gel particles on 4-NP can reach 70.26mg/G, the adsorption capacity on PQ can reach 27.67mg/G to the maximum, the adsorption capacity on MB can reach 13.95mg/G to the maximum, and the adsorption capacity on R-6G can reach 15.47mg/G to the maximum.
Example 4
Is equipped with a thermometer, N260g of vinylphosphonic acid monomer and 62g of vinylpyrrolidone were weighed into a 500mL four-necked flask with inlet, dropping funnel and mechanical stirring, and both monomers were thoroughly dissolved in 300mL of water. After the polymerization temperature reached 80 ℃ and became constant, 1.1g of azobisisobutyronitrile initiator solution dissolved in an appropriate amount of solvent was added dropwise to the polymerization system, and the polymerization was carried out for 6 hours in a closed state. After the reaction is finished, taking out the prepared hydrogel product for soakingAnd (3) removing the monomers which do not participate in the polymerization reaction in the hydrogel in deionized water for 48 hours, and periodically replacing the deionized water until the deionized water is neutral. Finally, the hydrogel product was dried under vacuum at 40 ℃ to constant weight.
Taking 100mL of uranium-containing wastewater into a closed flask, adjusting the pH value of the wastewater to 4, putting 1g of hydrogel product into the uranium-containing wastewater, continuously vibrating the closed flask at the constant temperature of 25 ℃, and keeping the temperature for 3 days to achieve adsorption balance. The maximum adsorption capacity of uranium per gram of product can reach 220 mg.
Example 5
And adding 120 parts of weighed vinylphosphonic acid, 80 parts of acrylamide and 2 parts of cross-linking agent ethylene glycol diacrylate into a 1000mL three-necked bottle, adding 600mL of deionized water, starting mechanical stirring to fully dissolve the three substances, and uniformly mixing. Heating to 80 ℃, keeping a constant temperature state, adding an initiator 2' 2-azobisisobutylamidine dihydrochloride with the mass fraction of 0.1% of two monomers into a polymerization system, keeping constant temperature polymerization for 2 hours, taking out a generated transparent solid, soaking the transparent solid for 24 hours by deionized water, periodically replacing the deionized water during the soaking period, and measuring the pH value of the water solution until the pH value of the water solution is neutral. The soaked hydrogel product was dried to constant weight with hot air at 60 ℃.
Taking initial MB waste liquid with initial MB concentration of 250mg/L, controlling the magnetic stirring speed to be 300rpm at the environmental temperature of 25 ℃, using 25mg hydrogel to carry out contact time of 3 hours to study the influence of the adsorbent on MB adsorption, adjusting the initial pH value of the waste water by 0.1M of sodium hydroxide and sulfuric acid solution, and finally controlling the pH value to be 7, wherein the removal rate of the hydrogel product to MB in the waste water can reach 95%.

Claims (12)

1. The application of the phosphorus-containing polymer hydrogel in the treatment of wastewater, wherein the wastewater is dye wastewater or heavy metal wastewater,
the wastewater treatment comprises the following steps:
1) taking the wastewater, adjusting the temperature to room temperature, and adjusting the pH to 4-8 for later use;
2) adding the phosphorus-containing polymer hydrogel, and uniformly stirring;
3) until reaching the adsorption balance, the wastewater treatment is finished;
4) after the adsorption is balanced, the added phosphorus-containing polymer hydrogel is taken out and soaked in ethanol or EDTA disodium to realize regeneration,
the phosphorus-containing polymer hydrogel is prepared by the following steps:
mixing a phosphonic acid olefin compound with an acrylate compound or an acrylamide compound or a vinyl azole compound, dissolving the mixture serving as a comonomer in a first solvent, adding a cross-linking agent to obtain a monomer solution for later use, wherein the phosphonic acid olefin compound is any one or a mixture of more of 1-propenyl phosphonic acid, vinyl phosphonic acid and (1E) -1-butene-1-yl phosphonic acid, the acrylate compound is any one or a mixture of more of acrylic acid, methacrylic acid, 2-ethacrylic acid, methyl acrylate, ethyl acrylate, glycidyl methacrylate, triethylene glycol dimethacrylate and acrylonitrile, the acrylamide compound is methacrylamide and/or acrylamide, and the vinyl azole compound is N-vinyl imidazole, N-allyl, or allyl-1-butylene-1-yl phosphonic acid, or acrylonitrile, Any one or a mixture of 1-vinyl 1,2, 4-triazole, N-1,2, 3-triazole, 5-vinyl tetrazole and vinyl indazole;
dissolving an initiator in a second solvent to obtain an initiator solution for later use;
thirdly, the monomer solution is heated to 60 to 80 ℃, and initiator solution is dripped to copolymerize to obtain the hydrogel product with a reticular structure.
2. The use according to claim 1, wherein the molar ratio of the phosphonic acid alkene compound of step (1) to the acrylate compound or the acrylamide compound or the vinyl azole compound is 1-10: 1-10.
3. The use according to claim 2, wherein the molar ratio of the phosphonic acid alkene compound to the acrylate compound or the acrylamide compound or the vinyl azole compound in step (1): 1.
4. the use as claimed in claim 1, wherein the first solvent in step (r) is deionized water, and the second solvent in step (r) is deionized water or a solvent having water solubility.
5. The use according to claim 4, wherein the second solvent of step (II) is methanol or ethanol.
6. The use as claimed in claim 1, wherein the crosslinking agent in step (i) is polyethylene glycol diacrylate or N-maleamide chitosan, and the amount of the crosslinking agent added is 1-3% by mass of the comonomer.
7. Use according to claim 6, characterized in that the crosslinking agent is added in an amount of 1% by mass of the comonomer.
8. The use according to claim 1, wherein the initiator of step (ii) is any one or a mixture of N, N-azobisisobutyronitrile, ammonium persulfate, 2' -azobisisobutylamidine dihydrochloride and benzoyl peroxide, and the amount of the initiator added is 0.01 to 3% by mass of the comonomer.
9. Use according to claim 8, characterized in that the initiator is added in an amount of 1% by mass of the comonomer.
10. The use of claim 1, wherein the dropping time of the third step is 0.5 to 8 hours, and the obtained hydrogel product is soaked in deionized water and/or ethanol to remove impurities and dried to obtain the phosphorus-containing polymer hydrogel product.
11. The use according to claim 10, wherein the dropping time of step (c) is 0.5 to 6 hours.
12. The use as claimed in claim 1, wherein the pH adjustment in step (i) is carried out by using dilute hydrochloric acid, dilute nitric acid, dilute sulfuric acid, sodium hydroxide, sodium carbonate and sodium bicarbonate, and the concentrations of the dilute hydrochloric acid, the dilute nitric acid, the dilute sulfuric acid, the sodium hydroxide, the sodium carbonate and the sodium bicarbonate are 0.1 mol/L.
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