CN117024673A - Super absorbent polymer and preparation method thereof - Google Patents
Super absorbent polymer and preparation method thereof Download PDFInfo
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- CN117024673A CN117024673A CN202311018946.6A CN202311018946A CN117024673A CN 117024673 A CN117024673 A CN 117024673A CN 202311018946 A CN202311018946 A CN 202311018946A CN 117024673 A CN117024673 A CN 117024673A
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- 229920000247 superabsorbent polymer Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 54
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004021 humic acid Substances 0.000 claims abstract description 46
- 239000003999 initiator Substances 0.000 claims abstract description 32
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 40
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 230000003472 neutralizing effect Effects 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000008367 deionised water Substances 0.000 abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 abstract description 27
- 238000010521 absorption reaction Methods 0.000 abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 229920000058 polyacrylate Polymers 0.000 abstract description 9
- 239000002250 absorbent Substances 0.000 abstract description 8
- 230000002745 absorbent Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 abstract description 7
- 239000011780 sodium chloride Substances 0.000 abstract description 5
- 230000015784 hyperosmotic salinity response Effects 0.000 abstract description 2
- 239000008399 tap water Substances 0.000 abstract description 2
- 235000020679 tap water Nutrition 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000010355 oscillation Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000004583 superabsorbent polymers (SAPs) Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- IUXKEHURPNDODV-UHFFFAOYSA-N 3-(dimethylamino)-1-(2-methylprop-2-enoyloxy)pentane-3-sulfonic acid Chemical compound CN(C)C(CC)(S(=O)(=O)O)CCOC(C(=C)C)=O IUXKEHURPNDODV-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- YSCHCBVNGBHFJV-UHFFFAOYSA-N dimethyl(3-sulfopropyl)azanium hydroxide Chemical compound [OH-].C[NH+](C)CCCS(O)(=O)=O YSCHCBVNGBHFJV-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- -1 methacryloyloxy Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K17/00—Soil-conditioning materials or soil-stabilising materials
- C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
- C09K17/18—Prepolymers; Macromolecular compounds
- C09K17/20—Vinyl polymers
- C09K17/22—Polyacrylates; Polymethacrylates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2105/00—Erosion prevention
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2109/00—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE pH regulation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Soil Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a super absorbent polymer. The super absorbent polymer is prepared from humic acid, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, acrylic acid, a neutralizer, a cross-linking agent and an initiator through an aqueous solution polymerization method. Compared with the single humic acid or DMAPS modified polyacrylate super absorbent resin, the invention adopts the humic acid and the DMAPS modified polyacrylate, can obviously improve the capability of the polymer for absorbing tap water, deionized water and 0.9 percent sodium chloride solution, has good water absorption and salt tolerance, and has wide pH value application range.
Description
Technical Field
The invention belongs to the field of water-absorbing materials, and particularly relates to a super-absorbent polymer and a preparation method thereof.
Background
Polyacrylate superabsorbent resins are one of the most important varieties of superabsorbent resins because of their high water absorption rate, rapid water absorption rate, and low tendency to mildew. The solution polymerization method is one of the methods commonly used for synthesizing polyacrylate superabsorbent resins (Liu Tingdong and the like,synthetic resin and plastic1993, 10 (2): 68-72; qian Xin and the like,functional polymer newspaper，1997，10(2): 184-188）。
Humic acid is natural organic acid, as shown in figure 1, the main molecular structure body is aromatic nucleus, and various functional groups such as hydroxyl, carboxyl, ketone group, aldehyde group, amino, amide and the like are added. The peat, lignite and weathered coal are particularly rich in humic acid, which is shown in figure 3 under microscopic lens. Because humic acid has various active groups, the method has been used for modifying polyacrylate super absorbent resin, for example, chinese patent CN107722196A discloses a method for preparing weathered coal humic acid super absorbent resin by an aqueous solution polymerization method, the method takes an aqueous solution as a solvent, takes an acrylic acid monomer and humic acid as raw materials, N, N' -methylene bisacrylamide solution as a cross-linking agent, ammonium persulfate solution as an initiator, and sodium hydroxide solution as a neutralizer, and prepares the humic acid super absorbent resin by the aqueous solution polymerization method in the aqueous solution, wherein the mass of the humic acid is 3% -5% of that of the acrylic acid monomer. The deionized water absorption rate of the prepared humic acid-based superabsorbent tree is 1039.2 g/g-1331.2 g/g, and the multiplying power of physiological saline (0.9% NaCl aqueous solution) is 80.4 g/g-87.2 g/g.
[2- (methacryloyloxy) ethyl ]]Dimethyl- (3-sulfopropyl) ammonium hydroxide (DMAPS) is a zwitterionic, and the coexistence of oppositely charged groups imparts extremely high polarity and excellent hydrophilicity to zwitterionic polymers. Chinese patent CN110942927a discloses a zwitterionic supramolecular hydrogel electrolyte material, whichZwitterionic supramolecular hydrogel electrolyte materials are prepared by dissolving acrylic acid monomers and 3-dimethyl (methacryloyloxyethyl) propane ammonium sulfonate monomers in H 2 SO 4 And adding Ammonium Persulfate (APS) as an initiator into the mixed solution to initiate copolymerization reaction at 60-70 ℃ for 10-20h to obtain the material with good self-repairing capability. Chinese patent CN115725022a discloses an ion-responsive hydrogel prepared from the following raw materials: 32-36wt% of polymer monomer, 3-5wt% of chitosan, 3-8wt% of N, N-dimethyl (methacryloyloxyethyl) aminopropanesulfonic acid inner salt, 0.5-1.5wt% of cross-linking agent, 0.3-1wt% of initiator, 1-3wt% of defoamer and the balance of water. However, DMAPS has not been found to be useful in polyacrylate superabsorbent resins.
Disclosure of Invention
Based on the prior art, the invention aims to provide a polyacrylate super absorbent resin modified by humic acid and DMAPS, and the super absorbent polymer has higher water absorption performance.
The technical scheme adopted by the invention for achieving the purpose is as follows:
a superabsorbent polymer characterized by: the super absorbent polymer is prepared from humic acid, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, acrylic acid, a neutralizer, a cross-linking agent and an initiator through an aqueous solution polymerization method.
Preferably, the mass ratio of the humic acid to the acrylic acid is 0.001-0.01:1.
More preferably, the mass ratio of the humic acid to the acrylic acid is 0.001-0.005:1.
Preferably, the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the acrylic acid is 0.01-0.1:1.
More preferably, the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the acrylic acid is 0.05-0.06:1.
Most preferably, the mass ratio of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to acrylic acid is 0.055:1.
Preferably, the neutralizing agent is added according to the neutralization degree of acrylic acid of 55% -85%.
More preferably, the neutralizing agent is added so that the neutralization degree of acrylic acid is 65% -75%.
Most preferably, the neutralizing agent is added at a neutralization degree of 70% of acrylic acid.
More preferably, the neutralizing agent is sodium hydroxide.
Preferably, the crosslinking agent is N, N-methylenebisacrylamide.
Preferably, the amount of the crosslinking agent is 0.02% -0.15% of the sum of the mass of the acrylic acid and the mass of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
More preferably, the amount of the crosslinking agent is 0.02% -0.10% of the sum of the mass of acrylic acid and the mass of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
Most preferably, the amount of the crosslinking agent is 0.06% -0.07% of the sum of the mass of acrylic acid and the mass of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
Preferably, the initiator is potassium persulfate.
Preferably, the amount of the initiator is 0.1% -1.1% of the sum of the mass of the acrylic acid and the mass of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
More preferably, the initiator is used in an amount of 0.2% -0.8% by mass of the mass and mass of the acrylic acid and [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
Most preferably, the initiator is used in an amount of 0.5% -0.6% of the sum of the mass of acrylic acid and the mass of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide.
The preparation method of the super absorbent polymer comprises the following steps:
(1) Dispersing humic acid with water to obtain humic acid dispersion liquid;
(2) Mixing a neutralizing agent with acrylic acid for neutralization reaction to obtain an acrylic acid solution;
(3) Adding acrylic acid solution, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent and an initiator into humic acid dispersion liquid, and carrying out polymerization reaction to obtain the super absorbent polymer.
Preferably, the polymerization temperature is 60-80 ℃, and the reaction is continued for 3-4 hours after the reaction is performed to gel.
Preferably, the polymerization reaction product is washed with absolute ethyl alcohol, dried and crushed.
The super absorbent polymer is applied to desertification control and saline-alkali soil improvement.
The beneficial effects are that:
compared with the single humic acid or DMAPS modified polyacrylate super absorbent resin, the humic acid and DMAPS modified polyacrylate super absorbent resin can obviously improve the capability of the polymer for absorbing tap water, deionized water and 0.9% sodium chloride solution, has good water absorption and salt tolerance, and has wide pH value application range.
Drawings
FIG. 1 is a schematic diagram of the structure of humic acid.
FIG. 2 is a schematic illustration of the mechanism of the free radical polymerization reaction of the present invention.
FIG. 3 is a scanning electron microscope image of humic acid.
FIG. 4 is a scanning electron microscope image of the super absorbent polymer prepared in example 2.
FIG. 5 is a graphical representation of swelling of superabsorbent polymers after absorption of deionized water.
FIG. 6 shows the water absorption in solutions of different pH values for example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical scheme of the invention is further described in detail below by combining examples.
FIG. 4 is a scanning electron microscope image of the super absorbent polymer obtained in example 2, and it can be seen that the polymer has a good three-dimensional network structure. The polymerization mechanism is shown in figure 2, the initiator is heated to decompose to generate primary free radicals, and each monomer is grafted on humic acid through free radical polymerization under the action of the primary free radicals, and meanwhile, the polymer chain and the cross-linking agent interact to form a final three-dimensional network structure.
Example 1
Adding 0.0076 and g humic acid into 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.8g of sodium hydroxide was dissolved in 10. 10 ml water, and the resulting lye was mixed with 6.87. 6.87 ml acrylic acid (0.1 mol) to obtain a neutralized acrylic acid solution for use.
0.0038 g of N, N-Methylenebisacrylamide (MBA) is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
0.0380 g potassium persulfate is dissolved in 1 ml deionized water to obtain an initiator solution for later use.
Sequentially adding an acrylic acid solution, 0.3990 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide (DMAPS) and an initiator solution into humic acid dispersion liquid at the rotating speed of 250r/min in a water bath kettle at the temperature of 70 ℃, removing the water bath kettle after the materials are gelled, transferring the water bath kettle into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Water absorption properties of the resulting superabsorbent polymers: the amount of water taken in was 253 g/g, the amount of deionized water taken in was 2004 g/g, and the amount of 0.9% sodium chloride solution taken in was 109g/g. In the range of ph=4 to ph=11, the water absorption rate is 1600 g/g or more as shown in fig. 6.
Examples 2 to 3 were prepared substantially the same as example 1, except that the raw materials were added in the amounts shown in Table 1. The mass percentages of crosslinker and initiator relative to monomer in comparative examples 1-2 remain substantially equivalent to example 2.
Comparative example 1
2.8g of sodium hydroxide is dissolved in 20. 20 ml water, and the obtained alkali liquor is mixed with 6.87. 6.87 ml acrylic acid to obtain a neutralized acrylic acid solution for later use.
0.0053 g of N, N-methylenebisacrylamide is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
The 0.0456 g potassium persulfate was dissolved in 1 ml deionized water to obtain an initiator solution for use.
And (3) sequentially adding 0.3990 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent solution and an initiator solution into an acrylic acid solution in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Water absorption properties of the resulting superabsorbent polymers: the amount of water absorbed was 195 g/g, the amount of deionized water absorbed was 997 g/g, and the amount of 0.9% sodium chloride solution absorbed was 69g/g.
Comparative example 2
Adding 0.0076 and g humic acid into 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.8g of sodium hydroxide is dissolved in 10. 10 ml water, and the obtained alkali liquor is mixed with 6.87. 6.87 ml acrylic acid to obtain a neutralized acrylic acid solution for later use.
0.0050g of N, N-methylenebisacrylamide is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
The 0.0432 g potassium persulfate was dissolved in 1 ml deionized water to obtain an initiator solution for use.
Sequentially adding an acrylic acid solution, a cross-linking agent solution and an initiator solution into the humic acid dispersion liquid in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring the water bath kettle into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying the obtained product at the temperature of 60 ℃ for 24h, and crushing the product into 20-40 meshes to obtain the super absorbent polymer particles.
Water absorption properties of the resulting superabsorbent polymers: the amount of water taken in was 253 g/g, the amount of deionized water taken in was 1802 g/g, and the amount of 0.9% sodium chloride solution taken in was 107g/g.
The water absorption properties of the super absorbent polymers prepared in examples 2 to 3 and comparative examples 1 to 2 are shown in the following table:
example 4
Adding 0.03. 0.03 g humic acid into 10. 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.6g of sodium hydroxide was dissolved in 10. 10 ml water, and the resulting lye was mixed with 6.87. 6.87 ml acrylic acid (0.1 mol) to obtain a neutralized acrylic acid solution for use.
0.0038 g of N, N-Methylenebisacrylamide (MBA) is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
0.0380 g potassium persulfate is dissolved in 1 ml deionized water to obtain an initiator solution for later use.
Sequentially adding an acrylic acid solution, 0.3990 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent solution and an initiator solution into humic acid dispersion liquid in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Example 5
Adding 0.0076 and g humic acid into 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.8g of sodium hydroxide was dissolved in 10. 10 ml water, and the resulting lye was mixed with 6.87. 6.87 ml acrylic acid (0.1 mol) to obtain a neutralized acrylic acid solution for use.
0.0038 g of N, N-Methylenebisacrylamide (MBA) is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
0.0380 g potassium persulfate is dissolved in 1 ml deionized water to obtain an initiator solution for later use.
Sequentially adding an acrylic acid solution, 0.36 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent solution and an initiator solution into humic acid dispersion liquid in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Example 6
Adding 0.0076 and g humic acid into 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.8g of sodium hydroxide was dissolved in 10. 10 ml water, and the resulting lye was mixed with 6.87. 6.87 ml acrylic acid (0.1 mol) to obtain a neutralized acrylic acid solution for use.
0.0038 g of N, N-Methylenebisacrylamide (MBA) is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
0.0380 g potassium persulfate is dissolved in 1 ml deionized water to obtain an initiator solution for later use.
Sequentially adding an acrylic acid solution, 0.433 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent solution and an initiator solution into humic acid dispersion liquid in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Example 7
Adding 0.036 g humic acid into 10 ml deionized water, and stirring on a magnetic stirrer for 30 min to obtain humic acid dispersion liquid for later use.
2.8g of sodium hydroxide was dissolved in 10. 10 ml water, and the resulting lye was mixed with 6.87. 6.87 ml acrylic acid (0.1 mol) to obtain a neutralized acrylic acid solution for use.
0.0038 g of N, N-Methylenebisacrylamide (MBA) is added into 1 ml deionized water, and the mixture is subjected to ultrasonic oscillation to be completely dissolved, so as to obtain a cross-linking agent solution for later use.
0.0380 g potassium persulfate is dissolved in 1 ml deionized water to obtain an initiator solution for later use.
Sequentially adding an acrylic acid solution, 0.2 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent solution and an initiator solution into humic acid dispersion liquid in a water bath kettle at the temperature of 70 ℃ at the rotating speed of 250r/min, taking out the water bath kettle after the materials are gelled, transferring into a blast oven at the temperature of 70 ℃ for continuous reaction for 210min, washing the obtained product with absolute ethyl alcohol, drying at the temperature of 60 ℃ for 24h, and crushing to 20-40 meshes to obtain the super absorbent polymer particles.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A superabsorbent polymer characterized by: the super absorbent polymer is prepared from humic acid, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, acrylic acid, a neutralizer, a cross-linking agent and an initiator through an aqueous solution polymerization method.
2. The superabsorbent polymer of claim 1 wherein: the mass ratio of the humic acid to the acrylic acid is 0.001-0.01:1; preferably, the mass ratio is 0.001-0.005:1.
3. The superabsorbent polymer of claim 1 wherein: the mass ratio of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide to the acrylic acid is 0.01-0.1:1; preferably, the mass ratio is 0.05-0.06:1; more preferably, the mass ratio is 0.055:1.
4. The superabsorbent polymer of claim 1 wherein: adding a neutralizing agent according to the neutralization degree of acrylic acid of 55% -85%; preferably, adding a neutralizing agent according to the neutralization degree of acrylic acid of 65% -75%; more preferably, the neutralizing agent is added at a neutralization degree of 70% of acrylic acid.
5. The super absorbent polymer according to claim 1 or 4, wherein: the neutralizer is sodium hydroxide.
6. The superabsorbent polymer of claim 1 wherein: the cross-linking agent is N, N-methylene bisacrylamide; preferably, the amount of the cross-linking agent is 0.02% -0.15% of the sum of the mass of the acrylic acid and the mass of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide; more preferably, the amount of the cross-linking agent is 0.02% -0.10% of the sum of the mass of the two monomers; most preferably, the amount of the crosslinking agent is 0.06-0.07% of the sum of the mass of the two monomers.
7. The superabsorbent polymer of claim 1 wherein: the initiator is potassium persulfate; preferably, the amount of the initiator is 0.1% -1.1% of the sum of the mass of the acrylic acid and the mass of the [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide; more preferably, the amount of the initiator is 0.2% -0.8% of the sum of the mass of the two monomers; most preferably, the initiator is used in an amount of 0.5 to 0.6% of the sum of the mass of the two monomers.
8. The method for preparing the super absorbent polymer according to any one of claims 1 to 7, comprising:
(1) Dispersing humic acid with water to obtain humic acid dispersion liquid;
(2) Mixing a neutralizing agent with acrylic acid for neutralization reaction to obtain an acrylic acid solution;
(3) Adding acrylic acid solution, [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide, a cross-linking agent and an initiator into humic acid dispersion liquid, and carrying out polymerization reaction to obtain the super absorbent polymer.
9. The method of manufacturing according to claim 8, wherein: the polymerization temperature is 60-80 ℃, and the reaction is continued for 3-4 hours after the reaction is performed until the gel is formed.
10. The use of the super absorbent polymer according to any one of claims 1 to 7 in desertification control and saline-alkali soil improvement.
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