CN109705255B - Preparation method of attapulgite-based high-molecular water-absorbent resin - Google Patents
Preparation method of attapulgite-based high-molecular water-absorbent resin Download PDFInfo
- Publication number
- CN109705255B CN109705255B CN201811609556.5A CN201811609556A CN109705255B CN 109705255 B CN109705255 B CN 109705255B CN 201811609556 A CN201811609556 A CN 201811609556A CN 109705255 B CN109705255 B CN 109705255B
- Authority
- CN
- China
- Prior art keywords
- water
- acid
- attapulgite clay
- attapulgite
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 87
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 87
- 239000011347 resin Substances 0.000 title claims abstract description 75
- 229920005989 resin Polymers 0.000 title claims abstract description 73
- 239000002250 absorbent Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000004927 clay Substances 0.000 claims abstract description 48
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 16
- 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 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000002745 absorbent Effects 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 57
- 239000000463 material Substances 0.000 abstract description 45
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- 239000004576 sand Substances 0.000 description 20
- 206010016807 Fluid retention Diseases 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 239000011780 sodium chloride Substances 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004568 cement Substances 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 235000010980 cellulose Nutrition 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a preparation method of attapulgite-based high-molecular water-absorbent resin, which comprises the following steps: (1) preparing acid modified attapulgite clay; (2) preparing a monomer solution; (3) preparing an acid modified attapulgite clay solution; (4) preparing an initiation-crosslinking agent solution; (5) and (3) adding the acid modified attapulgite clay solution obtained in the step (3) and the initiating-crosslinking agent solution obtained in the step (4) into the monomer solution obtained in the step (2), uniformly stirring, reacting at the temperature of 80 ℃, washing after the reaction is finished, and drying to obtain the attapulgite-based high polymer water-absorbing resin. According to the invention, the attapulgite clay modified by acidification and purification, acrylic acid, acrylamide and the like are subjected to graft copolymerization reaction under the conditions of common heating and ultrasonic action respectively to prepare the attapulgite-based high polymer water-absorbent resin material which has strong water absorption capacity and mechanical property and low material cost and can adapt to harsh environment.
Description
Technical Field
The invention relates to a preparation method of attapulgite-based high-molecular water-absorbent resin.
Background
The sand prevention and control is a practical problem in China and is also a worldwide problem. Although the land desertification conditions in China are improved and the development trend is restrained, a large area of desertification land still needs to be treated, and the tasks of sand prevention and sand control are still very difficult. The land desertification formation needs to increase the scientific and technological investment, develop ideas, develop more advanced and practical research and development, fix sand with low cost and good treatment effect and materials due to the complexity, and technically improve the sand prevention and control level.
The research of sand fixing materials has gone through half a century or more, and at present, hundreds of materials and chemical preparations are developed in the world for improving the land desertification condition and preventing wind and fixing sand. In addition to materials such as nylon nets, straws, cement sheet piles and the like which are commonly used for engineering sand stabilization, novel chemical and biological sand stabilization materials are also developed rapidly and mainly comprise the following types in combination: cement paste type sand fixing materials, water glass type sand fixing materials, gypsum type sand fixing materials, petroleum product type sand fixing materials, super absorbent resin type sand fixing materials, synthetic polymer type sand fixing materials, biomass type sand fixing materials, modified waste plastic type sand fixing materials, microorganism sand fixing materials and organic-inorganic composite sand fixing materials. Wherein, the biological and chemical synthesized polymer sand-fixing material has wider development prospect.
Many kinds of super absorbent resins have been developed, such as starch grafted acrylonitrile, polyacrylates, celluloses, and vinyl acetate. The super absorbent resin also has excellent water absorption and retention performance, but has poor ageing resistance, easy oxidative decomposition and high cost, so the super absorbent resin is not popularized and used, but the performance is obviously improved along with continuous research and development, and the super absorbent resin has considerable development potential.
The organic-inorganic composite sand-fixing material is a composite sand-fixing material prepared by organically combining inorganic materials and organic materials. The material can improve the mechanical property and the water retention property of a pure organic material, has higher research heat at present, and has wide application prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of attapulgite-based high-molecular water-absorbent resin.
The invention provides a preparation method of attapulgite-based high-molecular water-absorbent resin, which comprises the following steps:
(1) adding sulfuric acid into attapulgite clay powder, stirring at room temperature for a period of time, washing, drying and crushing to obtain acid-modified attapulgite clay;
(2) adding 15 parts by volume of acrylic acid into 40 parts by volume of sodium hydroxide solution for neutralization, wherein the neutralization degree is 85%, and then adding acrylamide to obtain a monomer solution;
(3) adding 30 parts by volume of water into the acid-modified attapulgite clay prepared in the step (1) to obtain an acid-modified attapulgite clay solution;
(4) dissolving a cross-linking agent and an initiator in 10 parts by volume of water to obtain an initiation-cross-linking agent solution; in the initiation-crosslinking agent solution, the weight fraction of the crosslinking agent is 0.05 percent, and the weight fraction of the initiator is 0.6 percent;
(5) and (3) adding the acid modified attapulgite clay solution obtained in the step (3) and the initiating-crosslinking agent solution obtained in the step (4) into the monomer solution obtained in the step (2), uniformly stirring, reacting at the temperature of 80 ℃, washing after the reaction is finished, and drying to obtain the attapulgite-based high polymer water-absorbing resin.
Preferably, in the step (1), the concentration of the sulfuric acid is 4mol/L, and the stirring time is 60-80 h.
Preferably, the preparation sequence of step (2) to step (4) can be adjusted to each other.
Preferably, in the step (2), the acrylic acid: the mass ratio of acrylamide was 15: 4.
Preferably, in the step (3), the mass fraction of the acid-modified attapulgite clay in the acid-modified attapulgite clay solution is 8-10%.
Preferably, in the step (3), the mass fraction of the acid-modified attapulgite clay in the acid-modified attapulgite clay solution is 10%.
Preferably, in the step (4), the crosslinking agent is N, N' -methylenebisacrylamide, and the initiators are potassium persulfate and sodium bisulfite; the molar ratio of the potassium persulfate to the sodium bisulfite is 1: 1.
Preferably, in the step (5), the reaction at 80 ℃ is carried out at 80 ℃ for 10 min.
Preferably, in the step (5), the reaction at a temperature of 80 ℃ is carried out under ultrasonic conditions for 10 min.
Preferably, in step (5), the power of the ultrasound is 200W.
The invention also provides the attapulgite-based high-molecular water absorbent resin prepared by the method.
The invention researches the influence of the addition of acid modified attapulgite clay and the ultrasonic action on the performance of the high-molecular water-absorbent resin material. The attapulgite-based high polymer water-absorbent resin material which has strong water absorption capacity and mechanical property and low material cost and can adapt to severe environment is prepared by respectively carrying out graft copolymerization on acidified, purified and modified attapulgite clay, acrylic acid, acrylamide and the like under the conditions of common heating and ultrasonic action, and the water absorption multiplying power, the saline absorption multiplying power, the water retention rate and the water absorption multiplying powers in solutions with different pH values are measured. The result shows that the addition amount of the acid modified attapulgite clay is 10 percent, the attapulgite-based high polymer water absorbent resin material prepared under the ultrasonic action of 200W has the best water absorption performance, the maximum water retention rate, the maximum water absorption multiplying power of 1257.54g/g and the maximum saline absorption multiplying power of 209.45g/g, and the material has wider pH adaptability.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 shows the effect of the addition amount of attapulgite clay on the water absorption capacity of the attapulgite-based super absorbent resin.
FIG. 2 shows the effect of the addition amount of attapulgite clay on the saline absorption capacity of the attapulgite-based super absorbent resin.
FIG. 3 shows the effect of the addition of attapulgite clay on the water retention of the attapulgite-based super absorbent resin.
FIG. 4 shows the effect of different ultrasonic powers on the water absorption capacity of the attapulgite-based super absorbent resin.
FIG. 5 shows the effect of different ultrasonic powers on the saline absorption capacity of the attapulgite-based super absorbent resin.
FIG. 6 shows the effect of different ultrasonic powers on the water retention of the attapulgite-based super absorbent resin.
Detailed Description
The following examples are given to facilitate a better understanding of the invention, but do not limit the invention. The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples are commercially available unless otherwise specified.
The invention takes attapulgite clay with large Gansu deposit quantity as a base material, researches a preparation method of the attapulgite-based high-molecular water-absorbent resin material, and prepares the attapulgite-based high-molecular water-absorbent resin material by graft copolymerization of the attapulgite clay with monomers such as acrylic acid, acrylamide and the like after acid modification, thereby preparing a high-molecular material which can be used for sand fixation and has good water absorption, water retention and biocompatibility.
Example 1
1. Acid modification method of attapulgite clay
The attapulgite clay of the ore deposit points (N39 degrees 15 'and E100 degrees 16') of the landplate bridge ballast in Gansu province is collected, and the main mineral content is as follows: 29.7 percent of attapulgite, 21.8 percent of quartz, 14.6 percent of feldspar, 6.3 percent of dolomite, 5.3 percent of montmorillonite and 5.1 percent of gypsum.
Crushing and grinding the collected attapulgite clay raw ore, and sieving the crushed raw ore through a 200-mesh standard sieve to obtain raw ore powder. Placing the powder in a beaker, adding sufficient distilled water, stirring thoroughly to disperse the powder in water uniformly, standing for 30min, and removing the upper impurities and the bottom black precipitate of the suspension. The washing was repeated until the black precipitate in the bottom layer was completely removed. Separating, oven drying at 105 deg.C, grinding, and sieving with 100 mesh sieve.
Weighing a certain mass of the standby attapulgite clay powder, placing the standby attapulgite clay powder into a beaker, adding 4mol/L sulfuric acid according to the mass ratio of 10:1, stirring for 72 hours at room temperature, then washing with distilled water until the pH value is 6-7, drying in a drying oven at 105 ℃, grinding, sieving with a 200-mesh sieve, and placing into a plastic package bag for standby.
2. Preparation method of attapulgite-based high-molecular water-absorbent resin material
(1) By ordinary heating
An amount of sodium hydroxide was weighed and dissolved in 40mL of distilled water in a beaker. Weighing 15mL of Acrylic Acid (AA) and slowly adding the Acrylic Acid (AA) into the NaOH solution, neutralizing the solution in an ice-water bath, wherein the neutralization degree is 85% after the addition is finished, and then adding a certain amount of Acrylamide (AM) to ensure that m (AA): m (am) 15:4, and a monomer solution was prepared. Respectively taking standby acid modified attapulgite clay with the mass fractions of 0% (CK), 5%, 8%, 10% and 15%, adding 30mL of distilled water, dispersing in a beaker, and stirring uniformly to prepare the acid modified attapulgite clay solution. Dissolving a crosslinking agent N, N' -methylene bisacrylamide, and initiators potassium persulfate and sodium bisulfite (the molar ratio of potassium persulfate to sodium bisulfite is 1: 1) in 10mL of distilled water to prepare an initiation-crosslinking agent solution, wherein the weight fraction of the crosslinking agent in the initiation-crosslinking agent solution is 0.05%, and the weight fraction of the initiator in the initiation-crosslinking agent solution is 0.6%.
Adding the prepared acid modified attapulgite clay solution and the initiating-crosslinking agent solution into the monomer solution, stirring uniformly, continuing stirring, transferring the beaker into a water bath kettle, and polymerizing for 10min at the water bath temperature of 80 ℃ to obtain a semisolid product. Cutting the product into pieces, washing the product with 1% ethanol water solution, putting the product into an oven, drying the product at 90 ℃, crushing the product, and sieving the product with a 100-mesh sieve to obtain a sample.
(2) Ultrasonic heating method
The preparation methods of the acid modified attapulgite clay solution, the monomer solution and the initiation-crosslinking agent solution are the same as those of the common heating method. Selecting the optimal attapulgite consumption, setting different ultrasonic powers (200W, 300W, 400W and 500W), controlling the water bath temperature at 80 deg.C, placing the acid modified attapulgite clay solution beaker into an ultrasonic cleaner when the temperature reaches 80 deg.C, adding monomer solution and initiator-cross-linking agent solution during stirring, performing polymerization reaction in the ultrasonic cleaner for 10min, and stopping stirring until the solution becomes viscous. After reacting for 10min, shearing the product, washing with 1% ethanol water solution, drying in an oven at 90 deg.C, pulverizing, and sieving with 100 mesh sieve to obtain the sample.
3. Water absorption performance test of attapulgite-based high-molecular water-absorbent resin material
3.1 Water absorption Capacity: putting a 200-mesh bag into a beaker filled with 1000mL of distilled water, weighing 0.5g of dry resin sample, uniformly spraying the resin sample on the distilled water surface in the mesh bag, standing, taking out the mesh bag and the resin sample after water absorption at regular intervals, draining till no water drops, weighing, putting the mesh bag back into the beaker, slightly stirring the mesh bag in the resin by a glass rod for two times, continuously standing for water absorption, and calculating the water absorption rate according to a formula:
Q＝(M2-M1)/M1
in the formula: q is the water absorption multiplying power, g/g; m1Is the resin sample mass before water uptake, g; m2Is the resin sample mass after water absorption, g.
3.2 saline absorption ratio: a200-mesh net bag was placed in a beaker containing 500mL of a 0.9% NaCl aqueous solution, and about 0.5g of a dried resin sample was accurately weighed, uniformly sprinkled on the distilled water surface in the net bag, and allowed to stand. Taking out the mesh bag and the resin sample after water absorption at regular intervals, draining until no water drops, weighing, putting the mesh bag back into a beaker, slightly stirring the mesh bag in the resin by using a glass rod for two times, continuously standing for water absorption, and calculating the water absorption rate according to a formula:
Q＝(M2-M1)/M1
in the formula: q is the saline absorption rate, g/g; m1Resin sample mass before saline absorption, g; m2Resin sample mass after saline uptake, g.
3.3 Water Retention: putting a 200-mesh bag into a beaker filled with 1000mL of distilled water, weighing 0.5g of dry resin sample, uniformly spraying the dry resin sample on the distilled water surface in the mesh bag, standing for 1.5h, transferring the resin sample into a container after the resin is saturated by water absorption, putting the container into a constant-temperature drying oven at 80 ℃, taking out the sample at certain time intervals, weighing the net mass of the resin, and calculating the water retention rate according to a formula:
R＝W2/W1×100％
in the formula: r is water retention,%; w2: mass of the resin sample after dehydration, g; w1: mass of resin sample, g, before water loss after saturation.
3.4 Water absorption Capacity of resin in solutions of different pH values. A200-mesh bag was placed in a beaker containing 1000mL of distilled water, and the initial pH of the distilled water was adjusted to the experimental value with 0.1mol/L HCl or NaOH solution. Weighing 0.5g of dry resin sample, uniformly spraying the resin sample on the distilled water surface in the mesh bag, standing, taking out the mesh bag together with the resin sample after water absorption at regular intervals, draining until no water drops, weighing, putting the resin sample back into a beaker, slightly stirring the resin sample in a glass rod for two times, continuously standing for water absorption, and calculating the water absorption rate according to a formula.
Q＝(M2-M1)/M1
In the formula: q is the water absorption multiplying power, g/g; m1Is the resin sample mass before water uptake, g; m2Is the resin sample mass after water absorption, g.
4. Water absorption performance test result of attapulgite-based high-molecular water-absorbent resin material
4.1 Water absorption Capacity test results are shown in FIG. 1.
FIG. 1 shows the effect of the addition amount of attapulgite clay on the water absorption capacity of the attapulgite-based super absorbent resin.
4.2 saline uptake test results are shown in FIG. 2.
FIG. 2 shows the effect of the addition amount of attapulgite clay on the saline absorption capacity of the attapulgite-based super absorbent resin.
4.3 Water Retention test results are shown in FIG. 3.
FIG. 3 shows the effect of the addition of attapulgite clay on the water retention of the attapulgite-based super absorbent resin.
4.4 the results of the resin absorbency test in solutions of different pH are shown in Table 1.
TABLE 1 influence (g/g) of solution pH and attapulgite clay addition on water absorption capacity of attapulgite-based high-water resin material
Note 1): the data in the table are in the form of mean ± standard deviation. The same lower case letters indicate that the difference between the water absorption rates of the concave-convex rod-based high-water-property resin materials in the same solution with different pH values and different acid-modified attapulgite clay addition amounts is not obvious, and the difference is obvious when different lower case letters indicate that the difference is obvious; the same capital letters indicate that the difference between the water absorption rates of the concave-convex rod-based high-water-property resin material with the same acid modified attapulgite clay addition amount and different solution pH values is not obvious, and the difference is obvious when different capital letters indicate that the difference is obvious; (P < 0.05).
4.5 Water absorption Capacity test results are shown in FIG. 4.
FIG. 4 shows the effect of different ultrasonic powers on the water absorption capacity of the attapulgite-based super absorbent resin.
The results of the 4.6 saline absorption capacity test are shown in FIG. 5.
FIG. 5 shows the effect of different ultrasonic powers on the saline absorption capacity of the attapulgite-based super absorbent resin.
4.7 Water Retention test results are shown in FIG. 6.
FIG. 6 shows the effect of different ultrasonic powers on the water retention of the attapulgite-based super absorbent resin.
The results of the resin water absorption capacity test in the solutions of 4.8 different pH values are shown in Table 2.
TABLE 2 influence of solution pH and different ultrasonic powers on the water absorption capacity (g/g) of the attapulgite-based high-water resin material
Influence (g/g) of solution pH and ultrasonic power on water absorption rate of attapulgite-based high-water resin material
Note 1): the data in the table are in the form of mean ± standard deviation. The same lower case letters indicate that the difference between the water absorption rates of the concave-convex rod-based high-water-property resin materials in the same solution is not obvious when the pH value is different and the ultrasonic power is different, and the difference is obvious when the different lower case letters indicate that the difference is obvious; the same capital letters indicate that the difference between the water absorption rates of the concave-convex rod-based high-water-content resin material under the same ultrasonic power and different solutions with different pH values is not obvious, and the difference is obvious when different capital letters indicate that the difference is obvious; (P < 0.05).
According to the invention, the acidified, purified and modified attapulgite clay, acrylic acid, acrylamide and the like are subjected to graft copolymerization reaction under the conditions of common heating and ultrasonic action respectively to prepare the attapulgite-based high-molecular water-absorbent resin material which has strong water absorption capacity and mechanical property and low material cost and can adapt to a severe environment, and the water absorption rate, the saline absorption rate, the water retention rate and the water absorption rates in solutions with different pH values are measured. The result shows that the addition amount of the acid modified attapulgite clay is 10 percent, the attapulgite-based high polymer water absorbent resin material prepared under the ultrasonic action of 200W has the best water absorption performance, the maximum water retention rate, the maximum water absorption multiplying power of 1257.54g/g and the maximum saline absorption multiplying power of 209.45g/g, and the material has wider pH adaptability.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement 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 preparation method of attapulgite-based high-molecular water-absorbent resin is characterized by comprising the following steps: the method comprises the following steps:
(1) adding sulfuric acid into attapulgite clay powder, stirring at room temperature for a period of time, washing, drying and crushing to obtain acid-modified attapulgite clay;
(2) adding 15 parts by volume of acrylic acid into 40 parts by volume of sodium hydroxide solution for neutralization, wherein the neutralization degree is 85%, and then adding acrylamide to obtain a monomer solution;
(3) adding 30 parts by volume of water into the acid-modified attapulgite clay prepared in the step (1) to obtain an acid-modified attapulgite clay solution;
(4) dissolving a cross-linking agent and an initiator in 10 parts by volume of water to obtain an initiation-cross-linking agent solution; in the initiation-crosslinking agent solution, the weight fraction of the crosslinking agent is 0.05 percent, and the weight fraction of the initiator is 0.6 percent;
(5) and (3) adding the acid modified attapulgite clay solution obtained in the step (3) and the initiating-crosslinking agent solution obtained in the step (4) into the monomer solution obtained in the step (2), uniformly stirring, carrying out ultrasonic reaction for 10min at the temperature of 80 ℃, washing after the reaction is finished, and drying to obtain the attapulgite-based high polymer water-absorbing resin.
2. The method of claim 1, wherein: in the step (1), the concentration of the sulfuric acid is 4mol/L, and the stirring time is 60-80 h.
3. The method of claim 1, wherein: the preparation sequence of the step (2) to the step (4) can be mutually adjusted.
4. The method of claim 1, wherein: in the step (2), the acrylic acid: the mass ratio of acrylamide was 15: 4.
5. The method of claim 1, wherein: in the step (3), the mass fraction of the acid-modified attapulgite clay in the acid-modified attapulgite clay solution is 8-10%.
6. The method of claim 5, wherein: in the step (3), the mass fraction of the acid-modified attapulgite clay in the acid-modified attapulgite clay solution is 10%.
7. The method of claim 5, wherein: in the step (4), the cross-linking agent is N, N' -methylene bisacrylamide, and the initiator is potassium persulfate and sodium bisulfite; the molar ratio of the potassium persulfate to the sodium bisulfite is 1: 1.
8. The method of claim 5, wherein: in the step (5), the reaction at the temperature of 80 ℃ is carried out for 10min at the water bath temperature of 80 ℃.
9. The method of claim 5, wherein: in the step (5), the power during the ultrasonic treatment is 200W.
10. An attapulgite-based high-molecular water absorbent resin prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811609556.5A CN109705255B (en) | 2018-12-27 | 2018-12-27 | Preparation method of attapulgite-based high-molecular water-absorbent resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811609556.5A CN109705255B (en) | 2018-12-27 | 2018-12-27 | Preparation method of attapulgite-based high-molecular water-absorbent resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109705255A CN109705255A (en) | 2019-05-03 |
| CN109705255B true CN109705255B (en) | 2021-04-06 |
Family
ID=66258618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811609556.5A Active CN109705255B (en) | 2018-12-27 | 2018-12-27 | Preparation method of attapulgite-based high-molecular water-absorbent resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705255B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590504A (en) * | 2003-08-26 | 2005-03-09 | 中国科学院兰州化学物理研究所 | Salt alkali resistance water preserving agent and its preparation method |
| CN102250276A (en) * | 2011-05-10 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method |
| CN108552222A (en) * | 2018-05-11 | 2018-09-21 | 中国农业大学 | A kind of water-retaining agent and preparation method thereof with antibacterial deactivation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9120963B2 (en) * | 2006-11-08 | 2015-09-01 | Schlumberger Technology Corporation | Delayed water-swelling materials and methods of use |
-
2018
- 2018-12-27 CN CN201811609556.5A patent/CN109705255B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590504A (en) * | 2003-08-26 | 2005-03-09 | 中国科学院兰州化学物理研究所 | Salt alkali resistance water preserving agent and its preparation method |
| CN102250276A (en) * | 2011-05-10 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method |
| CN108552222A (en) * | 2018-05-11 | 2018-09-21 | 中国农业大学 | A kind of water-retaining agent and preparation method thereof with antibacterial deactivation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109705255A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhou et al. | Synthesis composite hydrogels from inorganic-organic hybrids based on leftover rice for environment-friendly controlled-release urea fertilizers | |
| CN104231144A (en) | Polyacrylic water-absorbent resin powder and method for producing the same | |
| CN102229804A (en) | Clay-based compound sand consolidating material | |
| CN108948293B (en) | Humic acid-based composite water-retaining agent and preparation method thereof | |
| CN108865164A (en) | A kind of preparation method of inorganic clay-biogum composite water conservation material | |
| CN104891618A (en) | Novel compound water treatment flocculant as well as preparation method and application thereof | |
| CN103819615A (en) | Method of preparing starch-base highly-water-absorbent material by radiation | |
| CN110669148A (en) | Water-absorbing starch and preparation method and application thereof | |
| US4342858A (en) | Polymeric polyelectrolytes | |
| CN110437843A (en) | A kind of preparation method of oil shale semi-coke base compound water retaining agent | |
| CN109705255B (en) | Preparation method of attapulgite-based high-molecular water-absorbent resin | |
| CN104788604B (en) | Ecological moisture-retention water-storage composite material, and preparation method thereof | |
| CN111675453A (en) | Lake sediment curing agent | |
| CN105061698B (en) | A kind of preparation method of rice hull carbon base water-retaining agent | |
| CN103012682B (en) | Method for synthesizing composite water-retaining material by polymerization initiated plasmas electrolysis through glow discharge | |
| CN108191181B (en) | A kind of urban river sediment cleanser and its production method | |
| CN113023741A (en) | Formula and preparation method of salt-resistant polymerized bentonite for waterproof blanket interlayer | |
| CN102417564A (en) | Water-retaining agent and preparation method thereof by papermaking sludge | |
| Lin et al. | Synthesis and properties of poly (acrylic acid)/montmorillonite superabsorbent composites | |
| CN105131208A (en) | Rice husk carbon-based water retention agent preparation method and rice husk carbon-based water retention agent | |
| CN107652446A (en) | A kind of method of rubbish concentrate recycling | |
| CN105384882A (en) | Oxidized peat fulvic acid composite water retaining agent and preparation method thereof | |
| CN106699990B (en) | The non-dehydration state sludge high additive synthesis water-absorbing-retaining material of one kind and preparation method | |
| CN103509156A (en) | Preparation method of multi-copolymerized high salt tolerant acrylic resin | |
| CN102453207A (en) | Process for synthesizing sodium bentonite composite super absorbent material by controlling initiator amount |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231219 Address after: Room 18-4, Building A, Oil Garden, No. 2 Songshi Second Lane, Longshan Street, Yubei District, Chongqing, 401120 Patentee after: Jingnong (Chongqing) Agricultural Technology Co.,Ltd. Address before: 730070 Room 501, 104 tieyuanxin village, Anning District, Lanzhou City, Gansu Province Patentee before: Ren Jun Patentee before: Tao Ling |
|
| TR01 | Transfer of patent right |