CN113943393A - Super-absorbent salt-tolerant potassium ion-based high-molecular water-absorbent resin and preparation method and application thereof - Google Patents
Super-absorbent salt-tolerant potassium ion-based high-molecular water-absorbent resin and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin and a preparation method and application thereof, wherein the super water-absorbing salt-tolerant water-absorbing resin is composed of an anionic monomer, a cationic monomer, a cross-linking agent, a neutralizing agent, an initiator and a catalyst; wherein, the mass fraction of the cationic monomer is 25-75%, the mass fraction of the cationic monomer is 1-45%, the mass fraction of the crosslinking agent is 0.005-5%, the mass fraction of the neutralizing agent is 0-50%, the mass fraction of the initiating agent is 0.01-5%, and the mass fraction of the catalyst is 0.005-5%. According to the invention, the rice particles are used as a cross-linking agent, the cationic monomer is introduced as counter ions, the neutralization degree of the anionic monomer and the ion type of the water-absorbent resin are regulated by the neutralizing agent, the water absorption and salt tolerance of the water-absorbent resin are improved, and the application of the water-absorbent resin in multiple fields is promoted.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to super-absorbent salt-tolerant potassium ion-based polymer water-absorbent resin as well as a preparation method and application thereof.
Background
The water-absorbent resin has wide application in the industries of agriculture, industry, medical treatment and health, food, building and the like. The water absorption and salt resistance characteristics are the most basic characteristics of the water absorption resin and are closely related to the application of the water absorption resin. However, the development and utilization of the current water-absorbent resin still face a plurality of problems: the water absorption capacity, the salt tolerance and the cycling stability are difficult to meet the actual production requirements of the agriculture. Especially, the salt resistance is not good, and the water absorption performance of the water absorbent resin is seriously influenced. For example, in the agricultural field, after the water-absorbent resin is applied to saline-alkali soil as a water retention agent, the water absorption and retention performance of the water-absorbent resin is obviously restricted by salt ions, and the use value of the water-absorbent resin is limited. Although researchers have continuously searched for salt-tolerant water-absorbent resins in recent years, the description of the rule of mutual influence between the water absorption capacity and the salt-tolerant performance of the water-absorbent resins is still insufficient.
In addition, the water-absorbent resin sold in the market has the problems of high price, unstable water absorption performance, poor salt tolerance and the like, and limits the use willingness of farmers to the water-absorbent resin. Meanwhile, the sodium salt type water-absorbent resin used for the agricultural water-retaining agent can cause the content of sodium ions in soil to increase, and soil hardening is caused. The sylvite water-absorbent resin not only has the functions of water absorption and retention, but also can provide nutrient elements for plants, and is widely concerned by the industry.
However, the existing potassium salt type water-absorbing resin seriously faces the problems of poor water absorption and salt resistance and the like; in the industrial field, although water-absorbent resins have been used as an adsorbent material for purifying sewage, there are problems of low adsorption capacity, slow adsorption speed, and the like. The adsorption performance of the water-absorbent resin is also related to the water-absorbing salt-resistant property of the water-absorbent resin. The water absorption salt-resistant property of the water absorption resin is related to several characteristic parameters (including monomer type, ion type, cross-linking agent and the like) of the water absorption resin, and the currently reported water absorption resin is difficult to simultaneously coordinate the several material parameters. Therefore, a method for improving the water absorption and salt tolerance of the water-absorbent resin is explored, the application of the water-absorbent resin in the fields of agriculture, industry and the like is researched, and the method has strategic significance for promoting the national development of the water-absorbent resin.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The invention is provided in view of the above and/or the problems that the water absorption or salt tolerance of the water absorption resin material in the prior art is poor, especially the soil hardening is easily caused when the sodium ion-based water absorption resin is used as an agricultural water retention agent.
One of the purposes of the invention is to provide a super water-absorbing salt-resistant potassium ion-based high-molecular water-absorbing resin, which is a water-absorbing resin material with high water absorption and high salt resistance obtained by crosslinking a monomer through nanoparticles.
In order to solve the technical problems, the invention provides the following technical scheme: a super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin is composed of a monomer, a cross-linking agent, a neutralizing agent, an initiator and a catalyst;
wherein, the mass fraction of the cationic monomer is 25-75%, the mass fraction of the cationic monomer is 1-45%, the mass fraction of the crosslinking agent is 0.005-5%, the mass fraction of the neutralizing agent is 0-50%, the mass fraction of the initiating agent is 0.01-5%, and the mass fraction of the catalyst is 0.005-5%.
As a preferable scheme of the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin, the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin comprises the following components in percentage by weight: the anionic monomer comprises one of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid and 2-acrylamide-2-methylpropanesulfonic acid;
the cationic monomer comprises one of dimethyl diallyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride, allyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
As a preferable scheme of the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin, the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin comprises the following components in percentage by weight: the crosslinking agent is selected from nanoparticles or organic crosslinking agents;
wherein the nanoparticles comprise one or more of graphene oxide, silica, clay, or calcium hydroxide;
the organic cross-linking agent comprises one or more of methylene acrylamide, divinylbenzene, ethylene glycol, toluene diisocyanate and allyl cellulose.
As a preferable scheme of the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin, the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin comprises the following components in percentage by weight: the neutralizing agent comprises sodium hydroxide or potassium hydroxide.
As a preferable scheme of the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin, the super water-absorbing salt-tolerant potassium ion-based polymer water-absorbing resin comprises the following components in percentage by weight: the initiator comprises one of ammonium persulfate, potassium persulfate, sodium persulfate or 2,2' -azobisisobutylamidine dihydrochloride.
The invention also aims to provide a preparation method of the super water-absorbing salt-resistant potassium ion-based high-molecular water-absorbing resin, which is characterized in that a neutralizer is used for neutralizing a monomer, a cross-linking agent is added, an initiator and a catalyst are introduced, and the high-molecular water-absorbing resin is prepared through free radical copolymerization.
As a preferable scheme of the preparation method of the super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin, the preparation method comprises the following steps: dissolving a neutralizer in deionized water in an ice bath at 0 ℃, adding a neutralizer solution into the first monomer solution, and uniformly mixing;
adding a second monomer and the nano particles, and uniformly stirring;
adding an initiator and a catalyst, and stirring under the protection of nitrogen to obtain a mixed solution;
and at room temperature, preserving the mixed solution under the protection of nitrogen to obtain the super water-absorbing salt-resistant potassium ion-based high-molecular water-absorbent resin.
As a preferable scheme of the preparation method of the super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin, the preparation method comprises the following steps: the dosage of the neutralizer is 5-90 wt% of the dosage of the monomer.
As a preferable scheme of the preparation method of the super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin, the preparation method comprises the following steps: the reaction temperature of the free radical copolymerization is 0-80 ℃.
The invention also aims to provide application of the super-absorbent salt-tolerant potassium ion-based high-molecular water-absorbent resin in the fields of sewage treatment, agriculture, medical health, flexible sensors or buildings.
Compared with the prior art, the invention has the following beneficial effects:
the method is characterized in that rice particles are used as a cross-linking agent, a cationic monomer is introduced as counter ions, and the neutralization degree of the anionic monomer and the ion type of the water-absorbing resin are adjusted by a neutralizing agent, so that the super-absorbent salt-resistant potassium ion-based high-molecular water-absorbing resin is prepared. Improves the water absorption and salt tolerance of the water-absorbent resin and promotes the application of the water-absorbent resin in various fields.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 shows PAA/PDAC/Ca (OH)2Scanning electron micrographs of the water-absorbent resin.
FIG. 2 shows PAA/PDAC/Ca (OH)2A curve diagram of the adsorption removal rate of the water-absorbent resin to methylene blue; wherein (a) is a curve diagram of the adsorption removal rate of the water-absorbent resin to methylene blue solution under different pH values; (b) methylene blue solution for different water-absorbent resin dosageGraph of adsorption removal rate of (a).
FIG. 3 shows PAA/PDAC/Ca (OH)2Water-absorbent resin for different initial concentrations of Cu2+Adsorption removal capacity of the solution was determined.
FIG. 4 shows PAA/PDAC/Ca (OH)2The effect of the water-absorbing resin on the adsorption and removal of trace metal ions in tap water is shown.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, specific embodiments thereof are described in detail below with reference to examples of the specification.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
Dissolving 3.0g of potassium hydroxide (KOH) in deionized water at 0 ℃ in an ice bath, adding 6ml of Acrylic Acid (AA) into the KOH solution, and uniformly mixing; subsequently, different amounts of (3-Acrylamidopropyl) Trimethylammonium Chloride (ATC) (0.6, 1.0, 1.4ml, respectively) and 0.002g of nanoparticles (Ca (OH)2) Adding the mixed solution, and uniformly stirring; finally, 0.24g of initiator Ammonium Persulfate (APS) and 200ul of catalyst N, N, N ', N' -tetramethyl-ethylenediamine (TEMED) are added, and the mixture is magnetically stirred for 2 hours under the protection of nitrogen; then storing for 1 day at room temperature to obtain super water-absorbing salt-tolerant water-absorbing resin marked as PAA/PATC/Ca (OH)2A water-absorbent resin.
Drying PAA/PATC/Ca (OH) at 25 deg.C2Respectively soaking the water-absorbent resin samples in pure waterWater, 0.9 wt% NaCl solution and 0.9 wt% KCl solution. At intervals, the samples were removed from the solution and the surface of the samples were blotted off with absorbent paper. The weight of the sample was weighed using an electronic balance and recorded one by one. The sample is then returned to the solution and taken out again after a period of time and weighed. The above process was repeated until the sample weight was unchanged, i.e. swelling equilibrium was reached. Wherein: water absorption ═ (weight of sample after adsorption equilibration-weight of dry sample)/weight of dry sample.
The results of the water absorption are shown in table 1.
TABLE 1
As can be seen from the data in Table 1, the water absorption of the water-absorbent resin in pure water gradually increased with the gradual increase in the ATC addition amount; the water absorption of the water-absorbent resin in 0.9 wt% NaCl solution is slightly increased when the ATC addition amount is 1.0ml, and the ATC amount is continuously increased without obvious change; the water absorption of the water-absorbent resin in 0.9 wt% KCl solution slightly decreased when the ATC addition amount was increased from 0.6ml to 1.0ml, but rapidly decreased when the ATC amount was continuously increased.
Example 2
Dissolving 3.5g of sodium hydroxide (NaOH) in deionized water at 0 ℃ in an ice bath, adding 6ml of Acrylic Acid (AA) into the NaOH solution, and uniformly mixing; subsequently 0.8g Acrylamide (AM) and 0.009g nanoparticles (Ca (OH)2) Adding the mixed solution, and uniformly stirring; finally, 0.28g of initiator Ammonium Persulfate (APS) and 250ul of catalyst N, N, N ', N' -tetramethyl-ethylenediamine (TEMED) are added, and the mixture is magnetically stirred for 2 hours under the protection of nitrogen; then storing for 1 day at room temperature to obtain super water-absorbing salt-tolerant water-absorbing resin marked as PAA/PAM/Ca (OH)2A water-absorbent resin.
By adopting the embodiments1 same test method, test PAA/PAM/Ca (OH)2Water absorption of the water-absorbent resin in pure water, 0.9 wt% NaCl solution. The test results showed that the water absorbing resin had a water absorption of 1500g/g in pure water and a water absorption of 50g/g in a 0.9 wt% NaCl solution.
Example 3
Dissolving 2.6g of potassium hydroxide (KOH) in deionized water at room temperature, adding 5ml of Acrylic Acid (AA) into the KOH solution, and uniformly mixing; then, 1.0ml of (3-Acrylamidopropyl) Trimethylammonium Chloride (ATC) and 0.08g of methylene acrylamide (BIS) were added to the above mixed solution, and stirred uniformly; finally, 0.20g of initiator Ammonium Persulfate (APS) and 280ul of catalyst N, N, N ', N' -tetramethyl-ethylenediamine (TEMED) are added, and the mixture is magnetically stirred for 2 hours under the protection of nitrogen; and then storing for 1 day at room temperature to obtain super water-absorbing salt-resistant water-absorbing resin marked as PAA/PATC/BIS water-absorbing resin.
PAA/PAM/Ca (OH) was tested using the same test method as in example 12Water absorption of the water-absorbent resin in pure water, 0.9 wt% NaCl solution. As a result of the test, the water absorption of the water absorbent resin in pure water was 500g/g, and the water absorption in a 0.9 wt% NaCl solution was 20 g/g.
Example 4
Dissolving 2.5g of potassium hydroxide (KOH) in deionized water at room temperature, adding 6ml of Acrylic Acid (AA) into the KOH solution, and uniformly mixing; 1.4ml of (3-Acrylamidopropyl) Trimethylammonium Chloride (ATC), 0.01g of nanoparticles (Ca (OH)2) And 0.06g of methylene acrylamide (BIS) are added into the mixed solution and stirred uniformly; finally, 0.28g of initiator Ammonium Persulfate (APS) and 200ul of catalyst N, N, N ', N' -tetramethyl-ethylenediamine (TEMED) are added, and the mixture is magnetically stirred for 2 hours under the protection of nitrogen; then storing for 1 day at room temperature to obtain super water-absorbing salt-tolerant water-absorbing resin marked as PAA/PATC/Ca (OH)2BIS water-absorbent resin.
PAA/PAM/Ca (OH) was tested using the same test method as in example 12Water absorption of the water-absorbent resin in pure water, 0.9 wt% NaCl solution. As a result of the test, the water absorption of the water absorbent resin in pure water was 200g/g, and the water absorption in a 0.9 wt% NaCl solution was 10 g/g.
Example 5
Dissolving 2.8g of sodium hydroxide (NaOH) in deionized water at 0 ℃ in an ice bath under the protection of nitrogen, adding 7ml of Acrylic Acid (AA) into the sodium hydroxide solution, and uniformly mixing; then 0.5ml of dimethyl Diallyl Ammonium Chloride (DAC) and 0.005g of nano particles (calcium hydroxide) are added into the mixed solution and stirred uniformly; finally, 0.25g of initiator Ammonium Persulfate (APS) and 200ul of catalyst N, N, N ', N' -tetramethyl-ethylenediamine (TEMED) are added, and the mixture is magnetically stirred for 2 hours under the protection of nitrogen; then storing for 1 day at room temperature to obtain super water-absorbing salt-tolerant water-absorbing resin marked as PAA/PDAC/Ca (OH)2A water-absorbent resin.
PAA/PAM/Ca (OH) was tested using the same test method as in example 12Water absorption of the water-absorbent resin in pure water, 0.9 wt% NaCl solution and 0.9 wt% KCl solution. The test results showed that the water absorbing resin had a water absorption of 4100g/g in pure water, a water absorption of 110g/g in 0.9 wt% NaCl solution, and a water absorption of 90g/g in 0.9 wt% KCl solution.
PAA/PDAC/Ca(OH)2The scanning electron microscope of the water-absorbent resin is shown in FIG. 1. As can be seen from FIG. 1, PAA/PDAC/Ca (OH)2The water-absorbent resin has a villous microstructure.
Example 6
PAA/PDAC/Ca (OH) prepared in example 5 was mixed at 25 ℃ and an initial methylene blue concentration of 200mg/L2The water-absorbent resin is soaked in the methylene blue solution, the adsorption removal capacity of the water-absorbent resin to the methylene blue is researched, and the test result is shown in figure 2.
FIG. 2a shows PAA/PDAC/Ca (OH)2Adsorption removal capacity of soaking water-absorbent resin (dosage 360mg/L) in 200mg/L methylene blue solution with different pH values (pH values of 3, 5, 7, 9 and 11); FIG. 2b shows different PAA/PDAC/Ca (OH)2The water-absorbing resin dosage (45, 90, 180, 270, 360 and 410mg/L) has adsorption removal capacity on a methylene blue solution of 200mg/L when the pH value is 7.
As can be seen from fig. 2a, under acidic conditions, the water absorbent resin has very poor adsorption removal capability to methylene blue; under the alkaline condition, the water-absorbing resin has very good adsorption removal capacity to methylene blue, and the adsorption removal rate does not change obviously with the increase of the pH value.
As can be seen from FIG. 2b, in PAA/PDAC/Ca (OH)2When the dosage of the water-absorbent resin is lower than 90mg/L, the adsorption and removal capacity of the water-absorbent resin on methylene blue is very poor; when PAA/PDAC/Ca (OH)2When the dosage of the water-absorbent resin is higher than 90mg/L, the water-absorbent resin has very good adsorption removal capacity to methylene blue, and the change of the adsorption removal rate is not obvious along with the increase of the dosage of the water-absorbent resin.
Example 7
PAA/PDAC/Ca (OH) prepared in example 5 was mixed at 25 ℃ C2Placing water-absorbent resin samples in Cu with different initial concentrations2+Investigation of PAA/PDAC/Ca (OH) in solution (640ppb, 64ppb, 6.4ppb, 0.64ppb)2The water-absorbent resin has the copper ion adsorption removal capacity, as shown in figure 4. As a result, it was found that the water absorbent resin was resistant to Cu of as low as 0.64ppb level2+And the adsorption removal effect is also realized, which shows that the water-absorbent resin can be used for adsorbing and removing trace metal ions.
Example 8
PAA/PDAC/Ca (OH) at 25 ℃ C2The water-absorbent resin sample was placed in tap water, see fig. 5. As a result, the water-absorbent resin is found to have an adsorption removal effect on trace metal ions in tap water, which indicates that the water-absorbent resin can be used for softening hard water.
The method is characterized in that rice particles are used as a cross-linking agent, a cationic monomer is introduced as counter ions, and the neutralization degree of the anionic monomer and the ion type of the water-absorbing resin are adjusted by a neutralizing agent, so that the super-absorbent salt-resistant potassium ion-based high-molecular water-absorbing resin is prepared. Improves the water absorption and salt tolerance of the water-absorbent resin and promotes the application of the water-absorbent resin in various fields.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A super-absorbent salt-tolerant potassium ion-based polymer water-absorbent resin is characterized in that: the super water-absorbing salt-tolerant water-absorbing resin consists of an anionic monomer, a cationic monomer, a cross-linking agent, a neutralizer, an initiator and a catalyst;
wherein, the mass fraction of the cationic monomer is 25-75%, the mass fraction of the cationic monomer is 1-45%, the mass fraction of the crosslinking agent is 0.005-5%, the mass fraction of the neutralizing agent is 0-50%, the mass fraction of the initiating agent is 0.01-5%, and the mass fraction of the catalyst is 0.005-5%.
2. The super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin as claimed in claim 1, wherein: the anionic monomer comprises one of acrylic acid, sodium acrylate, potassium acrylate, methacrylic acid and 2-acrylamide-2-methylpropanesulfonic acid;
the cationic monomer comprises one of dimethyl diallyl ammonium chloride, (3-acrylamide propyl) trimethyl ammonium chloride, allyl trimethyl ammonium chloride, methacryloyloxyethyl trimethyl ammonium chloride and acryloyloxyethyl trimethyl ammonium chloride.
3. The method for preparing the super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin as claimed in claim 1 or 2, wherein: the crosslinking agent is selected from nanoparticles or organic crosslinking agents;
wherein the nanoparticles comprise one or more of graphene oxide, silica, clay, or calcium hydroxide;
the organic cross-linking agent comprises one or more of methylene acrylamide, divinylbenzene, ethylene glycol, toluene diisocyanate and allyl cellulose.
4. The method for preparing super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin according to claim 3, wherein the method comprises the following steps: the neutralizing agent comprises sodium hydroxide or potassium hydroxide.
5. The method for preparing the super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin as claimed in any one of claims 1, 2 and 4, wherein: the initiator comprises one of ammonium persulfate, potassium persulfate, sodium persulfate or 2,2' -azobisisobutylamidine dihydrochloride.
6. A method for preparing the super water-absorbing salt-tolerant potassium ion-based high-molecular water-absorbing resin as claimed in any one of claims 1 to 5, which is characterized in that: neutralizing the anionic monomer with neutralizing agent, adding cross-linking agent, introducing initiator and catalyst, and free radical copolymerization to obtain the water absorbing polymer resin.
7. The method for preparing super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin according to claim 6, wherein: dissolving a neutralizer in deionized water, adding a neutralizer solution into an anionic monomer solution, and uniformly mixing;
adding a cationic monomer and nano particles, and uniformly stirring;
adding an initiator and a catalyst, and stirring under the protection of nitrogen to obtain a mixed solution;
and at room temperature, preserving the mixed solution under the protection of nitrogen to obtain the super water-absorbing salt-resistant potassium ion-based high-molecular water-absorbent resin.
8. The method for preparing super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin according to claim 7, wherein: the dosage of the neutralizing agent is 5-90 wt% of the dosage of the anionic monomer.
9. The method for preparing the super water-absorbing salt-tolerant potassium ion-based polymeric water-absorbent resin according to any one of claims 6 to 8, wherein the method comprises the following steps: the reaction temperature of the free radical copolymerization is 0-80 ℃.
10. The super water-absorbing salt-tolerant potassium ion-based polymer water-absorbent resin as claimed in any one of claims 1 to 5, which is applied to the fields of sewage treatment, agriculture, medical treatment and health, flexible sensors or buildings.
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