CN111363284A - Shell-core structure super absorbent resin/kaolin composite ball moisture absorption material and preparation method thereof - Google Patents
Shell-core structure super absorbent resin/kaolin composite ball moisture absorption material and preparation method thereof Download PDFInfo
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- CN111363284A CN111363284A CN202010206610.2A CN202010206610A CN111363284A CN 111363284 A CN111363284 A CN 111363284A CN 202010206610 A CN202010206610 A CN 202010206610A CN 111363284 A CN111363284 A CN 111363284A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention relates to a shell-core structure super absorbent resin/kaolin composite ball moisture absorption material and a preparation method thereof, the composite ball moisture absorption material is a porous ball body, the composite ball moisture absorption material comprises a super absorbent resin matrix as a core part and a shell layer coated on the core part, the shell layer is a composite porous transmission layer formed by compounding kaolin and super absorbent resin, and the content of kaolin in the composite ball moisture absorption material is 25-40 wt%. In addition, the preparation method takes the super absorbent resin as a matrix, a kaolin-polymer composite porous transmission shell layer is formed on the surface of the super absorbent resin through the steps of activation, swelling, coating, drying, screening and the like, the composite porous transmission shell layer absorbs water vapor in a gas phase to form liquid water, and then the liquid water is transferred to the polymer resin at the core part, so that the moisture absorption mechanism of the original super absorbent resin is changed, and the moisture absorption performance of the super absorbent resin is improved. The moisture absorption capacity and the moisture absorption rate of the composite particle ball prepared by the invention in 10 hours can reach 1.95 times of those of the original resin, the moisture absorption rate is improved by 30 percent compared with the original resin, and the size of the composite particle ball can be regulated and controlled.
Description
Technical Field
The invention belongs to the technical field of composite moisture absorption materials, and particularly relates to a shell-core structure super absorbent resin/kaolin composite ball moisture absorption material and a preparation method thereof.
Background
The humidity in the air has great influence on the production and life of human beings, and the excessive humidity can have adverse effects on the health of people, the growth of crops, the storage of goods and the like. The moisture absorbent material is capable of reducing the humidity of the air by absorbing moisture in the environment. The moisture absorbent material is generally classified into organic polymer materials, inorganic salts, mineral materials, and the like. Although the moisture absorption rate of the inorganic salt moisture-absorbing material and the mineral material is high, the moisture absorption capacity is not high, and the inorganic salt is easily deliquesced and unstable. The polymer hygroscopic material is generally a high water absorption resin modified by physical and chemical methods, and has better comprehensive hygroscopic property. The sodium polyacrylate macromolecule (PAAS) is a novel super absorbent resin, has very strong water absorption, and the water absorption rate in water can reach more than 1000%.
However, the moisture absorption process of the sodium Polyacrylate (PAAS) is carried out in the air, and the hydrophilic groups in the PAAS absorb moisture. The moisture absorption process is mainly divided into two stages: the first stage is physical adsorption, which is the contact of moisture in the air through the surface of polymer particles through gas circulation, and is called an external transfer process or external diffusion; the second stage is chemisorption, which is the transport of water molecules from the surface of the polymer particles to the interior of the particle voids, either by internal transport processes or by internal diffusion.
Because the specific surface area of the macromolecule is small, and the water in the air is gaseous water with low content, the theoretical water absorption rate of the macromolecule is high, but the macromolecule has the problems of slow moisture absorption rate, low efficiency, small moisture absorption capacity and poor moisture absorption performance, cannot meet the requirements of people on high-performance moisture absorption materials, and how to improve the moisture absorption performance of the macromolecule is the problem to be solved at present.
In the prior art, chemical methods such as blending or graft copolymerization are used for modifying macromolecules so as to achieve the purpose of improving the moisture absorption performance of the macromolecules. Wherein the blending method is shown as a high-efficiency humidity-controlling material with Chinese patent publication No. CN 101108902A; the graft copolymerization method is as described in "journal of macromolecules", 2013 (7): 915-. However, these methods do not change the moisture absorption mechanism, and have the disadvantages of complicated process, low efficiency and high cost.
Disclosure of Invention
In order to solve the problems and the defects in the prior art, the invention aims to provide a super absorbent resin/kaolin composite ball moisture absorption material with a shell-core structure and a preparation method thereof. According to the technical scheme, the composite porous transmission layer is constructed on the surface of the super absorbent resin, so that the problems of low moisture absorption rate, low efficiency and small capacity of the existing super absorbent resin are solved.
In order to achieve the above objects, the first aspect of the present invention provides a shell-core structured sodium polyacrylate/kaolin composite sphere moisture absorption material and a preparation method thereof. The composite ball moisture absorption material is a porous ball body, and comprises a super absorbent resin matrix as a core part and a shell layer coated on the core part, wherein the shell layer is a composite porous transmission layer formed by compounding kaolin and super absorbent resin, and the content of the kaolin in the composite ball moisture absorption material is 25-40 wt%.
The super absorbent resin is further arranged to be sodium polyacrylate resin balls.
It is further provided that the kaolin has a particle size of less than 80 μm.
The average grain diameter of the composite ball moisture absorption material is further set to be 0.25 cm-0.65 cm. Through the setting, the particle size of the composite ball moisture absorption material can be regulated and controlled, so that the composite ball moisture absorption material can meet the requirements of different moisture absorption performance (such as moisture absorption rate) conditions, and meanwhile, the size of the composite ball moisture absorption material can be controlled to meet various size requirements of the material in use.
The second aspect of the invention provides a preparation method of the composite ball moisture absorption material, which comprises the following steps:
s1, activation, namely suspending kaolin in a salt solution for activation, and then drying and grinding the kaolin to obtain activated kaolin;
s2 swelling, namely soaking the spherical super absorbent resin into deionized water for water absorption and swelling;
s3, coating, namely, draining the swelled super absorbent resin, taking out the resin, mixing the resin with activated kaolin, and uniformly coating the activated kaolin to obtain coated particles;
s4 drying and sieving: and drying the coated particles until the surfaces of the coated particles become hard, simultaneously removing a small amount of activated kaolin powder from the surfaces of the dried particles, and screening to remove the excess kaolin which falls off to obtain the super absorbent resin/kaolin composite sphere moisture absorption material with the core-shell structure.
Further setting that in the step 1, the salt solution is saturated aqueous solution of sodium chloride, salt and industrial salt, and the activation time is controlled to be more than 2 hours.
Further, in the step S2, the super absorbent resin is immersed in deionized water for 1-6 hours.
According to the invention, the super absorbent resin is immersed in the deionized water for 1-6 hours, so that the swelling volume of the super absorbent resin can be controlled, and the ratio of the resin to the clay can be better controlled in the subsequent coating stage. The invention controls the water absorption of the super absorbent resin to 2-6 times of the original volume, ensures the performance of the super absorbent resin, and can reduce the moisture absorption performance of the composite ball moisture absorption material or cause larger damage rate because the water absorption swelling volume of the super absorbent resin is too high or too low.
Further setting that in the step 3, the mass ratio of the swelled super absorbent resin to the activated kaolin is 1: (10-30) coating for 10 minutes. Through the setting, the time is controlled within 10 minutes, and the coating effect is ensured; if the blending time is too long, the resin will release excessive water, which affects the coating effect.
Further setting that in the S4, the composite ball is dried for 1-4 h at the temperature of 110-130 ℃. Through the arrangement, under the temperature condition and the drying time, the activated clay particles and the surface of the swelling resin can fully act, the prepared composite ball moisture absorption material is ensured to form a porous structure on the surface layer after being dried, and meanwhile, the high yield and the small breakage rate are ensured.
In the step S2, the super absorbent resin is spherical.
The technical scheme has the following beneficial effects that: according to the invention, the shell kaolin-polymer composite porous transmission layer absorbs water vapor in a gas phase to form liquid water, and then the liquid water is transferred to the core polymer resin, so that the moisture absorption mechanism of the original super absorbent resin is changed, and the moisture absorption performance of the original super absorbent resin is improved; meanwhile, the mass ratio is selected, so that the prepared composite ball moisture absorption material is stable in void structure, large in specific surface area and good in moisture absorption performance; if the proportion is too low, the moisture absorption performance of the composite ball moisture absorption material is not good; if the proportion is too high, the damage rate of the prepared composite ball moisture absorption material is higher.
In addition, the PAAS resin has the characteristics of large water storage capacity, large and stable specific surface of kaolin minerals, and the characteristics of no toxicity, no harm and low cost of sodium chloride, salt or industrial salt, and the preparation method is simple and the cost is low.
In summary, the invention has the advantages that:
(1) in the preparation process, a pore structure is constructed on the surface of the composite of the activated kaolin and the polymer to form a porous transmission layer, so that the specific surface area of the composite ball is increased; meanwhile, the transmission layer can rapidly liquefy water vapor to form liquid water which is transmitted to the internal super absorbent resin (such as PAAS), so that the moisture absorption mechanism of the original super absorbent resin (such as PAAS) is changed, and the moisture absorption performance of the material is obviously improved;
(2) the moisture absorption capacity and the moisture absorption rate of the composite granular ball prepared by the invention in 10 hours are up to 1.95 times of those of the original resin, and the moisture absorption rate reaches 7.12% h-1Compared with pure PAAS, the PAAS is improved by 30 percent, and the size of the PAAS can be regulated and controlled;
(3) the preparation process provided by the invention is simple and rapid, has low cost, is easy to realize and operate, and has good application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art 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 within the scope of the present invention for those skilled in the art to obtain other drawings based on the drawings without inventive exercise.
FIG. 1 is a schematic structural diagram and SEM image of a shell-core structure sodium polyacrylate resin/kaolin composite sphere moisture absorption material
FIG. 2 is a graph comparing the moisture absorption curves of PK8-25-1 and neat resin;
FIG. 3 is a graph comparing the moisture absorption curves of PK5-30-2 with those of pure resin;
FIG. 4 is a graph comparing the moisture absorption curves of PK4-30-3 with those of pure resin;
FIG. 5 is a graph comparing the moisture absorption curves of PK1-35-4 with those of pure resin;
FIG. 6 is a graph comparing the moisture absorption curves of PK2-40-6 with those of pure resin;
FIG. 7 is a flow chart of the manufacturing process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings.
A flow chart of the manufacturing process of the present invention is shown in fig. 7. Which comprises the following steps
S1, activation, namely suspending kaolin in a salt solution for activation, and then drying and grinding the kaolin to obtain activated kaolin;
s2 swelling, namely soaking the spherical super absorbent resin into deionized water for water absorption and swelling;
s3, coating, namely, draining the swelled super absorbent resin, taking out the resin, mixing the resin with activated kaolin, and uniformly coating the activated kaolin to obtain coated particles;
s4 drying and sieving: and drying the coated particles until the surfaces of the coated particles become hard, simultaneously removing a small amount of activated kaolin powder from the surfaces of the dried particles, and screening to remove the excess kaolin which falls off to obtain the super absorbent resin/kaolin composite sphere moisture absorption material with the core-shell structure.
The details of the invention will now be further elucidated with respect to specific embodiments:
example 1
Kaolin with the particle size of 80um is suspended in saturated sodium chloride solution for 2.5 hours, and then the activated kaolin is obtained by drying and grinding. Soaking the super absorbent resin balls into deionized water to swell for 1 hour, then draining the swelled balls, taking out and wiping the balls, and mixing the water and the water according to a mass ratio of 1: 30, mixing with activated kaolin to ensure that the surface of the small ball is uniformly coated with the activated kaolin, and controlling the coating time within 10 minutes; and then drying the mixture at 110 ℃ for 4h, and sieving the dried product to remove excessive kaolin powder to obtain the shell-core structure PAAS/kaolin composite sphere hygroscopic material PK 8-25-1. The average particle size of the composite spheres is 0.657cm, and the content of kaolin in the composite spheres of the embodiment is 26.08%.
FIG. 2 is a moisture absorption curve of PK8-25-1 and pure resin balls measured under the conditions of constant temperature of 30 ℃, humidity of 100% and the same moisture absorption time. From the results, it can be seen that the moisture absorption amount and the moisture absorption rate of the composite particle spheres are 1.25 times of those of the pure resin spheres.
Example 2
Kaolin having a particle size of 50um was suspended in a saturated saline solution for 2.5 hours, and then dried and pulverized to obtain activated Kaolin. Soaking the super absorbent resin balls into deionized water for swelling for 2 hours, then draining the swollen balls, taking out the swollen balls, and wiping the swollen balls to dry, wherein the mass ratio of the water to the water is 1: 20, mixing with activated kaolin to ensure that the surface of the small ball is uniformly coated with the activated kaolin, and controlling the coating time within 10 minutes; and then drying the mixture at 120 ℃ for 2h, and sieving the dried product to remove excessive kaolin powder to obtain the shell-core structure PAAS/kaolin composite sphere hygroscopic material PK 5-30-2. The average particle size of the composite spheres was 0.457cm, and the content of kaolin in the composite spheres of this example was 29.16%.
The moisture absorption amount and moisture absorption rate of PK5-30-2 were 1.36 times that of the pure resin beads, as shown in FIG. 3.
Example 3
Kaolin having a particle size of 30um was suspended in a saturated saline solution for 2.5 hours, and then dried and pulverized to obtain activated Kaolin. Soaking the super absorbent resin balls into deionized water for swelling for 3 hours, then draining the swollen balls, taking out the swollen balls, and wiping the swollen balls to dry, wherein the mass ratio of the water to the water is 1: 10, mixing the active kaolin with the active kaolin to ensure that the active kaolin is uniformly coated on the surfaces of the small balls, wherein the coating time is controlled within 10 minutes; and then drying the mixture at 130 ℃ for 1h, and sieving the dried product to remove excessive kaolin powder to obtain the shell-core structure PAAS/kaolin composite sphere hygroscopic material PK 3-30-3. The average particle size of the composite spheres was 0.257cm, and the content of kaolin in the composite spheres of this example was 30.22%.
The moisture absorption amount and moisture absorption rate of PK3-30-3 were 1.57 times that of the pure resin beads, as shown in FIG. 4.
Example 4
Kaolin with the particle size of 20um is suspended in a saturated salt solution for 2.5 hours, and then the activated kaolin is obtained by drying and grinding. Soaking the super absorbent resin balls into deionized water to swell for 4 hours, then draining the swelled balls, taking out and wiping the balls, wherein the mass ratio of the balls to the water is 1: 20, mixing with activated kaolin to ensure that the surface of the small ball is uniformly coated with the activated kaolin, and controlling the coating time within 10 minutes; and then drying the mixture at 120 ℃ for 2h, and sieving the dried product to remove excessive kaolin powder to obtain the shell-core structure PAAS/kaolin composite sphere hygroscopic material PK 2-35-4. The average particle size of the composite spheres was 0.285cm, and the content of kaolin in the composite spheres of this example was 34.82%.
The moisture absorption amount and moisture absorption rate of PK2-35-4 were 1.95 times that of the pure resin beads, as shown in FIG. 5.
Example 5
Kaolin with the particle size of 20um is suspended in a saturated salt solution for 2.5 hours, and then the activated kaolin is obtained by drying and grinding. Soaking the super absorbent resin balls into deionized water to swell for 6 hours, then draining the swelled balls, taking out and wiping the balls, wherein the mass ratio of the balls to the water is 1: 10, mixing the active kaolin with the active kaolin to ensure that the active kaolin is uniformly coated on the surfaces of the small balls, wherein the coating time is controlled within 10 minutes; and then drying the mixture at 110 ℃ for 3h, and sieving the dried product to remove excessive kaolin powder to obtain the shell-core structure PAAS/kaolin composite sphere hygroscopic material PK 2-40-6. The average particle size of the composite spheres was 0.385cm, and the content of kaolin in the composite spheres of this example was 38.41%. The moisture absorption amount and moisture absorption rate of PK2-40-6 were 1.47 times that of the pure resin beads, as shown in FIG. 6.
The above disclosure is only for the purpose of illustrating the preferred embodiments of the present invention, and it is therefore to be understood that the invention is not limited by the scope of the appended claims.
Claims (10)
1. The shell-core structure super absorbent resin/kaolin composite ball moisture absorption material is characterized in that: the composite ball moisture absorption material is a porous ball body, and comprises a super absorbent resin matrix as a core part and a shell layer coated on the core part, wherein the shell layer is a composite porous transmission layer formed by compounding kaolin and super absorbent resin, and the content of the kaolin in the composite ball moisture absorption material is 25-40 wt%.
2. The shell-core structured sodium polyacrylate/kaolin composite sphere hygroscopic material of claim 1, wherein: the super absorbent resin is sodium polyacrylate resin balls.
3. The shell-core structured sodium polyacrylate/kaolin composite sphere hygroscopic material of claim 1, wherein: the particle size of the kaolin is less than 80 μm.
4. The shell-core structured sodium polyacrylate/kaolin composite sphere hygroscopic material of claim 1, wherein: the average grain diameter of the composite ball moisture absorption material is 0.25 cm-0.65 cm.
5. A method for preparing a composite ball absorbent material as claimed in any one of claims 1 to 4, characterized in that it comprises the following steps:
s1, activation, namely suspending kaolin in a salt solution for activation, and then drying and grinding the kaolin to obtain activated kaolin;
s2 swelling, namely soaking the spherical super absorbent resin into deionized water for water absorption and swelling;
s3, coating, namely, draining the swelled super absorbent resin, taking out the resin, mixing the resin with activated kaolin, and uniformly coating the activated kaolin to obtain coated particles;
s4 drying and sieving: and drying the coated particles until the surfaces of the coated particles become hard, simultaneously removing a small amount of activated kaolin powder from the surfaces of the dried particles, and screening to remove the excess kaolin which falls off to obtain the super absorbent resin/kaolin composite sphere moisture absorption material with the core-shell structure.
6. The method of claim 5, wherein: in the step 1, the salt solution is a saturated aqueous solution of sodium chloride, salt and industrial salt, and the activation time is controlled to be more than 2 hours.
7. The method of claim 5, wherein: and in the S2, the super absorbent resin is immersed in deionized water for 1-6 hours.
8. The method of claim 5, wherein: in the step 3, the mass ratio of the swelled super absorbent resin to the activated kaolin is 1: (10-30) coating for 10 minutes.
9. The method of claim 5, wherein: in the S4, the composite ball is dried for 1-4 h at the temperature of 110-130 ℃.
10. The method of claim 5, wherein: in S2, the super absorbent resin is spherical.
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Cited By (1)
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| CN115400556A (en) * | 2022-08-23 | 2022-11-29 | 广州锦创环境科技有限公司 | Water-based ink drying and alcohol recovery system |
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