CN110746532B - High water absorption resin with high reverse osmosis resistance and preparation method and application thereof - Google Patents
High water absorption resin with high reverse osmosis resistance and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
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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
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0033—Use of organic additives containing sulfur
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
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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
Abstract
The invention discloses a high water absorption resin with high reverse osmosis resistance, a preparation method and application thereof, wherein the preparation method of the high water absorption resin comprises the following steps: s1, dissolving the basic compound in deionized water, and adding the deionized water into an acrylic acid monomer solution to obtain a neutralized solution; s2, adding dodecyl mercaptan into the neutralization solution, adding an initiator, a cross-linking agent and a foaming agent, and polymerizing to obtain hydrogel; s3, cooling the hydrogel obtained in the step S2 to room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, and carrying out granulation, drying and crushing again to obtain resin particles; s4, spraying the surface cross-linking liquid on the surface of the resin particle in the step S3. The super absorbent resin can be used for disposable paper diapers and has the advantages of high absorption capacity, high liquid absorption speed, excellent water retention performance and excellent reverse osmosis resistance of the super absorbent resin prepared by the method.
Description
Technical Field
The invention relates to the technical field of resin preparation, in particular to a high-water-absorption resin with high reverse osmosis resistance, and a preparation method and application thereof.
Background
Super Absorbent Polymer (SAP) is a cross-linked network Polymer containing a large number of strong polar groups, and was first prepared by Fanta et al by grafting polyacrylonitrile with starch and then saponifying. From the last 60 s to date, super absorbent resins have been developed globally and can be divided into two main categories according to raw materials, wherein the first category is natural polymers such as starch and cellulose; the second type is a synthetic polymer, such as polyacrylic acid, polyoxyethylene, polyvinyl alcohol, wherein at present more than 80% of the super absorbent resin is polymerized from acrylic acid monomers. Since the crosslinked acrylic acid water-absorbent resin has a network structure, it can absorb hundreds or thousands of times of pure water by mass and lock water from bleeding. Therefore, the acrylic acid water-absorbent resin is widely applied to sanitary industries such as baby diapers and paper diapers, and also has wide application in the industries such as agriculture and forestry water retention, desert control, oil field water shutoff and the like, particularly the consumption of the super-absorbent resin in the domestic sanitary product market is continuously increased, and the super-absorbent resin is increased at a speed of 10% -15% every year.
Disclosure of Invention
In view of the disadvantages of the prior art, the first object of the present invention is to provide a method for preparing a super absorbent resin with high anti-reverse osmosis performance, which has the advantages of high absorption capacity, high liquid absorption speed, excellent water retention performance and excellent anti-reverse osmosis performance.
The second object of the present invention is to provide a high water-absorbent resin having high reverse osmosis resistance, which has the advantages of high absorption capacity, high liquid absorption rate, excellent water retention property and excellent reverse osmosis resistance.
The third purpose of the invention is to provide the application of the super absorbent resin in disposable paper diapers.
In order to achieve the first object, the invention provides the following technical scheme: a preparation method of a high water absorption resin with high reverse osmosis resistance comprises the following steps:
s1, dissolving the basic compound in deionized water, slowly adding the solution into an acrylic monomer solution, and controlling the reaction temperature to be 25-30 ℃ to obtain a neutralized solution;
s2, cooling the neutralized liquid to room temperature, adding dodecyl mercaptan, and then adding an initiator, a cross-linking agent and a foaming agent in a nitrogen atmosphere for polymerization to obtain hydrogel;
s3, cooling the hydrogel obtained in the step S2 to room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, wherein a medium is absolute ethyl alcohol, the ball milling rotation speed is 100-500 rpm, and the ball milling time is 1-2h, then carrying out granulation again, drying and crushing to obtain resin particles;
s4, spraying the surface cross-linking liquid on the surface of the resin particles in the step S3, and carrying out surface cross-linking at 80-100 ℃ for 1.5-2 h.
By adopting the technical scheme, the dodecyl mercaptan is added into the neutralization solution, the crosslinking degree of acrylic acid can be controlled, so that the liquid absorption performance of the finally prepared super absorbent resin is obviously improved, the foaming agent is added during polymerization, the holes in the gel are increased, the internal surface area of particles is improved, the crosslinking degree is controlled by combining the addition of the dodecyl mercaptan, the molecular weight of the gel is changed, and the finally prepared super absorbent resin has high absorption capacity, high liquid absorption speed, excellent water retention performance and excellent anti-reverse osmosis performance. The polymerized hydrogel is subjected to wet ball milling operation to obtain resin particles, the surface roughness of the resin particles can be improved, and then the surface crosslinking liquid is sprayed on the resin particles, so that the surface roughness of the resin particles and holes in the gel are further improved, and the super absorbent resin with excellent anti-reverse osmosis performance is obtained.
In addition, the surface cross-linking liquid is sprayed on the resin particles obtained after wet ball milling operation, namely, a film is coated on the resin particles with increased surface roughness, so that ions in the solution can not enter, and water can enter the resin, so that the low ion concentration in the resin can be kept, the internal and external osmotic pressures of the spatial network structure of the super absorbent resin are kept not to be reduced, the higher absorption rate of the ion-containing solution is kept, the problem that the water absorption rate of the existing super absorbent resin in the ion-containing solution is obviously reduced is solved, and the water absorption performance and the reverse osmosis resistance of the prepared super absorbent resin are obviously improved.
The invention is further configured to: the basic compound added in the step S1 is sodium hydroxide or potassium hydroxide, and the addition amount of the basic compound in the step S1 is 30-40 parts by weight, the addition amount of the deionized water is 110 parts by weight, the mass percent of the acrylic acid monomer solution is 90wt%, and the addition amount of the acrylic acid monomer solution is 800 parts by weight.
By adopting the technical scheme, the acrylic acid monomer solution with higher neutralization degree is prepared by the proportion, the liquid absorption capacity of the super absorbent resin finally prepared under the neutralization degree is higher, and the polymerized product is less in adhesion.
The invention is further configured to: after the initiator, the cross-linking agent and the foaming agent are added in the step S2, the polymerization reaction time is 1.5-2h, and the reaction temperature is 25-30 ℃.
The invention is further configured to: in the step S2, the dodecyl mercaptan is tert-dodecyl mercaptan or n-dodecyl mercaptan, the addition amount of the dodecyl mercaptan is 0.5-1.0% of the mass of the neutralization solution, the addition amount of the initiator is 0.5-1.0% of the mass of the neutralization solution, the addition amount of the cross-linking agent is 5-7% of the mass of the neutralization solution, and the addition amount of the foaming agent is 8-10% of the mass of the neutralization solution.
By adopting the technical scheme, the crosslinking degree of the polymerization reaction can be controlled by controlling the adding amount of the dodecyl mercaptan, the initiator, the crosslinking agent and the foaming agent, so that the water absorption characteristics, especially the water absorption rate and the water absorption multiplying power of the product super absorbent resin can be improved.
The invention is further configured to: in step S2, the cross-linking agent is one or more of N, N-methylene bisacrylamide, methyl bisacrylamide, ethylene glycol, polyethylene glycol diacrylate, glycerin, and sorbitol, preferably, the mass ratio of N, N-methylene bisacrylamide to sorbitol is 2:1 and mixing.
The invention is further configured to: the initiator in the step S2 selects potassium persulfate and sodium bisulfite as a redox system initiator; the foaming agent is prepared from sodium n-methyldibutylnaphthalenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 2-3 of a mixed mixture.
By adopting the technical scheme, the final high-water-absorptivity resin has the best liquid absorption effect and anti-reverse osmosis performance effect by selecting the foaming agent.
The invention is further configured to: the surface cross-linking liquid in the step S4 is prepared by mixing the following raw materials in parts by weight: 15-30 parts of glycerol, 10-15 parts of ethylene glycol diglycidyl ether, 10-15 parts of deionized water and 25-30 parts of aluminum sulfate.
By adopting the technical scheme and selecting the surface cross-linking agent, the distribution condition of the surface cross-linking liquid inside and outside the resin particles can be improved, so that the water absorption performance and the anti-reverse osmosis performance of the finally prepared super absorbent resin are obviously improved.
The invention is further configured to: the mass ratio of the spraying amount of the sprayed surface cross-linking liquid in step S4 to the total mass of the resin particles obtained in step S3 is 1: 200-300.
In order to achieve the second object, the invention provides the following technical scheme: the high water absorption resin with high reverse osmosis resistance is prepared by the preparation method of the high water absorption resin with high reverse osmosis resistance.
In order to achieve the third object, the invention provides the following technical scheme, and the invention provides the application of the super absorbent resin with high anti-permeability in disposable diapers.
By adopting the technical scheme, the super absorbent resin prepared by the method is used in disposable paper diapers, and has the advantages of high absorption rate, high liquid absorption speed, excellent water retention performance and excellent anti-reverse osmosis performance, the disposable paper diapers have high liquid absorption speed, larger liquid absorption rate, excellent anti-reverse osmosis performance and good dryness, the skin of a baby can be protected from being soaked and damaged by urine, and the phenomena of swelling, even diaper rash and the like can be avoided.
In conclusion, the invention has the following beneficial effects:
1. according to the invention, the foaming agent is added during polymerization, so that the holes in the gel are increased, the internal surface area of the particles is increased, the dodecyl mercaptan is added to control the crosslinking degree, the molecular weight of the gel is changed, the polymerized hydrogel is subjected to wet ball milling operation to obtain resin particles, the surface roughness of the resin particles can be improved, the surface crosslinking liquid is sprayed on the resin particles, the surface roughness of the resin particles and the holes in the gel are further improved, and the finally prepared super absorbent resin has high absorption rate, high liquid absorption speed, excellent water retention property and excellent reverse osmosis resistance;
2. when the super absorbent resin prepared by the invention is used in disposable paper diapers, the paper diapers have high liquid absorption speed, larger liquid absorption multiple, excellent anti-reverse osmosis performance and good dryness, can protect the skin of a baby from being damaged by urine immersion, and can not generate red swelling, even diaper rash and other phenomena.
Detailed Description
The present invention is further illustrated in detail by the following examples.
The starting materials referred to in the present invention are all commercially available.
Preparation example 1 of surface crosslinking liquid
Stirring 25g of glycerol, 12g of ethylene glycol diglycidyl ether, 13g of deionized water and 28g of aluminum sulfate to obtain the surface crosslinking liquid.
Preparation example 2 of surface crosslinking liquid
Stirring 15g of glycerol, 10g of ethylene glycol diglycidyl ether, 10g of deionized water and 25g of aluminum sulfate to obtain the surface crosslinking liquid.
Preparation example 3 of surface crosslinking liquid
Stirring 30g of glycerol, 15g of ethylene glycol diglycidyl ether, 15g of deionized water and 30g of aluminum sulfate to obtain the surface crosslinking liquid.
Examples
Example 1
A preparation method of a high water absorption resin with high reverse osmosis resistance comprises the following steps:
s1, dissolving 35g of basic compound in 105g of deionized water to obtain alkali liquor, slowly adding 750g of 90wt% acrylic acid monomer solution into the alkali liquor to neutralize, controlling the reaction temperature in the neutralization reaction process to be 25-30 ℃ by controlling the dropping amount of the alkali liquor, and obtaining neutralized liquid, wherein the basic compound is sodium hydroxide;
s2, cooling the neutralization solution to room temperature of 25 ℃, adding n-dodecyl mercaptan accounting for 0.8% of the mass of the neutralization solution, then adding an initiator accounting for 0.8% of the mass of the neutralization solution, a cross-linking agent accounting for 6% of the mass of the neutralization solution and a foaming agent accounting for 9% of the mass of the neutralization solution in a nitrogen atmosphere for polymerization to obtain hydrogel, wherein the polymerization reaction time is 110min, and the reaction temperature is 28 ℃;
wherein, the initiator is selected from the following components in a mass ratio of 1: 1 of potassium persulfate and sodium bisulfite, wherein the foaming agent is selected from sodium n-methyl dibutylnaphthalenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 2.5, selecting N, N-methylene bisacrylamide and sorbitol which are mixed according to the mass ratio of 2:1 as a cross-linking agent;
s3, cooling the hydrogel obtained in the step S2 to 25 ℃ at room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, wherein a medium is absolute ethyl alcohol, the ball milling rotation speed is 300 rpm, the ball milling time is 1.5h, then carrying out granulation again, drying and crushing to obtain resin particles;
s4, spraying the surface cross-linking liquid prepared in the preparation example 1 on the surface of the resin particles obtained in the step S3, wherein the mass ratio of the spraying amount of the surface cross-linking liquid to the total mass of the resin particles obtained in the step S3 is 1: 250, and spraying is carried out at 90 ℃, so as to realize surface crosslinking, and the crosslinking time is 110 min.
Example 2
A preparation method of a high water absorption resin with high reverse osmosis resistance comprises the following steps:
s1, dissolving 30g of basic compound in 100g of deionized water to obtain an alkali liquor, slowly adding 700g of acrylic acid monomer solution with the mass percent of 90wt% to neutralize, controlling the reaction temperature in the neutralization reaction process to be 25-30 ℃ by the dropping amount of the alkali liquor to obtain a neutralized solution, and selecting potassium hydroxide as the basic compound;
s2, cooling the neutralization solution to room temperature of 25 ℃, adding tert-dodecyl mercaptan accounting for 0.5% of the mass of the neutralization solution, then adding an initiator accounting for 0.5% of the mass of the neutralization solution, a cross-linking agent accounting for 5% of the mass of the neutralization solution and a foaming agent accounting for 8% of the mass of the neutralization solution in a nitrogen atmosphere for polymerization to obtain hydrogel, wherein the polymerization reaction time is 1.5h, and the reaction temperature is 25 ℃;
wherein, the initiator is selected from the following components in a mass ratio of 1: 1 of potassium persulfate and sodium bisulfite, wherein the foaming agent is selected from sodium n-methyl dibutylnaphthalenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 2, selecting N, N-methylene bisacrylamide as a cross-linking agent;
s3, cooling the hydrogel obtained in the step S2 to 25 ℃ at room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, wherein the medium is absolute ethyl alcohol, the ball milling rotation speed is 100 rpm, the ball milling time is 1h, then carrying out granulation again, drying and crushing to obtain resin particles;
s4, spraying the surface cross-linking liquid prepared in the preparation example 2 on the surface of the resin particles obtained in the step S3, wherein the mass ratio of the spraying amount of the surface cross-linking liquid to the total mass of the resin particles obtained in the step S3 is 1: 200, and the spraying is carried out at 80 ℃, so that the surface crosslinking is realized, and the crosslinking time is 1.5 h.
Example 3
A preparation method of a high water absorption resin with high reverse osmosis resistance comprises the following steps:
s1, dissolving 40g of basic compound in 110g of deionized water to obtain an alkali liquor, slowly adding 800g of 90wt% acrylic acid monomer solution into the alkali liquor to neutralize, controlling the reaction temperature in the neutralization reaction process to be 25-30 ℃ by the dropping amount of the alkali liquor to obtain a neutralized solution, and selecting sodium hydroxide as the basic compound;
s2, cooling the neutralization solution to room temperature of 25 ℃, adding n-dodecyl mercaptan accounting for 1.0% of the mass of the neutralization solution, then adding an initiator accounting for 1.0% of the mass of the neutralization solution, a cross-linking agent accounting for 7% of the mass of the neutralization solution and a foaming agent accounting for 10% of the mass of the neutralization solution in a nitrogen atmosphere for polymerization to obtain hydrogel, wherein the polymerization reaction time is 2 hours, and the reaction temperature is 30 ℃;
wherein, the initiator is selected from the following components in a mass ratio of 1: 1 of potassium persulfate and sodium bisulfite, wherein the foaming agent is selected from sodium n-methyl dibutylnaphthalenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 3, mixing the mixture, wherein the cross-linking agent is methyl bisacrylamide;
s3, cooling the hydrogel obtained in the step S2 to 25 ℃ at room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, wherein the medium is absolute ethyl alcohol, the ball milling speed is 500 rpm, the ball milling time is 2 hours, and then carrying out granulation, drying and crushing again to obtain resin particles;
s4, spraying the surface cross-linking liquid prepared in the preparation example 3 on the surface of the resin particles in the step S3, wherein the mass ratio of the spraying amount of the surface cross-linking liquid to the total mass of the resin particles obtained in the step S3 is 1: 300 and spraying is carried out at 80-100 ℃, so as to realize surface crosslinking, and the crosslinking time is 2 hours.
Example 4
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that n-dodecylmercaptan is added in step S2 in an amount of 0.5% by mass based on the amount of the neutralized liquid.
Example 5
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that n-dodecylmercaptan is added in step S2 in an amount of 1.0% by mass based on the amount of the neutralized liquid.
Example 6
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that a blowing agent is added in an amount of 8% by mass based on the amount of the neutralized liquid in step S2.
Example 7
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that a blowing agent is added in an amount of 10% by mass based on the amount of the neutralized liquid in step S2.
Example 8
A method for preparing a super absorbent resin with high anti-reverse osmosis performance is carried out according to the method in the example 1, except that sorbitol is selected as the cross-linking agent added in the step S2.
Example 9
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1, wherein glycerol is used as the crosslinking agent in step S2.
Example 10
A method for preparing a super absorbent resin with high anti-reverse osmosis performance is carried out according to the method in the example 1, except that the crosslinking agent added in the step S2 is selected from polyethylene glycol diacrylate.
Comparative example 1
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises cooling the neutralized solution in step S2, and adding an initiator, a crosslinking agent and a foaming agent in a nitrogen atmosphere.
Comparative example 2
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1, wherein the step S3 is conducted by subjecting a hydrogel to crushing, granulating, drying and pulverizing in this order to obtain resin primary particles, and the step S4 is conducted as it is.
Comparative example 3
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that n-dodecylmercaptan is added in step S2 in an amount of 0.3% by mass based on the amount of the neutralized liquid.
Comparative example 4
A process for producing a super absorbent resin having high reverse osmosis resistance, which comprises the steps of EXAMPLE 1 except that n-dodecylmercaptan is added in step S2 in an amount of 1.2% by mass based on the amount of the neutralized liquid.
Performance detection
The measurements of the reverse osmosis amount and the liquid permeability of the super absorbent resins prepared in examples 1 to 10 and comparative examples 1 to 4 were carried out in the following manner.
The reverse osmosis measurement method comprises the following steps:
pouring 50g of physiological saline into a culture dish with a diameter of 9.5cm, rapidly adding 2.00g of super absorbent resin SAP weighed in advance, gently swinging the culture dish to uniformly disperse the SAP in the culture dish, weighing 5 sheets after 5min to obtain total mass (calculated as W)1) A filter paper with a diameter of 9cm was placed on the SAP gel after the water absorption, then a petri dish with a diameter of 8.5cm was placed on the filter paper with the lower mouth facing upwards, and a 500g weight was pressed against the center of the petri dish and the time was again counted. Taking out the filter paper after 30min, and accurately weighing the total weight (calculated as W) of 5 pieces of filter paper after absorbing water2) The reverse osmosis amount (g) = W of the SAP2- W1。
The overnight speed measurement method is as follows:
the liquid passing time (time from up to down) of the physiological saline in the detection tube is firstly measured and is used as blank comparison time and is counted as W1Adding 0.02g of SAP into 150g of normal saline, transferring the absorbent gel and the normal saline into a detection tube after 30min, putting a pressure rod into the detection tube, adding a 100g weight, and starting timing. Opening a water outlet valve after 1min, observing and recording the time of the liquid level from the upper line to the lower line, and counting as W2The liquid passing time(s) of the SAP is W2- W1。
Meanwhile, the super absorbent resins prepared in examples 1 to 10 and comparative examples 1 to 4 were subjected to vortex method liquid absorption rate (vortex method)(s), pressure absorption amount (g/g), physiological saline absorption capacity (g/g), water retention amount (g/g) and water absorption capacity (g/g) measurement according to GB/T22905-2008, and the measurement results are shown in Table 1 below.
Table 1:
| examples | Absorption Capacity of physiological saline (g/g) | Water retention (g/g) | Imbibition rate(s) by vortex method | Absorption capacity under pressure (g/g) | Water absorption Rate (g/g) | Reverse osmosis amount (g） | Speed(s) in whole night |
| Example 1 | 67.9 | 48.6 | 26 | 39.6 | 630 | 0.25 | 18 |
| Example 2 | 66.8 | 44.8 | 32 | 37.5 | 610 | 0.37 | 20 |
| Example 3 | 67.1 | 42.9 | 36 | 36.8 | 605 | 0.41 | 22 |
| Example 4 | 67.4 | 46.7 | 30 | 40.5 | 624 | 0.32 | 19 |
| Example 5 | 67.2 | 45.1 | 28 | 41.1 | 619 | 0.36 | 20 |
| Example 6 | 67.5 | 47.8 | 28 | 39.8 | 618 | 0.28 | 20 |
| Example 7 | 67.4 | 43.9 | 27 | 40.6 | 612 | 0.31 | 21 |
| Example 8 | 66.9 | 47.6 | 28 | 38.4 | 625 | 0.28 | 19 |
| Example 9 | 67.1 | 47.9 | 29 | 38.2 | 619 | 0.31 | 20 |
| Example 10 | 67.5 | 47.6 | 29 | 38.0 | 619 | 0.30 | 20 |
| Comparative example 1 | 58.9 | 28.1 | 55 | 29.8 | 589 | 8.9 | 28 |
| Comparative example 2 | 60.3 | 32.1 | 48 | 30.5 | 601 | 11.5 | 29 |
| Comparative example 3 | 63.8 | 34.5 | 41 | 27.8 | 574 | 1.2 | 24 |
| Comparative example 4 | 63.1 | 31.2 | 43 | 26.4 | 568 | 1.5 | 26 |
As can be seen from the above Table 1 in example 1 and comparative examples 1 to 4, the absorption performance and the anti-permeability performance of the super absorbent resin can be improved by the addition of dodecyl mercaptan and the wet ball milling in step S2, and if the addition amount of dodecyl mercaptan is too large or too small, the absorption performance of the super absorbent resin is weak and the anti-permeability performance is low, and when the addition amount of dodecyl mercaptan is selected to be 0.5 to 1.0% of the mass of the neutralized liquid, the super absorbent resin has high absorption capacity, high absorption speed, excellent water retention performance and optimal anti-permeability performance, and by combining the settings of examples 4 and 5, it can be seen that the water absorption capacity and the physiological saline absorption capacity of the prepared super absorbent resin are increased and then decreased along with the increase of the addition amount of dodecyl mercaptan, and at the same time, along with the increase of the water absorption capacity and the physiological saline absorption capacity, the absorption capacity under pressure tends to decrease, and when the amount of dodecylmercaptan added is selected to be 0.8% by mass of the neutralizing solution, the liquid-absorbing property and the anti-reverse-permeation property of the resulting super absorbent resin are optimized.
Through the settings of the examples 1, 6 and 7, it can be seen that with the increase of the amount of the foaming agent, the water absorption capacity and the normal saline absorption capacity of the prepared super absorbent resin are increased firstly and then reduced, the reverse osmosis amount is decreased firstly and then increased, and when the addition amount of the foaming agent is 8-10% of the mass of the neutralization solution, the liquid absorption performance and the impermeability performance of the prepared super absorbent resin are optimal.
The high anti-reverse osmosis super absorbent resin prepared by the preparation method of the high anti-reverse osmosis super absorbent resin provided by the invention is applied to disposable paper diapers, the disposable paper diapers comprise dust-free paper, the high anti-reverse osmosis super absorbent resin prepared by the preparation method of the high anti-reverse osmosis super absorbent resin, non-woven fabric, the high anti-reverse osmosis super absorbent resin prepared by the preparation method of the high anti-reverse osmosis super absorbent resin and the dust-free paper at one time, the high anti-reverse osmosis super absorbent resin prepared by the preparation method of the high anti-reverse osmosis super absorbent resin is applied to the disposable paper diapers, the high absorption rate of the paper diapers is high, the liquid absorption rate is high, the water retention performance is excellent, the anti-reverse osmosis performance is excellent, the dryness is good, the skin of infants can be protected from being soaked and damaged by urine, and the phenomena of red swelling, even diaper rash and the like can not occur.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.
Claims (9)
1. A preparation method of a high water absorption resin with high reverse osmosis resistance is characterized by comprising the following steps:
s1, dissolving the basic compound in deionized water, slowly adding the solution into an acrylic monomer solution, and controlling the reaction temperature to be 25-30 ℃ to obtain a neutralized solution;
s2, cooling the neutralized liquid to room temperature, adding dodecyl mercaptan, and then adding an initiator, a cross-linking agent and a foaming agent in a nitrogen atmosphere for polymerization to obtain hydrogel;
s3, cooling the hydrogel obtained in the step S2 to room temperature, then sequentially carrying out crushing, granulation, drying and crushing to obtain resin primary particles, then carrying out wet ball milling on the resin primary particles, wherein a medium is absolute ethyl alcohol, the ball milling rotation speed is 100-500 rpm, and the ball milling time is 1-2h, then carrying out granulation again, drying and crushing to obtain resin particles;
s4, spraying the surface cross-linking liquid on the surface of the resin particles in the step S3, and carrying out surface cross-linking at 80-100 ℃ for 1.5-2 h;
wherein the addition amount of the dodecyl mercaptan in the step S2 is 0.5-1.0% of the mass of the neutralizing solution, and the crosslinking agent in the step S2 is N, N-methylene bisacrylamide and sorbitol which are mixed according to the mass ratio of 2: 1.
2. The method as claimed in claim 1, wherein the basic compound added in step S1 is sodium hydroxide or potassium hydroxide, and the weight portions of the basic compound added in step S1 are 30-40 parts, the weight portion of deionized water is 110 parts, the weight percentage of the acrylic acid monomer solution is 90wt%, and the weight portion of the acrylic acid monomer solution is 800-700 parts.
3. The method as claimed in claim 1, wherein the polymerization time of step S2 after the initiator, the cross-linking agent and the foaming agent are added is 1.5-2h, and the reaction temperature is 25-30 ℃.
4. The method of claim 1, wherein in step S2, the dodecyl mercaptan is tert-dodecyl mercaptan or n-dodecyl mercaptan, the amount of the initiator is 0.5-1.0% of the mass of the neutralized solution, the amount of the cross-linking agent is 5-7% of the mass of the neutralized solution, and the amount of the foaming agent is 8-10% of the mass of the neutralized solution.
5. The method for preparing a super absorbent resin with high reverse osmosis resistance according to claim 1, wherein the initiator in step S2 is selected from potassium persulfate and sodium bisulfite as redox system initiator; the foaming agent is prepared from sodium n-methyldibutylnaphthalenesulfonate and sodium dodecylsulfate in a mass ratio of 1: 2-3 of a mixed mixture.
6. The method for preparing a super absorbent resin with high anti-reverse osmosis performance as claimed in claim 1, wherein the surface cross-linking solution in step S4 is prepared by mixing the following raw materials in parts by weight: 15-30 parts of glycerol, 10-15 parts of ethylene glycol diglycidyl ether, 10-15 parts of deionized water and 25-30 parts of aluminum sulfate.
7. The method according to claim 1, wherein the mass ratio of the spraying amount of the surface cross-linking liquid in the step S4 to the total mass of the resin particles obtained in the step S3 is 1: 200-300.
8. A high water-absorbent resin with high reverse osmosis resistance, which is prepared by the method for preparing the high water-absorbent resin with high reverse osmosis resistance of any one of claims 1 to 7.
9. The use of the high reverse osmosis resistant superabsorbent resin of claim 8 in disposable diapers.
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| CN113683718B (en) * | 2021-08-13 | 2022-12-09 | 浙江工业大学 | Preparation method of low reverse osmosis high water absorption resin suitable for hygienic products |
| CN116531183B (en) * | 2023-05-16 | 2023-11-03 | 广东美登新材料科技有限公司 | 3D composite core body of sanitary article and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725548A (en) * | 2015-03-10 | 2015-06-24 | 乐山职业技术学院 | Hydrogel as well as preparation method and application thereof |
| CN105837725A (en) * | 2015-01-30 | 2016-08-10 | Sk新技术株式会社 | Water-absorbing resin and preparing method thereof |
| CN106750475A (en) * | 2017-02-27 | 2017-05-31 | 江苏虹创新材料有限公司 | It is a kind of to resist the preparation method for returning the super absorbent resin for oozing performance with height |
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| CN105837725A (en) * | 2015-01-30 | 2016-08-10 | Sk新技术株式会社 | Water-absorbing resin and preparing method thereof |
| CN104725548A (en) * | 2015-03-10 | 2015-06-24 | 乐山职业技术学院 | Hydrogel as well as preparation method and application thereof |
| CN106750475A (en) * | 2017-02-27 | 2017-05-31 | 江苏虹创新材料有限公司 | It is a kind of to resist the preparation method for returning the super absorbent resin for oozing performance with height |
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