CN112011007B - High water absorption resin capable of multiple absorption and preparation method thereof - Google Patents

High water absorption resin capable of multiple absorption and preparation method thereof Download PDF

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CN112011007B
CN112011007B CN202010735861.XA CN202010735861A CN112011007B CN 112011007 B CN112011007 B CN 112011007B CN 202010735861 A CN202010735861 A CN 202010735861A CN 112011007 B CN112011007 B CN 112011007B
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super absorbent
absorbent resin
colloid
time
drying
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CN112011007A (en
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杨卫东
刘健
吕志平
阮玉林
韩伟恒
朱雅亮
刘新
裴小苏
邵东
刘若铎
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Zhejiang Satellite Science & Technology Co ltd
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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
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a super absorbent resin capable of being absorbed for multiple times and a preparation method thereof. The preparation method of the super absorbent resin capable of absorbing for multiple times comprises the following steps: a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid; b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time; c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time; d. and c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time. The super absorbent resin capable of being absorbed for multiple times and the preparation method thereof disclosed by the invention have excellent absorption performance, particularly have multiple absorption capacity, and the multiple absorption coefficient is less than 150.

Description

High water absorption resin capable of multiple absorption and preparation method thereof
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a preparation method of a super absorbent resin capable of being absorbed for multiple times and the super absorbent resin capable of being absorbed for multiple times.
Background
Super Absorbent Polymer (SAP) is a novel functional Polymer material with a three-dimensional network structure and low degree of crosslinking. The molecular chain of the SAP contains a plurality of strong hydrophilic groups such as carboxyl and the like, and can absorb water which is hundreds of times to thousands of times of the self weight. The SAP is not only strong in water-absorbing ability but also excellent in water-retaining ability, and is also called a high water-retaining material because it is not dehydrated even when pressurized after absorbing water. SAP is mainly used in daily chemical industry, agriculture and forestry water retention, petrochemical industry, building, cable, medical auxiliary material and food desiccant, etc., and at present more than 90% of SAP is used in the field of disposable sanitary materials.
The high-absorptivity resin is applied to the field of disposable sanitary materials, has excellent water retention performance and important multiple absorption capacity, particularly the baby diaper, generally needs to absorb more than 3 times, the high-absorptivity resin products on the market at present have the problem of insufficient multiple absorption capacity, gel becomes sticky after the first absorption, the second absorption capacity is obviously reduced, and the third absorption is difficult to absorb again. This causes an increase in rewet of the diaper and even leakage of urine. In patent CN104582833, insoluble water inorganic particles (silica) are added in the surface treatment process to improve the problem of multiple absorption, but the addition of hydrophobic substance can seriously affect the absorption speed of the super absorbent resin product.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a preparation method of a super absorbent resin capable of being absorbed for multiple times and a super absorbent resin capable of being absorbed for multiple times.
The invention discloses a high water absorption resin capable of being absorbed for multiple times and a preparation method thereof, and mainly aims to introduce different alkaline substances into a polymerization process for multiple neutralization and drying, form different neutralization gradients in the high water absorption resin, and mutually match parts with different neutralization degrees in the multiple absorption process to ensure that the high water absorption resin has certain gel strength and certain absorption capacity but can be absorbed for multiple times.
The invention adopts the following technical scheme that the preparation method of the super absorbent resin capable of being absorbed for multiple times comprises the following steps:
a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid;
b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time;
c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time;
d. c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time;
e. and d, crushing, screening and surface treating the material dried in the step d to obtain the super absorbent resin capable of being absorbed for multiple times.
According to the technical scheme, as a further preferable technical scheme of the technical scheme, the water-soluble initiator adopts an oxidant/reducing agent initiation system, wherein the oxidant is selected from one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate and ascorbic acid, the proportion of the oxidizing agent to the reducing agent is 1:1, and the dosage of the water-soluble initiator is 0.001-0.1% of the mass of the acrylic acid.
According to the technical scheme, as a further preferable technical scheme of the technical scheme, the bridging agent is one or more selected from pentaerythritol tetraacrylic acid, N' -methylene bisacrylamide, polyethylene glycol diacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and triallylamine ester, and the dosage of the bridging agent is 0.05-5% of the mass of acrylic acid.
According to the above technical solution, as a further preferable technical solution of the above technical solution, the neutralization degree of the first granulation in the step b is 10 to 20%, and the water content of the first dried colloid is 40 to 60%.
According to the above technical solution, as a further preferable technical solution of the above technical solution, the neutralization degree of the second granulation in the step c is 20 to 40%, and the water content of the second dried colloid is 20 to 40%.
According to the above technical scheme, as a further preferable technical scheme of the above technical scheme, the neutralization degree of the third granulation in the step d is 50-80%, and the water content of the third drying colloid is 1-10%.
According to the above technical solution, as a further preferable technical solution of the above technical solution, the super absorbent resin capable of multiple absorption further comprises a surface cross-linking agent, and the surface cross-linking agent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyglycerol, isopropanol, 1, 4-butanediol, diethanolamine, triethanolamine, polyoxypropylene ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerol diglycidyl ether (the amount is 1% to 10% of the semi-finished product of the super absorbent resin).
According to the above aspect, as a more preferable aspect of the above aspect, the temperature of the surface treatment in the method for producing a super absorbent resin capable of multiple absorption is 60 to 200 ℃.
According to the above aspect, as a more preferable aspect of the above aspect, the method for producing a super absorbent resin capable of multiple absorption has a multiple absorption coefficient of less than 150.
The invention also discloses a super absorbent resin capable of being absorbed for multiple times, which is prepared by the preparation method of the super absorbent resin capable of being absorbed for multiple times disclosed by any one technical scheme.
The super absorbent resin capable of being absorbed for multiple times and the preparation method thereof disclosed by the invention have the beneficial effects that the product has excellent absorption performance, particularly has multiple absorption capacity, and the multiple absorption coefficient is less than 150.
Detailed Description
The invention discloses a preparation method of a multiple-absorption high water-absorption resin and a multiple-absorption high water-absorption resin, and the specific implementation mode of the invention is further described by combining the preferred embodiments.
Preferred embodiments.
Preferably, the preparation method of the multiple-time absorbable super absorbent resin comprises the following steps:
a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid;
b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time;
c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time;
d. c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time;
e. and d, crushing, screening and surface treating the material dried in the step d to obtain the super absorbent resin capable of being absorbed for multiple times.
Further, the water-soluble initiator adopts an oxidant/reducing agent initiation system, wherein the oxidant is selected from one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate and ascorbic acid, the proportion of the oxidizing agent to the reducing agent is 1:1, and the dosage of the water-soluble initiator is 0.001-0.1% of the mass of the acrylic acid.
Furthermore, the bridging agent is selected from one or more of pentaerythritol tetraacrylic acid, N' -methylene bisacrylamide, polyethylene glycol diacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and triallylamine ester, and the dosage of the bridging agent is 0.05-5% of the mass of the acrylic acid.
Furthermore, the neutralization degree of the first granulation in the step b is 10-20%, and the water content of the first drying colloid is 40-60%.
Furthermore, the neutralization degree of the second granulation in the step c is 20-40%, and the water content of the second drying colloid is 20-40%.
Furthermore, the neutralization degree of the third granulation in the step d is 50-80%, and the water content of the third drying colloid is 1-10%.
Furthermore, the super absorbent resin capable of absorbing for multiple times also comprises a surface cross-linking agent, wherein the surface cross-linking agent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyglycerol, isopropanol, 1, 4-butanediol, diethanolamine, triethanolamine, polyoxypropylene ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and glycerol diglycidyl ether.
Further, the temperature of the surface treatment of the preparation method of the super absorbent resin capable of absorbing for many times is 60-200 ℃.
Further, the multiple absorption coefficient of the preparation method of the super absorbent resin capable of multiple absorption is less than 150.
The embodiment also discloses a super absorbent resin capable of absorbing for multiple times, which is prepared by the preparation method of the super absorbent resin capable of absorbing for multiple times as disclosed in any one of the technical schemes of the embodiment.
A first variant embodiment.
Preferably, the preparation method of the multiple-time absorbable super absorbent resin comprises the following steps:
a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid;
b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time;
c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time;
d. c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time;
e. and d, crushing, screening and surface treating the dried material in the step d to obtain a high-absorptivity resin finished product.
Purified acrylic acid is used as the acrylic acid, and the monomer concentration of the aqueous acrylic acid solution in step a is 15 to 50%, preferably 20 to 35%, particularly preferably 22 to 32%. The monomer concentration of the acrylic acid aqueous solution is lower than 15 percent, the polymerization is difficult to initiate, the monomer concentration of the acrylic acid aqueous solution is higher than 50 percent, the polymerization reaction is difficult to control, and the implosion reaction is easy to occur.
The water-soluble initiator is an oxidant/reductant initiating system. Wherein the oxidant is selected from one or more of sodium persulfate, potassium persulfate, ammonium persulfate and hydrogen peroxide; the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate and ascorbic acid. The mass ratio of the oxidant to the reducing agent is 1:1, and the dosage of the oxidant to the reducing agent is 0.001-0.1% of the mass of the acrylic acid.
The bridging agent is selected from one or more of pentaerythritol tetraacrylic acid, N' -methylene bisacrylamide, polyethylene glycol diacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and triallylamine ester, and the dosage of the bridging agent is 0.05-5 percent of the mass of acrylic acid, and is preferably 0.1-2 percent. The bridging agent is less than 0.05 percent, the internal crosslinking density of the high-absorptivity resin product is low, the gel strength is poor, and the high-absorptivity resin product is not suitable for being used on sanitary products; the bridging agent is higher than 5 percent, the internal crosslinking density of the high-absorptivity resin product is too high, the water absorption performance of the high-absorptivity resin product is obviously reduced, and the high-absorptivity resin product is not suitable for being used on sanitary articles;
the polymerization temperature of the acrylic monomer solution is 0 to 60 ℃ and preferably 0 to 30 ℃. The polymerization time is 20-90 minutes. After the polymerization reaches the highest temperature, the colloid is placed at the temperature of 50-120 ℃ and is kept for 0.5-10 hours.
And c, neutralizing the colloid formed in the step a by using one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, wherein the neutralization degree is 10-20%, and performing first drying, wherein the water content of the dried colloid is 40-60%.
And c, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, wherein the neutralization degree is 20-40%, and drying for the second time, wherein the water content of the dried colloid is 20-40%.
C, granulating the dried colloid for the third time, neutralizing by using a potassium hydroxide solution, wherein the neutralization degree is 50-80%, and drying for the third time, wherein the water content of the dried colloid is 1-10%.
And d, crushing, screening and surface treating the dried material in the step d to obtain a high-absorptivity resin finished product.
The surface cross-linking agent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyglycerol, isopropanol, 1, 4-butanediol, diethanolamine, triethanolamine, polyoxypropylene ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and glycerol diglycidyl ether, and the dosage of the surface cross-linking agent is 1-10% of that of the semi-finished product of the high-absorptivity resin.
The surface treatment temperature is 60-200 deg.C, preferably 100-200 deg.C, and the surface treatment time is 20-120 min, preferably 30-90 min.
The embodiment also discloses a super absorbent resin capable of absorbing for multiple times, which is prepared by the preparation method of the super absorbent resin capable of absorbing for multiple times as disclosed in any one of the technical schemes of the embodiment.
A second variant embodiment.
Preferably, the method for preparing the multiple absorbable high absorbent resin comprises the following steps:
a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid;
b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time;
c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time;
d. c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time;
e. and d, crushing, screening and surface treating the dried material in the step d to obtain a high-absorptivity resin finished product.
The aqueous initiator adopts an oxidant/reducing agent initiation system. Wherein the oxidant is selected from one or more of sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate and ascorbic acid. The proportion of the oxidant to the reducing agent is 1:1, and the dosage of the oxidant to the reducing agent is 0.001-0.1% of the mass of the acrylic acid.
The bridging agent is selected from one or more of pentaerythritol tetraacrylic acid, N' -methylene bisacrylamide, polyethylene glycol diacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and triallylamine ester, and the dosage of the bridging agent is 0.05-5% of the mass of the acrylic acid.
In the step b, the neutralization degree of the first granulation is 10-20%, and the water content of the first drying colloid is 40-60%.
And c, the neutralization degree of the second granulation is 20-40%, and the water content of the second drying colloid is 20-40%.
And d, the neutralization degree of the third granulation is 50-80%, and the water content of the third drying colloid is 1-10%.
The surface cross-linking agent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyglycerol, isopropanol, 1, 4-butanediol, diethanolamine, triethanolamine, polyoxypropylene ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and glycerol diglycidyl ether, and the dosage of the surface cross-linking agent is 1-10% of that of the semi-finished product of the high-absorptivity resin.
The surface treatment temperature is 60-200 ℃.
Its multiple absorption coefficient is less than 150.
The embodiment also discloses a super absorbent resin capable of absorbing for multiple times, which is prepared by the preparation method of the super absorbent resin capable of absorbing for multiple times as disclosed in any one of the technical schemes of the embodiment.
It is worth mentioning that the product performance test method of the specific examples and the comparative examples is as follows:
(1) multiple absorption coefficient
The multiple absorption coefficient refers to the ability of the super absorbent resin to absorb multiple times, particularly the absorption ability after the second time.
Specifically, 1.00g of super absorbent resin is placed in a 100mL beaker, 15mL of weighed 0.9 wt% aqueous sodium chloride solution is poured in, after 15 minutes, 15mL of 0.9 wt% aqueous sodium chloride solution is poured in again, timing is started until the liquid is completely absorbed by the super absorbent resin, timing is stopped, the second absorption time is T2, after 15 minutes of complete absorption, 15mL of 0.9 wt% aqueous sodium chloride solution is poured in, timing is started until the liquid is completely absorbed by the super absorbent resin, timing is stopped, and the third absorption time is T3.
Multiple absorption coefficient T2+ T3.
(2) Saline water absorption rate
The saline absorption Capacity (Free Swelling Capacity) refers to the Free Swelling Capacity of a superabsorbent resin per unit mass in saline over a certain period of time.
Specifically, 0.2000g of super absorbent resin was weighed in a tea bag, immersed in a 0.9 wt% aqueous sodium chloride solution for 30min to allow free expansion, and then suspended for 10min to remove water, thereby obtaining a water absorption capacity (unit; g/g).
Saline absorption rate ═ mAfter absorbing water-mSample (A)-mBlank space)/mSample (A)。
(3) Centrifugal water retention
The centrifugal Retention Capacity (Centrifuge Retention Capacity) is a water absorption Capacity obtained by freely swelling a high-absorbent resin per unit mass in saline water for a certain period of time and then removing water by a Centrifuge.
Specifically, 0.2000g of super absorbent resin was weighed in a tea bag, immersed in a 0.9 wt% aqueous sodium chloride solution for 30min to be freely swollen, and then dehydrated by a centrifuge (centrifugal force: 250g) to obtain a water absorption capacity (unit; g/g).
Centrifuge retention rate ═ mAfter centrifugation-mSample (A)-mBlank space)/mSample (A)。
(4) Absorption rate under pressure
The Absorption Under Pressure (Absorption Under Pressure) refers to the water Absorption rate of a high-absorbent resin per unit mass Under a certain Pressure for a certain time.
Specifically, the water absorption capacity (unit: g/g) was obtained by swelling 0.9000g of a super absorbent resin in a 0.9 wt% aqueous sodium chloride solution for 1 hour under a load of 0.7 psi.
Absorption rate under pressure (m)After absorbing water-mBefore water absorption)/mSample (A)。
(5) Absorption rate
The Absorption Speed (Absorption Speed) refers to how fast a mass of superabsorbent resin absorbs saline.
Specifically, 50mL of 0.9 wt% sodium chloride aqueous solution is added into a 100mL beaker, 2.0000g of high-absorptivity resin is added into the beaker under magnetic stirring (rotating speed of 600r/min), timing is started, the timing is stopped after the liquid level vortex disappears to the recovery level, and the recorded time is the absorption speed (unit: s).
Detailed description of the preferred embodiment 1
Adding 25.00kg of fine acrylic acid, 50.00kg of water and 2.1kg of 10 wt% of bridging agent pentaerythritol triallyl ether into a reaction kettle, uniformly mixing, cooling the reaction liquid to 15 ℃, and adding an initiator: 1.25kg of 1 wt% hydrogen peroxide and 0.60kg of 1 wt% ferrous sulfate. After the polymerization reaction is finished, the temperature of a reactor jacket is kept for 4 hours at 80 ℃, then the colloid is extruded from a reaction kettle and crushed and granulated, 5.5kg of sodium carbonate is added in the first granulation, the colloid is dried for 20 minutes at 150 ℃, and the water content of the first dried material is 49.7 percent; performing secondary granulation on the primary dried material and 5.0kg of 48% sodium hydroxide solution, drying the colloid at 150 ℃ for 15 minutes, wherein the water content of the secondary dried material is 34.4%; the second oven dried material and 20.5kg of 30% potassium hydroxide solution were granulated for the third time, the colloid was dried at 150 ℃ for 20 minutes, and the water content of the third oven dried material was 3.6%. The dried material is crushed and sieved to obtain particles with the particle size of 45-850 mu m. The particles are treated by surface treatment liquid to obtain a high-absorptivity resin product, the surface treatment liquid is prepared from polyoxypropylene ether, butanediol and water according to the proportion of 5:35:60, the dosage of the surface treatment liquid is 2.5% of the mass of SAP, the surface treatment temperature is 140 ℃, and the treatment time is 50 min.
Specific example 2
Adding 25.00kg of fine acrylic acid, 50.00kg of water and 2.1kg of 10 wt% of bridging agent pentaerythritol triallyl ether into a reaction kettle, uniformly mixing, cooling the reaction liquid to 15 ℃, and adding an initiator: 1.25kg of 1 wt% hydrogen peroxide and 0.60kg of 1 wt% ferrous sulfate. After the polymerization reaction is finished, keeping the temperature of a reactor jacket at 80 ℃ for 4h, then extruding the colloid out of a reaction kettle, crushing and granulating, adding 7.8kg of 30% potassium hydroxide solution into the first granulation, drying the colloid for 20 minutes at 150 ℃, and drying the material for the first time to obtain 52.7% of water content; carrying out secondary granulation on the primary dried materials and 12.5kg of 48% sodium hydroxide solution, drying the colloid for 15 minutes at 150 ℃, wherein the water content of the secondary dried materials is 37.6%; the second drying material and 6.3kg of sodium carbonate are granulated for the third time, the colloid is dried for 20 minutes at 150 ℃, and the water content of the third drying material is 3.8 percent. The dried material is crushed and sieved to obtain particles with the particle size of 45-850 mu m. The particles are treated by surface treatment liquid to obtain a high-absorptivity resin product, the surface treatment liquid is prepared from polyoxypropylene ether, butanediol and water according to the proportion of 5:35:60, the dosage of the surface treatment liquid is 2.5% of the mass of SAP, the surface treatment temperature is 140 ℃, and the treatment time is 50 min.
Specific example 3
Adding 25.00kg of fine acrylic acid, 55.00kg of water and 2.1kg of 10 wt% of bridging agent pentaerythritol tetraacrylate into a reaction kettle, uniformly mixing, cooling the reaction liquid to 15 ℃, and adding an initiator: 1.25kg of 1 wt% hydrogen peroxide and 0.60kg of 1 wt% ferrous sulfate. After the polymerization reaction is finished, the temperature of a reactor jacket is kept for 4 hours at 80 ℃, then the colloid is extruded from a reaction kettle and crushed and granulated, 5.5kg of sodium carbonate is added in the first granulation, the colloid is dried for 20 minutes at 150 ℃, and the water content of the first dried material is 48.7 percent; performing secondary granulation on the primary dried material and 5.0kg of 48% sodium hydroxide solution, drying the colloid at 150 ℃ for 15 minutes, wherein the water content of the secondary dried material is 34.8%; the second oven dried material and 20.5kg of 30% potassium hydroxide solution were granulated for the third time, the colloid was dried at 150 ℃ for 20 minutes, and the water content of the third oven dried material was 3.5%. The dried material is crushed and sieved to obtain particles with the particle size of 45-850 mu m. The particles are treated by surface treatment liquid to obtain a high-absorptivity resin product, the surface treatment liquid is prepared by glycerol diglycidyl ether, butanediol and water according to the proportion of 8:32:60, the dosage of the surface treatment liquid is 3.0 percent of the mass of SAP, the surface treatment temperature is 150 ℃, and the treatment time is 50 min.
Specific example 4
Adding 25.00kg of fine acrylic acid, 60.00kg of water, 1.3kg of 10 wt% of bridging agent pentaerythritol triallyl ether and 1.7kg of 10% of N, N' -methylene bisacrylamide into a reaction kettle, uniformly mixing, cooling the reaction solution to 15 ℃, and adding an initiator: 1.25kg of 1 wt% hydrogen peroxide and 0.60kg of 1 wt% ferrous sulfate. After the polymerization reaction is finished, keeping the temperature of a reactor jacket at 80 ℃ for 4h, then extruding the colloid out of a reaction kettle, crushing and granulating, adding 7.8kg of 30% potassium hydroxide solution into the first granulation, drying the colloid for 20 minutes at 150 ℃, and drying the material for the first time to obtain 52.7% of water content; carrying out secondary granulation on the primary dried materials and 12.5kg of 48% sodium hydroxide solution, drying the colloid for 15 minutes at 150 ℃, wherein the water content of the secondary dried materials is 37.6%; the second drying material and 6.3kg of sodium carbonate are granulated for the third time, the colloid is dried for 20 minutes at 150 ℃, and the water content of the third drying material is 3.8 percent. The dried material is crushed and sieved to obtain particles with the particle size of 45-850 mu m. The particles are treated by surface treatment liquid to obtain a high-absorptivity resin product, the surface treatment liquid is prepared from polyoxypropylene ether, butanediol and water according to the proportion of 5:35:60, the dosage of the surface treatment liquid is 2.5% of the mass of SAP, the surface treatment temperature is 140 ℃, and the treatment time is 50 min.
Comparative example 1
Adding 25.00kg of fine acrylic acid, 50.00kg of water and 2.1kg of 10 wt% of bridging agent pentaerythritol triallyl ether into a reaction kettle, uniformly mixing, cooling the reaction liquid to 15 ℃, and adding an initiator: 1.25kg of 1 wt% hydrogen peroxide and 0.60kg of 1 wt% ferrous sulfate. After the polymerization reaction is finished, the jacket of the reactor is kept at 80 ℃ for 4 hours, and then the colloid is extruded out of the reaction kettle and crushed and granulated, and 18.9kg of 48 percent liquid caustic soda is added for neutralization during granulation. After granulation, the colloid is dried for 60min at 160 ℃, and the water content of the dried material is 3.8%. . The dried material is crushed and sieved to obtain particles with the particle size of 45-850 mu m. The particles are treated by surface treatment liquid to obtain a high-absorptivity resin product, the surface treatment liquid is prepared from polyoxypropylene ether, butanediol and water according to the proportion of 5:35:60, the dosage of the surface treatment liquid is 2.5% of the mass of SAP, the surface treatment temperature is 140 ℃, and the treatment time is 50 min.
The product properties of each of the specific examples and comparative examples are shown in Table 1.
Watch 1
Figure BDA0002604903030000131
It should be noted that the technical features such as specific type selection of the reaction kettle and the like related to the present patent application should be regarded as the prior art, the specific structure, the operation principle, the control mode and the spatial arrangement mode of the technical features may be selected conventionally in the field, and should not be regarded as the invention point of the present patent, and the present patent is not further specifically described in detail.
It will be apparent to those skilled in the art that modifications and equivalents may be made in the embodiments and/or portions thereof without departing from the spirit and scope of the present invention.

Claims (10)

1. A preparation method of a super absorbent resin capable of absorbing for many times is characterized by comprising the following steps:
a. acrylic acid, deionized water, a water-soluble initiator and a bridging agent are polymerized in a reactor to generate colloid;
b. neutralizing the colloid formed in the step a with one or more of sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate and potassium bicarbonate in the first granulation process, and drying for the first time;
c. b, granulating the dried colloid in the step b for the second time, neutralizing by using a sodium hydroxide solution, and drying for the second time;
d. c, granulating the dried colloid in the step c for the third time, neutralizing by using a potassium hydroxide solution, and drying for the third time;
e. and d, crushing, screening and surface treating the material dried in the step d to obtain the super absorbent resin capable of being absorbed for multiple times.
2. The method for preparing the multiple-absorption super absorbent resin as claimed in claim 1, wherein the water-soluble initiator is an oxidant/reducer initiation system, wherein the oxidant is one or more selected from sodium persulfate, potassium persulfate and ammonium persulfate; the reducing agent is selected from one or more of sodium bisulfite, ferrous sulfate and ascorbic acid, the proportion of the oxidizing agent to the reducing agent is 1:1, and the dosage of the water-soluble initiator is 0.001-0.1% of the mass of the acrylic acid.
3. The method for preparing a multiple absorbable super absorbent resin as claimed in claim 1, wherein the bridging agent is selected from one or more of pentaerythritol tetraacrylate, N' -methylenebisacrylamide, polyethylene glycol diacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and triallylamine, and the amount of the bridging agent is 0.05-5% by mass of acrylic acid.
4. The method for preparing a superabsorbent polymer of claim 1 wherein the neutralization degree of the first granulation of step b is 10-20% and the water content of the first dried gel is 40-60%.
5. The method for preparing a multiple absorbable super absorbent resin as claimed in claim 1, wherein the neutralization degree of the second granulation in step c is 20-40%, and the water content of the second drying gel is 20-40%.
6. The method according to claim 1, wherein the neutralization degree of the third granulation in step d is 50-80%, and the water content of the third drying gel is 1-10%.
7. The method for preparing a multiple-absorbable super absorbent resin as claimed in claim 1, wherein the multiple-absorbable super absorbent resin further comprises a surface cross-linking agent, and the surface cross-linking agent is selected from one or more of ethanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerol, polyglycerol, isopropanol, 1, 4-butanediol, diethanolamine, triethanolamine, polyoxypropylene ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and glycerol diglycidyl ether.
8. The method for producing a multiple absorbable superabsorbent resin of claim 1 wherein the surface treatment temperature of the method for producing a multiple absorbable superabsorbent resin is 60 to 200 ℃.
9. The method for producing a multiple absorbable superabsorbent resin of claim 1 wherein the multiple absorption coefficient of the multiple absorbable superabsorbent resin is less than 150.
10. A multiple-absorbable super absorbent resin, which is prepared by the method for preparing a multiple-absorbable super absorbent resin according to any one of claims 1 to 9.
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