CN115505064A - Preparation method of low-soluble substance super absorbent resin - Google Patents

Preparation method of low-soluble substance super absorbent resin Download PDF

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CN115505064A
CN115505064A CN202211183099.4A CN202211183099A CN115505064A CN 115505064 A CN115505064 A CN 115505064A CN 202211183099 A CN202211183099 A CN 202211183099A CN 115505064 A CN115505064 A CN 115505064A
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mass
gel
absorbent resin
particles
super absorbent
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于婷
朱倩虹
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Lianyungang Minglei 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/04—Azo-compounds
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • 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
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • 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 preparation method of a low soluble substance super absorbent resin, belonging to the technical field of high polymer materials and comprising the following steps: diluting 23-40% of refined acrylic acid by water, and adding liquid alkali for neutralization to obtain a neutralization solution with the neutralization degree of 0-80%; adding a composite cross-linking agent and a composite initiator into the obtained neutralized solution to obtain a polymerization solution, and conveying the polymerization solution to a reaction device through a polymerization solution conveying pipeline to initiate polymerization reaction to obtain blocky gel; extruding and granulating the obtained massive gel for multiple times by an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles; drying the prepared gel particles, and crushing and screening to obtain base particles with the particle size of 20-35 meshes; the surface treatment liquid is sprayed on the surface of the obtained basic particles, and the super absorbent resin particles are prepared after heat treatment, so that the technical problem of high soluble substance content in the prior art is solved, and the super absorbent resin particles are mainly applied to ice bags.

Description

Preparation method of low-soluble substance super absorbent resin
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a low-soluble substance super absorbent resin.
Background
The super absorbent resin (sodium polyacrylate, SAP) is a polymer which contains strong hydrophilic groups, is insoluble in water, and can absorb tens, hundreds or even thousands of times of water by weight. Has excellent water absorption and retention performance, and is widely applied to sanitary products such as paper diapers, physiological sanitary towels, adult incontinence products, pet pads and the like, agricultural and forestry soil moisturizing agents, petroleum exploitation and other fields. In recent years, with the improvement of the quality of life of people and the continuous improvement of internet technology and e-commerce platform, the on-line vegetable and fruit fresh frozen food and medical supplies are increasingly popularized and show an increasingly rapid development trend. In the huge market of fresh food, ice bags become an important part in cold chain logistics transportation.
The ice bag prepared by SAP is commonly used in the fields of medical and physical cooling of aquatic products, dairy product fresh keeping, fruit beverage refrigeration, biological reagents, blood plasma, vaccine cold insulation, wounds, fever and the like, and provides multiple guarantees for the health of human bodies in vivo and in vitro; compared with the traditional dry ice and ice blocks with the same low-temperature fresh-keeping effect, the SAP ice bag is not limited by the transportation modes of aviation, trains and the like, is high in quality and low in price, has wide purchasing approach and is convenient to popularize; the filler is basically non-toxic and harmless, and can be repeatedly used under the condition of no damage.
Therefore, the SAP has good market prospect in the fields of cold-chain logistics transportation ice bags, medical ice bags and the like. The prior ice bag sold in the market has less special SAP, and the prior product generally has the problems of small particle size, high soluble substance under pressure and large back seepage after imbibition and swelling, thereby seriously influencing the application experience of the product.
Chinese patent CN102731802B controls the drying temperature in stages and the stacking height of the dried gel particles, so as to reduce the chain transfer between the high polymers in the gel particles due to the heat which is not easy to dissipate and increase the content of the soluble substance high polymer. However, this approach has the following drawbacks: 1. the content of soluble matters can be reduced to a certain degree only to reach about 10 percent. 2. The internal crosslinking polymerization is not changed, and the soluble substance content is high only because the macromolecule is physically prevented from being broken. During the subsequent transportation and use of SAP, polymer is broken and soluble content is increased.
Aiming at the defects, the internal structure of the high-molecular SAP is changed by changing the initiation mode and the internal crosslinking mode, so that a dense three-dimensional space network structure is formed, the content of soluble substances is low, the SAP is not easy to break, the swelling rate after water absorption is high, and water can be locked. Particularly, the ice bag is used in the ice bag, full particles are formed after water is absorbed, the ice bag is not easy to seep polluted food from the ice bag when being used as a cold chain logistics transportation ice bag, and the ice bag can be effectively used as a medical ice bag and can ensure that the ice bag is not in contact with the skin.
The invention content is as follows:
the invention aims to solve the technical problem of the prior art and provides a preparation method of a super absorbent resin with low soluble substances, which adopts the following technical scheme:
the preparation method of the low-soluble substance super absorbent resin is characterized by comprising the following steps:
step (1): diluting 23-40% of refined acrylic acid by water, and adding liquid alkali for neutralization to obtain a neutralization solution with the neutralization degree of 0-80%;
step (2): adding the neutralization solution obtained in the step (1) into a composite cross-linking agent and a composite initiator to obtain a mixed solution, and conveying the mixed solution to a reaction device through a polymerization solution conveying pipeline to initiate polymerization reaction for 5-45 min to obtain blocky gel;
and (3): extruding and granulating the block-shaped gel obtained in the step (2) for multiple times through an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles;
and (4): drying the gel particles prepared in the step (3) at the drying temperature of 90-200 ℃ for 15-120 min, and crushing and screening to obtain base particles with the particle size of 20-35 meshes;
and (5): and (4) spraying surface treatment liquid on the surface of the base particle obtained in the step (4), and performing heat treatment to obtain the super absorbent resin particle, wherein the heat treatment temperature is 70-200 ℃, and the time is 10-30 min.
Preferably: in order to better reduce the generation of soluble substances, the mass concentration of the acrylic acid in the step (1) is 25-35%, and the neutralization degree of the neutralization solution is 40-80%.
Preferably: in order to better reduce the generation of soluble substances, the polymerization reaction temperature of the step (2) is controlled to be 0-15 ℃, and the reaction time is 10-45 min.
Preferably: in order to better reduce the generation of soluble substances, the polymerization liquid is mixed by introducing N into a conveying pipeline 2 And the mixture is deoxidized and uniformly mixed by a dynamic mixer and a static mixer on a pipeline and is conveyed to a reaction device to initiate polymerization reaction.
Preferably: in order to better reduce the generation of soluble substances, the composite cross-linking agent is one or more of pentaerythritol triallyl ether composite polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, trimethylolpropane triacrylate and triethoxylated glycerol triacrylate, and the addition mass of the composite cross-linking agent accounts for 0.10-0.60% of the total mass of acrylic acid in the neutralizing solution.
Preferably: in order to better reduce the generation of soluble substances, the composite initiator comprises a front-stage initiator and a rear-stage initiator;
the former stage initiator is selected from: one or two of sodium sulfite, sodium bisulfite, L-ascorbic acid (salt), ferrous sulfate, sodium hyposulfite and sodium metabisulfite, wherein the adding mass of the front-stage initiator accounts for 0.005-0.500 percent of the total mass of acrylic acid in the neutralizing solution;
the latter stage initiator is selected from: sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 4' -azobis (4-cyanovaleric acid) two or more of 2,2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis (2-methylpropylimidine) dihydrochloride, 2' -azobis [ N- (2-hydroxyethyl) -2-methylpropionamidine ] tetrahydrate, and azobisisobutyretherhydrochloride, the addition mass of the composite initiator accounts for 0.006-1.00 percent of the total mass of the acrylic acid in the neutralization solution.
Preferably, in order to better reduce the generation of soluble substances, the gel cutting auxiliary agent in the step (3) is as follows: one or two of sodium carbonate, sodium bicarbonate, potassium carbonate, ammonium carbonate, potassium bicarbonate and ammonium bicarbonate, wherein the addition mass of the gel cutting auxiliary agent accounts for 2-40% of the total mass of acrylic acid in the neutralization solution.
Preferably: in order to better reduce the generation of soluble substances, the gel cutting auxiliary agent in the step (3) is as follows: one or more of sodium stearate, sucrose ester, sodium sulfite and sodium metabisulfite, wherein the addition mass of the sodium stearate, the sucrose ester, the sodium sulfite and the sodium metabisulfite accounts for 0.01-3% of the total mass of acrylic acid in the neutralization solution.
Preferably: in order to better reduce the generation of soluble substances, the extrusion granulator in the step (3) is a single-screw extrusion granulator or a double-screw extrusion granulator, the extrusion granulation times are 3-5 times, the diameter of a pore plate of a combined extruder is optimized, and the particle size of the basic particles obtained by crushing and screening in the step (4) is 20-35 meshes.
Preferably: in order to better reduce the generation of soluble substances, the surface treatment liquid in the step (5) is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, wherein the mass of the propylene glycol accounts for 0.02-3% of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.002-0.4% of the total mass of the basic particles; the mass of the sulfate accounts for 0.1 to 4.0 percent of the total mass of the basic particles.
The invention has the following beneficial effects:
(1) Compared with a single ester crosslinking agent, the method of compounding the ether crosslinking agent with the ester crosslinking agent improves the crosslinking degree and crosslinking uniformity of the polymer, and improves the structural stability and gel strength of the polymer, thereby reducing the generation of soluble substances;
(2) By adopting a composite initiation mode, the initiation and polymerization rate are improved, the polymerization reaction time is shortened, the polymerization temperature is reduced, higher polymer molecular weight is obtained at lower polymerization temperature, and the occurrence of chain transfer reaction is inhibited by adopting lower polymerization initiation reaction temperature, so that the generation of soluble substances is reduced;
(3) The mixing mode of the polymerization liquid adopts the way of introducing N into a conveying pipeline 2 And the polymer is deoxidized and uniformly mixed by a dynamic mixer and a static mixer on a pipeline, so that the initiation and polymerization rate is improved, the polymerization reaction time is shortened, the neutralization degree of a reaction system is adjusted by adopting a partial post-neutralization process and a multi-stage neutralization process, the polymerization rate is effectively regulated and controlled, and the crosslinking uniformity of the polymer is improved, so that the generation of soluble substances is reduced.
Detailed Description
Example 1
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a composite cross-linking agent and a composite initiator into the neutralization solution to obtain a polymerization solution, and introducing N into the polymerization solution in a polymerization solution conveying pipeline 2 And deoxidizing and uniformly mixing the mixture by using a dynamic mixer and a static mixer on a pipeline, and then conveying the mixture to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 5 ℃, and the reaction time is 45min, so as to obtain the block gel, the composite cross-linking agent is pentaerythritol triallyl ether and polyethylene glycol 300, the adding mass of the composite cross-linking agent accounts for 0.12% of the total mass of acrylic acid in the neutralizing liquid, the composite initiator is L-ascorbic acid, sodium persulfate and azobisisobutyryl ether hydrochloride, and the adding mass of the composite initiator accounts for 0.25% of the total mass of acrylic acid in the neutralizing liquid.
(3) And extruding and granulating the blocky gel for multiple times by using an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the adding mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min to obtain base particles with the particle size of 20-35 meshes after crushing and screening;
(5) Spraying surface treatment liquid on the surface of the base particle, and performing heat treatment to obtain the super absorbent resin particle, wherein the heat treatment temperature is 150 ℃, the time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1% of the total mass of the base particle; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
Example 2
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a composite cross-linking agent and a composite initiator into the neutralization solution to obtain a polymerization solution, and introducing N into the polymerization solution in a polymerization solution conveying pipeline 2 And deoxidizing and uniformly mixing the mixture by using a dynamic mixer and a static mixer on a pipeline, and then conveying the mixture to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 10 ℃, and the reaction time is 35min, so that massive gel is obtained, the composite cross-linking agent is pentaerythritol triallyl ether and trimethylolpropane triacrylate, the adding mass of the cross-linking agent accounts for 0.10% of the total amount of acrylic acid in the neutralizing liquid, the composite initiator is L-ascorbic acid, sodium persulfate and azobisisobutyryl ether hydrochloride, and the adding mass of the composite initiator accounts for 0.25% of the total amount of acrylic acid in the neutralizing liquid.
(3) And extruding and granulating the blocky gel for multiple times by using an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the adding mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min, and crushing and screening to obtain base particles with the particle size of 20-35 meshes;
(5) Spraying a surface treatment liquid on the surface of the base particles, and performing heat treatment to obtain super absorbent resin particles, wherein the heat treatment temperature is 150 ℃, the heat treatment time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1 percent of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
Example 3
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a composite cross-linking agent and a composite initiator into the neutralization solution to obtain a polymerization solution, and introducing N into the polymerization solution in a polymerization solution conveying pipeline 2 Deoxidizing and uniformly mixing the gel by a dynamic mixer and a static mixer on a pipeline, and conveying the mixture to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 15 ℃, and the reaction time is 26min, so as to obtain blocky gel; the composite cross-linking agent is pentaerythritol triallyl ether and polyethylene glycol 600, the addition mass of the composite cross-linking agent accounts for 0.10% of the total amount of acrylic acid in the neutralizing liquid, the composite initiator is L-ascorbic acid, sodium persulfate and azobisisobutyric ether hydrochloride, and the addition mass of the composite initiator accounts for 0.25% of the total amount of acrylic acid in the neutralizing liquid.
(3) And extruding and granulating the blocky gel for multiple times through an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the addition mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min to obtain base particles with the particle size of 20-35 meshes after crushing and screening;
(5) Spraying a surface treatment liquid on the surface of the base particles, and performing heat treatment to obtain super absorbent resin particles, wherein the heat treatment temperature is 150 ℃, the heat treatment time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1 percent of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
Comparative example 1
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a cross-linking agent polyethylene glycol 600 and an initiator sodium persulfate into the neutralized liquid to obtain a polymer liquid, and introducing N into the polymer liquid conveying pipeline 2 Deoxidizing and uniformly mixing the gel by a dynamic mixer and a static mixer on a pipeline, and conveying the mixture to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 5 ℃, and the reaction time is 45min, so as to obtain blocky gel; the addition mass of the cross-linking agent polyethylene glycol 600 accounts for 0.10% of the total amount of acrylic acid in the neutralizing solution, and the addition mass of the initiator sodium persulfate accounts for 0.25% of the total amount of acrylic acid in the neutralizing solution.
(3) And extruding and granulating the blocky gel for multiple times by using an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the adding mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min to obtain base particles with the particle size of 20-35 meshes after crushing and screening;
(5) Spraying a surface treatment liquid on the surface of the base particles, and performing heat treatment to obtain super absorbent resin particles, wherein the heat treatment temperature is 150 ℃, the heat treatment time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1 percent of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
Comparative example 2
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a cross-linking agent polyethylene glycol 600 and an initiator sodium persulfate into the neutralized liquid to obtain a polymer liquid, and introducing N into the polymer liquid conveying pipeline 2 Deoxidizing and uniformly mixing the materials by a dynamic mixer and a static mixer on a pipeline, and conveying the materials to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 10 ℃, and the reaction time is 35min, so that block gel is obtained; polyethylene glycol as cross-linking agentThe added mass of 600 accounts for 0.10% of the total amount of acrylic acid in the neutralizing liquid, and the added mass of the initiator sodium persulfate accounts for 0.25% of the total amount of acrylic acid in the neutralizing liquid.
(3) And extruding and granulating the blocky gel for multiple times by using an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the adding mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min to obtain base particles with the particle size of 20-35 meshes after crushing and screening;
(5) Spraying surface treatment liquid on the surface of the base particle, and performing heat treatment to obtain the super absorbent resin particle, wherein the heat treatment temperature is 150 ℃, the time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1% of the total mass of the base particle; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
Comparative example 2
(1) Diluting the fine acrylic acid with the mass concentration of 28% by water, and neutralizing by using a sodium hydroxide solution to obtain a neutralization solution with the neutralization degree of 50%;
(2) Adding a cross-linking agent polyethylene glycol 600 and an initiator sodium persulfate into the neutralization solution to obtain a polymerization solution, and introducing N into the polymerization solution in a polymerization solution conveying pipeline 2 Deoxidizing and uniformly mixing the materials by a dynamic mixer and a static mixer on a pipeline, and conveying the materials to a reaction device to initiate polymerization reaction, wherein the polymerization reaction temperature is 15 ℃, and the reaction time is 26min, so that block gel is obtained; the addition mass of the cross-linking agent polyethylene glycol 600 accounts for 0.10% of the total amount of acrylic acid in the neutralizing liquid, and the addition mass of the initiator sodium persulfate accounts for 0.25% of the total amount of acrylic acid in the neutralizing liquid.
(3) And extruding and granulating the blocky gel for multiple times by using an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles, wherein the gel cutting auxiliary agent is sodium carbonate and sodium sulfite, and the adding mass of the gel cutting auxiliary agent accounts for 10% of the total amount of acrylic acid in the neutralization solution.
(4) Drying the prepared gel particles at 160 ℃ for 50min to obtain base particles with the particle size of 20-35 meshes after crushing and screening;
(5) Spraying a surface treatment liquid on the surface of the base particles, and performing heat treatment to obtain super absorbent resin particles, wherein the heat treatment temperature is 150 ℃, the heat treatment time is 20min, the surface treatment liquid is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, and the mass of the propylene glycol accounts for 0.1 percent of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.003 percent of the total mass of the basic particles; the mass of the sulfate accounts for 0.2 percent of the total mass of the basic particles.
The main performance indexes of the product prepared by the invention are as follows:
Figure BDA0003866072280000081
Figure BDA0003866072280000091
in the examples, the soluble matter content was further reduced to about 5% as compared with the comparative examples. The water absorption multiplying power and the centrifugal water retention capacity are correspondingly increased, and the device is more suitable for market demands.
Furthermore, it should be understood that although the present specification describes embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and it is to be understood that all embodiments may be combined as appropriate by one of ordinary skill in the art to form other embodiments as will be apparent to those of skill in the art from the description herein.

Claims (10)

1. A method for preparing a low-soluble substance super absorbent resin is characterized by comprising the following steps:
step (1): diluting 23-40% of refined acrylic acid by water, and adding liquid alkali for neutralization to obtain a neutralization solution with the neutralization degree of 0-80%;
step (2): adding a composite cross-linking agent and a composite initiator into the neutralized liquid obtained in the step (1) to obtain a polymerization liquid, and conveying the polymerization liquid to a reaction device through a polymerization liquid conveying pipeline to initiate polymerization reaction for 5-45 min to obtain block gel;
and (3): extruding and granulating the block-shaped gel obtained in the step (2) for multiple times through an extrusion granulator, and uniformly adding a gel cutting auxiliary agent into the extruder in the extrusion process to obtain gel particles;
and (4): drying the gel particles prepared in the step (3) at the drying temperature of 90-200 ℃ for 15-120 min, and crushing and screening to obtain base particles with the particle size of 20-35 meshes;
and (5): and (4) spraying surface treatment liquid on the surface of the base particle obtained in the step (4), and performing heat treatment to obtain the super absorbent resin particle, wherein the heat treatment temperature is 70-200 ℃, and the time is 10-30 min.
2. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the mass concentration of the acrylic acid in the step (1) is 25-35%, and the neutralization degree of the neutralization solution is 40-80%.
3. The method for preparing a low extractable material superabsorbent resin of claim 1, wherein: the polymerization reaction temperature of the step (2) is controlled to be 0-15 ℃, and the reaction time is 10-45 min.
4. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the polymerization liquid mixing mode in the step (2) adopts the way of introducing N into a conveying pipeline 2 And the mixture is deoxidized and uniformly mixed by a dynamic mixer and a static mixer on a pipeline and is conveyed to a reaction device to initiate polymerization reaction.
5. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the composite cross-linking agent is one or more of pentaerythritol triallyl ether composite polyethylene glycol 300, polyethylene glycol 400, polyethylene glycol 600, polyethylene glycol 800, trimethylolpropane triacrylate and triethoxy glycerol triacrylate, and the addition mass of the composite cross-linking agent accounts for 0.10-0.60% of the total mass of acrylic acid in the neutralizing solution.
6. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the composite initiator comprises a front-stage initiator and a rear-stage initiator;
the former stage initiator is selected from: one or two of sodium sulfite, sodium bisulfite, L-ascorbic acid (salt), ferrous sulfate, sodium hyposulfite and sodium metabisulfite, wherein the adding mass of the front-stage initiator accounts for 0.005-0.500% of the total mass of acrylic acid in the neutralizing solution;
the latter stage initiator is selected from: sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2' -azobis (2-methylbutyronitrile), 4' -azobis (4-cyanovaleric acid) two or more of 2,2' -azobis [ 2-methyl-N- (2-hydroxyethyl) propionamide ], 2' -azobis [2- (2-imidazolin-2-yl) propane ] dihydrochloride, 2' -azobis (2-methylpropylimidine) dihydrochloride, 2' -azobis [ N- (2-hydroxyethyl) -2-methylpropionamidine ] tetrahydrate, and azobisisobutyretherhydrochloride, the addition mass of the composite initiator accounts for 0.006-1.00 percent of the total mass of the acrylic acid in the neutralization solution.
7. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the gel cutting auxiliary agent in the step (3) is as follows: one or two of sodium carbonate, sodium bicarbonate, potassium carbonate, ammonium carbonate, potassium bicarbonate and ammonium bicarbonate, wherein the addition mass of the gel cutting auxiliary agent accounts for 2-40% of the total mass of acrylic acid in the neutralization solution.
8. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the gel cutting auxiliary agent in the step (3) is as follows: one or more of sodium stearate, sucrose ester, sodium sulfite and sodium metabisulfite, wherein the addition mass of the sodium stearate, the sucrose ester, the sodium sulfite and the sodium metabisulfite accounts for 0.01-3% of the total mass of acrylic acid in the neutralization solution.
9. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the extrusion granulator in the step (3) is a single-screw extrusion granulator or a double-screw extrusion granulator, and the obtained basic particles in the step (4) are ground and sieved to obtain particles with the particle size of 20-35 meshes.
10. The method for preparing a low-soluble substance super absorbent resin as claimed in claim 1, wherein: the surface treatment liquid in the step (5) is formed by mixing propylene glycol, ethylene glycol diglycidyl ether and sulfate, wherein the mass of the propylene glycol accounts for 0.02-3% of the total mass of the base particles; the mass of the ethylene glycol diglycidyl ether accounts for 0.002-0.4% of the total mass of the basic particles; the mass of the sulfate accounts for 0.1 to 4.0 percent of the total mass of the basic particles.
CN202211183099.4A 2022-09-27 2022-09-27 Preparation method of low-soluble substance super absorbent resin Pending CN115505064A (en)

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WO1999055267A1 (en) * 1998-04-28 1999-11-04 The Procter & Gamble Company Absorbent articles with distribution materials positioned underneath storage material
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EP0206808A2 (en) * 1985-06-24 1986-12-30 American Colloid Company Continuous method for preparing polyacrylate resins
WO1999047184A1 (en) * 1998-03-13 1999-09-23 The Procter & Gamble Company Absorbent members comprising a high surface area material for absorbing body liquids
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