CN112266435B - Super-absorbent resin with super-strong conductivity and preparation method and application thereof - Google Patents
Super-absorbent resin with super-strong conductivity and preparation method and application thereof Download PDFInfo
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- CN112266435B CN112266435B CN202011211676.7A CN202011211676A CN112266435B CN 112266435 B CN112266435 B CN 112266435B CN 202011211676 A CN202011211676 A CN 202011211676A CN 112266435 B CN112266435 B CN 112266435B
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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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- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
Abstract
The invention relates to super-absorbent resin with super-strong conductivity, a preparation method and application thereof. The method comprises the following steps: uniformly mixing acrylic acid and water to obtain an acrylic acid solution, and then neutralizing the acrylic acid solution with a sodium hydroxide solution to obtain a mixed solution; adding a cross-linking agent, an initiator and fluff pulp into the mixed solution, uniformly mixing to obtain a reaction solution, introducing nitrogen into the reaction solution to remove oxygen, and then initiating a polymerization reaction to obtain hydrogel; sequentially crushing, drying, crushing and screening the hydrogel to obtain super absorbent resin particles; spraying surface treatment liquid on the surface of the super absorbent resin particles, and then carrying out heat preservation treatment to obtain the super absorbent resin with super strong conductivity. The fluff pulp is added for the first time in the polymerization process, so that the conductivity of the super absorbent resin is greatly improved, the absorption speed and the liquid passing capacity of the super absorbent resin are further improved, the reverse osmosis after the super absorbent resin is applied to the diaper, and the surface dryness of the diaper is greatly improved.
Description
Technical Field
The invention belongs to the technical field of functional polymeric chemical additives, and particularly relates to a super-absorbent resin with super-strong conductivity, and a preparation method and application thereof.
Background
The paper diaper sold in the market at present can be mainly divided into two types of structures, one type is a fluff pulp structure, the other type is a composite core structure, the composite core structure does not contain fluff pulp, so the diaper is very light and thin, the risk of fluff pulp liquid absorption fault is avoided due to the structural particularity, the structure is highly accepted by the market, but the structure does not contain fluff pulp, so the conductivity of the diaper becomes a key factor restricting the quality of the diaper when absorbing liquid, and the conductivity of the diaper not only is influenced by a surface layer material, but also plays a decisive role in the conductivity of the super absorbent resin.
In view of the above problems, it is desirable to provide a super absorbent resin having superior conductivity and a method for preparing the same.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a super absorbent resin with super conductivity, and a preparation method and application thereof. The super absorbent resin prepared by the invention is particularly suitable for composite core high-end paper diapers with higher requirements on the conduction and liquid permeability of the super absorbent resin.
In order to achieve the above objects, the present invention provides, in a first aspect, a method for preparing a super absorbent resin having superior conductivity, the method comprising the steps of:
(1) uniformly mixing acrylic acid and water to obtain an acrylic acid solution, and then neutralizing the acrylic acid solution with a sodium hydroxide solution to obtain a mixed solution;
(2) adding a cross-linking agent, an initiator and fluff pulp into the mixed solution, uniformly mixing to obtain a reaction solution, introducing nitrogen into the reaction solution to remove oxygen, and then initiating a polymerization reaction to obtain hydrogel;
(3) sequentially crushing, drying, crushing and screening the hydrogel to obtain super absorbent resin particles;
(4) spraying surface treatment liquid on the surfaces of the super absorbent resin particles, and then carrying out heat preservation treatment to obtain the super absorbent resin with super conductivity.
Preferably, the amount of the cross-linking agent is 0.01-0.8% of the mass of the acrylic acid; and/or the dosage of the initiator is 0.01-0.15% of the mass of the acrylic acid; and/or the amount of the fluff pulp is 0.1-20% of the mass of the acrylic acid.
Preferably, the amount of the fluff pulp is 0.5-3% of the mass of the acrylic acid.
Preferably, in step (1): the mass ratio of the acrylic acid to the water is 1: (1-4); and/or neutralizing the acrylic acid solution with a sodium hydroxide solution until the neutralization degree is 60-80%.
Preferably, in the step (3), the particle size of the obtained super absorbent resin particles is 150-750 μm; and/or in the step (4), the surface treatment liquid accounts for 0.1-6% of the mass of the super absorbent resin particles.
Preferably, in the step (3), the drying temperature is 100-200 ℃, preferably 100-120 ℃, and the drying time is 6-8 h; and/or in the step (4), the temperature of the heat preservation treatment is 100-200 ℃, preferably 100-120 ℃, and the time of the heat preservation treatment is 0.5-2 h.
Preferably, the cross-linking agent is one or more of N, N-methylene bisacrylamide, polyvinyl alcohol, piperazine bisacrylamide and tetraallyloxyethane; the initiator is a redox initiator, an oxidant in the redox initiator is one or more of benzoyl peroxide, cumene hydroperoxide, persulfate and hydrogen peroxide, and a reducing agent in the redox initiator is one or more of sulfite and ascorbic acid; and/or the surface treatment liquid is one or more of a polyol compound, a polyamine compound, an epoxy compound and a halogenated epoxy compound.
Preferably, the polyalcohol compound is one or more of ethylene glycol, triethylene glycol, tetraethylene glycol, 1, 3-butanediol, 1, 4-butanediol, glycerol, polyglycerol, 1, 5-pentanediol, 1, 6-hexanediol, and 1, 2-cyclohexanedimethanol; the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and polyethylene polyamine; the epoxy compound is one or more of butanediol diglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether; and/or the halogenated epoxy compound is one or more of epichlorohydrin, epibromohydrin, alpha-methyl epichlorohydrin.
In a second aspect, the present invention provides a super absorbent resin having superior conductivity, which is prepared by the preparation method of the first aspect of the present invention.
In a third aspect, the invention provides an application of the super-absorbent resin with super-conductivity prepared by the preparation method in the first aspect in a paper diaper.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) aiming at the existing requirements of the diaper market, the invention provides the super-absorbent resin with super-strong conductivity, and the fluff pulp is added for the first time in the polymerization process, and the conductivity of the fluff pulp on liquid is greatly improved by utilizing the fiber conductivity of the fluff pulp, so that the absorption speed and the liquid permeability of the super-absorbent resin are further improved, the reverse osmosis amount of the diaper after imbibing is greatly reduced after the super-absorbent resin is applied to the diaper, and the surface dryness and smoothness of the diaper are greatly improved. The super absorbent resin prepared by the invention is particularly suitable for composite core high-end paper diapers with higher requirements on the conduction and liquid permeability of the super absorbent resin.
(2) In the process of preparing the super-absorbent resin with super-strong conductivity, a large number of creative experiments show that the appropriate amount of the fluff pulp is obtained, namely the amount of the fluff pulp is preferably controlled to be 0.1-20% of the mass of the acrylic acid, and more preferably 0.5-3%; the invention discovers that the absorption speed of Super Absorbent Polymer (SAP) can be improved and the liquid passing speed of the SAP can be greatly improved by adding a proper amount of fluff pulp in the polymerization process, the dosage of the fluff pulp is controlled within a reasonable range, otherwise, the water retention performance of the SAP can be reduced by excessive dosage.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of super absorbent resin with super conductivity in a first aspect, which comprises the following steps:
(1) uniformly mixing acrylic acid and water (such as deionized water) to obtain an acrylic acid solution, and then neutralizing the acrylic acid solution with a sodium hydroxide solution to obtain a mixed solution; in the present invention, the acrylic acid solution may be neutralized with, for example, a 50 wt% aqueous sodium hydroxide solution;
(2) adding a cross-linking agent, an initiator and fluff pulp into the mixed solution, uniformly mixing to obtain a reaction solution, introducing nitrogen into the reaction solution to remove oxygen, and then initiating a polymerization reaction to obtain hydrogel; specifically, for example, a cross-linking agent and an initiator are added into the mixed solution, the mixed solution is uniformly mixed, fluff pulp is added and uniformly mixed, then high-purity nitrogen is blown in to remove oxygen (the oxygen content is not more than or equal to 1ppm), and then polymerization is initiated at 30-50 ℃ to obtain hydrogel (elastic hydrogel); in the present invention, it is preferable that the fluff pulp is wood pulp;
(3) sequentially crushing, drying, crushing and screening the hydrogel to obtain super absorbent resin particles; in the invention, the crushing is the crushing of hydrogel blocks, and the crushing is the crushing of dried gel particles; in the invention, preferably, the hydrogel is crushed and dried at 100-200 ℃, more preferably 100-120 ℃, and the moisture content of the dried gel (gel particles) is less than or equal to 5 percent;
(4) spraying surface treatment liquid on the surfaces of the super absorbent resin particles, and then carrying out heat preservation treatment to obtain super absorbent resin with super conductivity; in the invention, for example, the surface treatment solution is sprayed on the surfaces of the super absorbent resin particles screened in the step (3), the mixture is uniformly stirred, and then the mixture is kept at 100-200 ℃, preferably 100-120 ℃ for 1h, so that the super absorbent resin with super conductivity is obtained.
Aiming at the existing requirements of the diaper market, the invention provides the super-absorbent resin with super-strong conductivity, and the fluff pulp is added for the first time in the polymerization process, and the conductivity of the fluff pulp on liquid is greatly improved by utilizing the fiber conductivity of the fluff pulp, so that the absorption speed and the liquid permeability of the super-absorbent resin are further improved, the reverse osmosis amount of the diaper after imbibing is greatly reduced after the super-absorbent resin is applied to the diaper, and the surface dryness and smoothness of the diaper are greatly improved. The super absorbent resin prepared by the invention is particularly suitable for composite core high-end paper diapers with strict requirements on the conduction and liquid permeability of the super absorbent resin.
According to some preferred embodiments, the cross-linking agent is used in an amount of 0.01 to 0.8% (e.g., 0.01%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, 0.5%, 0.55%, 0.6%, 0.65%, 0.7%, 0.75%, or 0.8%) by mass of the acrylic acid; and/or the initiator is used in an amount of 0.01 to 0.15% (e.g., 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, or 0.15%) of the mass of the acrylic acid. In the present invention, when the initiator is a redox initiator, the amount of the initiator refers to the sum of the amounts of the oxidizing agent and the reducing agent in the redox initiator.
According to some preferred embodiments, the fluff pulp is used in an amount of 0.1 to 20% (e.g., 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%) of the mass of the acrylic acid.
According to some preferred embodiments, the fluff pulp is used in an amount of 0.5 to 3% (e.g., 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.5%, or 3%) of the mass of the acrylic acid. In the process of preparing the super-absorbent resin with super-strong conductivity, a large number of creative experiments show that the appropriate amount of the fluff pulp is obtained, namely the amount of the fluff pulp is preferably controlled to be 0.1-20% of the mass of the acrylic acid, and more preferably 0.5-3%; the invention discovers that the addition of a proper amount of fluff pulp in the polymerization process can not only improve the absorption speed of Super Absorbent Polymer (SAP) but also greatly improve the liquid passing speed of the SAP, the dosage of the fluff pulp is controlled within a reasonable range, otherwise, the water retention performance of the SAP is reduced due to excessive dosage.
According to some preferred embodiments, in step (1): the mass ratio of the acrylic acid to the water is 1: (1-4) (e.g., 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, or 1: 4); and/or neutralizing the acrylic acid solution with a sodium hydroxide solution to a neutralization degree of 60-80% (e.g., 60%, 65%, 70%, 75%, or 80%).
According to some preferred embodiments, in the step (3), the particle size of the obtained super absorbent resin particles is 150 to 750 μm; and/or in step (4), the surface treatment liquid is 0.1-6% (e.g., 0.1%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, or 6%) of the mass of the superabsorbent resin particles.
According to some specific embodiments, the method for preparing the super absorbent resin with super conductivity comprises the following steps:
firstly, taking high-purity acrylic acid as a monomer, mixing acrylic acid with water according to a ratio of 1: 4-1: 1, and then adding sodium hydroxide for neutralization, wherein the neutralization degree is 60-80%, so as to obtain a mixed solution;
adding a cross-linking agent and an initiator into the mixed solution, uniformly mixing, adding fluff pulp, uniformly mixing, blowing high-purity nitrogen to remove oxygen and obtain hydrogel at the temperature of 30-50 ℃, wherein the dosage of the cross-linking agent is 0.01-0.8 percent of the mass of acrylic acid in the step I, the dosage of the initiator is 0.01-0.15 percent of the mass of the acrylic acid, and the dosage of the fluff pulp is 0.1-20 percent of the mass of the acrylic acid, preferably 0.5-3 percent;
crushing and drying the hydrogel obtained in the step two, wherein the drying temperature is 100 ℃, and the drying time is 6-8 h;
fourthly, crushing and screening the dried gel in the third step, and selecting 150-750 mu m super absorbent resin particles;
fifthly, spraying surface treatment liquid on the surfaces of the super absorbent resin particles screened in the step IV, uniformly stirring, and then preserving heat for 1h at 100 ℃ to obtain the super absorbent resin with super conductivity, wherein the dosage of the surface treatment liquid is 0.1-6% of the weight of the super absorbent resin particles.
According to some preferred embodiments, in the step (3), the temperature of the drying is 100-200 ℃, preferably 100-120 ℃, and the time of the drying is 6-8h (for example, 6, 6.5, 7, 7.5 or 8 h); and/or in the step (4), the temperature of the heat preservation treatment is 100-200 ℃, preferably 100-120 ℃, and the time of the heat preservation treatment is 0.5-2 h (for example, 0.5, 1, 1.5 or 2 h).
According to some preferred embodiments, the cross-linking agent is one or more of N, N-methylene bisacrylamide (N, N-methylene bisacrylamide), polyvinyl alcohol, piperazine bisacrylamide, tetraallyloxyethane; the initiator is a redox initiator, an oxidant in the redox initiator is one or more of benzoyl peroxide, cumene hydroperoxide, persulfate and hydrogen peroxide, and a reducing agent in the redox initiator is one or more of sulfite and ascorbic acid; and/or the surface treatment liquid is one or more of a polyol compound, a polyamine compound, an epoxy compound and a halogenated epoxy compound.
According to some preferred embodiments, the polyol compound is one or more of ethylene glycol, triethylene glycol, tetraethylene glycol, 1, 3-butanediol, 1, 4-butanediol, glycerol, polyglycerol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-cyclohexanedimethanol; the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and polyethylene polyamine; the epoxy compound is one or more of butanediol diglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether; and/or the halogenated epoxy compound is one or more of epichlorohydrin, epibromohydrin, alpha-methyl epichlorohydrin.
In a second aspect, the present invention provides a super absorbent resin having superior conductivity, which is prepared by the preparation method of the first aspect of the present invention.
In a third aspect, the invention provides an application of the super absorbent resin with super conductivity prepared by the preparation method in the first aspect in paper diapers.
The invention also provides a composite core body paper diaper which comprises a paper diaper main body, wherein the paper diaper main body sequentially comprises a surface layer, a flow guide layer, an absorption core body layer and a bottom film layer from top to bottom, the absorption core body layer sequentially comprises a first dust-free paper layer, a first high water-absorbent resin layer, a fluffy cotton layer, a second high water-absorbent resin layer and a second dust-free paper layer from top to bottom, and the first high water-absorbent resin layer and the second high water-absorbent resin layer are both formed by the high water-absorbent resin with super-strong conductivity prepared by the preparation method in the first aspect of the invention; the surface layer, the flow guide layer, the bottom film layer, the first dust-free paper layer, the second dust-free paper layer and the fluffy cotton layer are not specifically limited, and the surface layer, the flow guide layer, the bottom film layer, the dust-free paper layer and the fluffy cotton layer which are commonly used for manufacturing the paper diaper in the prior art are adopted; in the present invention, the material of the surface layer and/or the flow guide layer may be, for example, hot air, spun-bonded or spun-laced nonwoven fabric, and preferably, the surface layer is further provided with flow guide embossings; the base film layer is, for example, a breathable base film layer having breathability; preferably, the base film layer is a PE breathable base film layer.
The present invention will be further described with reference to the following examples. These examples are merely illustrative of preferred embodiments of the present invention and the scope of the present invention should not be construed as being limited to these examples.
Example 1
The super absorbent resin with super conductivity is prepared from the following raw materials in parts by weight: 200 parts of acrylic acid, 644 parts of deionized water, 50 weight percent aqueous sodium hydroxide 156, 1 part of fluff pulp (wood pulp), N, N-methylene bisacrylamide, 0.15 part of sodium persulfate, 0.09 part of ascorbic acid, 5 parts of aqueous propylene glycol (containing 50 mass percent of propylene glycol), and 2 parts of aqueous butylene glycol diglycidyl ether (containing 50 mass percent of butylene glycol diglycidyl ether);
the preparation process comprises the following steps:
adding acrylic acid and deionized water into a reactor, neutralizing with a sodium hydroxide aqueous solution, and neutralizing the acrylic acid to a neutralization degree of 70% to obtain a mixed solution;
adding N, N-methylene bisacrylamide, sodium persulfate and ascorbic acid into the mixed solution, uniformly mixing, adding fluff pulp, uniformly mixing, blowing high-purity nitrogen to remove oxygen, and initiating polymerization at 50 ℃ to obtain hydrogel;
thirdly, crushing the hydrogel and drying the hydrogel at 100 ℃ for 8 hours;
crushing and screening the dried gel, and selecting 100 parts by weight of 150-750 mu m super absorbent resin particles for later use;
spraying the mixed solution of propylene glycol aqueous solution and butanediol diglycidyl ether aqueous solution on the surfaces of 100 parts by weight of the sieved super absorbent resin particles, uniformly stirring, and then preserving heat at 100 ℃ for 1h to obtain the super absorbent resin with super conductivity.
Example 2
The super-absorbent resin with super-strong conductivity is prepared from the following raw materials in parts by weight: 300 parts of acrylic acid, 500 parts of deionized water, 200 parts of a 50 wt% sodium hydroxide aqueous solution, 3 parts of fluff pulp (wood pulp), 2 parts of polyvinyl alcohol, 0.2 part of potassium persulfate, 0.12 part of ascorbic acid, 5 parts of a 1, 3-butanediol aqueous solution (containing 50 mass percent of 1, 3-butanediol), and 3 parts of a polyglycerol polyglycidyl ether aqueous solution (containing 50 mass percent of polyglycerol polyglycidyl ether);
the preparation process comprises the following steps:
adding acrylic acid and deionized water into a reactor, neutralizing with a sodium hydroxide aqueous solution, and neutralizing the acrylic acid to 60% of neutralization degree to obtain a mixed solution;
secondly, adding polyvinyl alcohol, potassium persulfate and ascorbic acid into the mixed solution, uniformly mixing, then adding fluff pulp, uniformly mixing, blowing high-purity nitrogen to remove oxygen, so that the oxygen content is less than or equal to 1ppm, and initiating polymerization at 40 ℃ to obtain hydrogel;
thirdly, crushing the hydrogel and drying at 100 ℃ for 7 hours;
crushing and screening the dried gel, and selecting 100 parts by weight of 150-750 mu m super absorbent resin particles for later use;
spraying the mixed solution of 1, 3-butanediol aqueous solution and polyglycerol polyglycidyl ether aqueous solution on the surface of 100 parts by weight of the sieved super absorbent resin particles, uniformly stirring, and then keeping the temperature at 100 ℃ for 1h to obtain the super absorbent resin with super conductivity.
Example 3
The super-absorbent resin with super-strong conductivity is prepared from the following raw materials in parts by weight: 250 parts of acrylic acid, 569 parts of deionized water, a 50 wt% sodium hydroxide aqueous solution 181 parts of fluff pulp (wood pulp) 7 parts of N, N-methylene bisacrylamide 0.8 parts of fluff pulp, 0.7 parts of polyvinyl alcohol, 0.2 parts of hydrogen peroxide, 0.12 parts of sodium sulfite, 6 parts of a triethylene glycol aqueous solution (containing 50 mass percent of triethylene glycol), 2 parts of a sorbitol polyglycidyl ether aqueous solution (containing 50 mass percent of sorbitol polyglycidyl ether), and 2 parts of ethylenediamine aqueous solution (containing 50 mass percent of ethylenediamine);
the preparation process comprises the following steps:
adding acrylic acid and deionized water into a reactor, neutralizing with a sodium hydroxide aqueous solution, and neutralizing the acrylic acid until the neutralization degree is 65% to obtain a mixed solution;
adding N, N-methylene bisacrylamide, polyvinyl alcohol, hydrogen peroxide and sodium sulfite into the mixed solution, uniformly mixing, adding fluff pulp, uniformly mixing, blowing high-purity nitrogen to remove oxygen, and initiating polymerization at 45 ℃ to obtain hydrogel;
thirdly, crushing the hydrogel and drying the hydrogel at 100 ℃ for 8 hours;
crushing and screening the dried gel, and selecting 100 parts by weight of 150-750 mu m super absorbent resin particles for later use;
fifthly, spraying the mixed solution of triethylene glycol aqueous solution, sorbitol polyglycidyl ether aqueous solution and ethylenediamine aqueous solution on the surface of 100 parts by weight of the sieved super absorbent resin particles, uniformly stirring, and then keeping the temperature at 100 ℃ for 1h to obtain the super absorbent resin with super conductivity.
Example 4
The super-absorbent resin with super-strong conductivity is prepared from the following raw materials in parts by weight: 350 parts of acrylic acid, 358 parts of deionized water, 50 weight percent aqueous sodium hydroxide 292 parts, 10 parts of fluff pulp (wood pulp), 1 part of piperazine bisacrylamide, 0.7 part of tetraallyloxyethane, 0.21 part of hydrogen peroxide, 0.15 part of ascorbic acid, 6 parts of an aqueous solution of 1, 4-butanediol (the mass fraction of the 1, 4-butanediol is 50%), and 5 parts of an aqueous solution of butanediol diglycidyl ether (the mass fraction of the butanediol diglycidyl ether is 50%);
the preparation process comprises the following steps:
adding acrylic acid and deionized water into a reactor, neutralizing with a sodium hydroxide aqueous solution, and neutralizing the acrylic acid to a neutralization degree of 75% to obtain a mixed solution;
adding piperazine bisacrylamide, tetraallyloxyethane, hydrogen peroxide and ascorbic acid into the mixed solution, uniformly mixing, adding fluff pulp, uniformly mixing, blowing high-purity nitrogen to remove oxygen, and initiating polymerization at 30 ℃ to obtain hydrogel;
thirdly, crushing the hydrogel and drying at 100 ℃ for 6 hours;
crushing and screening the dried gel, and selecting 100 parts by weight of 150-750 mu m super absorbent resin particles for later use;
fifthly, spraying a mixed solution of 1, 4-butanediol aqueous solution and butanediol diglycidyl ether aqueous solution on the surfaces of 100 parts by weight of the sieved super absorbent resin particles, uniformly stirring, and then preserving heat at 100 ℃ for 1h to obtain the super absorbent resin with super conductivity.
Comparative example 1
Comparative example 1 is substantially the same as example 1 except that: no fluff pulp is added in the second step.
Comparative example 2
Comparative example 2 is substantially the same as example 2 except that: no fluff pulp is added in the second step.
Comparative example 3
Comparative example 3 is substantially the same as example 3 except that: no fluff pulp is added in the second step.
Comparative example 4
Comparative example 4 is substantially the same as example 4 except that: no fluff pulp is added in the second step.
Comparative example 5
Comparative example 5 is substantially the same as example 1 except that: the amount of the fluff pulp (wood pulp) added was 20 parts by weight.
In the invention, the super absorbent resins prepared in examples 1 to 4 and comparative examples 1 to 5 were subjected to absorption performance and liquid permeability measurement under the conditions specified in GB/T22905-2008. The absorption properties described in the present invention include the following: water absorption multiplying power, water retention rate, 0.7Psi pressurized water absorption multiplying power and absorption speed; the liquid passing performance comprises the index of the liquid passing speed; the detection indexes of the super absorbent resin prepared in the examples 1 to 4 and the comparative examples 1 to 5 are shown in the following table 1.
As can be seen from the data in Table 1, the addition of a proper amount of fluff pulp during the polymerization process can not only increase the absorption rate of SAP, but also greatly increase the liquid passing rate of SAP, and the amount of fluff pulp should be controlled within a reasonable range, otherwise, the water retention performance of SAP is reduced due to excessive amount of fluff pulp.
Through the verification of sample application on a machine, when the SAP (super absorbent polymer) synthesized by the invention is applied to the composite core paper diaper, the SAP has the advantages of large liquid absorption amount, high absorption speed, long diffusion distance, low reverse osmosis amount and dry and comfortable surface layer, and has more outstanding performance compared with the paper diaper sold on the market at present. When the composite core body paper diaper is applied, the composite core body paper diaper comprises a paper diaper main body, the paper diaper main body sequentially comprises a surface layer, a flow guide layer, an absorption core layer and a bottom film layer from top to bottom, the absorption core layer sequentially comprises a first dust-free paper layer, a first high-water-absorption resin layer, a fluffy cotton layer, a second high-water-absorption resin layer and a second dust-free paper layer from top to bottom, and the first high-water-absorption resin layer and the second high-water-absorption resin layer are formed by any one of the high-water-absorption resins prepared in the embodiments 1-4 and the comparative examples 1-5 of the invention.
The test method of the composite core paper diaper comprises the following steps: 240mL of physiological saline (added with a proper amount of brilliant blue) is added to the center point of the diaper for 3 times (the interval time between each liquid adding is 10min), the infiltration speed (absorption speed) and the diffusion length of liquid are recorded, the reverse osmosis amount is tested by using a weight which is placed on a liquid adding point by using filter paper with the same weight and bears a load of 3.5kg at regular intervals, and the dryness is sensed by hand, the test data of the SAP in the composite core body diapers in the examples 1 to 4 is shown in the following table 2, and the test data of the SAP in the comparative examples 1 to 5 when the SAP in the composite core body diapers is used is shown in the following table 3.
Table 2: test data of SAP used in composite core diapers of examples 1-4.
Table 3: test data of the SAP applied to the composite core diaper in comparative examples 1 to 5.
| SAP type | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| 0min absorption Rate/s | 16 | 15 | 16 | 17 | 9 |
| 10min absorption Rate/s | 23 | 25 | 25 | 27 | 10 |
| 20min absorption Rate/s | 33 | 35 | 34 | 38 | 9 |
| 4min diffusion length/cm | 18.9 | 19.2 | 17.6 | 18.6 | 27.1 |
| Diffusion length/cm of 14min | 23.2 | 24.5 | 23.1 | 22.5 | 30.6 |
| Diffusion length/cm of 24min | 27.8 | 28.2 | 27.2 | 28.2 | 31.9 |
| Reverse osmosis/g at 5min | 0.52 | 0.78 | 0.66 | 0.71 | 0.34 |
| Reverse osmosis/g in 15min | 8.92 | 8.26 | 9.05 | 8.89 | 7.89 |
| Reverse osmosis/g at 25min | 28.93 | 27.93 | 29.18 | 28.83 | 25.36 |
| 6min Damp feeling | Dry and comfortable | Dry and comfortable | Dry and comfortable | Dry and comfortable | Dry and comfortable |
| Moisture sensation for 16min | Moisture content | Moisture content | Moisture content | Moisture content | Moisture content |
| 26min damp feeling | Moisture content | Moisture content | Moisture content | Moisture content | Moisture content |
As can be seen from the comparison of the data in tables 1 and 2, the diaper made from the SAP prepared in examples 1-4 has faster penetration speed, longer conduction distance, lower reverse penetration amount and drier surface when absorbing liquid, and the super absorbent resin prepared by the invention has super strong conduction capability and is more suitable for being applied to the composite core body diaper.
Finally, the description is as follows: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the embodiments can still be modified, or some technical features can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the present invention in its spirit and scope.
Claims (10)
1. A preparation method of super absorbent resin with super conductivity is characterized by comprising the following steps:
(1) uniformly mixing acrylic acid and water to obtain an acrylic acid solution, and then neutralizing the acrylic acid solution with a sodium hydroxide solution to obtain a mixed solution;
(2) adding a cross-linking agent, an initiator and fluff pulp into the mixed solution, uniformly mixing to obtain a reaction solution, introducing nitrogen into the reaction solution to remove oxygen, and then initiating a polymerization reaction to obtain hydrogel; the using amount of the fluff pulp is 0.5-3% of the mass of the acrylic acid; the cross-linking agent is one or more of N, N-methylene bisacrylamide, piperazine bisacrylamide and tetraallyloxyethane; the initiator is a redox initiator; the oxidant in the redox initiator is one or more of benzoyl peroxide, cumene hydroperoxide, persulfate and hydrogen peroxide, and the reducing agent in the redox initiator is one or more of sulfite and ascorbic acid;
(3) sequentially crushing, drying, crushing and screening the hydrogel to obtain super absorbent resin particles;
(4) spraying surface treatment liquid on the surfaces of the super absorbent resin particles, and then carrying out heat preservation treatment to prepare super absorbent resin with super conductivity; the surface treatment liquid is one or more of polyalcohol compounds, polyamine compounds, epoxy compounds and halogenated epoxy compounds.
2. The method of claim 1, wherein:
the dosage of the cross-linking agent is 0.01-0.8% of the mass of the acrylic acid; and/or
The amount of the initiator is 0.01-0.15% of the mass of the acrylic acid.
3. The production method according to claim 1, wherein in step (1):
the mass ratio of the acrylic acid to the water is 1: (1-4); and/or
And neutralizing the acrylic acid solution by using a sodium hydroxide solution until the neutralization degree is 60-80%.
4. The method of claim 1, wherein:
in the step (3), the particle size of the obtained super absorbent resin particles is 150-750 μm; and/or
In the step (4), the surface treatment liquid accounts for 0.1-6% of the mass of the super absorbent resin particles.
5. The production method according to any one of claims 1 to 4, characterized in that:
in the step (3), the drying temperature is 100-200 ℃, and the drying time is 6-8 h; and/or
In the step (4), the temperature of the heat preservation treatment is 100-200 ℃, and the time of the heat preservation treatment is 0.5-2 h.
6. The method of claim 5, wherein:
in the step (3), the drying temperature is 100-120 ℃.
7. The production method according to claim 5, characterized in that:
in the step (4), the temperature of the heat preservation treatment is 100-120 ℃.
8. The method of claim 1, wherein:
the polyalcohol compound is one or more of ethylene glycol, triethylene glycol, tetraethylene glycol, 1, 3-butanediol, 1, 4-butanediol, glycerol, polyglycerol, 1, 5-pentanediol, 1, 6-hexanediol and 1, 2-cyclohexanedimethanol;
the polyamine compound is one or more of ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethyleneimine and polyethylene polyamine;
the epoxy compound is one or more of butanediol diglycidyl ether, polyglycerol polyglycidyl ether and sorbitol polyglycidyl ether; and/or
The halogenated epoxy compound is one or more of epichlorohydrin, epibromohydrin and alpha-methyl epichlorohydrin.
9. The super absorbent resin having superior conductivity, which is prepared by the preparation method of any one of claims 1 to 8.
10. Use of the super absorbent resin having super conductivity prepared by the preparation method of any one of claims 1 to 8 in diapers.
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Denomination of invention: A super absorbent resin with strong conductivity and its preparation method and application Effective date of registration: 20230904 Granted publication date: 20220826 Pledgee: Dongying Bank Co.,Ltd. Xianhe sub branch Pledgor: SHANDONG NUOER BIOLOGICAL TECHNOLOGY Co.,Ltd. Registration number: Y2023980055138 |