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WO2019112150A1 - Polymère absorbant et procédé de préparation associé - Google Patents

Polymère absorbant et procédé de préparation associé Download PDF

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Publication number
WO2019112150A1
WO2019112150A1 PCT/KR2018/010305 KR2018010305W WO2019112150A1 WO 2019112150 A1 WO2019112150 A1 WO 2019112150A1 KR 2018010305 W KR2018010305 W KR 2018010305W WO 2019112150 A1 WO2019112150 A1 WO 2019112150A1
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WO
WIPO (PCT)
Prior art keywords
acrylate
cross
meth
polymer
linking agent
Prior art date
Application number
PCT/KR2018/010305
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English (en)
Korean (ko)
Inventor
김수진
남대우
김기현
조준일
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020180104572A external-priority patent/KR102584203B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18857399.2A priority Critical patent/EP3521343B1/fr
Priority to JP2019520362A priority patent/JP6837141B2/ja
Priority to CN201880004132.8A priority patent/CN110139892B/zh
Priority to US16/348,657 priority patent/US11278866B2/en
Publication of WO2019112150A1 publication Critical patent/WO2019112150A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
    • 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

Definitions

  • the present invention relates to a superabsorbent resin exhibiting an improved rewetting property and an excellent absorption property and a method for producing the same.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing moisture from about 500 to 1,000 times the weight of lanzai, and each developer can use SAM (Super Absorbent Material), AGM
  • SAM Super Absorbent Material
  • AGM Super Absorbent Material
  • the above-mentioned superabsorbent resin has been put into practical use as a sanitary article, and nowadays, in addition to the diapers and sanitary napkin products for children, it is now used as a soil remover for gardening, an index material for civil engineering and construction, Sheet, a freshness-retaining agent in the field of food distribution, and a material for fomentation.
  • pressure may be applied to sanitary materials such as diapers and sanitary napkins by the weight of the user.
  • sanitary materials such as diapers and sanitary napkins
  • a superabsorbent resin applied to a sanitary material such as a diaper or sanitary napkin absorbs a liquid and then a pressure due to the weight of the user is applied to the absorbent resin, Leakage of urine (a symptom for the eyes may occur.
  • the basic absorption characteristics such as absorption capacity under pressure and beam SAT excellent, and to represent the improved rewet properties provide an absorbent resin and a production method thereof.
  • the present invention relates to a process for producing a crosslinked acrylic acid-based monomer and a crosslinked acrylic acid- ;
  • the base resin is subjected to surface modification with respect to the base resin in the presence of a surface crosslinking agent and a metal salt
  • the internal crosslinking agent comprises a poly (meth) acrylate ester of a polyol, a first internal crosslinking agent, and a polyglycidyl ether second internal crosslinking agent of a polyol in a weight ratio of 1:20 to 1: 300 .
  • the present invention also relates to a base resin comprising a crosslinked polymer obtained by crosslinking an acrylic acid-based monomer in which at least a part of an acidic group is neutralized, via an internal crosslinking agent; 2019/112150 1 »(: 1 ⁇ 1 ⁇ 2018/010305
  • a polyvalent metal salt formed on the surface cross-linked layer is formed on the surface cross-linked layer
  • the internal crosslinking agent comprises a poly (meth) acrylate first internal crosslinking agent of polyol: polyglycidyl ether secondary internal crosslinking agent of polyol in a weight ratio of 1:20 to 1: 300.
  • the base resin is subjected to surface modification with respect to the base resin in the presence of a surface crosslinking agent and a metal salt
  • the internal crosslinking agent comprises a poly (meth) acrylate first internal crosslinking agent of polyol: polyglycidyl ether second internal crosslinking agent of polyol in a weight ratio of 1:20 to 1: 300 / RTI >
  • base resin "or base polymer powder " refer to a polymer matrix obtained by drying, crushing and classifying polymerized water-soluble ethylenically unsaturated monomers, typically acrylic acid monomers of acrylic acid and / Refers to a polymer in the form of a powder, which is not subjected to the surface modification or surface cross-linking steps described below.
  • the hydrogel polymer obtained by the polymerization reaction of the acrylic acid-based monomer is subjected to a process such as drying, crushing, classification, surface crosslinking and the like, and is marketed as a superabsorbent resin which is powdery product.
  • the superabsorbent resin obtained by the production method according to an embodiment of the present invention has excellent physical properties such as water retention capacity, pressure absorption capacity and liquid permeability, It is possible to effectively prevent the rewet and leakage of urine, which is absorbed in the superabsorbent resin, from being re-wetted and leaked.
  • the internal cross-linking structure of the base resin and the super absorbent resin including the same can be optimized by using the internal cross-linking agent of a specific combination and composition, and further, by using the multi-valent metal salt during surface cross- The strength is also optimized, and it seems that the superabsorbent resin can retain the moisture once absorbed, despite the external pressure and the like.
  • the monomer composition which is a raw material of the superabsorbent resin
  • the monomer composition may be prepared by first mixing an acrylic acid-based monomer having an acidic group and neutralizing at least a part of the acidic group, And a polymerization initiator are polymerized to obtain a hydrogel polymer, which is then dried, pulverized, and classified to prepare a base resin.
  • the monomer composition which is a raw material of the superabsorbent resin includes an acrylic acid-based monomer having an acidic group and at least a part of the acidic groups neutralized and a polymerization initiator.
  • the acrylic acid-based monomer is a compound represented by the following Formula 1: 2019/112150 1 »(: 1 ⁇ 1 ⁇ 2018/010305
  • the acrylic acid-based monomer includes at least one selected from the group consisting of acrylic acid, methacrylic acid, monovalent metal salts thereof, bivalent metal salts, ammonium salts and organic amine salts thereof.
  • the acrylic acid-based monomer may have an acidic group and at least a part of the acidic group may be neutralized.
  • the monomer is partially neutralized with an alkylene material such as sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like.
  • the neutralization degree of the acrylic acid monomer may be 40 to 95 mol%, or 40 to 80 mol%, or 45 to 75 mol%.
  • the range of the degree of neutralization can be adjusted according to the final properties. However, if the degree of neutralization is too high, the neutralized monomer tends to be streaked, and polymerization may be difficult to proceed smoothly. On the other hand, if the degree of neutralization is too low, the absorption capacity of the polymer is greatly lowered, .
  • the concentration of the acrylic acid monomer may be 20 to 60% by weight, preferably 40 to 50% by weight, based on the monomer composition including the raw material of the superabsorbent resin and the solvent, It can be an appropriate concentration. However, if the concentration of the monomer is excessively low, the yield of the superabsorbent resin may be low and economical efficiency may be deteriorated. On the other hand, if the concentration is excessively high, a part of the monomer may precipitate or the pulverization efficiency may be low And the like, may cause problems in the process, and the physical properties of the superabsorbent resin may be deteriorated.
  • the polymerization initiator used in the polymerization in the method for producing a superabsorbent resin of one embodiment is not particularly limited as long as it is generally used for producing a superabsorbent resin.
  • a thermal polymerization initiator or a photopolymerization initiator upon irradiation may be used depending on the polymerization method.
  • a certain amount of heat is generated by irradiation with ultraviolet light or the like, and a certain amount of heat is generated as the polymerization reaction, which is an exothermic reaction, proceeds, so that it may further include a thermal polymerization initiator.
  • the photopolymerization initiator can be used without limitation in the constitution as long as it is a compound capable of forming a radical by light such as ultraviolet rays.
  • the photopolymerization initiator includes, for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal
  • acylphosphine Dimethyl Ketal, acyl phosphine, and t-aminoketone can be used.
  • acylphosphine lucyrin TPO, that is, , 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used.
  • More photoinitiators are well described in Reinhold Schwalm, UV Coatings: Basics, Recent Developments and New Applications (Elsevier 2007) pl 15, and are not limited to the above examples.
  • the photopolymerization initiator may be contained in the monomer composition at a concentration of 0.01 to 1.0% by weight. If the concentration of such a photopolymerization initiator is too low, the polymerization rate may be slow. If the concentration of the photopolymerization initiator is too high, the molecular weight of the high absorption resin may be small and the physical properties may become uneven.
  • the thermal polymerization initiator at least one selected from persulfate-based initiators, azo-based initiators, initiators consisting of hydrogen peroxide and ascorbic acid can be used.
  • the sulfate-based initiator sodium persulfate (Sodium persulfate; Na 2 S 2 C> 8), potassium persulfate (Potassium persulfate; 3 ⁇ 43 ⁇ 40 8), ammonium persulfate (Ammonium persulfate; (NH 4) 2 S 20
  • the azo initiator include 2, 2-azobis (2-amidinopropane) dihydrochloride, 2, 2-azo (N, N-dimethylene) isobutyramidine dihydrochloride, 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride, 2- (carbamoyl azo) isobutyronitrile carbamoylazo) isobutylonitril), 2, 2-azobis [2- (2-amidinopropan
  • the monomer composition includes an internal cross-linking agent as a raw material for a superabsorbent resin.
  • an internal cross-linking agent is distinguished from a surface cross-linking agent for cross-linking the surface of the polymer, that is, a polymer in which an acrylic acid-based monomer is polymerized, that is, an inside of a base resin.
  • the poly (meth) acrylate-based first internal crosslinking agent of the polyol and the polyglycidyl ether-based second internal crosslinking agent of the polyol are used in combination, and the first internal crosslinking agent:
  • the crosslinking agent may be used in a weight ratio of 1:20 to 1: 300, or 1:20 to 1: 250, or 1:22 to 1: 245, or 1:25 to 1: 240.
  • the rewet characteristics can be further improved while keeping the basic absorbency, the shelf life, the water retention capacity and the pressure absorption capacity and the absorption rate of the superabsorbent resin produced from the above production method. If the weight ratio of the first and second internal cross-linking agents is out of the range, the basic absorption properties may be deteriorated or the re-wetting properties may not be improved.
  • a poly (meth) acrylate-based compound of a polyol for example, a poly (meth) acrylate-based compound of a polyol having 2 to 10 carbon atoms can be used, and more specific examples thereof include trimethylol Acrylate, propylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di Acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di Tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate Site, there may be mentioned at least one selected from the group consisting of glycerol tri (meth) acrylate and penta Era stall tetraacrylate.
  • a polyglycidyl ether compound of a polyol having a polyfunctional epoxy group for example, a polyol having 2 to 10 carbon atoms
  • Polyglycidyl ether compounds may be used. More specific examples thereof include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, Cidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • first and second internal cross-linking agents may be included in a concentration of 0.01 to 0.5% by weight based on the monomer composition, so that the polymerized polymer can be crosslinked.
  • the monomer composition may further include a foaming agent, and / or a foam stabilizer.
  • the foaming agent acts to increase the surface area by foaming during polymerization to form pores in the hydrogel polymer.
  • the foaming agent include carbonates such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, calcium bicarbonate, calcium bicarbonate, Calcium carbonate, calcium bicarbonate, magnesium bicarbonate or magnesium carbonate can be used.
  • the blowing agent may be added in a concentration of 0.01 to 0.2 parts by weight based on 100 parts by weight of the acrylic acid monomer.
  • the amount of the blowing agent is more than 0.2 parts by weight, the pores become too large, and the strength of the gel with the superabsorbent resin becomes low and the density becomes low, which may cause problems in distribution and storage. If the amount is less than 0.01 part by weight, the role as a blowing agent may be insignificant.
  • the bubble stabilizer serves to uniformly distribute the bubbles in the entire region of the polymer while maintaining the shape of the bubble formed by the foaming agent, thereby increasing the surface area of the polymer.
  • an anionic surfactant may be used, and examples of the anionic surfactant that can be used include sodium dodecyl sulfate dodecyl sulfate, sodium stearate, ammonium lauryl sulfate, sodium lauryl ether sulfate (SLES), sodium myreth sulfate, or the like Alkyl-ether sulfate compounds.
  • the anionic surfactant that can be used is not limited thereto, but preferably sodium dodecyl sulfate or sodum stearate can be used.
  • the anionic surfactant may be added in an amount of 0.01 to 0.05 parts by weight based on 100 parts by weight of the acrylic acid monomer. If the concentration of the anionic surfactant is too low, the surfactant may not act as a foam stabilizer, On the contrary, if the concentration is too high, the water-holding ability and the absorption rate during polymerization may be rather low, which may be undesirable. On the other hand, in the manufacturing method of one embodiment described above, the monomer composition may further include additives such as a thickener, a plasticizer, a storage stabilizer, and an antioxidant, if necessary.
  • the starting materials such as the acrylic acid monomer, the photopolymerization initiator, the thermal polymerization initiator, the first and second internal crosslinking agents and the additives having the above-mentioned acid groups and neutralized at least a part of the acid groups are prepared in the form of a monomer composition solution dissolved in a solvent .
  • the solvent which can be used at this time can be used without limitation of its constitution as long as it can dissolve the above-mentioned components.
  • examples thereof include water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-
  • the organic solvent include glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl
  • At least one selected from ether, toluene, xylene, butylolactone, carbitol, methylcellosolve acetate and N, N-dimethylacetamide can be used in combination.
  • the solvent may be included in the balance of the total amount of the monomer composition excluding the components described above.
  • Such a monomer composition is heat-polymerized or photopolymerized, 2019/112150 1 » (: 1 ⁇ 1 ⁇ 2018/010305
  • the method for forming the polymer is not particularly limited as long as it is a commonly used polymerization method.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization depending on the polymerization energy source.
  • thermal polymerization when thermal polymerization is carried out, it may proceed in a reactor having a stirring axis such as a kneader (furnace)
  • stirring axis such as a kneader (furnace)
  • the polymerization method described above is merely an example, and the invention is not limited to the polymerization method described above.
  • the function gel polymer obtained by the thermal polymerization in a reactor by supplying hot air, or heating the reactor, such as a kneader (] 1 ⁇ 2 & (1 member having an axis stirred as described above, depending on the type of stirring shaft provided in the reactor,
  • the hydrogel polymer discharged into the reactor outlet may be in the range of a few centimeters to a few millimeters.
  • the size of the resulting hydrogel polymer may vary depending on the concentration of the monomer composition to be injected, the rate of injection, etc.
  • a gel polymer having a weight average particle diameter of 2 to 50 1 ⁇ 1111 can be obtained.
  • the form of the hydrogel polymer that is usually obtained may be a hydrogel polymer on a sheet having a belt width.
  • the thickness of the polymer sheet depends on the concentration of the monomer composition to be injected and the injection rate, but it is preferable to supply the monomer composition so that a polymer in the form of a sheet having a thickness of usually 0.5 to 5 11 can be obtained.
  • the monomer composition is supplied to such an extent that the thickness of the polymer in the sheet is too thin, it is undesirable because the production efficiency is low.
  • the thickness of the polymer on the sheet exceeds 5 11 , due to the excessively thick thickness, I can not get up.
  • the normal water content of the hydrogel polymer obtained by such a method may be 40 to 80% by weight.
  • water content as used throughout the present specification means a value obtained by subtracting the weight of the hydrogel polymer from the weight of the hydrogel polymer in terms of the content of water with respect to the weight of the total functional gel polymer.
  • the weight loss due to evaporation of moisture in the polymer during drying is defined as a value calculated by measuring the weight loss.
  • the condition is that the temperature is raised from room temperature to 180 ° C and then maintained at 180 ° C.
  • the total drying time is set to 20 minutes including 5 minutes of temperature rise step, and the water content is measured.
  • the step of coarse grinding may be further carried out before drying in order to increase the efficiency of the drying step.
  • the pulverizer to be used is not limited in its constitution, but may be a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, A crusher, a disc mill, a disc mill, a shred crusher, a crusher, a chopper, and a disc cutter.
  • the present invention is not limited to the above-described example.
  • the pulverization step can be carried out such that the diameter of the hydrogel polymer is 2 to 10 -.
  • the pulverization with a particle diameter of less than 2 mm is not technically easy due to the high water content of the hydrogel polymer, and may also result in coagulation between the pulverized particles.
  • the particle size is larger than 10 mm, the effect of increasing the efficiency of the subsequent drying step is insignificant.
  • the drying temperature is lower than 150 ° C, the drying time becomes excessively long and the physical properties of the ultrafine water-absorbent resin to be finally formed may deteriorate.
  • the drying temperature exceeds 250 ° C, only the polymer surface is excessively dried, Fine powder may be generated in the pulverizing step, and the physical properties of the ultrafine water-absorbent resin to be finally formed may be lowered.
  • the drying can be carried out at a temperature of from 150 to 200 ° C, more preferably from 160 to 180 ° C.
  • the drying time may be 20 to 90 minutes in consideration of process efficiency and the like, but is not limited thereto.
  • the drying method of the drying step is also a drying step of the hydrogel polymer It can be selected and used without limitation of its configuration as long as it is normally used. Specifically, the drying step can be carried out by hot air supply, infrared irradiation, microwave irradiation, ultraviolet irradiation, or the like.
  • the water content of the polymer after such a drying step may be 0.1 to 10% by weight.
  • the polymer powder obtained after the pulverization step may have a particle size of 150 to 850 / M.
  • the pulverizer used for crushing with such a particle size is specifically a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill or a jog mill a jog mill, or the like may be used, but the invention is not limited to the examples described above.
  • the base resin is obtained in the form of powder through the classification step described above, the base resin is increased in the presence of the surface cross-linking agent to progress the surface modification to the base resin.
  • a surface crosslinking solution containing a surface crosslinking agent is mixed with a polymer to be dried, crushed and classified, that is, a base resin, and then the mixture is heated by heating, The reaction is carried out.
  • the surface crosslinking step is a step of inducing a crosslinking reaction on the surface of the pulverized polymer in the presence of a surface crosslinking agent to form a superabsorbent resin having improved physical properties.
  • a surface crosslinked layer (surface modified layer) is formed on the surface of the pulverized and classified polymer particles.
  • the surface cross-linked superabsorbent resin particles have a 2019/112150 1 »(: 1 ⁇ 1 ⁇ 2018/010305
  • the crosslinked polymer is further crosslinked to have a higher degree of crosslinking near the surface than in the interior.
  • the surface cross-linking agent a compound capable of reacting with the functional group of the base resin is used.
  • the surface cross-linking agent include polyvalent alcohol compounds, polyvalent epoxy compounds, polyamine compounds, haloepoxy compounds, condensation products of haloepoxy compounds, oxazoline compounds, Or an alkylene carbonate compound can be used without any limitation.
  • polyhydric alcohol compound examples include di-, tri-, tetra- or polyethylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3-pentanediol, polypropylene But are not limited to, glycols, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5- Dimethanol, and the like. .
  • polyvalent epoxy compound ethylene glycol diglycidyl ether and glycidol may be used.
  • polyamine compound ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene nucleus At least one selected from the group consisting of silica, polyethyleneimine and polyamidepolyamines can be used.
  • haloepoxy compound epichlorohydrin, epibromohydrin, and (X -methyl epichlorohydrin can be used.
  • examples of mono-, di- or polyoxazolidinone compounds include 2-oxa Etc.
  • alkylene carbonate compound ethylene carbonate and the like can be used. These may be used alone or in combination with each other.
  • the amount of the surface crosslinking agent to be added may be appropriately selected depending on the kind of the surface crosslinking agent to be added and the reaction conditions. It is usually 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, , And more preferably 0.05 to 2 parts by weight.
  • the progress of the surface cross-linking reaction may cause degradation of absorption properties such as water retention ability.
  • the surface cross-linking agent When the surface cross-linking agent is added, water can be further mixed together and added in the form of a surface cross-linking solution. When water is added, there is an advantage that the surface cross-linking agent can be uniformly dispersed in the polymer. At this time, the amount of added water is preferably 1 to 10 parts by weight per 100 parts by weight of the polymer for the purpose of inducing even dispersion of the surface cross-linking agent and preventing the polymer powder from aggregating and optimizing the surface penetration depth of the surface cross- . ≪ / RTI >
  • the surface cross-linking step (surface modification step) described above may be carried out in addition to the surface cross-linking agent, for example, a polyvalent metal salt such as an aluminum salt, more specifically a sulphate, potassium salt, ammonium salt, sodium salt, We will continue to use more of the above.
  • a polyvalent metal salt such as an aluminum salt, more specifically a sulphate, potassium salt, ammonium salt, sodium salt
  • the multivalent metal salt may be added to the surface cross-linking solution together with the surface cross-linking agent and may be added in an amount of 0.01 to 4 parts by weight, or 0.05 to 1 part by weight, or 0.1 to 0.5 parts by weight, or 0.15 to 0.3 parts by weight, Can be used as the content of parts by weight.
  • the surface modification step is performed on the base resin by heating the mixture of the base resin and the surface cross-linking solution.
  • the surface modification step may be carried out under well-known conditions depending on the kind of the surface cross-linking agent.
  • the surface modification step may be carried out at a temperature of 100 to 200 DEG C for 20 to 60 minutes.
  • the surface cross-linking agent is a polyvalent epoxy compound, at a temperature of 120 to 180 ° 0, or 120 to 150
  • the temperature raising means for the surface reforming reaction is not particularly limited.
  • a heating medium can be supplied, or a heating source can be directly supplied and heated.
  • the type of heat medium that can be used steam, hot air, hot fluid, or the like can be used, but the present invention is not limited thereto, and the temperature of the heat medium to be supplied is controlled by means of heating medium, It can be selected appropriately considering the temperature.
  • a heat source to be directly supplied a heating method using electricity or a heating method using gas may be mentioned, but the present invention is not limited to the above-mentioned examples.
  • a superabsorbent resin can finally be produced according to the method of one embodiment.
  • Such a superabsorbent resin can exhibit improved rewet characteristics, excellent retention ability, pressure absorbing ability and absorption speed, etc., as it has an optimized internal crosslinking structure by using a specific internal crosslinking agent combination.
  • the thus-prepared superabsorbent resin comprises a base resin comprising a crosslinked polymer obtained by crosslinking an acrylic acid-based monomer in which at least a part of an acid group is neutralized, via an internal crosslinking agent;
  • a polyvalent metal salt formed on the surface cross-linked layer is formed on the surface cross-linked layer
  • the internal cross-linking agent may comprise a poly (meth) acrylate first internal crosslinking agent of polyol: polyglycidyl ether second internal crosslinking agent of polyol in a weight ratio of 1:20 to 1: 300.
  • the super absorbent resin further comprises a polyvalent metal salt formed on the surface cross-linked layer, as the surface of the polyvalent metal salt such as an aluminum salt is selectively used as a teacher. Since the polyvalent metal salt such as an aluminum salt is already described above, further explanation is omitted.
  • the superabsorbent resin can basically exhibit absorption properties such as excellent water retention ability, pressure absorption ability and absorption speed.
  • the superabsorbent resin may have a water retention capacity (01 (:) of 26 or more, or 27 ⁇ / < / RTI > or more, or 30 or more, 38 or less, or 35 or less.
  • the superabsorbent resin prepared by the above-mentioned method has a pressure absorption capacity (AUP) of 0.7 psi according to EDANA method WSP 242.3 of 8 g / g or more, 10 g / g or more, or 11 g / g or more , 30 g / g or less, or 20 g / g or less, or 17 g / g or less.
  • AUP pressure absorption capacity
  • the superabsorbent resin prepared by the above-mentioned production method can be produced by EDANA method WSP
  • the water content measured according to the method of 270.2 may be 10 wt% or less, or 8 wt% or less, or 7 wt% or less, 0 wt% or more, 1 wt% or more, or 3 wt% or more.
  • the superabsorbent resin produced by the above-described method may have a vortex time of 40 seconds or less, or 38 seconds or less, or 35 seconds or less.
  • the absorption rate refers to a time (unit: sec) in which a vortex of a liquid disappears due to rapid absorption when a superabsorbent resin is added to physiological saline and stirred. When the time is shorter, Can be seen to have a fast initial absorption rate.
  • the superabsorbent resin is immersed in 100 g of water and swelled for 10 minutes, and then 50 g of 50 g of the superabsorbent resin is added to the superabsorbent resin.
  • the above superabsorbent resin may exhibit excellent reabsorption characteristics, Min., Or 0.9 g or less, or 0.8 g or less, defined by the weight of water repelled from the superabsorbent resin to the filter paper after being allowed to stand on the filter paper for at least 0.1 g , Or 0.15 g or more, or 0.25 g or more.
  • the electrical conductivity of the water used in the measurement of the rewet property may be 170 to 180 y S / cm, and the electrical conductivity may be, for example, Orion Star A222 (trade name: Thermo Scientific).
  • Orion Star A222 trade name: Thermo Scientific
  • the electrical conductivity of tap water influences product properties, so rewet measurements should be made using tap water having an equivalent level of electrical conductivity.
  • a superabsorbent resin powder was obtained in the same manner as in Example 1, except that aluminum sulfate was not used in the preparation of the surface cross-linking solution.
  • the retention capacity of each resin by the zero-load capacity was measured according to EDANA WSP 241.3.
  • the high-water-based resin Wo (g) (about 0.2 g) was uniformly put into an envelope made of a nonwoven fabric, sealed, and then immersed in physiological saline (0.9 wt%) at room temperature. After 30 minutes, water was drained from the envelope for 3 minutes under a condition of 250 G using a centrifuge, and the mass W 2 ( g) of the envelope was measured. In addition, after the same operation was performed without using a resin, the mass at that time was measured. Using the obtained masses, CRC (g / g) was calculated according to the following equation.
  • a 400-mesh stainless steel mesh was attached to a cylindrical bottom of an inner diameter 25 _.
  • a superabsorbent resin ((0.9) was uniformly sprayed on the wire net, and 0.7
  • the piston which can evenly apply the load, is slightly smaller than the outer diameter 25 111111, so that there is no gap between the inner wall of the cylinder and the vertical movement is not obstructed.
  • the weight ( 3 ) of the apparatus was measured.
  • a glass filter having a diameter of 90111111 and a thickness of 5111111 was placed inside a Petro dish having a diameter of 150 111111, and physiological saline composed of 0.9 wt% sodium chloride was made to have the same level as the upper surface of the glass filter.
  • physiological saline composed of 0.9 wt% sodium chloride was made to have the same level as the upper surface of the glass filter.
  • one filter paper with a diameter of 90_ was placed. The measuring device was placed on the filter paper, and the solution was immersed for 1 hour under load
  • the short-term rewetting characteristics were measured in the following manner. In the measurement of the rewet characteristics, the water conductivity was 170 to 180wt%. This electrical conductivity was measured using an Orion Star A222 (company: Thermo Scientific) electrical conductivity meter.
  • Examples 1 to 3 exhibited a water retention capacity, a pressure absorption capacity and an absorption rate equal to or higher than those of Comparative Examples 1 and 2, And showed improved rewet properties.
  • Comparative Example 3 relates to a superabsorbent resin prepared without using a polyvalent metal salt (aluminum sulfate) in the example of the present invention, and it was confirmed that the pressure absorption capacity and rewetting characteristics were poor as compared with the examples.
  • a polyvalent metal salt aluminum sulfate

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

La présente invention concerne un polymère superabsorbant présentant des caractéristiques de remouillages améliorées et d'excellentes caractéristiques d'absorption et un procédé de préparation associé. Le procédé de préparation du polymère superabsorbant comprend les étapes consistant à : former une résine de base dans laquelle un monomère à base d'acide acrylique, dont au moins une partie de groupes acides est neutralisée, et un agent de réticulation interne sont réticulés ; et modifier la surface de la résine de base par chauffage de la résine de base en présence d'un agent de réticulation de surface, l'agent de réticulation interne pouvant comprendre un premier agent de réticulation interne à base de polyol-poly(méth)acrylate et un deuxième agent de réticulation interne à base de polyol-polyglycidyléther dans un rapport pondéral prédéterminé.
PCT/KR2018/010305 2017-12-08 2018-09-04 Polymère absorbant et procédé de préparation associé WO2019112150A1 (fr)

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EP18857399.2A EP3521343B1 (fr) 2017-12-08 2018-09-04 Polymère absorbant et procédé de préparation associé
JP2019520362A JP6837141B2 (ja) 2017-12-08 2018-09-04 高吸水性樹脂およびその製造方法
CN201880004132.8A CN110139892B (zh) 2017-12-08 2018-09-04 超吸收性聚合物及其制备方法
US16/348,657 US11278866B2 (en) 2017-12-08 2018-09-04 Super absorbent polymer and its preparation method

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KR20170168684 2017-12-08
KR10-2018-0104572 2018-09-03
KR1020180104572A KR102584203B1 (ko) 2017-12-08 2018-09-03 고흡수성 수지 및 이의 제조 방법

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