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WO2019117541A1 - Polymère superabsorbant et son procédé de préparation - Google Patents

Polymère superabsorbant et son procédé de préparation Download PDF

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Publication number
WO2019117541A1
WO2019117541A1 PCT/KR2018/015468 KR2018015468W WO2019117541A1 WO 2019117541 A1 WO2019117541 A1 WO 2019117541A1 KR 2018015468 W KR2018015468 W KR 2018015468W WO 2019117541 A1 WO2019117541 A1 WO 2019117541A1
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WO
WIPO (PCT)
Prior art keywords
water
resin
weight
polymer
sodium
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
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PCT/KR2018/015468
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English (en)
Korean (ko)
Inventor
정선정
남대우
성보현
윤형기
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020180155292A external-priority patent/KR102566286B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to CN201880078532.3A priority Critical patent/CN111433261B/zh
Priority to US16/771,479 priority patent/US11633719B2/en
Priority to JP2020530506A priority patent/JP7038825B2/ja
Priority to EP18887781.5A priority patent/EP3708606A4/fr
Publication of WO2019117541A1 publication Critical patent/WO2019117541A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F20/00—Homopolymers and 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—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
    • 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
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • the present invention relates to a superabsorbent resin and a method for producing the same. More particularly, the present invention relates to a superabsorbent resin having improved rewet characteristics and absorption rates and a method for producing the same.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing moisture of about 500 to 1,000 times its own weight. As a result, it is possible to use SAM (Super Absorbent Material), AGM Material), and so on. Such a superabsorbent resin has started to be put into practical use as a sanitary article and is currently being used for diapers and sanitary napkins for children, as well as soil repair agents for horticultural use, exponents for civil engineering and construction, sheet for seedling growing, , And as a material for fomentation and the like.
  • SAP Super Absorbent Polymer
  • 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
  • Urine A phenomenon Urine A phenomenon may occur.
  • an acrylic resin composition which comprises, in the presence of water-dispersed silica, a base having an acidic group and at least a part of the acidic group neutralized with an acrylic acid-based monomer and an internal cross-
  • Step 2 of a hydrophobic substance and a surface cross-linking agent
  • step 3 Performing the surface modification on the bead resin by raising the mixture of step 2 (step 3); 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • a base resin comprising a cross-linked polymer obtained by cross-linking an acrylic acid-based monomer in which at least a part of an acidic group is neutralized;
  • the surface modification layer comprises a hydrophobic material having an HLB of not less than 0 and not more than 6, and a vortex time of not more than 35 seconds.
  • a method of manufacturing a superabsorbent resin according to an embodiment of the present invention includes:
  • Step 1 of preparing a base resin crosslinked with an acrylic acid-based monomer and an internal cross-linking agent having an acidic group and neutralizing at least a part of the acidic group in the presence of the water-dispersed silica;
  • step 2 Mixing the base resin with a hydrophobic substance having an HLB of not less than 0 and not more than 6, and a surface cross-linking agent (step 2); and
  • base resin or “base resin powder” means a polymer obtained by drying and pulverizing a polymer obtained by polymerizing a water-soluble ethylenically unsaturated monomer, Means a polymer in a state where the surface modification or surface cross-linking step described later is not performed.
  • 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 one embodiment of the present invention is excellent in physical properties such as water repellency, pressure absorbing ability and liquid permeability and exhibits excellent absorption performance and remains dry even after being swollen with salt water It is possible to effectively prevent the re-wetting 0 and the urine leakage (1-year) phenomenon in which the urine absorbed in the superabsorbent resin is re-exuded, leading to the present invention.
  • the monomer composition which is a raw material of the superabsorbent resin, is prepared by first mixing an acrylic acid-based monomer having an acidic group and at least a part of the acidic groups neutralized, an internal crosslinking agent, Polymerized to obtain a hydrogel polymer, which is dried, pulverized and classified to obtain a base (Step 1).
  • 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:
  • 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, neutralized monomers may precipitate 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 decreased, .
  • the concentration of the acrylic acid monomer may be about 20 to about 60 wt%, preferably about 40 to about 50 wt%, based on the monomer composition including the raw material of the superabsorbent resin and the solvent, The concentration may be appropriate considering the conditions and the like. 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 polymerization is not particularly limited as long as it is generally used in the production of 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 of ultraviolet light or the like, and a certain amount of heat is generated as the polymerization reaction, which is an exothermic reaction, proceeds.
  • the photopolymerization initiator may form a radical by light such as ultraviolet light 2019/117541 1 »(: 1/10/0/0 018/015468
  • photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyl dimethyl ketal Ketal, acyl phosphine, and a-aminoketone may be used.
  • acylphosphine commercial lucirin TPO, that is, 2, 4, 6, which - may be trimethyl phosphine oxide (2, 4, -trimethyl-6-trimethyl benzoyl phosphine oxide) - trimethyl-benzoyl
  • the photopolymerization initiator may be included in the monomer composition at a concentration of about 0.01 to about 1.0 wt%. 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.
  • 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.
  • persulfate-based initiator examples include sodium persulfate (Na 2 S 2 () 8) , potassium sulphate (K 2 S 2 O 8), ammonium persulfate NH 2) 2 S 2 C) 8).
  • azo initiators include 2, 2-azobis- (2-amidinopropane)
  • N-dimethylene isobutyramidine dihydrochloride 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride
  • the monomer composition includes an internal cross-linking agent as a raw material for a superabsorbent resin.
  • the internal crosslinking agent include a crosslinking agent having at least one functional group capable of reacting with the acrylic acid-based monomer and having at least one ethylenic unsaturated group; Or a crosslinking agent having two or more functional groups capable of reacting with a substituent formed by hydrolysis of a substituent and / or a monomer of the acrylic acid-based monomer may be used.
  • the internal cross-linking agent examples include '-methylenebisacrylamide, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di (Meth) acrylate, butylene diol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, (Meth) acrylate such as triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri Triarylamine, ethylene Recall diglycidyl may be used at least one member selected from ether, propylene glycol, the group consisting of glycerin, and ethylene carbonate.
  • Such an internal cross-linking agent may be present in the monomer composition at a level of from about 0.01 to about
  • the monomer composition includes water-dispersed silica.
  • the dispersion of silica ( ⁇ 11 0 ⁇ is, means silica in a state where stable dispersion of the silica particles in water without precipitation or flocculation, and, means silica which at least is partly ionized in the silica particle surface.
  • the method for producing the water-dispersed silica is not particularly limited, and those produced by known methods such as electrodialysis, sol-gel method, ion exchange method, and acid-neutralization method may be used.
  • Particle size of the dispersion of silica is not more than 11111, yet about 5, or at least about 10 11111, preferably about 1101 to 100, or up to about 50 11111, or no more than about 30 wave 11. 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the water-dispersed silica may be added in an amount of about 0.01 to about 1.0 part by weight, or about 0.02 to about 0.5 part by weight based on 100 parts by weight of the acrylic acid monomer.
  • the amount of the water-dispersed silica exceeds 1.0 part by weight , The water retention ability of the superabsorbent resin may be deteriorated. If the amount is less than 0.01 part by weight, rewetting may not be improved.
  • the water-dispersed silica can not obtain the effect of improving the rewetting property when the colloid is not retained in the monomer composition, it is preferable that the water-dispersed silica maintains a stable colloid state in the monomer composition .
  • powdery or hydrophobic silica that is not in a colloidal state does not have an effect of improving rewetting, so that the intended effect of the present invention can not be achieved.
  • the above-mentioned water-dispersed silica is added at the time of polymerization, and polymerization is carried out in the presence of the water-dispersed silica to form a gel of the superabsorbent resin particle by hydrogen bonding between the superabsorbent resin and the water-
  • the strength can be improved, and the rewet property can be improved.
  • 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. 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the blowing agent may be added at a concentration of about 0.005 to about 1 part by weight, or about 0.01 to about 0.3 part by weight based on 100 parts by weight of the acrylic acid monomer. If the amount of the foaming agent is more than 1 part by weight, the pores become too large, the gel strength of the superabsorbent resin decreases, and the density becomes low, which may cause problems in distribution and storage. When the amount is less than 0.005 parts by weight, the role as the 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.
  • anionic surfactant examples include anionic surfactants such as sodium dodecyl sulfate, sodium stearate, ammonium lauryl sulfate, ), Sodium lauryl ether sulfate, sodium myreth sulfate, or alkylether sulfate compounds similar thereto.
  • anionic surfactant that can be used is not limited thereto, but preferably sodium dodecyl sulfate or sodium stearate can be used.
  • the anionic surfactant may be added in a concentration of about 0.001 to about 1 part by weight, or about 0.005 to about 0.05 part by weight based on 100 parts by weight of the acrylic acid monomer. If the concentration of the anionic surfactant is excessively low, it is difficult to achieve an improvement in absorption rate due to its insufficient function as a foam stabilizer. On the other hand, if the concentration is excessively high, surface tension after polymerization may become too low to adversely affect the physical properties of the diaper.
  • the monomer composition of the superabsorbent resin may further contain additives such as a thickener, a plasticizer, a preservative stabilizer, and an antioxidant, if necessary.
  • Raw materials such as acrylic acid-based monomer, photopolymerization initiator, thermal polymerization initiator, internal cross-linking agent and additive having the above-mentioned acid group and at least part of which is neutralized can be 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
  • One or more selected from ether, toluene, xylenes, butylolactone, carbitol, methylcellosolve acetate and benz-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.
  • the method of forming a hydrogel polymer by thermal polymerization or photopolymerization of such a monomer composition is not particularly limited as long as it is a commonly used polymerization method.
  • the polymerization method is divided into thermal polymerization and photopolymerization largely depending on the polymerization energy source.
  • the polymerization can proceed in a reactor having agitation such as kneader,
  • the polymerization method described above is only one example, and the present invention is not limited to the polymerization method described above.
  • the function gelled polymer obtained in the reactor such as a kneader (10 (1) 1 having an axis stirred, by the thermal polymerization by supplying hot air or heating of the reactor as described above in accordance with the form of a 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 obtained hydrogel polymer may vary depending on the concentration of the monomer composition to be injected, the injection rate, etc. In general, a gel polymer having a weight average particle diameter of 2 to 50 111111 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 varies depending on the concentration and the injection rate of the monomer composition to be injected, 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the monomer composition it is preferable to supply the monomer composition so that a polymer in the form of a sheet having a thickness of usually about 0.5 to about 5 cm can be obtained.
  • the monomer composition is supplied to such an extent that the thickness of the polymer in the sheet is too thin, the production efficiency is low, which is undesirable.
  • the thickness of the polymer on the sheet exceeds 5 cm, the polymerization reaction occurs evenly over the entire thickness due to the excessively thick thickness I can not.
  • the normal water content of the hydrogel polymer obtained by this method may be about 40 to about 80 wt%.
  • 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. Specifically, The temperature is increased from room temperature to about 180 ° C, and then maintained at 180 ° C. In this case, , And the total drying time is set to 20 minutes including the temperature rising step of 5 minutes, 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 milling step may be milled so that the hydrous gel polymer has a particle size of about 2 to about 10 mm.
  • the drying is carried out on the hydrogel polymer immediately after the polymerization, which has not been pulverized or pulverized as described above, wherein the drying temperature of the drying step may be about 150 to about 25 C.
  • the drying temperature is lower than 150 ° C, There is a possibility that the drying time is too long and the physical properties of the superabsorbent resin to be finally formed are lowered.
  • the drying temperature exceeds 250 ° C, only the polymer surface is dried excessively, There is a possibility that the physical properties of the superabsorbent resin finally formed are lowered.
  • the drying can proceed at a temperature of from about 150 to about 200 ° C, more preferably from about 160 to about 180 ° C.
  • the drying method in the drying step may be selected and used as long as it is usually used as a drying step of the hydrogel polymer.
  • 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 may be about 0.1 to about 10 wt%.
  • the polymer powder obtained after the pulverization step may have a particle size of about 150 to about 850 m.
  • the pulverizer used for pulverizing with such a particle size is specifically a pin mill, a hammer mill, a screw a roll mill, a disc mill, or a jog mill may be used.
  • the present invention is not limited to the above-described examples.
  • a hydrophobic substance having an HLB of 0 or more and 6 or less and a surface cross-linking agent are mixed in the base resin (Step 2).
  • a surface cross-linking solution containing a surface cross-linking agent is mixed with a base resin, and then the surface cross-linking reaction is performed on the ground polymer by heating the mixture by heating.
  • 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 modifying layer) is formed on the surface of the pulverized polymer particles.
  • the surface cross-linking agent is applied to the surface of the superabsorbent resin particles, so that the surface cross-linking reaction occurs on the surface of the superabsorbent resin particles, which improves the crosslinkability on the surface of the particles without substantially affecting the inside of the particles.
  • the surface cross-linked superabsorbent resin particles have a higher degree of crosslinking in the vicinity of the surface than in the interior.
  • the pressure absorption ability and the permeability can be improved by the surface cross-linking reaction, but the rewetting and maintenance ability can be weakened.
  • the surface crosslinking efficiency is improved, so that the absorption rate and the liquid permeability can be further improved as compared with the resin not using a hydrophobic substance.
  • the hydrophobic substance may be a material that satisfies 0 or more, or 1 or more, or 2 or more, and 6 or less, or 5 or less, or 5.5 or less as the lower limit of HLB.
  • a material having a melting point lower than the surface cross-linking reaction temperature may be used.
  • a usable hydrophobic substances include, for example, glyceryl stearate (glyceryl stearate), glycol stearate (glycol stearate), magnesium stearyl 6-rate (magnesium stearate), glyceryl monolaurate (glyceryl laurate), sorbitan stearate Sorbitan stearate, sorbitan trioleate, or PEG-4 dilaurate.
  • glyceryl stearate can be used, but it is not limited thereto. It is not. 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the hydrophobic substance is distributed in the surface modified layer of the surface of the base resin so that the swollen resin particles in the process of absorbing and swelling the liquid of the super absorbency resin are prevented from aggregating or aggregating according to the increased pressure, It is possible to more easily transmit and diffuse the liquid, thereby contributing to improvement of the re-wetting property of the superabsorbent resin.
  • the hydrophobic material may be present in an amount of at least about 0.02 part by weight, or at least about 0.025 part by weight, or at least about 0.05 part by weight, and up to about 0.5 part by weight, or up to about 0.3 part by weight, or up to about 0.1 part by weight, If the content of the hydrophobic substance is less than 0.02 part by weight, the rewet property may not be improved. If the content of the hydrophobic substance is more than 0.5 part by weight, the base resin and the hydrophobic substance may be separated from each other There may be a problem that the rewetting improving effect does not exist or may act as an impurity, so the weight range may be preferable from this point of view.
  • the method of mixing the hydrophobic substance is not particularly limited as long as it can mix the base resin uniformly and can be suitably employed.
  • the hydrophobic substance may be mixed by dry mixing before mixing the surface cross-linking solution containing the surface cross-linking agent into the base resin, or by first dispersing the surface cross-linking solution in the base cross- Alternatively, separately from the surface cross-linking solution, the hydrophobic substance may be heated to a melting temperature or higher to be mixed in a solution state.
  • the above-mentioned surface cross-linking agent When the above-mentioned surface cross-linking agent is added, water can be further mixed together and added in the form of a surface cross-linking solution.
  • the surface crosslinking agent When water is added, there is an advantage that the surface crosslinking agent can be uniformly dispersed in the polymer.
  • the added water content is preferably from about 1 to about 10 wt. Parts per 100 parts by weight of the polymer for the purpose of inducing uniform dispersion of the surface cross-linking agent and preventing the polymer powder from aggregating and optimizing the surface penetration depth of the surface cross- By weight.
  • the surface cross-linking agent is not limited in its constitution as long as it is a compound capable of reacting with a functional group contained in the polymer.
  • polyhydric alcohol compound examples include mono-, di-, tri-, tetra- or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4- - pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,2-cyclic nucleic acid dimethanol, and the like.
  • Examples of the epoxy compounds include ethylene glycol diglycidyl ether and glycidol.
  • Examples of the polyamine compounds include ethylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylene nucleus amine, Polyethyleneimine and polyamidepolyamines can be used.
  • haloepoxy compound epichlorohydrin, epibromohydrin, and (X-methyl epichlorohydrin can be used.
  • mono-, di- or polyoxazolidinone compounds for example, 2-oxazolidinone Dinonone, etc.
  • alkylene carbonate compounds ethylene carbonate and the like can be used. These can be used alone or in combination with each other.
  • polyhydric alcohol compounds having 2 to 10 carbon atoms may be used.
  • 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, but is usually about 0.001 to about 5 parts by weight, preferably about 0.01 to about 5 parts by weight, About 3 parts by weight, more preferably about 0.05 to about 2 parts by weight may be used.
  • the progress of the surface cross-linking reaction may cause a decrease in the absorption capacity and physical properties.
  • the surface-crosslinking agent described above may further include at least one selected from the group consisting of polyvalent metal salts such as aluminum salts, more specifically, aluminum sulfate, potassium salt, ammonium salt, sodium salt and hydrochloride.
  • polyvalent metal salts such as aluminum salts, more specifically, aluminum sulfate, potassium salt, ammonium salt, sodium salt and hydrochloride.
  • the liquid permeability and the like of the superabsorbent resin produced by the method of one embodiment can be further improved.
  • the multivalent metal salt may be added to the surface cross-linking solution together with the surface cross-linking agent, and may be used in an amount of 0.01 to 4 parts by weight based on 100 parts by weight of the base resin.
  • step 3 the base resin, the surface cross-linking agent, and the mixture of the hydrophobic substances are heated to raise the temperature, thereby performing the surface modification step (step 3).
  • the surface modification step may be carried out by heating at a temperature of from about 80 to about 190 (preferably from about 100 to about 180 (preferably from about 10 to about 90 minutes, preferably from about 20 to about 70 minutes) .
  • 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.
  • the base resin has excellent gel strength due to the water-dispersed silica added at the time of polymerization, and further, by the surface modification step, the surface cross-linking agent and the base resin A surface crosslinked structure formed by reaction with a functional group is formed, and the surface crosslinked structure 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the superabsorbent resin produced by the production method of the present invention is superior in the properties of such a base resin and the surface reforming layer formed on the base resin to improve the rewetting properties without deteriorating properties such as water retention capacity and pressure absorption capacity Properties and initial absorption rates.
  • a base resin comprising a base resin comprising a cross-linked polymer obtained by crosslinking at least part of an acidic group with an acrylic acid-based monomer, and a base resin formed on the surface of the base resin,
  • the surface modifying layer comprises a hydrophobic substance having an HLB of not less than 0 and not more than 6, and has a vortex time of 35 seconds or less.
  • the superabsorbent resin has a CRC of at least about 30 g / g, or at least about 31 g / g, or at least about 32 g / g, and at least about 40 g / g, as measured according to EDANA method WSP 241.3 , Or about 38 g / g or less, or about 35 g / g or less.
  • the superabsorbent resin preferably has a pressure absorption capacity (AUP) of about 0.7 g / g or more, about 22 g / g or more, or about 23 g / g or more, measured according to EDANA method WSP 242.3 35 g / g or less, or about 33 g / g or less, or about 32 g / g or less.
  • AUP pressure absorption capacity
  • the high viscosity aqueous resin may have a vortex time of 35 seconds or less, or about 32 seconds or less, or about 30 seconds, or 28 seconds or less.
  • the lower limit of the absorption rate is theoretically 0 seconds, but may be, for example, about 5 seconds or more, or about 10 seconds or more, or about 12 seconds or more.
  • the regeneration speed means a time (unit: second) during which the vortex of the liquid disappears due to the rapid top water when high-viscosity aqueous resin is added to the physiological saline solution and the time is short, Can be seen to have a fast initial absorption rate.
  • the superabsorbent resin is preferably a resin which is measured according to the following formula 1 2019/117541 1 »(1 ⁇ 1 ⁇ 2018/015468
  • the permeability (unit: sec) may be about 20 seconds or less, or about 18 hours or less, or about 16 seconds or less.
  • the liquid permeability is better as the value is smaller, About 5 seconds or more, or about 10 seconds or more, or about 12 seconds or more.
  • the superabsorbent resin can exhibit excellent absorption characteristics while exhibiting improved rewet characteristics.
  • Non-pressurized water supply water or long-term rewet may be 3.0 g or less, or 2.5 g or less, or 2.0 g or less.
  • the lower the weight of the water is, the better the lower theoretical value may be 0 g, for example, 0.1 g or more, or 0.5 g or more, or 1.0 g or more.
  • the rewet property defined as the weight of water reabsorbed to the filter paper may be less than 1.0 g, or not more than 0.9 g, or not more than 0.8 g.
  • the tap water used in the re-wetting property evaluation has an electrical conductivity of 170 to ISOtiS / cm. Since the electrical conductivity of the tap water greatly affects the physical properties of the tap water, it is necessary to measure the physical properties such as rewet using tap water having an equivalent level of electrical conductivity.
  • the superabsorbent resin of the present invention has excellent absorption ability, and excellent rewetting and leakage of urine can be suppressed even when a large amount of urine is absorbed.
  • Sodium bicarbonate (SBC) as a blowing agent 0.6 g of sodium persulfate (SPS) as a photoinitiator, 0.008 g of bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 0.15 g of sodium persulfate 0.08 g of a surfactant, 0.035 g of sodium dodecylsulfate (SDS), 0.4 g of water-dispersed silica (ST-O), 123.3 g of 31.5% caustic soda (NaOH) and 38.53 g of water to prepare a monomer aqueous solution composition .
  • SBC sodium bicarbonate
  • SPS sodium persulfate
  • SPS bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide
  • 0.15 g of sodium persulfate 0.08 g of a surfactant 0.035 g of sodium dodecylsulfate (S
  • UV light was irradiated (irradiated amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C, aging for 2 minutes, A polymer sheet was prepared.
  • the polymerized sheet was taken out and cut into a size of 3 cm x 3 cm, followed by chopping using a meat chopper to prepare a crumb.
  • the crumb was dried in an oven capable of airflow transfer up and down.
  • the hot air of 185 ° C was flowed from the lower side to the upper side for 15 minutes and the lower side was flowed from the upper side to the lower side for 15 minutes. After drying, the water content of the dried body was made to be 2% or less.
  • the polymerized sheet was taken out and chopped using a meatchopper cut to a size of 3 cm x 3 cm to prepare a crumb.
  • the crumb was dried in an oven capable of airflow transfer up and down. 185 ° C hot air was uniformly dried by flowing from below to upward for 15 minutes and from downward to upward for 15 minutes. After drying, 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the water content was adjusted to 2% or less. After drying, the mixture was pulverized by a pulverizer, and then Amplitute
  • UV light was irradiated (irradiated amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C, aging for 2 minutes, A polymer sheet was prepared.
  • the polymerized sheet was taken out and cut into a size of 3 cm x 3 cm, followed by chopping using a meat chopper to prepare a crumb.
  • the crumb was dried in an oven capable of airflow transfer up and down.
  • the hot air at 185 ° C was turned upside down for 15 minutes, 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • UV light was irradiated (irradiated amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C, aging for 2 minutes, A polymer sheet was prepared.
  • the polymerized sheet was taken out and cut into a size of 3 cm x 3 cm, followed by chopping using a meat chopper to prepare a crumb.
  • the crumb is placed in an oven capable of airflow transfer up and down 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • UV light was irradiated (irradiated amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C, aging for 2 minutes, A polymer sheet was prepared.
  • the polymerized sheet was taken out, cut into a size of 3 cm x 3 cm, and chopped using a meat chopper to obtain a crumb 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the crumb was dried in an oven capable of airflow transfer up and down.
  • the hot air of 185 ° C was flowed from the lower side to the upper side for 15 minutes and the lower side was flowed from the upper side to the lower side for 15 minutes.
  • the water content of the dried body was made to be 2% or less. (5% / 75% / 20%) were collected from each sample, and then classified for 10 minutes in an Amplitute 1.5 mm (classification mesh combination: # 20-30 / # 30-50 / # 50-100)
  • a polymer having a particle diameter of about 150 to 850 / was obtained by classification, and a base resin powder was obtained in this way.
  • glyceryl stearate 7.7 parts by weight of water, 5.5 parts by weight of methanol, ethylene glycol diglycidyl ether (EX-810), and 0.1 part by weight of glyceryl stearate were added to 100 parts by weight of the base resin, 0.05 parts by weight of sodium metabisulfite, 0.1 part by weight of aluminum sulfate 18 hydrate (Al-S), and 0.03 parts by weight of aluminum oxide (Alu 130) were uniformly mixed , And the surface cross-linking reaction was carried out at 140 ° C for 35 minutes. After completion of the surface treatment, a water absorbent resin having an average particle size of 150 to 850 g was obtained using a sieve.
  • SPS sodium persulfate
  • SPS sodium persulfate
  • SDS sodium dodecylsulfate
  • UV polymerization was carried out by irradiating ultraviolet ray (irradiation amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C and aging for 2 minutes to prepare a hydrogel polymer sheet.
  • the polymerized sheet was taken out, cut into a size of 3 cm x 3 cm, chopped using a meat chopper to obtain a crumb 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the crumb was dried in an oven capable of airflow transfer up and down.
  • the hot air of 185 ° C was flowed from the lower side to the upper side for 15 minutes and the lower side was flowed from the upper side to the lower side for 15 minutes.
  • the water content of the dried body was made to be 2% or less. (10% / 75% / 15%) were collected from each sample, and then classified by Amplitute 1.5 mm for 10 minutes (classification mesh combination: # 20-30 / # 30-50 / # 50-100)
  • a polymer having a particle diameter of about 150 m to 850 was obtained by classification, and a base resin powder was obtained in this manner.
  • UV light was irradiated (irradiated amount: 10 mW / cm 2 ) with a UV irradiator for 1 minute while maintaining the polymerization atmosphere temperature at 80 ° C, aging for 2 minutes, A polymer sheet was prepared.
  • the polymerized sheet was taken out and chopped using a meat chopper cut into a size of 3 cm x 3 cm to prepare a crumb. 2019/117541 1 »(: 1 ⁇ ⁇ 2018/015468
  • the crumb was dried in an oven capable of airflow transfer up and down.
  • the hot air of 185 ° C was flowed from the lower side to the upper side for 15 minutes and the lower side was flowed from the upper side to the lower side for 15 minutes.
  • the water content of the dried body was made to be 2% or less. and then, 10 minutes classified as Amplitute 1.5 mm pulverized to (classification mesh combination: # 20-30 / 0 # 3 50 / # 50-100) were each classified min (10% / 75% / 15 %) was collected and classified to obtain a polymer having a particle diameter of about 150 pm to 850.
  • the base resin powder was obtained in this manner.
  • the base resin thus prepared was mixed with 7.6 parts by weight of water, 7.6 parts by weight of methanol, 0.075 part by weight of ethylene glycol diglycidyl ether (EX-810), sodium metabisulfite, 0.03 part by weight of aluminum sulfate 18, 0.1 part by weight of aluminum sulfate 18 hydrate (Al-S) and 0.03 part by weight of aluminum oxide (Alu 130) were uniformly mixed and then subjected to surface crosslinking reaction at 140 ° C for 35 minutes After the completion of the surface treatment, a sieve was used to average
  • the superabsorbent resin W 0 ( g) (about 0.2 g) was uniformly put in an envelope made of a nonwoven fabric and sealed, followed by immersion 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. Also, after the same operation was performed without using a resin, the mass Wg at that time was measured. Using the obtained masses, CRC (g / g) was calculated according to the following equation.
  • a 400 mesh wire mesh made of stainless steel was mounted on a cylindrical bottom of a plastic having an inner diameter of 60 mm.
  • the piston capable of uniformly applying a load of 0.7 psi uniformly over the superabsorbent resin W 0 ( g) (0.9 grains) on the wire net under conditions of room temperature and humidity of 50% is slightly smaller than the outer diameter of 60 mm.
  • the inner wall of the cylinder was free from cracks and the up and down movement was not disturbed, and the weight W 3 ( g) of the apparatus was measured.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside a Petro dish having a diameter of 150 mm and a physiological saline solution composed of 0.9% by weight sodium chloride was made to have the same level as the upper surface of the glass filter. And a filter paper having a diameter of 90 mm was placed thereon.
  • the measuring device was placed on a filter paper, and the solution was absorbed under a load for 1 hour. After one hour, the measuring device was lifted and its weight W 4 ( g) was measured.
  • the pressure absorption capacity (g / g) was calculated by using the obtained masses according to the following equation. .
  • AUP (g / g) [ W 4 (g) - W 3 (g)] / W 0 (g)
  • the liquid permeability measuring device is a chromatography tube having an inner diameter of 20 mm and a glass filter at the lower end. Lines were indicated on the liquid surface of 20 ml and 40 ml with the piston in the chromatographic tube. Thereafter, water was added in an amount of about 10 ml to prevent air bubbles between the lower glass filter and the cock of the chromatography tube, and the mixture was washed 2-3 times with brine and filled with 0.9% brine to a volume of 40 ml or more. Put the piston into the chromatography tube and open the lower valve to record the time (in millimeters) of reducing the liquid level from 40 ml to the 20 ml marking line.
  • the vortex time was measured in the first place according to the method described in International Patent Application No. 1987-003208.
  • Examples 1 to 5 of the present invention all exhibited excellent absorption rate and liquid permeability, and it was confirmed that the rewetting amount with respect to the tap water was very small under pressureless pressure and pressure, showing improved rewetting characteristics .

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un polymère superabsorbant et son procédé de préparation. La présente invention permet de fournir un polymère superabsorbant dans lequel un matériau hydrophobe ayant un HLB situé dans la plage allant de 0 à 6 et un agent de réticulation de surface sont mélangés dans une résine de base préparée en présence de silice dispersible dans l'eau, ce qui permet d'obtenir des caractéristiques de remouillage et une perméabilité améliorées par modification de surface de la résine de base.
PCT/KR2018/015468 2017-12-11 2018-12-07 Polymère superabsorbant et son procédé de préparation Ceased WO2019117541A1 (fr)

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CN201880078532.3A CN111433261B (zh) 2017-12-11 2018-12-07 超吸收性聚合物组合物及其制备方法
US16/771,479 US11633719B2 (en) 2017-12-11 2018-12-07 Superabsorbent polymer composition and method for preparing the same
JP2020530506A JP7038825B2 (ja) 2017-12-11 2018-12-07 高吸水性樹脂およびその製造方法
EP18887781.5A EP3708606A4 (fr) 2017-12-11 2018-12-07 Polymère superabsorbant et son procédé de préparation

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US11613591B2 (en) 2019-09-18 2023-03-28 Lg Chem, Ltd. Method for preparing super absorbent polymer
CN116057112A (zh) * 2020-12-18 2023-05-02 株式会社Lg化学 超吸收性聚合物及其制备方法
CN116438226A (zh) * 2020-12-18 2023-07-14 株式会社Lg化学 制备超吸收性聚合物的方法
JP2023540592A (ja) * 2020-12-18 2023-09-25 エルジー・ケム・リミテッド 高吸水性樹脂の製造方法
EP4186945A4 (fr) * 2020-12-18 2024-02-14 Lg Chem, Ltd. Polymère super absorbant et son procédé de préparation

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US11613591B2 (en) 2019-09-18 2023-03-28 Lg Chem, Ltd. Method for preparing super absorbent polymer
US12264211B2 (en) 2019-09-18 2025-04-01 Lg Chem, Ltd. Method for preparing super absorbent polymer
EP4190842A4 (fr) * 2020-12-18 2024-02-14 Lg Chem, Ltd. Procédé de préparation d'un polymère superabsorbant
EP4186945A4 (fr) * 2020-12-18 2024-02-14 Lg Chem, Ltd. Polymère super absorbant et son procédé de préparation
JP2023540592A (ja) * 2020-12-18 2023-09-25 エルジー・ケム・リミテッド 高吸水性樹脂の製造方法
JP2023540766A (ja) * 2020-12-18 2023-09-26 エルジー・ケム・リミテッド 高吸水性樹脂およびその製造方法
US20230347317A1 (en) * 2020-12-18 2023-11-02 Lg Chem, Ltd. Method for Preparing Super Absorbent Polymer
EP4186944A4 (fr) * 2020-12-18 2024-02-14 Lg Chem, Ltd. Procédé de préparation d'un polymère superabsorbant
CN116438226A (zh) * 2020-12-18 2023-07-14 株式会社Lg化学 制备超吸收性聚合物的方法
JP2023540290A (ja) * 2020-12-18 2023-09-22 エルジー・ケム・リミテッド 高吸水性樹脂の製造方法
EP4190843A4 (fr) * 2020-12-18 2024-02-21 Lg Chem, Ltd. Polymère superabsorbant et son procédé de préparation
JP7475771B2 (ja) 2020-12-18 2024-04-30 エルジー・ケム・リミテッド 高吸水性樹脂およびその製造方法
JP7520450B2 (ja) 2020-12-18 2024-07-23 エルジー・ケム・リミテッド 高吸水性樹脂の製造方法
JP7578325B2 (ja) 2020-12-18 2024-11-06 エルジー・ケム・リミテッド 高吸水性樹脂の製造方法
CN116057112A (zh) * 2020-12-18 2023-05-02 株式会社Lg化学 超吸收性聚合物及其制备方法
CN116057112B (zh) * 2020-12-18 2025-08-05 株式会社Lg化学 超吸收性聚合物及其制备方法
US12516161B2 (en) 2020-12-18 2026-01-06 Lg Chem, Ltd. Super absorbent polymer and preparation method thereof
US12516160B2 (en) 2020-12-18 2026-01-06 Lg Chem, Ltd. Method for preparing super absorbent polymer

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