WO2019117511A1 - Polymère superabsorbant et son procédé de préparation - Google Patents

Polymère superabsorbant et son procédé de préparation Download PDF

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Publication number
WO2019117511A1
WO2019117511A1 PCT/KR2018/014840 KR2018014840W WO2019117511A1 WO 2019117511 A1 WO2019117511 A1 WO 2019117511A1 KR 2018014840 W KR2018014840 W KR 2018014840W WO 2019117511 A1 WO2019117511 A1 WO 2019117511A1
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Prior art keywords
resin
water
weight
polymer
superabsorbent resin
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PCT/KR2018/014840
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English (en)
Korean (ko)
Inventor
허영재
남대우
박보희
허성범
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180148009A external-priority patent/KR102568226B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201880078011.8A priority Critical patent/CN111448241B/zh
Priority to JP2020528394A priority patent/JP7247187B2/ja
Priority to EP18888466.2A priority patent/EP3705510A4/fr
Priority to US16/768,981 priority patent/US11931720B2/en
Publication of WO2019117511A1 publication Critical patent/WO2019117511A1/fr

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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
    • 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
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • 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
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/10—Esters; Ether-esters
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings

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 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
  • pressure may be applied to sanitary materials such as diapers and sanitary napkins by the weight of the user.
  • a superabsorbent resin applied to a sanitary material such as a diaper or sanitary napkin absorbs a liquid
  • Urine A phenomenon may occur.
  • Step 2 To the base resin, (Step 2) of a hydrophobic substance and an epoxy-based surface cross-linking agent;
  • step 3 Performing the surface modification to the base resin by raising the mixture of step 2 (step 3); And a method of producing the superabsorbent resin.
  • 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 is formed on the particle surface of the base resin and the cross-linking polymer is additionally crosslinked via an epoxy-based surface cross-linking agent, and the surface modification layer comprises a hydrophobic substance having a B- Thereby providing a superabsorbent resin.
  • a method of manufacturing a superabsorbent resin according to an embodiment of the present invention includes:
  • Step 1 of preparing a base resin having an acidic group and at least a part of which is neutralized, and a base resin crosslinked and polymerized with an acrylic acid-based monomer and an internal cross-linking agent;
  • step 2 Mixing the base resin with a hydrophobic substance having an HLB of not less than 0 and not more than 6, and an epoxy-based surface cross-linking agent (step 2);
  • step 3 Performing the surface modification to the base resin by raising the mixture of step 2 (step 3);
  • base resin or “base resin powder” refers to a product obtained by drying and pulverizing a polymer obtained by polymerizing a water-soluble ethylenically unsaturated monomer to form particles or powder knowledge (1) Quot; means a polymer that has not undergone surface modification or surface cross-linking steps.
  • 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 Reabsorption of urine absorbed in the superabsorbent resin again) and urine And thus the present invention has been accomplished.
  • the monomer composition which is a raw material of the superabsorbent resin, is a monomer composition comprising an acrylic acid-based monomer having an acidic group and at least a part of the acidic groups neutralized, an internal crosslinking agent and a polymerization initiator Polymerized to obtain a hydrogel polymer, which is then 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, divalent metal salts, ammonium salts and organic amine salts.
  • the acrylic acid-based monomer may have an acidic group and at least a part of the acidic group may be neutralized .
  • sodium hydroxide to the above monomers, potassium hydroxide, may be used that was partially neutralized with an alkali substance such as ammonium hydroxide.
  • 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 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 a-aminoketone may be used.
  • acylphosphine commercial liicirin TPO that is, 2, 4, 6, which-trimethyl-benzoyl-trimethyl phosphine oxide (2, 4 ⁇ , 6- trimethyl-benzoyl-trimethyl phosphine oxide) available
  • photoinitiators are well described in Reinhold Schwalm, UV Coatings: Basics, Recent Developments and New Applications (Elsevier 2007), p. 15, and are not limited to the above examples.
  • the concentration of the photopolymerization initiator is too low, the polymerization rate may be slowed. If the concentration of the photopolymerization initiator is excessively high, the concentration of the photopolymerization initiator may be lowered The molecular weight may be small and the physical properties may be 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 C> 8), potassium persulfate (K 2 S 2 O 8), ammonium persulfate (NH 2 4) 2 S 2 0 g).
  • azo initiators include 2, 2-azobis- (2-amidinopropane) dihydrochloride ( 2 ,
  • 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 is for crosslinking the interior of the polymerized polymer of the acrylic acid-based monomer, and is distinguished from the surface cross-linking agent for cross-linking the surface of the polymer.
  • the internal crosslinking agent examples include N, N'-methylenebisacrylamide, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di Butylene diol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, nucleic acid diol di (meth) acrylate, Acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri Styrene tetraacrylate, triallyl amine, Ethylene glycol diglycidyl may be used at least one member selected from ether, propylene glycol, the group consisting of glycerin, and ethylene
  • Such an internal crosslinking agent may be included at a concentration of about 0.01 to about 1.0 wt% based on the monomer composition to crosslink the polymerized polymer.
  • 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.
  • the above-mentioned acrylic acid-based monomer having an acidic group and at least part of the acidic group being neutralized, a photopolymerization initiator, a thermal polymerization initiator, an internal cross- 2019/117511 1 »(: 1 ⁇ 1 ⁇ 2018/014840
  • the same raw materials 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 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.
  • 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 largely divided into thermal polymerization and photopolymerization depending on the polymerization energy source.
  • the polymerization can proceed in a reactor having a stirring die such as a kneader (1 1 ⁇ 2 seeds (1) .
  • the polymerization method described above is only one example, and the present invention is not limited to the polymerization method described above.
  • the hydrogel polymer obtained by supplying hot air or heating the reactor to a reactor such as the kneader 10 &lt ; 1 > (1) having an agitating shaft as described above 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 from 2 to 50 ⁇ m can be obtained.
  • the form of the hydrogel polymer which is usually obtained is Gel-like polymer on the sheet having the width of the belt.
  • the thickness of the polymer sheet depends on the concentration and the injection rate of the monomer composition to be injected, but 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%.
  • moisture content means the moisture content of the total functional gelated polymer weight minus the weight of the hydrogel polymer in dry state. Specifically, it is defined as a value calculated by measuring the weight loss due to moisture evaporation in the polymer in the process of raising the temperature of the polymer through infrared heating.
  • the drying condition is a method of raising the temperature from room temperature to about 180 ° C and then keeping it at 180 ° C, and the total drying time is set to 20 minutes including 5 minutes of the temperature raising step, and 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 polymerization, which has not been pulverized or pulverized as described above, wherein the drying temperature of the drying step may be from about 150 to about 250 ° C.
  • the drying temperature is lower than 150 ° C.
  • the drying time is too long and the physical properties of the superabsorbent resin to be finally formed may be deteriorated.
  • the drying temperature exceeds 250 ° C, only the polymer surface is excessively dried, and a fine powder may be generated in a subsequent pulverizing step 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.
  • drying time it may proceed for about 20 to about 90 minutes in consideration of the process efficiency and the like, but is not limited thereto.
  • 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. 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 from about 0.1 to about 10% by weight.
  • the polymer powder obtained after the pulverization step may have a particle diameter of about 150 to about 850 1.
  • the pulverizer used for pulverizing with such a particle size is specifically a pin mill, a hammer mill, a screw mill a screw mill, a roll mill, a disc mill or a jog mill may be used.
  • the present invention is not limited to the above examples.
  • a hydrophobic substance having an HLB of 0 or more and 6 or less, and Epoxy-based surface cross-linking agent is mixed (step 2).
  • a surface cross-linking solution containing a surface cross-linking agent is mixed with a dried and ground polymer, that is, a base resin, and then the surface cross-linking reaction .
  • 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 surface cross-linking agent a compound capable of reacting with a functional group contained in the polymer is used, and examples thereof include polyvalent alcohol compounds, epoxy compounds, polyamine compounds, haloepoxy compounds, condensation products of haloepoxy compounds, oxazoline compounds, Or an alkylene carbonate compound can be used.
  • epoxy-based surface cross-linking agent satisfying these conditions include ethyleneglycol diglycidyl ether, diethyleneglycol diglycidyl ether, triethyleneglycol diglycidyl ether, ether, tetraethyleneglycol diglycidyl ether, glycerin polyglycidyl ether, sorbitol polyglycidyl ether, and the like.
  • the amount of the epoxy-based surface cross-linking agent to be added is not particularly limited, About 0.005 parts by weight or more, or about 0.01 parts by weight or more, or about 0.02 parts by weight or more, about 0.2 parts by weight or less, or about 0.1 parts by weight or less, or 0.05 parts by weight or less, based on the weight of the composition.
  • the content of the epoxy-based surface cross-linking agent is too small, the cross-linking density of the surface cross-linked layer becomes too low to lower the absorption characteristics such as absorbency under pressure and liquid permeability. If too much is used, The re-wetting property may be deteriorated.
  • the epoxy-based surface cross-linking agent When the epoxy-based surface cross-linking agent is added, water may be further mixed together and added in the form of a surface cross-linking solution.
  • water When water is added, there is an advantage that the surface cross-linking 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-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.
  • the pressure absorption ability and the permeability can be improved by the surface cross-linking reaction, but the re-wetting property needs to be further supplemented.
  • the hydrophilic material can be mixed with the base resin to improve the re-wetting property before the surface cross-linking reaction is performed by mixing the surface cross-linking agent with the base resin.
  • the absorption rate and the liquid permeability can be further improved as compared with a resin not using a hydrophobic substance.
  • the hydrophobic substance has a HLB lower limit value of 0 or more, or 1 or more, or 2 Or less, and 6 or less, or 5 or less, or 5.5 or less in the upper limit value.
  • a material having a melting point lower than the surface cross-linking reaction temperature may be used.
  • Hydrophobic materials that can be used include, for example, glyceryl stearate, glycol stearate, magnesium stearate, glyceryl laurate, sorbitan stearate, stearate, sorbitan trioleate, or PEG-4 dilaurate.
  • glyceryl stearate or glyceryl laurate may be preferably used.
  • the present invention is not limited thereto.
  • the hydrophobic substance is distributed in the surface-modified layer of the surface of the base resin to prevent the swollen resin particles from agglomerating or agglomerating due to the increased pressure during the swelling of the high- 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 based on 100 parts by weight of the base resin,
  • the rewet property may be insufficient, If the amount is more than the weight part, the base resin and the hydrophobic substance may be separated from each other, and there may be a problem that the rewetting is not improved or impurities may be present.
  • 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 with the base resin by dry mixing before mixing the surface cross-linking solution containing the epoxy surface cross-linking agent, or by dispersing the surface cross-linking agent together with the surface cross- 2019/117511 1 »(: 1 ⁇ 1 ⁇ 2018/014840
  • the hydrophobic substance may be heated to a melting point or higher and mixed in a solution state.
  • a surface modification step is performed on the base resin by heating the mixture of the base resin and the epoxy surface cross-linking agent (step 3).
  • the surface modification step may be performed at a temperature of from about 120 to about 190 (preferably, from about 130 to about 1801: about 10 to about 90 minutes, preferably from about 20 to about
  • 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 superabsorbent resin produced by the production method of the present invention can have improved rewet characteristics and initial absorption rate without deteriorating physical properties such as water solubility and pressure absorption ability as the surface modifying layer.
  • a resin composition comprising: a base resin comprising a cross-linked polymer wherein at least a part of an acidic group is neutralized with an acrylic acid-based monomer; And a surface modification layer formed on the particle surface of the base resin, wherein the cross-linking polymer is additionally crosslinked via a surface cross-linking agent, By weight or more and not more than 6% by weight, to provide.
  • the superabsorbent resin has a CRC of at least about 28 g / g, or at least about 29 g / g, or at least about 30 g / g, and at least about 40 g / g of CRC 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 0.3 g / g or more, about 23 g / g or about 25 g / g or more, and about 0.3 g / 37 g / g or less, or about 35 g / g or less, or about 32 g / g or less.
  • AUP pressure absorption capacity
  • the aqueous resin may have a yortex time of 40 seconds or less, or 35 seconds or less, or about 30 seconds or less, or about 28 seconds or less.
  • the lower the absorbing rate, the better the lowering of the absorbing rate is theoretically 0 seconds, for example about 5 seconds or more, about 10 seconds or more, or about 12 seconds or more.
  • the absorption rate refers to a time (unit: second) in which the vortex of the liquid disappears due to the rapid top water when the superabsorbent resin is added to the physiological saline solution and stirred.
  • the time is short, Can be seen to have a fast initial absorption rate.
  • the superabsorbent resin may have a permeability (unit: second) measured according to the following formula 1: about 35 seconds or less, about 30 seconds or less, or about 27 seconds or less.
  • the liquid permeability is better as the value is smaller, and the theoretical lower limit value may be 0 seconds, for example, 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.
  • the superabsorbent resin is immersed in water of 100 ⁇
  • Water-repellent water-repellency water-repellency of 2.0 ⁇ or less, 1.5 ⁇ or less, or 1.4 ⁇ or less, or 1.3 or less.
  • the weight of the water is excellent as the value is small and theoretically the lower limit is 3 ⁇ 4, ⁇ or more, or 0.3 ⁇ or more, or 0.5 ⁇ or more.
  • the tap water used in the re-wetting property evaluation has an electrical conductivity of 170 -
  • 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.
  • the obtained gel-like polymer functions 21111x1 * 2_ and then ground to a size, followed seuteinreseugwa the resulting gel-like resin having a pore size of 600 _ place expanding 30 111 111 thickness on the gauze 1801: and then dried for 30 minutes in a hot-air oven.
  • the dry polymer thus obtained was pulverized using a pulverizer, Classified into a standard standard network
  • a base resin having a particle size of 150 to 850_ was obtained.
  • glyceryl stearate (1 part by 3.8 parts) was mixed with 100 parts by weight of the base resin, and then 0.02 part by weight of ethylene glycol diglycidyl ether, 0.01 part by weight of glycerol polyglycidyl ether, 0.025 part by weight of polyethylene glycol, and 0.2 part by weight of aluminum sulfate was injected into a container made of a stirrer and a double jacket, and the surface cross-linking reaction was carried out at 140 ° C for 40 minutes. Classifying the powder after the surface treatment standard sieve mesh of ASTM standard, and having a particle size of 150 to 850 Thyssen 1 to obtain a water-absorbent resin powder. Then, 0.1 part by weight of silica was dry-mixed with 100 parts by weight of the surface-treated superabsorbent resin to obtain a final high-water absorbent resin product.
  • the resultant gel-like polymer was pulverized to a size of 21111x1 * 2_, and then the resulting gel-like resin was spread on a stainless steel wire gauze having a pore size of 600 g and then dried in a hot air oven for 180 minutes.
  • the dried polymer thus obtained was pulverized using a pulverizer, and classified with a standard mesh of Show 811 to obtain a base resin having a particle size of 150 to 850_.
  • glyceryl stearate And 0.075 part by weight of a surfactant were dry mixed, and then 0.02 part by weight of ethylene glycol diglycidyl ether, 0.01 part by weight of glycerol polyglycidyl ether, 8 parts by weight of water, 0.025 part by weight of polyethylene glycol and 0.2 part by weight of aluminum sulfate, The solution was sprayed, mixed and placed in a container made of a stirrer and a double jacket, and the surface cross-linking reaction was carried out at 1401: for 40 minutes. Then, the surface-treated powder To obtain a superabsorbent resin powder having a particle size of 150 to 850_. Then, 0.1 part by weight of silica was dry-mixed with 100 parts by weight of the surface-treated superabsorbent resin to obtain a final high-water absorbent resin product.
  • a stirrer, a nitrogen injector, acrylate, 518 the third glass container equipped with a thermometer 3 ⁇ 4 polyethylene glycol diacrylate (1> 01 61; 11> 46116 ⁇ ⁇ 01 (400)) 3.3 ⁇ 4 and diphenyl (2,4, 6- Trimethylbenzoyl) -phosphine oxide was added and dissolved.
  • a solution of 24.5% sodium hydroxide solution (822.2) was added, and nitrogen was continuously added to prepare an aqueous solution of a water-soluble unsaturated monomer.
  • the water-soluble unsaturated monomer aqueous solution was cooled to 40 ° C.
  • This aqueous solution (50/4) was applied to a container made of stainless steel having a width of 250 111111 , a length of 250_, a height of 3 Polymerization was carried out to obtain a hydrogel polymer.
  • the resultant hydrogel polymer was pulverized to a size of 2 * 2111111, 2019/117511 1 »(: 1 ⁇ 1 ⁇ 2018/014840
  • hydrogel polymer Irradiated with ultraviolet rays (dose: 10111 ⁇ 7011 2 ) Polymerization was carried out to obtain a hydrogel polymer.
  • the resultant hydrogel polymer was pulverized to a size of 2 * 2111111, and then the resulting gel resin was spread on a stainless wire gauze having a pore size of 600 mm to a thickness of about 30 ⁇ and dried in a 180 hot air oven for 30 minutes.
  • the dried polymer thus obtained was pulverized using a pulverizer and classified with a standard mesh of ASTM standard to obtain a base resin having a particle size of 150 to 850_.
  • a surface cross-linking solution containing 0.01 part by weight of ether, 8 parts by weight of water, 0.025 part by weight of polyethylene glycol and 0.2 part by weight of aluminum sulfate was mixed and sprayed in a container made of a stirrer and a double jacket, The reaction proceeded. Thereafter, the surface-treated powder was classified into a standard mesh of Show Standard to obtain a superabsorbent resin powder having a particle size of 150 to 850 / L. Then, 0.1 part by weight of silica was dry-mixed with 100 parts by weight of the surface-treated superabsorbent resin to obtain a final high-water absorbent resin product.
  • Acrylic acid 518 and polyethyleneglycol diacrylate 3.2 out of diphenyl (2, 4, 6-trimethylbenzoyl) - (meth) acrylate were added to three glass containers equipped with a stirrer, a nitrogen introducer and a thermometer.
  • phosphine oxide was dissolved by the addition of 0.04 ⁇ , 24.5% sodium hydroxide solution, 822.2 is a water-soluble unsaturated monomer aqueous solution with added nitrogen is continuously added was prepared.
  • the water-soluble unsaturated monomer aqueous solution was cooled to 40 ° C.
  • the aqueous solution 500 has a width 250 111 111, 250 111 111 vertically, the height 30Inm was added to the container of the stacking Nu-less material is irradiated with ultraviolet rays (dose: wave /! 2 ) Polymerization was carried out to obtain a hydrogel polymer. After the resulting hydrogel polymer was pulverized to a size of 2 111111 * 2111111, the obtained gel resin was spread on a stainless steel wire gauze having a pore size of 600 g and then dried in a hot air oven for 180 minutes. The dry polymer thus obtained was pulverized using a pulverizer and classified with a standard mesh of ASTM standard to obtain a base resin having a particle size of 150 to 850 / L.
  • glyceryl laurate (1 part by weight, 5.2 parts by weight) was added to 100 parts by weight of the base resin. Then, 0.02 part by weight of ethylene glycol diglycidyl ether, 0.01 part by weight of glycerol polyglycidyl ether, , Polyethylene glycol
  • a superabsorbent resin was prepared in the same manner as in Example 1, except that the content of glyceryl stearate was changed to 0.15 parts by weight in Example 1.
  • Example 7
  • a superabsorbent resin was prepared in the same manner as in Example 1, except that the content of glyceryl stearate was changed to 0.5 parts by weight. Comparative Example 1
  • Acrylic acid 518 and polyethylene glycol diacrylate (1 5 01 > 1 ⁇ 2 1 1 6116 ⁇ ⁇ 01 (400)) were added to a 31 ⁇ glass vessel equipped with a stirrer, a nitrogen introducer and a thermometer.
  • 3.2. trimethyl benzoyl) phosphine oxide was dissolved by the addition of 0.04 ⁇ , 24.5% sodium hydroxide solution, 822.2 aqueous unsaturated monomer solution was added to the ⁇ input of nitrogen was continuously prepared.
  • the water-soluble unsaturated monomer aqueous solution was cooled to 40 ° C.
  • silica 0.1 part by weight was mixed with 100 parts by weight of the base resin, and then 0.02 part by weight of ethylene glycol diglycidyl ether, 8 parts by weight of water and 0.2 part by weight of aluminum sulfate was injected and mixed, and a 140 ° double put in a jacket made of a container (: from 40 minutes to proceed with the surface cross-linking reaction and the water-absorbent resin powder to a subsequent surface-treated powder having the particle size of the classified to 150 to 850 Thyssen first body standard web of ASTM standards ≪ / RTI > Then the surface 2019/117511 1 »(: 1 ⁇ 1 ⁇ 2018/014840
  • the solution of 50 (250 to 111111 3 ⁇ 4 horizontal, vertical 250 111 111, was added to a stainless steel container of a height 3 ( ⁇ wave 1 is irradiated with ultraviolet rays (dose: 10 to 111 ⁇ ⁇ / 0 11 2) Polymerization was carried out to obtain a hydrogel polymer.
  • the resultant gel-like polymer was pulverized to a size of 2 mm, and then the obtained gel-like resin was spread on a stainless steel wire gauze having a pore size of 600 mm and a thickness of about 30 mm and dried in a 180 l hot air oven for 30 minutes.
  • the dry polymer thus obtained was pulverized using a pulverizer, and classified with a standard mesh of Show Standard to obtain a base resin having a particle size of 150 to 850_.
  • Example (400) ⁇ 1 071) 3.2 was prepared by dissolving 0.04 ⁇ of diphenyl (2,4,6-trimethylbenzoyl) after that, by the addition of 24.5% sodium hydroxide solution 822.2 8 while nitrogen is continuously introduced to prepare an aqueous solution of water-soluble unsaturated monomer.
  • the water-soluble unsaturated monomer aqueous solution was cooled to 40 ° C.
  • glyceryl stearate 0.025 part by weight was dry mixed, and then a surface cross-linking solution containing 0.03 part by weight of ethylene carbonate, 8 parts by weight of water, 0.025 part by weight of polyethylene glycol and 0.2 part by weight of aluminum sulfate was injected and mixed.
  • the surface cross - linking reaction was carried out at 1401: for 40 minutes.
  • the surface-treated powder was classified into a standard mesh having a standard of show standard to obtain a superabsorbent resin powder having a particle size of 150 to 850 sun !.
  • 0.1 part by weight of silica was dry-mixed with 100 parts by weight of the surface-treated superabsorbent resin to obtain a final highly hydrous resin product.
  • the tap water used in the re-wetting property evaluation described below has an electrical conductivity of from 170 to 180, as measured by Orion Star A222 (company: Thermo Scientific) pS / cm was used.
  • the retention capacity of each resin by the zero-load capacity was measured according to EDANA WSP 241.3.
  • the superabsorbent resin W 0 ( g) (about 0. 3) was uniformly put in an envelope made of a nonwoven fabric and 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. Also, after the same operation was performed without using a resin, the mass WJg 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. Piston that is under conditions of normal temperature and humidity of 50%, and on the wire evenly spraying the water-absorbing resin W 0 (g) (0.90, even more give a load of 0.3 psi on it is slightly smaller cylinder than an outer diameter 60 mm And the upper and lower movements were not disturbed at this time, the weight W 3 ( g) of the device was immediately given.
  • 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 1 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 formula. &Quot; (2) "
  • AUP (g / g) [ W 4 (g) - W 3 (g)] AV 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.
  • Comparative Example 3 in which a non-epoxy surface cross-linking agent was used did not have satisfactory transparency and remanence 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)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un polymère superabsorbant et son procédé de préparation. La présente invention peut fournir un polymère superabsorbant dans lequel un agent de réticulation à surface de base époxy et un matériau hydrophobe ayant un indice HLB de 0 à 6 sont mélangés dans une résine de base, ayant ainsi des caractéristiques améliorées de remouillage et une perméabilité par la modification de surface de la résine de base.
PCT/KR2018/014840 2017-12-11 2018-11-28 Polymère superabsorbant et son procédé de préparation WO2019117511A1 (fr)

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CN201880078011.8A CN111448241B (zh) 2017-12-11 2018-11-28 超吸收性聚合物组合物及其制备方法
JP2020528394A JP7247187B2 (ja) 2017-12-11 2018-11-28 高吸水性樹脂およびその製造方法
EP18888466.2A EP3705510A4 (fr) 2017-12-11 2018-11-28 Polymère superabsorbant et son procédé de préparation
US16/768,981 US11931720B2 (en) 2017-12-11 2018-11-28 Superabsorbent polymer composition and method for preparing the same

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Cited By (1)

* Cited by examiner, † Cited by third party
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EP3885396A4 (fr) * 2019-09-18 2022-02-16 LG Chem, Ltd. Polymère superabsorbant et son procédé de préparation

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3885396A4 (fr) * 2019-09-18 2022-02-16 LG Chem, Ltd. Polymère superabsorbant et son procédé de préparation
US12071523B2 (en) 2019-09-18 2024-08-27 Lg Chem, Ltd. Superabsorbent polymer and preparation method for the same

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