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WO2019083211A9 - Procédé de préparation d'un polymère superabsorbant - Google Patents

Procédé de préparation d'un polymère superabsorbant Download PDF

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Publication number
WO2019083211A9
WO2019083211A9 PCT/KR2018/012127 KR2018012127W WO2019083211A9 WO 2019083211 A9 WO2019083211 A9 WO 2019083211A9 KR 2018012127 W KR2018012127 W KR 2018012127W WO 2019083211 A9 WO2019083211 A9 WO 2019083211A9
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Prior art keywords
polymer
monomer
super absorbent
crosslinking
solution
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PCT/KR2018/012127
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English (en)
Korean (ko)
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WO2019083211A1 (fr
Inventor
김무곤
이상기
남혜미
이창훈
김태윤
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LG Chem Ltd
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LG Chem Ltd
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Publication date
Priority claimed from KR1020180121994A external-priority patent/KR102566942B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP18871353.1A priority Critical patent/EP3546503B1/fr
Priority to CN201880012410.4A priority patent/CN110312755B/zh
Priority to US16/474,850 priority patent/US11407848B2/en
Priority to JP2019529927A priority patent/JP6806903B2/ja
Publication of WO2019083211A1 publication Critical patent/WO2019083211A1/fr
Publication of WO2019083211A9 publication Critical patent/WO2019083211A9/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention provides a method for producing a superabsorbent polymer, which enables the production of a superabsorbent polymer that can exhibit an excellent absorption rate, including a uniform porous structure, through a simple and economical process.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight. Each developer has a super absorbent material (AM) and an absorbent gel material (AGM). They are named differently. As the above-mentioned high-knit resin is practically used as a sanitary ware, it is currently used in sanitary products such as diapers for children, horticultural soil repair agent, civil engineering, building index material, seedling sheet, freshness keeping agent in the field of food distribution, and It is widely used as a material for steaming.
  • sanitary products such as diapers for children, horticultural soil repair agent, civil engineering, building index material, seedling sheet, freshness keeping agent in the field of food distribution, and It is widely used as a material for steaming.
  • the superabsorbent resin basically needs to exhibit high absorption performance and absorption rate.
  • the present invention is to provide a method for producing a high-knit resin, which enables the production of a high-knot resin that can exhibit an excellent absorption rate, including a uniform porous structure through a simple and economic process without using a special additive. .
  • the pulverized polymer is classified into polymer particles having a particle size of at least 10 to 150_, polymer particles having a particle size of 150 to 200; and polymer particles having a particle size of 200 to 850; Base resin with particle diameter 2019/083211 1 »(: 1 ⁇ 1 ⁇ 2018/012127
  • the crosslinking polymerization step there is provided a method for producing a super absorbent polymer, which undergoes foam polymerization in the presence of an anionic surfactant and a polymer particle having a particle size of 10 to 200; obtained in the classification step.
  • a method of preparing a super absorbent polymer according to an embodiment of the present invention will be described in detail.
  • the fine powder obtained in the classification step that is, polymer particles having a particle size of 10 to 200 is used as a kind of blowing agent in the crosslinking polymerization for the preparation of the high-top water-based resin, and together with the anionic surfactant Used as a kind of foam stabilizer.
  • the expansion polymerization was carried out using the fine powder and the anionic surfactant, it was confirmed that uniform pores corresponding to the particle size of the fine powder were stably formed in the base resin powder and the super absorbent polymer obtained through the crosslinking polymerization and subsequent processes.
  • the superabsorbent resin may exhibit an improved absorption rate.
  • the superabsorbent resin particles can exhibit a uniform absorption speed as a whole.
  • porous additives using a fine powder generally obtained in the manufacturing process of the superabsorbent polymer, in particular, the classification process, and anionic surfactant, without expensive additives such as capsule foaming agent, or applying a separate process As the superabsorbent polymer having a stable structure is introduced, the process cost of the superabsorbent polymer as a whole can be greatly reduced, and the superabsorbent polymer having excellent absorption rate can be obtained through a simplified process.
  • the manufacturing method and the super absorbent polymer obtained through the embodiment will be described in more detail.
  • the water-soluble ethylenically unsaturated monomer constituting may be any monomer conventionally used in the preparation of the fine resin.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by the following Chemical Formula 1:
  • IV! 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
  • the monomer may be at least one selected from the group consisting of (meth) acrylic acid, and monovalent (alkali) metal salts, divalent metal salts, ammonium salts and organic amine salts of these acids.
  • (meth) acrylic acid and / or its salt is used as the water-soluble ethylenically unsaturated monomer, it is advantageous to obtain a superabsorbent polymer having improved water absorption.
  • the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, diacryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid or 2- (meth) acrylic acid.
  • the water-soluble ethylenically unsaturated monomer has an acidic group, at least a portion of the acidic group may be neutralized.
  • a partial neutralization of the monomer with an alkaline substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like may be used.
  • the degree of neutralization of the monomer may be 55 to 95 mol%, or 60 to 80 mol%, or 65 to 75 mol%.
  • the range of the degree of neutralization may vary depending on the final physical properties. If the degree of neutralization is too high, the neutralized monomer may precipitate and polymerization may be difficult to proceed smoothly. Properties such as elastic rubber, which are difficult to do, can be exhibited. 2019/083211 1 »(1 ⁇ 1 ⁇ 2018/012127
  • a monomer composition comprising at least a portion of a water-soluble ethylenically unsaturated monomer having a neutralized acidic group as described above may be cross-polymerized.
  • the water-soluble ethylenically unsaturated monomer is as described above.
  • the concentration of the water-soluble ethylenically unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of the polymerization time and the reaction conditions, preferably 20 to 90% by weight, or 40 to 65% by weight. This concentration range may be advantageous to control the grinding efficiency during the grinding of the polymer to be described later, while eliminating the need to remove unreacted monomers after polymerization by using a gel effect phenomenon that occurs in the polymerization reaction of a high concentration aqueous solution. However, when the concentration of the monomer is excessively low, the yield of the super absorbent polymer may be lowered.
  • the concentration of the monomer is too high, a problem may occur in the process, such as when the monomer is partially precipitated or the pulverization efficiency of the polymerized hydrogel polymer is decreased, and the physical properties of the super absorbent polymer may be reduced.
  • the internal crosslinking agent is a 1 ⁇ 1 '-methylenebisacrylamide, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol die ( Meth) acrylate, polypropylene glycol (meth) acrylate, butanediol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, nucleic acid diol di (meth) Acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipent
  • Such internal crosslinking agent may be added at a concentration of about 0.001 to 1% by weight based on the monomer composition.
  • concentration of the internal crosslinking agent when the concentration of the internal crosslinking agent is too low, the absorption rate of the resin may be low and the gel strength may be weak.
  • concentration of the internal crosslinking agent when the concentration of the internal crosslinking agent is too high, the absorption power of the resin may be low, which may not be desirable as an absorber. have.
  • the polymer particles i.e., a uniform porous structure corresponding to the particle size of the fine powder can be introduced into the base resin powder and the super absorbent polymer, and the crosslinking polymerization proceeds properly to exhibit a uniform but improved absorption rate with excellent physical properties.
  • Superabsorbent resins can be obtained.
  • anionic surfactant sodium dodecyl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, dioctyl sodium sulfosuccinate, perfluorooctane sulfonate , perfluorobutane
  • anionic surfactants enable the porous structure to be better formed through the foaming polymerization using the fine powder, and stabilize the porous structure.
  • the superabsorbent resin can exhibit an improved absorption rate.
  • Such anionic surfactant may be used in an amount of 0.002 to 0.05 parts by weight, or 0.005 to 0.02 parts by weight based on 100 parts by weight of the monomer. In this way, a super absorbent polymer having a uniform porous structure can be properly introduced to exhibit an improved absorption rate and suppressed from deterioration of other physical properties can be obtained.
  • the monomer composition for example, the monomer aqueous solution is a monomer, an internal crosslinking agent, polymer particles having a particle diameter of 10 to 200 and anionic as described above
  • the surfactant it may further include one or more additives selected from the group consisting of polyvalent metal salts, photoinitiators, thermal initiators and polyalkylene glycol-based polymers.
  • Such additives may be used to further improve the fluid permeability of the superabsorbent polymer (such as polyvalent metal salts or polyalkylene glycol-based polymers), or facilitate crosslinking polymerization to further improve the physical properties of the superabsorbent polymer.
  • the superabsorbent polymer such as polyvalent metal salts or polyalkylene glycol-based polymers
  • crosslinking polymerization to further improve the physical properties of the superabsorbent polymer.
  • the additive described above may be used in an amount of 2000 ppmw or less, 0 to 2000 ppmw, or 10 to 1000 ppmw, or 50 to 500 ppmw, based on 100 parts by weight of the monomer.
  • the physical properties such as liquid permeability or water absorption performance of the super absorbent polymer can be further improved.
  • polyethylene glycol, polypropylene glycol, or the like can be used as the polyalkylene glycol-based polymer.
  • any of the polymerization initiators generally used in the production of superabsorbent polymers may be used as the photo (polymerization) initiator and / or the thermal (polymerization) initiator.
  • the photo (polymerization) initiator and / or the thermal (polymerization) initiator may be used as the photo (polymerization) initiator and / or the thermal (polymerization) initiator.
  • the photopolymerization method even with the photopolymerization method, As a result, a certain amount of heat is generated and a certain amount of heat is generated according to the progress of the polymerization reaction, which is an exothermic reaction.
  • the thermal (polymerization) initiator one or more compounds selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide, and ascorbic acid may be used.
  • the persulfate-based initiators include sodium persulfate (Na 2 S 2 0 8 ), potassium persulfate (K 2 S 2 0 8 ), ammonium persulfate (NH 4 ) 2 S 2 0 8 ) and the like.
  • azo (Azo) -based initiators include 2,2-azobis- (2-idinopropane) dihydrochloride (2,2-azobis (2-amidinopropane) dihydrochloride), 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride (2,2-azobis-
  • photo (polymerization) initiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate,
  • acylphosphine commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used.
  • More photopolymerization initiators are disclosed on page 115 of the Reinhold Schwalm book, "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)".
  • Such an initiator may be added in an amount of 500 ppmw or less, based on 100 parts by weight of the monomer. That is, when the concentration of the polymerization initiator is excessively low, the polymerization rate may be slowed down, and residual monomer may be extracted in a large amount in the final product. Not desirable On the contrary, when the concentration of the polymerization initiator is higher than the above range, the polymer chain constituting the network is shortened, so that the physical properties of the resin may be lowered such that the content of the water-soluble component is increased and the pressure absorption ability is lowered.
  • the monomer composition may further include additives such as thickeners, plasticizers, preservative stabilizers, antioxidants, if necessary.
  • the monomer composition may be prepared in the form of a solution in which the raw materials such as the monomers described above are dissolved in a solvent.
  • any solvent that can be used may be used without limitation as long as it can dissolve the above-described raw materials.
  • the solvent includes water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Methyl ethyl ketone, acetone, methyl amyl ketone, cyclonucleanone, cyclopentanone, 2019/083211 1 »(: 1 ⁇ 1 ⁇ 2018/012127
  • Diethylene glycol monomethyl ether diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate, Acetamide, or mixtures thereof may be used.
  • the monomer composition having the form of the above-described aqueous solution or the like can be controlled to have an initial temperature of 30 to 60 (:), and light energy or heat energy can be added thereto to form a crosslinking polymerization.
  • the formation of a functional gel polymer through crosslinking polymerization of such a monomer composition can be carried out by a conventional polymerization method, and the process is not particularly limited.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the type of polymerization energy source, in the case of the thermal polymerization may be carried out in a reactor having a stirring axis such as kneader kneader), photopolymerization If proceeding, it may be carried out in a reactor equipped with a movable conveyor belt.
  • the hydrogel polymer may be obtained by adding the monomer composition to a reactor such as a kneader equipped with a stirring shaft and supplying hot air thereto or by heating the reactor to thermally polymerize it.
  • a reactor such as a kneader equipped with a stirring shaft and supplying hot air thereto or by heating the reactor to thermally polymerize it.
  • the hydrous gel polymer discharged to the reactor outlet according to the shape of the stirring shaft provided in the reactor may be obtained in the particles of several millimeters to several centimeters .
  • the hydrous gel polymer obtained may be obtained in various forms depending on the concentration and injection speed of the monomer composition to be injected, and a hydrogel polymer having a particle size of 2 to 50 micrometers (usually a weight average) may be obtained.
  • the photopolymerization of the monomer composition in the reactor equipped with a mobile-functional conveyor belt can be obtained a hydrous gel polymer in the form of a sheet.
  • the thickness of the sheet may vary depending on the concentration and the injection speed of the monomer composition to be injected, in order to ensure the production rate and the like while the entire sheet is polymerized evenly , is usually adjusted to a thickness of 0.5 to 5 ( ⁇ It is preferable.
  • the normal water content of the hydrogel polymer obtained by the above method may be 40 to 80% by weight.
  • water content refers to the amount of water occupied in relation to the total weight of the hydrous gel polymer, which is dried at the weight of the hydrogel polymer. Means the subtracted weight of the polymer in the 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 and drying. At this time, the drying conditions are raised to a temperature of about 180 ° C at room temperature and then maintained at 18 CTC, the total drying time is set to 20 minutes, including 5 minutes of temperature rise step, the moisture content is measured.
  • the step of drying and pulverizing the hydrogel polymer can be carried out prior to such drying. Prior to such drying, the step of first roughly grinding the hydrous gel polymer to prepare a functional gel polymer having a small average particle diameter may be performed.
  • the hydrogel polymer can be ground from 1.0 mm to 2.0 mm.
  • the pulverizer used in the coarse pulverization is not limited, but specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill Selected from the group of grinding machines consisting of a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, and a disc cutter. It may include, but is not limited to the above examples.
  • coarse grinding may be performed in a plurality of times depending on the size of the particle diameter for the efficiency of coarse grinding.
  • the hydrogel polymer may be first coarsely pulverized with an average particle diameter of about 10 mm, secondly coarsely pulverized with an average particle diameter of about 5 mm, and then tertiary coarsely pulverized with the aforementioned particle diameter.
  • the hydrogel polymer may be dried.
  • a drying temperature may be 50 to 250 ° C. If the drying temperature is less than 50 ° C, the drying time may be too long, and the properties of the superabsorbent polymer to be finally formed may be lowered, and the drying temperature may exceed 250 ° C. In this case, only the surface of the polymer may be excessively dried, fine powder may be generated, and the physical properties of the superabsorbent polymer to be finally formed may be lowered. More preferably, the drying may be carried out at a temperature of 150 to 200 ° C, more preferably at a temperature of 160 to 19CTC. On the other hand, the drying time can be carried out for 20 minutes to 15 hours in consideration of the process efficiency, but is not limited thereto.
  • the drying step can be carried out by hot wind supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the water content of the polymer after such a drying step may be 0.05 to 10% by weight.
  • the polymer powder obtained after the grinding step may have a particle diameter of 150 to 850.
  • the grinder used to grind to such a particle size is specifically, a ball mill, a pin mill, a hammer mill, a screw mill, a roll mill, a disk A mill or jog mill may be used, but is not limited to the example described above.
  • a separate process of classifying the polymer powder obtained after grinding according to the particle size may be performed.
  • the pulverized polymer is classified into polymer particles having a particle size of at least 10 to 150 mm 3, polymer particles having a particle size of 150 to 200 / , and polymer particles having a particle size of 200 to 850_. can do.
  • the polymer particles obtained by particle diameter all of the polymer particles having a particle size of 10 to 150 and optionally some of the polymer particles having a particle size of 150 to 200 ash! It can be recycled and used as a kind of blowing agent. As such, it is already possible to provide a super absorbent polymer having a uniform porous structure and a more improved uniform absorption rate as described above.
  • the base having a particle size of 150 to 850 by taking all of the remainder of the remaining polymer particles except for the fine powder, for example, the remainder of the polymer particles having a particle size of 150 to 200, and the polymer particles having a particle size of 200 to 850 n.
  • Resin powder can be formed.
  • This classification step depends on the general method of classifying superabsorbent polymers, 2019/083211 1 »(: 1 ⁇ 1 ⁇ 2018/012127
  • the base resin powder having such a particle diameter that is, a particle diameter of 150 to 850 II, can be commercialized through a surface crosslinking reaction step to be described later.
  • the kind of surface crosslinking agent contained in the surface crosslinking liquid is not particularly limited.
  • the surface crosslinking agent is ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene Carbonate, ethylene glycol, diethylene glycol, propyleneglycol, triethylene glycol, tetraethylene glycol, propane diol, dipropylene glycol, polypropylene glycol, glycerin, polyglycerol, butanediol , heptanediol, nucleic acid diol trimethyl It may be one or more compounds selected from the group consisting of roll propane, pentaerythritol, sorbitol, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, calcium chloride, magnesium
  • the content of the surface cross-linking agent may be appropriately adjusted according to the kind or reaction conditions thereof, and preferably may be adjusted to 0.001 to 5 parts by weight based on 100 parts by weight of the base resin powder.
  • the content of the surface crosslinking agent is too low, the surface crosslinking may not be properly introduced, and the physical properties of the final superabsorbent polymer may be reduced.
  • the surface crosslinking agent is used in an excessively large amount, the absorption power of the super absorbent polymer may be lowered due to excessive surface crosslinking reaction, which is not preferable.
  • the surface cross-linking liquid is water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Methyl ethyl ketone, acetone, methyl amyl ketone, cyclonucleanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, It may further comprise at least one solvent selected from the group consisting of butyrolactone, carbitol, methyl cellosolve acetate and N, N-dimethylacetamide. The solvent may be included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the base resin.
  • the surface crosslinking liquid may further include a thickener.
  • the thickener in may be used at least one selected of the polysaccharide and a hydroxy-containing polymer.
  • a gum-based thickener and a cellulose-based thickener may be used as the polysaccharide.
  • Specific examples of the gum thickeners include xanthan gum, arabic gum, karaya gum, tragacanth gum, ghatti gum and guar gum ( guar gum, locust bean gum, and silium seed gum.
  • cellulose-based thickener examples include hydroxypropylmethyl cellulose, carboxymethyl cellulose, methyl cellulose, Hydroxymethyl cellulose , hydroxyethyl cellulose , hydroxypropyl cellulose , hydroxyethyl methyl cellulose , hydroxymethyl propyl cellulose, hydroxyethyl hydroxypropyl cellulose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose and the like.
  • hydroxy-containing polymers include polyethylene glycol and polyvinyl alcohol.
  • a method of mixing the surface crosslinking solution and the base resin in a reaction tank, a method of spraying a surface crosslinking solution on the base resin, and a crosslinking of the base resin and the surface to a mixer operated continuously A method of continuously supplying and mixing liquids may be used.
  • the surface crosslinking may be performed at a temperature of 100 to 250 C, and may be continuously performed after the drying and pulverizing step proceeded at a relatively high temperature. At this time.
  • the surface crosslinking reaction may be performed for 1 to 120 minutes, or 1 to 100 minutes, or 10 to 60 minutes. That is, in order to induce a minimum surface crosslinking reaction and to prevent the polymer particles from being damaged due to excessive reactions and deteriorating physical properties, the above-described surface crosslinking reaction may be performed.
  • the superabsorbent polymer prepared as described above may have a bulk density of 0.55 to 0.65 g / ml, or 0.57 to 0.64 g / ml as a uniform porous structure is introduced.
  • the measured absorption rate can be improved from 30 seconds to 53 seconds, 33 seconds to 50 seconds, or 35 seconds to 48 seconds.
  • the absorption rate refers to the time at which the liquid vortex disappears due to rapid absorption when the superabsorbent resin is added to the physiological saline solution and is stirred. The method is more specific in the following examples.
  • the superabsorbent polymer has a centrifugal water retention (CRC) of 28 to 35 g / g, or 30 to 33 g / g, measured according to EDANA WSP 241.3, and 0.9 psi measured according to EDANA WSP 242.3. It may exhibit a characteristic that the pressure absorption capacity (AUL) is 16 to 23 g / g, or 17 to 20 g / g. As such, the superabsorbent polymer can maintain the excellent absorption capacity / pressure absorption capacity while exhibiting the improved absorption rate as described above.
  • CRC centrifugal water retention
  • AUL pressure absorption capacity
  • the superabsorbent polymer has an average particle diameter of 300 to 600.
  • the superabsorbent polymer according to the present invention may contain 45 to 85 wt% of a super absorbent polymer having a particle size of 300 to 600 _. Also preferably, 15% by weight or more of the superabsorbent polymer having a particle diameter of 300 or less in the superabsorbent polymer.
  • a super-absorbent resin that can exhibit excellent and overall uniform absorption rate, including a uniform porous structure, through a simple and economical process without using a special additive such as a capsule foaming agent.
  • Example 1 2019/083211 1 » (: 1 ⁇ 1 ⁇ 2018/012127
  • the mixed solution prepared in Step 1 above was placed at 80 ° (inside the tray arc transverse 15 071 X 15 0 installed in a square polymerizer preheated to 3) with a light irradiation apparatus at the top. Poured. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed from the surface after about 20 seconds from the time of light irradiation, and it was confirmed that the polymerization reaction occurred simultaneously with foaming after about 30 seconds from the time of light irradiation. Subsequently, the polymerization reaction was further performed for 2 minutes, and the polymerized sheet was taken out. Cut to size. Then, the cut sheet was made into powder (wife 71
  • a powder (the "My 71
  • the dried powder was pulverized with a grinder and classified to 150 to 850 A base resin having a size was obtained, and the polymer particles of the base resin powder having a particle diameter of 10 to 150_ were recycled and used in Step 1 described above.
  • the base resin 100 prepared in Step 3 was mixed with water 4 ethylene carbonate 1 Aerosil 200 (0 1 200, Fig./011) 0.1 steel and the crosslinking agent solution, and then the surface at 1903 ⁇ 4 for 30 minutes.
  • the crosslinking reaction was carried out.
  • the obtained product was pulverized to obtain a surface-crosslinked superabsorbent polymer having a sieve (with a particle diameter of 150 to 850).
  • 0.1% of Aerosil 200 was added dry to the obtained superabsorbent polymer and mixed in a dry state to prepare a superabsorbent polymer.
  • Example 2
  • the acrylic acid 490 supernatant solution was injected into a 21 volume glass reactor surrounded by a jacket in which a heat medium previously cooled to 25 was circulated. Then, a% caustic soda solution 850 9 (0 solution) was slowly added dropwise to the glass reactor and mixed. After confirming that the temperature of the mixed liquid rose to about 72 kPa by the heat of neutralization, the mixed solution waited for cooling. The degree of neutralization of acrylic acid in the mixed solution thus obtained was about 70 mol%. 25 (5% by weight of acrylic acid) of the fine powder (polymer particles of the base resin powder having a particle size of 10 to 150; It was added to the aqueous monomer solution.
  • the amount of 490 acrylic acid and the above solution was injected into a 21-volume glass reactor surrounded by a jacket through which a heat medium previously cooled to 25 ° was circulated. Then, 24% caustic soda solution 850 9 (0 solution) was slowly added dropwise to the glass reactor and mixed. After confirming that the temperature of the mixed solution rose to about 72 by the heat of neutralization, the mixed solution waited for cooling. The degree of neutralization of acrylic acid in the thus obtained mixed solution was about 70 mol%.
  • ⁇ /) diluted to 2% in water was prepared.
  • step 1 a superabsorbent polymer was prepared in the same manner as in Example 1 except that sodium dodecyl sulfate (80 ( ⁇ ni ⁇ 1 sunniri solution (13-1 solution)) was not used. Comparative Example 3
  • step 1 a superabsorbent polymer was prepared in the same manner as in Example 2 except that sodium dodecyl sulfate (beanie 0
  • the absorption rate of the superabsorbent polymers of Examples and Comparative Examples was measured in seconds according to the method described in International Patent Publication No. 1987-003208.
  • the absorption rate (or vortex time) is put 2 g of a super absorbent resin in 50 ml_ physiological saline of 23 ° C to 24 C, stirring the magnetic bar (diameter 8 mm, length 31.8 mm) at 600 rpm It was calculated by measuring the time in seconds until the vortex disappeared.
  • the 0.9 psi pressurized absorption capacity of each resin was measured according to the EDANA method WSP 242.3.
  • a stainless steel 400 mesh wire was mounted on the bottom of a plastic cylinder having an inner diameter of 25 mm.
  • the absorbent resin Wo (g) (0.16 g) was uniformly sprayed on the wire mesh under conditions of room temperature and 50% humidity.
  • the piston which can give a 0.9 psi more uniform load, is slightly smaller than the outer diameter of 25 mm, is not large with the inner wall of the cylinder, and the up and down movement is not disturbed.
  • the weight W 3 ( g) of the apparatus was measured.
  • a 90 mm diameter and 5 mm thick glass filter was placed inside a 150 mm diameter petri dish, and the physiological saline consisting of 0.9 wt% sodium chloride was brought to the same level as the top surface of the glass filter.
  • One sheet of filter paper having a diameter of 90 mm was placed thereon.
  • the instantaneous device was placed on the filter paper and the liquid was absorbed for 1 hour under load. After 1 hour, the measuring device was lifted up and the weight W 4 ( g) was measured. Using each mass obtained, the pressure absorption capacity (g / g) was computed according to following Formula.
  • AUL (g / g) [W 4 ( g)-W 3 ( g)] / W 0 ( g)
  • the measurement results as described above are shown in Table 1 below. 2019/083211 1 »(: 1/10 ⁇ 018/012127

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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 procédé de préparation d'un polymère superabsorbant permettant, par un procédé simple et économique, la préparation d'un polymère superabsorbant pouvant présenter un excellent taux d'absorption par le fait de comprendre une structure poreuse uniforme. Le procédé de préparation de polymère superabsorbant comprend les étapes consistant à : former un polymère d'hydrogel comprenant un premier polymère réticulé par réalisation d'une polymérisation par réticulation sur un monomère éthyléniquement insaturé soluble dans l'eau présentant des groupes acides dont au moins une partie sont neutralisés, en présence d'un agent de réticulation interne; sécher et pulvériser le polymère d'hydrogel; former une poudre de résine de base présentant un diamètre de 150-850 µm par classification du polymère pulvérisé en particules de polymère présentant un diamètre d'au moins 10-150 µm, en particules de polymère présentant un diamètre de 150-200 µm et en particules de polymère présentant un diamètre de 200-850 µm; et réticuler en surface la poudre de résine de base, dans l'étape de polymérisation par réticulation, une polymérisation par moussage étant effectuée en présence d'un tensioactif anionique et des particules de polymère présentant un diamètre de 10-200 µm, qui sont obtenues dans l'étape de classification.
PCT/KR2018/012127 2017-10-27 2018-10-15 Procédé de préparation d'un polymère superabsorbant Ceased WO2019083211A1 (fr)

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EP18871353.1A EP3546503B1 (fr) 2017-10-27 2018-10-15 Procédé de préparation d'un polymère super absorbant
CN201880012410.4A CN110312755B (zh) 2017-10-27 2018-10-15 超吸收性聚合物的制备方法
US16/474,850 US11407848B2 (en) 2017-10-27 2018-10-15 Method for preparing super absorbent polymer
JP2019529927A JP6806903B2 (ja) 2017-10-27 2018-10-15 高吸水性樹脂の製造方法

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KR1020180121994A KR102566942B1 (ko) 2017-10-27 2018-10-12 고흡수성 수지의 제조 방법
KR10-2018-0121994 2018-10-12

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FR2590501B1 (fr) 1985-11-22 1994-01-14 Beghin Say Sa Composition absorbant les liquides
JP4736316B2 (ja) * 2003-10-21 2011-07-27 Ｄｉｃ株式会社 高吸収性樹脂の製造方法
US7910688B2 (en) * 2008-10-22 2011-03-22 Evonik Stockhausen Inc. Recycling superabsorbent polymer fines
CN106029220B (zh) * 2014-02-28 2020-08-18 株式会社日本触媒 聚(甲基)丙烯酸(盐)系颗粒状吸水剂和制造方法
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