WO2016085123A1 - Procédé de préparation d'un polymère superabsorbant et polymère superabsorbant préparé par ce procédé - Google Patents

Procédé de préparation d'un polymère superabsorbant et polymère superabsorbant préparé par ce procédé Download PDF

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WO2016085123A1
WO2016085123A1 PCT/KR2015/011035 KR2015011035W WO2016085123A1 WO 2016085123 A1 WO2016085123 A1 WO 2016085123A1 KR 2015011035 W KR2015011035 W KR 2015011035W WO 2016085123 A1 WO2016085123 A1 WO 2016085123A1
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polymer
super absorbent
weight
glycol
polycarboxylic acid
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PCT/KR2015/011035
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English (en)
Korean (ko)
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이용훈
안태빈
한장선
정화윤
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주식회사 엘지화학
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Priority claimed from KR1020150144203A external-priority patent/KR101752384B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP15863265.3A priority Critical patent/EP3070107A4/fr
Priority to US15/105,331 priority patent/US9700873B2/en
Priority to CN201580004494.3A priority patent/CN105916902B/zh
Publication of WO2016085123A1 publication Critical patent/WO2016085123A1/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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters

Definitions

  • the present invention relates to a method for producing a super absorbent polymer having a high absorption rate and high pressure absorption characteristics.
  • a super absorbent polymer is a synthetic polymer material that can absorb about 500 to 1,000 times its own weight. It is a super absorbent mater (AL) and an absorbent gel mater (ALM). It is also called.
  • Super absorbent resins have been put into practical use as sanitary devices and are now widely used in various materials such as hygiene products such as paper diapers for children, horticultural soil repair agents, civil engineering materials, seedling sheets, and freshness retainers in food distribution. It is used.
  • As a method for producing such a super absorbent polymer a method by reverse phase suspension polymerization, a method by aqueous solution polymerization, or the like is known.
  • the production of superabsorbent polymers through reverse phase suspension polymerization is disclosed in, for example, Japanese Patent Laid-Open Nos. 56-161408, 57-158209, and 57-198714.
  • the production of superabsorbent polymers through polymerization of aqueous solution is a thermal polymerization method for polymerizing a hydrogel polymer in a kneader equipped with several shafts while breaking and angled, and polymerizing and drying by irradiating UV light to a high concentration of aqueous solution on a belt.
  • the photopolymerization method etc. which perform simultaneously are known.
  • absorption rate which is one of the important physical properties of super absorbent polymer
  • the surface dryness of the product in contact with the skin can be improved by increasing the surface area of the superabsorbent polymer.
  • a method of forming a porous structure on the particle surface of the super absorbent polymer by using a blowing agent has been applied.
  • a general blowing agent is not able to form a sufficient amount of porous structure has a disadvantage that the increase in the rate of absorption is not large.
  • the present invention is to provide a method for producing a super absorbent polymer having a high absorption rate and high pressure absorption characteristics at the same time.
  • the present invention provides a method for preparing a super absorbent polymer comprising the following steps:
  • R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R0 is an oxyalkylene group having 2 to 4 carbon atoms
  • M 1 is hydrogen or a monovalent metal or nonmetal ion
  • X is -C00-, an alkyloxy group having 1 to 5 carbon atoms or an alkyldioxy group having 1 to 5 carbon atoms,
  • n 1 to 100
  • n is an integer from 1 to 1000
  • p is an integer of 1 to 150, and when p is 2 or more, -R0-repeated two or more times may be the same or different from each other.
  • Superabsorbent polymers are water-retaining (CRC), pressure-absorbing (AUP) and fluid-permeable (GBP) o It is evaluated as an important physical property, and in particular, articles in which a superabsorbent resin is used, such as a diaper, are thinned, and it is important to have a high absorption rate and high pressure absorption characteristics at the same time.
  • a superabsorbent polymer having a high absorption rate and high pressure absorption characteristics is prepared using the polycarboxylic acid-based copolymer during hydrogel grinding.
  • step 1 Formation of hydrogel polymer (step 1)
  • the super-absorbent "to the manufacturing method of the resin has polymerized water-soluble ethylenically unsaturated monomer and a polymerization initiator or a thermal polymerization monomer composition containing a light includes a step of forming a gel polymer function.
  • the water-soluble ethylene-based unsaturated monomer contained in the monomer composition may be any monomer commonly used in the preparation of superabsorbent polymers.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by the following formula (3):
  • R 4 is an alkyl group having 2 to 5 carbon atoms containing an unsaturated bond
  • M 2 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 acrylic acid, methacrylic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts of these acids.
  • acrylic acid 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 monomer may be maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, or 2- (meth). ) Acrylamide-2-methyl S-ropanesulfonic acid, (meth) acrylamide, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Polyethylene glycol
  • (Meth) acrylate polyethylene glycol (meth) acrylate, ( ⁇ , ⁇ )-dimethylaminoethyl (meth) acrylate, ( ⁇ , ⁇ ) -dimethylaminopropyl (meth) acrylamide and the like can be used.
  • the water-soluble ethylenically unsaturated monomer has an acidic group, at least a portion of the acidic group may be neutralized.
  • those which have been partially neutralized with an alkali substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide and the like can be used.
  • the degree of neutralization of the monomer may be 40 to 95 mol%, or 40 to 80 mol% or 45 to 75 mol%.
  • the range of the degree of neutralization may vary depending on the final physical properties, but if the degree of neutralization is too high, the neutralized monomer may precipitate and polymerization may be difficult to proceed smoothly. On the contrary, if the degree of neutralization is too low, the absorbency of the polymer may be greatly reduced. It can exhibit the same properties as elastic rubber, which is difficult to handle.
  • the concentration of the water-soluble ethylene-based unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of the polymerization time and reaction conditions, Preferably from 20 to 90% by weight, or from 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 for removing the unbanung monomer after the polymerization by using the gel effect phenomenon appearing in the polymerization reaction of the high concentration aqueous solution.
  • concentration of the monomer when the concentration of the monomer is too low, the yield of the super absorbent polymer may be lowered.
  • concentration of the monomer if the concentration of the monomer is too high, some of the monomers may precipitate or process problems may occur such as when the pulverization efficiency of the polymerized hydrogel polymer is reduced, and the physical properties of the super absorbent polymer may be reduced.
  • the monomer composition may include a polymerization initiator generally used in the production of superabsorbent polymer.
  • a thermal polymerization initiator or a photopolymerization initiator may be used depending on the polymerization method.
  • a thermal polymerization initiator since a certain amount of heat is generated by ultraviolet irradiation or the like, and a certain amount of heat is generated in accordance with the progress of the polymerization reaction which is an exothermic reaction, a thermal polymerization initiator may be further included.
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • benzoin ether dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • acylphosphine commercially available lucirin TP0, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6_trimethyl_benzoyl_trimethyl phosphine oxide) may be used.
  • Zero is a persulfate initiator, azo initiator base 1 ,
  • One or more compounds selected from the group consisting of hydrogen peroxide, and ascorbic acid can be used.
  • the persulfate-based initiator sodium persulfate (Na 2 S 2 0 8 ), potassium persulfate (Potassium persulfate; K 2 S 2 0 8 ), ammonium persulfate (NH 4 ) 2 S 2 0 8 ) and the like.
  • azo initiators include 2,2-azobis- (2-amidinopropane) dihydrochloride (2, 2-azob is (2-am i di nopr opane) di hydrochloride), 2, 2- Azobis- ( ⁇ , ⁇ -dimethylene) isobutyramidine dihydrochloride (2,2- azobis- (N, N-dimethyl ene) is obut yr am idi ne di hydrochloride), 2-
  • the monomer composition may further include a crosslinking agent ("internal crosslinking agent") for improving the physical properties of the resin by polymerization of the water-soluble ethylenically unsaturated monomer.
  • the crosslinking agent is for internal crosslinking of the hydrogel polymer and may be used separately from a crosslinking agent ("surface crosslinking agent") for crosslinking the surface of the hydrogel polymer.
  • surface crosslinking agent any compound may be used as long as it enables the introduction of a crosslink in the polymerization of the water-soluble ethylenically unsaturated monomer.
  • the internal crosslinking agent is ⁇ , ⁇ '-methylenebisacrylamide ⁇ trimethyl propane 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 di (meth) acrylate , Triethylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, dipentaerythrone pentaacrylate, glycerin tri (meth) acrylate, pentaeryth Tetraacrylate, triarylamine, ethylene glycol diggle Polyfunctional crosslinking agents such as lycidyl di (meth)
  • Such internal crosslinking agent may be added at a concentration of about 0.001 to 1% by weight relative to the monomer composition. That is, 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 weakened, which is not preferable. On the contrary, when the concentration of the internal crosslinking agent is too high, the absorbing power of the resin may be low, which may be undesirable as an absorber.
  • the monomer composition may further include additives such as thickeners, plasticizers, storage stabilizers, antioxidants, and the like, as necessary.
  • the monomer composition may be prepared in the form of a solution in which raw materials such as the aforementioned monomer, polymerization initiator, internal crosslinking agent, and the like are dissolved in a solvent.
  • the solvent may be used to dissolve the above-described raw materials. If so, it can be used without limiting its configuration.
  • solvent 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, cyclonucleone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene butyrolactone, carbyl, methyl cellosolve acetate , N, N-dimethylacetamide, or a combination thereof may be used.
  • the formation of the hydrogel polymer through the polymerization of the monomer composition may be performed 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.
  • the thermal polymerization is performed, the polymerization method may be performed in a reaction vessel having a stirring shaft such as a kneader.
  • the reaction may be performed in a semi-unggi equipped with a movable conveyor belt.
  • a hydrogel polymer may be obtained by adding the monomer composition to a reaction vessel such as a kneader equipped with a stirring shaft, and supplying hot air thereto or heating and heating the reaction vessel.
  • the hydrous gel polymer discharged to the reactor outlet according to the shape of the stirring shaft provided in the reactor may be obtained from particles of several millimeters to several centimeters.
  • the resulting hydrogel polymer 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 kPa can be obtained.
  • a hydrous gel polymer in the form of a sheet may be obtained.
  • 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 allowing the entire sheet to be polymerized evenly, it is usually adjusted to a thickness of 0.5 to 5 cm.
  • the hydrogel polymer formed in this manner may exhibit a water content of about 40 to 80% by weight.
  • the moisture content is a weight of water in the total weight of the hydrogel polymer, and may be a value obtained by subtracting the weight of the dried polymer from the weight of the hydrogel polymer. Specifically, it may be defined as a value calculated by measuring the weight loss due to evaporation of water in the polymer in the process of drying the temperature of the polymer through infrared heating. At this time, the drying conditions may be set to 20 minutes, including the temperature rise step 5 minutes in such a way that the temperature is raised to about 180 ° C and then maintained at 180 ° C.
  • step 2 Mixing and grinding the hydrous gel phase polymer with a polycarboxylic acid co-polymer (step 2)
  • the hydrogel polymer is pulverized together with the polycarboxylic acid copolymer when pulverized (coarsely pulverized).
  • the polycarboxylic acid-based copolymer lowers the load of the grinder due to the lubrication action to induce uniform grinding of the polymer, and also can suppress the generation of water-soluble components during grinding. Through this, it is possible to manufacture a super absorbent polymer having a fast absorption rate and high pressure absorption characteristics.
  • the polycarboxylic acid copolymer may include an alkoxy polyalkylene glycol mono (meth) acrylic acid ester monomer (typically, methoxy polyethylene glycol monomethacrylate (MPEGMAA), etc.) and
  • R 1 , R 2 and R 3 are methyl.
  • R0 is- CH 2 -CH 2 -0-.
  • X is -C00-.
  • M 1 is hydrogen, Na or N3 ⁇ 4.
  • the polycarboxylic acid-based copolymer has a weight average molecular weight of 500 to 1,000, 000.
  • the weight average molecular weight is 1,000 to 500,000, 10,000 to 100,000, 20,000 to 90,000, 30,000 to 80,000, or 40,000 to 70,000.
  • the content of the polycarboxylic acid-based copolymer may be appropriately adjusted according to the type or reaction conditions of the copolymer.
  • the polycarboxylic acid-based copolymer is mixed at 0.001 to 5 parts by weight based on 100 parts by weight of the solid content of the hydrous gel polymer prepared in Step 1. When the content of the polycarboxylic acid copolymer is too low, the effect required in the present invention may not be sufficiently expressed.
  • the grinders available for the coarse grinding include a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting type Examples include a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, a disc cutter, and the like.
  • the coarse grinding may be performed so that the particle diameter of the hydrogel polymer is 1 mm to 10 mm 3.
  • the hydrous gel polymer is preferably pulverized into particles of 10 GPa or less.
  • the hydrous gel polymer is preferably pulverized into particles of 1 Pa or more.
  • the polymer may stick to the surface of the grinder because the polymer has a high water content.
  • the coarsely pulverizing step may include, as necessary, steam, water, a surfactant, a fine anti-dusting agent such as Clay or Si li ca; Thermal polymerization initiators such as persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid, epoxy crosslinkers, diol crosslinkers, crosslinking agents comprising acrylates of difunctional or trifunctional or polyfunctional groups or more, and hydroxyl groups. Crosslinking agents, such as a compound of monofunctional groups, may be added. Drying the ground polymer (step 3)
  • drying for the co-pulverized polymer as described above may be carried out at a temperature of 120 to 250 ° C, or 150 to 200 ° C, or 160 to 180 ° C (wherein the temperature is supplied for drying Can be defined as the temperature of the heat medium or the temperature inside the drying reactor containing the heat medium and the polymer in the drying process. That is, when the drying temperature is low due to a low drying temperature, the physical properties of the final resin may be lowered. In order to prevent this, the drying temperature is preferably 120 ° C. or more.
  • drying temperature may be a fine powder generated more in the milling process to be described later is dry only the surface of the function, the gel polymer is higher than necessary, the physical properties of the final resin can be lowered, a drying temperature in order to prevent this, is 250 ° It is preferable that it is C or less.
  • the drying time in the drying step is not particularly limited, but may be adjusted to 20 to 90 minutes under the drying temperature in consideration of process efficiency and the like.
  • the drying method of the drying step also dried the hydrous gel polymer The configuration can be applied without limitation as long as it can be commonly used in the process.
  • the drying step may be a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the polymer dried in this manner may exhibit a water content of about 0.1 to 10% by weight. In other words, if the water content of the polymer is less than 0.1% by weight, it is not advantageous because an increase in manufacturing cost and degradation of the crosslinked polymer may occur due to excessive drying. In addition, when the water content of the polymer exceeds 10% by weight, it is not preferable because the amount may be generated in a subsequent process. Grinding the dried polymer (step 4)
  • the grinding step may be performed to optimize the surface area of the dried polymer, and may be performed to have a particle diameter of 150 to 850. Mills that can be used to grind to these particle sizes include pin mills, hammer mills, screw mills, mills, disc mills and jog mills. jog mill) and the like. And, in order to manage the physical properties of the super absorbent polymer to be finalized, the step of selectively classifying particles having a particle size of 150 to 850 mm 3 from the polymer powder obtained through the grinding step may be further performed.
  • Surface crosslinking reaction of the ground polymer (step 5)
  • the manufacturing method of the super absorbent polymer includes the step of surface crosslinking the polymer pulverized through the above-described steps.
  • Surface crosslinking is a method of increasing the crosslinking density of the surface of a resin particle, and may be performed by mixing and crosslinking the pulverized polymer with a solution containing a crosslinking agent (surface crosslinking agent).
  • a crosslinking agent surface crosslinking agent
  • the kind of crosslinking agent (surface crosslinking agent) contained in the surface crosslinking solution is not particularly limited.
  • the surface crosslinking agent may be 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, propylene glycol, triethylene glycol, tetraethylene glycol, propane die, dipropylene glycol, polypropylene glycol, glycerin, polyglycerol, butanedi, heptanediol, nucleic acid diol trimethylolpropane , Pentaery recall, sorbate, calcium hydroxide, magnes .
  • the crosslinking agent may be at least one compound selected from the group consisting of hydroxide, aluminum hydroxide, iron hydroxide, chalc chloride, magnesium chloride, aluminum chloride, and iron chloride.
  • the crosslinking agent it is possible to use a polycarboxylic acid-based copolymer having a repeating unit represented by the above-described formulas 1-a and 1-b of the present invention.
  • the content of the surface crosslinking agent may be appropriately adjusted according to the type or reaction conditions of the crosslinking agent, and preferably may be adjusted to 0.001 to 5 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the surface crosslinking solution and the pulverized polymer are mixed in a semi-permanent mixture, a method of spraying the surface crosslinking solution on the pulverized polymer, a pulverized polymer and The method of supplying and mixing the surface crosslinking solution continuously can be used. Further, when the surface crosslinking solution is added, additional water may be added. Can be.
  • the amount of water added may be adjusted to 0.5 to 10 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the surface crosslinking reaction step may proceed under a temperature of 100 to 250 ° C, it may be made continuously after the drying and grinding step proceeds to 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.
  • the polymer particles may be damaged during excessive reaction, and thus the physical properties of the surface crosslinking reaction may be reduced.
  • a superabsorbent polymer having a small amount of coarse part ic les and fine particles (f ine part ic les) and excellent absorption characteristics such as water-retaining capacity and pressure-absorbing capacity can be produced.
  • a super absorbent polymer having a fast absorption rate and high pressure absorption characteristics can be prepared.
  • a polycarboxylic acid copolymer was obtained in the same manner as in Preparation Example 2, except that the reaction mixture was neutralized with an aqueous sodium hydroxide solution instead of an aqueous triethanolamine solution (weight average molecular weight 40, 000).
  • Preparation Example 4
  • a polycarboxylic acid copolymer was obtained in the same manner as in Preparation Example 5, except that the reaction mixture was neutralized with an aqueous sodium hydroxide solution instead of an aqueous triethanolamine solution (weight average molecular weight 45, 000).
  • Example 1
  • Acrylic acid 500 in a 3L glass vessel equipped with a stirrer, nitrogen injector and thermometer g 5.5 g of ethoxy lated (15) tr imethylolpropane tr i acrylate) and 0.04 g of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide
  • 896.4 g of a 24.5% sodium hydroxide aqueous solution was added thereto to continuously add nitrogen to prepare a water-soluble unsaturated monomer solution.
  • the aqueous unsaturated monomer aqueous solution was quenched to 70 ° C.
  • aqueous solution 500 g was added to a stainless steel container having a width of 250 mm, a length of 250 mm and a height of 30 mm, and irradiated with ultraviolet light (irradiation amount of 10 mW / cm 2 ) to perform UV polymerization for 90 seconds to obtain a hydrous gel polymer.
  • Meat chopper (made by SL (SL), discharge mesh hole diameter 10 mm) while uniformly spraying an aqueous solution in which 0.6 g of the polycarboxylic acid copolymer prepared in Preparation Example 1 and 60 g of water were uniformly sprayed on the obtained water-containing crosslinked polymer. And divided into 5 mm 3 or less.
  • the hydrous gel polymer obtained was pulverized to a size of 2 mm X 2 mm, and then spread on a stainless wire gauze having a pore size of 600 mm 3 in a thickness of about 30 mm and dried in a were hot air oven for 5 hours.
  • the dry polymer thus obtained was pulverized using a grinder and classified into a standard mesh of ASTM specification to obtain an absorbent resin powder having a particle size of 150 to 850 urn.
  • 100 g of the resin powder was mixed with 1.0 g of ethylene carbonate, 4.0 g of water, 0.01 g of the polycarboxylic acid copolymer prepared in Preparation Example 1, 0.3 g of oxalic acid, and 0.02 g of silica. Dry in a 180 ° C. hot air oven for 60 minutes.
  • the dried powder was classified into a standard mesh of ASTM specification to obtain a super absorbent polymer having a particle size of 150 to 850 urn.
  • Example 3 A superabsorbent polymer was obtained in the same manner as in Example 1, except that the polycarboxylic acid copolymer prepared in Preparation Example 3 was used instead of the polycarboxylic acid co-polymer prepared in Preparation Example 1.
  • Example 4 A superabsorbent polymer was obtained in the same manner as in Example 1, except that the polycarboxylic acid copolymer prepared in Preparation Example 3 was used instead of the polycarboxylic acid co-polymer prepared in Preparation Example 1.
  • the finely divided gel was spread about 30 mm thick on a stainless wire gauze having a pore size of 600 urn and dried in a 140 ° C. hot air oven for 5 hours.
  • the dry polymer thus obtained was pulverized using a grinder and classified into a standard mesh of ASTM specification to obtain an absorbent resin powder having a particle size of 150 to 850 urn.
  • 100 g of the resin powder, 0.9 g of ethylene carbonate, 0.01 g of silica (A rosi l 200), 2 g of methane, prepared in Preparation Example 4 0.1 g of polycarboxylic acid-based copolymer and 3 g of water were mixed evenly, and then dried in a 190 ° C. hot air oven for 30 minutes.
  • the dried powder was classified into a standard mesh of ASTM specification to obtain a super absorbent polymer having a particle size of 150 to 850 um.
  • Example 8 when dispersing in the meat chopper while uniformly spraying the aqueous solution of the polycarboxylic acid copolymer and water in the water-containing cross-linked polymer, the discharge mesh hole diameter of the meat chopper is 8 kPa, A super absorbent polymer was obtained in the same manner as in Example 1.
  • Example 8 when dispersing in the meat chopper while uniformly spraying the aqueous solution of the polycarboxylic acid copolymer and water in the water-containing cross-linked polymer, the discharge mesh hole diameter of the meat chopper is 8 kPa, A super absorbent polymer was obtained in the same manner as in Example 1.
  • Example 8 when dispersing in the meat chopper while uniformly spraying the aqueous solution of the polycarboxylic acid copolymer and water in the water-containing cross-linked polymer, the discharge mesh hole diameter of the meat chopper is 8 kPa, A super absorbent polymer was obtained in the same manner as in Example 1.
  • Example 8
  • Example 4 when splitting in the meat chopper while uniformly sprinkling an aqueous solution of a polycarboxylic acid copolymer and water in the water-containing crosslinked polymer, the discharge mesh hole diameter of the meat chopper is 8 kPa.
  • Superabsorbent polymer was obtained in the same manner as in Example 4, except that the polycarboxylic acid copolymer prepared in Preparation Example 2 was used instead of the polycarboxylic acid copolymer prepared in Preparation Example 4.
  • Comparative Example 1 In Example 1, except that the polycarboxylic acid-based copolymer is not used when the hydrous crosslinked polymer is divided in the meat chopper,
  • Example 4 a superabsorbent polymer was obtained in the same manner as in Example 4, except that the polycarboxylic acid copolymer was not used when the hydrous crosslinked polymer was divided in a meat chopper. Comparative Example 3
  • Example 7 the superabsorbent polymer was obtained in the same manner as in Example 7, except that the polycarboxylic acid copolymer was not used when the hydrous crosslinked polymer was divided in a meat chopper. Comparative Example 4
  • Example 7 0.5% aqueous surfactant (Sodium Dodecyl Sul fate, SDS) instead of 0.6 g of polycarboxylic acid copolymer prepared in Preparation Example 1 and 60 g of water when the hydrous crosslinked polymer was divided in a meat chopper. A super absorbent polymer was obtained in the same manner as in Example 7, except that 60 g was used.
  • aqueous surfactant Sodium Dodecyl Sul fate, SDS
  • the water holding capacity was measured with respect to the resin of the said Example and a comparative example. That is, the resin W (g) (about 0.2 g) obtained through the Examples and Comparative Examples were uniformly placed in a nonwoven fabric bag and sealed, and then impregnated in physiological saline (0.9 wt%) at room temperature. After about 30 minutes, drained from the bag for 3 minutes under the conditions of 250G using a centrifugal separator. Mass W2 (g) was measured. Moreover, mass W1 (g) at that time was measured after performing the same operation without using resin. Using each mass obtained, CRC ( g / g) was calculated according to the following equation:
  • the pressure absorption capacity was measured for the resins of the above Examples and Comparative Examples. That is, a stainless steel 400 mesh wire mesh was mounted on the bottom of a plastic cylinder with an inner diameter of 60 mm. A piston which can evenly spread the absorbent resin W (g) (about 0.90g) on the wire mesh under conditions of room temperature and humidity of 50%, and can further give a lowering of 4.83 kPa (0.7 ps i) on it. Slightly smaller than 60 mm, there is no gap with the inner wall of the cylinder and the up and down movement is not disturbed. At this time, the weight Wa (g) of the apparatus was measured.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed on the inside of the petri dish having a diameter of 150 mm 3, and the physiological saline composed of 0.90 wt% sodium chloride was set at the same level as the top surface of the glass filter.
  • One sheet of filter paper having a diameter of 90 mm was loaded thereon. The measuring 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 and the weight Wb (g) was measured.
  • AUP (g / g) ⁇ Wb-Wa ⁇ I W

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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)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'un polymère superabsorbant. Selon la présente invention, ce procédé de préparation d'un polymère superabsorbant permet de préparer un polymère superabsorbant à vitesse d'absorption élevée et caractéristique d'absorption à haute pression grâce à l'utilisation d'un copolymère à base d'acide polycarboxylique lors de la pulvérisation d'un hydrogel.
PCT/KR2015/011035 2014-11-27 2015-10-19 Procédé de préparation d'un polymère superabsorbant et polymère superabsorbant préparé par ce procédé WO2016085123A1 (fr)

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EP15863265.3A EP3070107A4 (fr) 2014-11-27 2015-10-19 Procédé de préparation d'un polymère superabsorbant et polymère superabsorbant préparé par ce procédé
US15/105,331 US9700873B2 (en) 2014-11-27 2015-10-19 Method for preparing super absorbent polymer and super absorbent polymer prepared therefrom
CN201580004494.3A CN105916902B (zh) 2014-11-27 2015-10-19 用于制备超吸收性聚合物的方法和由此制备的超吸收性聚合物

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KR1020150144203A KR101752384B1 (ko) 2014-11-27 2015-10-15 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170029576A1 (en) * 2014-11-27 2017-02-02 Lg Chem, Ltd. Method for preparing super absorbent polymer and super absorbent polymer prepared therefrom
US20210268475A1 (en) * 2019-01-17 2021-09-02 Lg Chem, Ltd. Super Absorbent Polymer and Method for Preparing Same
WO2021221642A1 (fr) * 2020-04-30 2021-11-04 Kimberly-Clark Worldwide, Inc. Polymères superabsorbants à base de copolymères de monomères chargés et de monomères neutres
WO2022196763A1 (fr) 2021-03-18 2022-09-22 株式会社日本触媒 Procédé de production d'une résine absorbant l'eau
WO2022197991A1 (fr) 2021-03-18 2022-09-22 The Procter & Gamble Company Procédé de production d'articles absorbants comprenant une résine absorbant l'eau

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KR20140063457A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이로부터 제조되는 고흡수성 수지
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KR20050036975A (ko) * 2002-08-23 2005-04-20 바스프 악티엔게젤샤프트 초흡수성 중합체 및 그의 제조 방법
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170029576A1 (en) * 2014-11-27 2017-02-02 Lg Chem, Ltd. Method for preparing super absorbent polymer and super absorbent polymer prepared therefrom
US9976003B2 (en) * 2014-11-27 2018-05-22 Lg Chem, Ltd. Method for preparing super absorbent polymer and super absorbent polymer prepared therefrom
US20210268475A1 (en) * 2019-01-17 2021-09-02 Lg Chem, Ltd. Super Absorbent Polymer and Method for Preparing Same
WO2021221642A1 (fr) * 2020-04-30 2021-11-04 Kimberly-Clark Worldwide, Inc. Polymères superabsorbants à base de copolymères de monomères chargés et de monomères neutres
WO2022196763A1 (fr) 2021-03-18 2022-09-22 株式会社日本触媒 Procédé de production d'une résine absorbant l'eau
WO2022197991A1 (fr) 2021-03-18 2022-09-22 The Procter & Gamble Company Procédé de production d'articles absorbants comprenant une résine absorbant l'eau

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