WO2016148397A1 - Procédé de préparation de polymère superabsorbant - Google Patents

Procédé de préparation de polymère superabsorbant Download PDF

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WO2016148397A1
WO2016148397A1 PCT/KR2016/001282 KR2016001282W WO2016148397A1 WO 2016148397 A1 WO2016148397 A1 WO 2016148397A1 KR 2016001282 W KR2016001282 W KR 2016001282W WO 2016148397 A1 WO2016148397 A1 WO 2016148397A1
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김지연
김의덕
심유진
오석헌
이민호
이혜연
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Hanwha Chemical Corp
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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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a method for producing a super absorbent polymer.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight.As a developer, super absorbent material (AMG) and absorbent gel material (AGM) They are named differently. Such super absorbent polymers have been put into practical use as physiological tools, and nowadays, in addition to hygiene products such as children's paper diapers, horticultural soil repair agents, civil engineering, building index materials, seedling sheets, freshness-retaining agents, and steaming in the food distribution sector. It is widely used as a material for articles.
  • a method for producing such a super absorbent polymer a method by reverse phase suspension polymerization or a solution polymerization is known.
  • Reverse phase suspension polymerization is disclosed in, for example, Japanese Patent Laid-Open Nos. 56-161408, 57-158209, and 57-198714.
  • a thermal polymerization method for applying polymerization to an aqueous solution and polymerizing it again, and a photopolymerization method for irradiating and polymerizing ultraviolet rays or the like are known.
  • water-soluble components and residual monomers which are polymers that are not crosslinked, are produced.
  • the water-soluble component and the residual monomer may show a difference in content depending on the content of the polymerization initiator used during the polymerization, the polymerization temperature, the content of the internal crosslinking agent, the surface crosslinking process conditions, and the like.
  • the surface of the diaper, etc. may become sticky or the liquid permeability may decrease, and may cause skin diseases and odors.
  • the present invention is to provide a method for producing a super absorbent polymer that can improve the processability by omitting the surface crosslinking process, and can obtain a superabsorbent polymer having reduced water-soluble components and residual monomers compared to the surface-crosslinked superabsorbent polymer. do.
  • the manufacturing method of the superabsorbent polymer of the present invention is a method of preparing a bare superabsorbent polymer that does not include a surface crosslinking layer, and polymerizing a monomer composition including hydrophilic monomers, a crosslinking agent, and a polymerization initiator to form a hydrogel-like crosslinked polymer.
  • the bare superabsorbent resin may have a water soluble component (EC) of greater than 0% and less than 15%, a residual monomer (RM) of greater than 0 ppm, less than 1000 ppm, preferably greater than 0 ppm and less than 600 ppm.
  • EC water soluble component
  • RM residual monomer
  • the method of preparing the super absorbent polymer further includes preparing a monomer composition, and the monomer composition may include the hydrophilic monomers, the crosslinking agent, the polymerization initiator, a neutralizing agent, and a solvent.
  • preparing the monomer composition may include preparing a first composition including the neutralizing agent and the solvent, preparing a second composition including the hydrophilic monomers, the crosslinking agent, and the polymerization initiator. Step and mixing the first composition and the second composition.
  • the preparing of the hydrogel-like crosslinked polymer may include polymerizing the monomer composition; and pulverizing the hydrogel-like crosslinked polymer.
  • the polymerization initiator may include a photopolymerization initiator or a complex polymerization initiator, and the complex polymerization initiator may include, for example, the photopolymerization initiator and a thermal polymerization initiator.
  • n is an integer of 1-20
  • Y is a hydrophilic group.
  • the hydrophilic group may be, for example, one of a hydroxyl group (-OH), a carboxyl group (-COOH) and an amino group (-NHR h , -NH 2 , -NR h2 , R h is a C 1-5 hydrocarbon group). have.
  • the hydrophilic group may be a hydroxyl group.
  • At least one of the compounds represented by the formula (1) may be, for example, at least one of the compounds represented by the following formula (2).
  • R 1 may be one of hydrogen, a C 1-2 alkyl group and a C 1-2 alkoxy group
  • R 2 may be a C 1-5 alkylene group (-( CH 2 ) m ⁇ , m is an integer from 1 to 5) and a C 1-5 alkyleneoxy group (— (CH 2 ) m —O—, m is an integer from 1 to 5).
  • Y may be a hydrophilic group.
  • the hydrophilic group may be, for example, one of a hydroxyl group (-OH), a carboxyl group (-COOH), and an amino group (-NHR h , -NH 2 , -NR h2 ).
  • n may be an integer of 1 to 20.
  • At least one of the compounds represented by the formula (2) may be, for example, at least one of the compounds represented by the following formulas (3) to (14).
  • the surface crosslinking process may be omitted, thereby improving processability.
  • the manufacturing method of the super absorbent polymer has a lower level of water-soluble component (EC) than the surface crosslinked superabsorbent polymer while exhibiting the same water-retaining capacity (CRC) and pressurized absorbent capacity (AUP) as the surface-crosslinked superabsorbent polymer. And a bare superabsorbent polymer having residual monomer (RM).
  • EC water-soluble component
  • CRC water-retaining capacity
  • AUP pressurized absorbent capacity
  • FIG. 1 is a schematic process flowchart of a method of preparing a super absorbent polymer according to an embodiment of the present invention.
  • surface crosslinked superabsorbent polymer is defined as a superabsorbent polymer having a core-shell structure in which a base resin is used as a core and a surface crosslinking layer is formed on the surface of the core.
  • bare superabsorbent resin is defined as a superabsorbent polymer in a state where no surface crosslinking layer is formed on the surface of the base resin.
  • water-containing gel crosslinker means any one of a sheet-like hydrogel-like crosslinker and a particulate water-containing gel-crosslinker.
  • C AB is defined as having more than A carbon atoms and less than B, for example, "C 1-5 alkyl group” is an alkyl group having 1 to 5 carbon atoms.
  • C and / or D is defined to include C, D, or C and D.
  • E to F is defined as being equal to or greater than E and equal to or less than F.
  • unsaturated hydrocarbon group is defined as a monovalent atomic group as a residue from which one hydrogen is removed in a hydrocarbon including an unsaturated bond, and may be, for example, a (meth) vinyl group, a (meth) allyl group, or the like. have.
  • an "alkyl group” includes a straight or branched alkyl group and may be, for example, an n-butyl group, a t-butyl group, or the like.
  • alkoxy group is a monovalent atomic group in which an alkyl group is bonded to oxygen, and is a derivative of an alkyl group, and the alkyl group may be a linear or branched alkyl group.
  • an "alkylene group” is a residue in which one hydrogen is removed from an alkyl group and is a divalent atomic group consisting of carbon and hydrogen, and may be represented by-(CH 2 ) m- , for example, methylene (-CH 2). -), Ethylene (-CH 2 CH 2- ) and the like.
  • alkyleneoxy group is a divalent atomic group in which one hydrogen is removed from an alkoxy group and the alkylene group is bonded to oxygen, and may be represented by-(CH 2 ) m -O-, for example , Methyleneoxy group (-CH 2 O-, -OCH 2- ), ethyleneoxy group (-CH 2 CH 2 O-, -OCH 2 CH 2- ) and the like.
  • amino group is a residue from which one hydrogen is removed from ammonia, and may be represented by -NHR h , -NH 2 , -NR h2 , and R h may be an alkyl group.
  • FIG. 1 is a schematic manufacturing process diagram of a manufacturing method of a super absorbent polymer according to an embodiment of the present invention.
  • the method of preparing a super absorbent polymer the step of preparing a monomer composition (P1), the step of preparing a hydrogel-like crosslinked polymer (P2), the compound represented by the following formula (1) in the hydrogel-like crosslinked polymer Adding at least one of these to prepare a base resin (P3), pulverizing the base resin (P4), drying the pulverized base resin (hereinafter referred to as "pulverized substance”) (P5), and Pulverizing the dried base resin (hereinafter referred to as "dry material”) (P6).
  • the step (P2) of preparing the hydrogel-like crosslinked polymer may further include a step (P21) of grinding the hydrogel-like crosslinked polymer, and the step (P21) of grinding the hydrogel-like crosslinked polymer may include preparing a base resin ( P2) may be performed before.
  • Preparing the monomer composition (P1) includes preparing a first composition comprising a neutralizing agent and a solvent (P11), preparing a second composition including hydrophilic monomers, a crosslinking agent, and a polymerization initiator (P12). And mixing the first composition and the second composition (P13).
  • the monomer composition may include the hydrophilic monomers, the crosslinking agent, the polymerization initiator, the neutralizing agent, and the solvent.
  • the hydrophilic monomers may be used without limitation as long as the monomers generally used in the production of superabsorbent polymers.
  • the hydrophilic monomers are monomers including a hydrophilic group, and the hydrophilic group is, for example, a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (amino group: -NHR h , -NH 2 , -NR h2 and R h may be, for example, a C 1-5 alkyl group.) Or the like.
  • the hydrophilic monomer may be a water-soluble ethylenically unsaturated monomer.
  • the water-soluble ethylenically unsaturated monomer may be at least one of an anionic monomer and a salt thereof, a nonionic hydrophilic-containing monomer, and an amino group-containing unsaturated monomer and a quaternized product thereof.
  • the anionic monomers and salts thereof are, for example, acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2- ( Meta) acryloylpropanesulfonic acid and at least one of 2- (meth) acrylamide-2-methylpropanesulfonic acid.
  • nonionic hydrophilic-containing monomer examples include (meth) acrylamide, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, It may be at least one of methoxy polyethylene glycol (meth) acrylate and polyethylene glycol (meth) acrylate.
  • the amino group-containing unsaturated monomer and its quaternized substance may be, for example, at least one of (N, N) -dimethylaminoethyl (meth) acrylate and (N, N) -dimethylaminopropyl (meth) acrylamide. have.
  • the concentration of the water-soluble ethylenically unsaturated monomer in the monomer composition may be appropriately selected and used in consideration of polymerization time and reaction conditions (feed rate of the monomer composition, irradiation time of heat and / or light, irradiation range, irradiation intensity, etc.).
  • the weight ratio may be in a range of 30 wt% or more and 60 wt% or less.
  • the crosslinking agent may include one or more atomic groups and ethylenically unsaturated groups each capable of reacting with the functional group of the hydrophilic monomer, or an atomic group capable of reacting with the functional group formed by hydrolyzing the functional group of the hydrophilic monomer and the hydrophilic monomer.
  • the compound containing two or more can be used.
  • the crosslinking agent is C 8-12 bisacrylamide, C 8-12 bismethacrylamide, poly (meth) acrylate of C 2-12 polyol or poly (meth) allyl of C 2-10 polyol Ether and the like.
  • the crosslinking agent is (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, ethoxyl (3) -trimethylol propane Tri (meth) acrylate, ethoxyl (6) -trimethylolpropane tri (meth) acrylate, ethoxyl (9) -trimethylolpropane tri (meth) acrylate, ethoxyl (15) -trimethylolpropane tree ( Meta) acrylate glycerin tri (meth) acrylate, glycerin acrylate methacrylate, 2,2-bis [(acryloxy) methyl] butyl acrylate (3EO), N, N'-methylene bis (meth) acrylate , Ethyleneoxy (meth) acrylate, polyethyleneoxy (meth) acrylate, propyleneoxy (meth) acrylate,
  • the crosslinking agent may be included in the range of 0.01 parts by weight to 0.5 parts by weight based on 100 parts by weight of the hydrophilic monomer, but is not limited thereto.
  • the polymerization initiator may be at least one of a photopolymerization initiator, a thermal polymerization initiator, and an oxidation-reduction initiator.
  • the polymerization initiator may be a complex polymerization initiator containing two or more kinds of polymerization initiators.
  • the complex polymerization initiator may include the photopolymerization initiator and the thermal polymerization initiator.
  • the complex polymerization initiator may include the thermal polymerization initiator and the oxidation-reduction initiator.
  • the photopolymerization initiator initiates photopolymerization of the monomer composition when irradiated with ultraviolet light
  • the thermal polymerization initiator initiates thermal polymerization of the monomer composition by heating
  • the oxidation-reduction initiator reacts to an oxidation-reduction reaction.
  • the polymerization of the monomer composition can be started.
  • polymerization by the thermal polymerization initiator may occur by heat generated during photopolymerization.
  • the thermal polymerization initiator may be initiated together with the heat generated during the oxidation-reduction reaction to cause polymerization.
  • the polymerization initiator is diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxy ethoxy) phenyl- (2-hydroxy)- Acetophenone derivatives such as 2-propyl ketone and 1-hydroxycyclohexylphenyl ketone; Benzoin alkyl ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone derivatives such as methyl o-benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, and (4-benzoyl benzyl) trimethylammonium chloride; Thioxanthone compounds; Acyl phosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide and
  • the polymerization initiator can exhibit a polymerization initiation effect, its content may be appropriately selected.
  • the photopolymerization initiator may be included in the monomer composition in a range of 0.005 parts by weight to 0.5 parts by weight based on 100 parts by weight of the hydrophilic monomers, and the thermal polymerization initiator may be included in 100 parts by weight of the hydrophilic monomers. It may be included in the monomer composition in the range of 0.01 parts by weight to 0.5 parts by weight.
  • the neutralizing agent may serve to neutralize the hydrophilic monomer.
  • Representative neutralizing agents include, but are not limited to, sodium hydroxide, sodium bicarbonate, and the like.
  • the neutralizing agent may be used in the range that the degree of neutralization of the monomer composition is 65 mol% to 75 mol%. However, this is not limited only.
  • the solvent may be water, and water may serve as a polymerization medium.
  • Step (P2) of preparing the hydrogel-like crosslinked polymer may include polymerizing the monomer composition (P21) and pulverizing the sheet-like hydrogel-like crosslinked polymer (P22).
  • Polymerizing the monomer composition (P21) is a step of performing a photopolymerization reaction and / or thermal polymerization by applying light and / or heat to the monomer composition.
  • a photopolymerization reaction may be initiated by the photopolymerization initiator.
  • the thermal polymerization initiator may initiate a thermal polymerization reaction by heat generated during the photopolymerization reaction.
  • the polymerization reaction can be carried out, for example, using a belt type polymerization reactor, and a sheet-like hydrogel-like crosslinked polymer can be obtained by the polymerization reaction.
  • the step of pulverizing a sheet-like hydrogel-like crosslinker (P22) is to grind or crush the sheet-like hydrogel-like crosslinker into a particulate hydrogel-like crosslinker having a particle size of about 1 cm to about 3 cm.
  • the water content can be, for example, about 40% to about 60% by weight.
  • a base resin is prepared by adding at least one of the compounds represented by the following Formula (1) to the hydrogel-like crosslinked polymer, preferably particulate hydrogel-like crosslinked polymer. Step P3 is performed.
  • At least one of the compounds represented by the following formula (1) may react with an uncrosslinked linear polymer chain to lower the value of the extractable content (EC) and react with unreacted monomers.
  • the level of residual monomer (RM) can be lowered.
  • X is an unsaturated hydrocarbon group or a derivative thereof.
  • n is an integer of 1 to 20
  • Y is a hydrophilic group.
  • the hydrophilic group may react with the unreacted monomers and the linear polymer chain to form a hydrogen bond.
  • Y may be, for example, one of a hydroxyl group (-OH), a carboxyl group (-COOH), and an amino group (-NHR h , -NH 2 , -NR h2 , R h is a C 1-5 hydrocarbon group). have.
  • Y may be a hydroxyl group.
  • At least one of the compounds represented by the formula (1) may improve the reactivity with the hydrous gel-like crosslinked polymer that is hydrophilic in the range of the carbon number and the value of n of the R.
  • the hydrophobicity may be increased to decrease the reactivity with the hydrophilic hydrogel-like crosslinked polymer.
  • the content of at least one of the compounds represented by the formula (1) may be in the range of 1% by weight to 10% by weight based on the total weight of the bare superabsorbent resin. At least one of the compounds represented by the formula (1) has a low level of the water-soluble component (EC) and the residual monomer (RM) at a lower level than the conventional surface cross-linked super absorbent polymer within the above-described content range. The value can be lowered and can exhibit the same level of water retention (CRC) as the surface-crosslinked superabsorbent polymer.
  • EC water-soluble component
  • RM residual monomer
  • At least one of the compounds represented by the formula (1) may be, for example, at least one of the compounds represented by the following formula (2):
  • R 1 may be one of hydrogen, a C 1-2 alkyl group and a C 1-2 alkoxy group
  • R 2 may be a C 1-5 alkylene group (-( CH 2 ) m ⁇ , m is an integer from 1 to 5) and a C 1-5 alkyleneoxy group (— (CH 2 ) m —O—, m is an integer from 1 to 5).
  • Y may be one of a hydroxyl group (-OH), a carboxyl group (-COOH), an amino group (-NHR h , -NH 2 , -NR h2 ).
  • n is an integer of 1 to 20.
  • At least one of the compounds represented by the formula (2) may be, for example, at least one of the compounds represented by the following formulas (3) to (14):
  • Crushing the base resin (P4) is to heavy chain the base resin into particles having a particle diameter of millimeters (mm).
  • the step P4 of crushing the base resin may be performed using, for example, a cutter type cutter, a chopper type cutter, a kneader type cutter, a vibratory grinder, an impact grinder, a friction grinder, or the like.
  • Drying the milled product (P5) may be carried out in a range of about 20 minutes to about 40 minutes at a temperature of about 150 °C to about 200 °C. Drying the pulverized product (P5) may be performed using, for example, a hot air dryer, a fluidized bed dryer, an airflow dryer, an infrared dryer, a dielectric heating dryer, or the like.
  • the step (P6) of pulverizing the dry matter is to pulverize the dry matter into particles having an average particle diameter of micrometer ( ⁇ m), and may include a process of selecting particles having an average particle diameter of 150 ⁇ m to 850 ⁇ m.
  • the manufacturing method of the super absorbent polymer may provide a bare super absorbent polymer.
  • the bare superabsorbent polymer may have a level of water retention (Centrifuge Retention Capacity (CRC) and Absorbency Under Pressure (AUP)) equivalent to that of the surface crosslinked superabsorbent polymer, and may be applied to the surface crosslinked superabsorbent polymer. It may have a lower level of extractable content (EC) and residual monomer (RM).
  • the monomer composition was introduced into a polymerizer consisting of a conveyor belt continuously moving at a temperature of 40 ° C., and then irradiated with ultraviolet rays (irradiation amount: 9 mW / cm 2) through a UV irradiation apparatus, followed by UV polymerization for 3 minutes, to obtain a sheet-like function.
  • Gel-like crosslinked polymers were prepared.
  • the sheet-like hydrogel polymer was transferred to a cutter and cut into 2 cm. At this time, the water content of the cut hydrogel-like crosslinked polymer was 50% by weight.
  • the monomer composition using 0.033 g of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide and 2.256 g of aqueous solution of Potassium persulfate was fed to a polymerizer consisting of a conveyor belt continuously moving at a temperature of 30 ° C. for 2 minutes.
  • a particulate hydrogel-like crosslinked polymer was prepared in the same manner as in Preparation Example 1, except that ultraviolet ray was irradiated.
  • the monomer composition using 0.033 g of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide and 2.256 g of aqueous solution of Potassium persulfate was fed to a polymerizer consisting of a conveyor belt continuously moving at a temperature of 20 ° C., for 2 minutes.
  • a particulate hydrogel-like crosslinked polymer was prepared in the same manner as in Preparation Example 1, except that ultraviolet ray was irradiated.
  • a bare superabsorbent polymer was prepared in the same manner as in Example 1, except that 1 g of an ethoxylated (6) methacrylate ester compound (Bisomer PEM6LD) was uniformly sprayed onto 100 g of a particulate hydrogel-like crosslinked polymer of Preparation Example 2.
  • a bare superabsorbent polymer was prepared in the same manner as in Example 1, except that 2 g of an ethoxylated (6) methacrylate ester compound (Bisomer PEM6LD) was uniformly sprayed onto 100 g of a particulate hydrogel-like crosslinked polymer of Preparation Example 2.
  • 2 g of an ethoxylated (6) methacrylate ester compound (Bisomer PEM6LD) was uniformly sprayed onto 100 g of a particulate hydrogel-like crosslinked polymer of Preparation Example 2.
  • a bare superabsorbent polymer was prepared in the same manner as in Example 1, except that 2 g of an ethoxylated (6) methacrylate ester compound (Bisomer PEM6LD) was uniformly sprayed onto 100 g of a particulate hydrogel-like crosslinked polymer of Preparation Example 3.
  • 2 g of an ethoxylated (6) methacrylate ester compound (Bisomer PEM6LD) was uniformly sprayed onto 100 g of a particulate hydrogel-like crosslinked polymer of Preparation Example 3.
  • the particulate hydrogel-like crosslinked polymer of Preparation Example 1 was chopped using a meat chopper. Subsequently, the pulverized particulate hydrogel-like crosslinked polymer was dried in a hot air dryer at 180 ° C. for 30 minutes, and the dried particulate hydrogel-like crosslinked polymer was ground with a pin mill grinder. Thereafter, a bare superabsorbent polymer having an average particle size of 150 to 850 ⁇ m was obtained using a sieve. The bare superabsorbent polymer thus obtained was sprayed onto the powder at a rate of 5 pph with a 20% aqueous solution of ethylene carbonate in a surface crosslinking mixer, and dried again at 180 ° C. for 30 minutes. The dried bare superabsorbent resin was classified into a standard mesh of ASTM standard to prepare a supercrosslinked superabsorbent polymer having a particle diameter of 150 ⁇ m to 850 ⁇ m.
  • a superabsorbent polymer having a surface crosslinking treatment was prepared in the same manner as in Comparative Example 1 except that the particulate hydrogel type crosslinked polymer of Preparation Example 2 was used instead of the particulate hydrogel type crosslinked polymer of Preparation Example 1.
  • a superabsorbent polymer having a surface crosslinking treatment was prepared in the same manner as in Comparative Example 1 except that the particulate hydrogel type crosslinked polymer of Preparation Example 3 was used instead of the particulate hydrogel type crosslinked polymer of Preparation Example 1.
  • the monomer composition was introduced into a polymerizer composed of a conveyor belt continuously moving at a temperature of 40 ° C., and then irradiated with ultraviolet rays (irradiation amount: 9 Mw / cm 2 ) through a UV irradiation apparatus, followed by UV polymerization for 3 minutes to form a sheet.
  • a hydrogel-like crosslinked polymer was prepared.
  • the sheet-like hydrogel-like crosslinked polymer was transferred to a cutter and cut into 2 cm. At this time, the water content of the cut particulate hydrogel-like crosslinked polymer was 50% by weight.
  • the particulate hydrogel-like crosslinked polymer was dried in a hot air dryer at 180 ° C. for 30 minutes, and the dried particulate hydrogel-based crosslinked polymer was ground in a pin mill grinder. Thereafter, a bare superabsorbent polymer having an average particle diameter of 150 ⁇ m to 850 ⁇ m was obtained using a sieve.
  • the bare superabsorbent polymers obtained in the examples have lower levels of water-soluble components (EC) and residual monomers (RM) than the surface-crosslinked superabsorbent polymers obtained in the corresponding comparative examples, respectively. Able to know.
  • the bare superabsorbent resins obtained in Examples are superior in water-retaining ability and less residual monomer (RM) content than the bare superabsorbent resins obtained in Comparative Example 4.

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Abstract

L'invention concerne un procédé de préparation d'un polymère superabsorbant comprenant les étapes consistant à : préparer une résine de base par l'ajout d'au moins un parmi les composés représentés par la formule chimique (1) suivante à un polymère réticulé en phase d'hydrogel; et préparer un polymère superabsorbant par séchage de la résine de base. Le procédé de préparation d'un polymère superabsorbant permet de fournir un polymère superabsorbant n'ayant pas subi de traitement de réticulation de surface. Le polymère superabsorbant n'ayant pas subi de traitement de réticulation de surface a une capacité de rétention centrifuge (CRC) et un pouvoir absorbant sous pression (AUP), qui sont équivalents à ceux d'un polymère superabsorbant ayant subi un traitement de réticulation de surface, et a une teneur en produits extractibles (EC) et des monomères résiduels (RM), qui diminuent en comparaison du polymère superabsorbant ayant subi un traitement de réticulation de surface. < Formule chimique (1) > X-(R)n-Y (Dans la formule, X est un groupe hydrocarboné insaturé ou un dérivé de ce dernier; R est au moins un groupe divalent choisi parmi un groupe alkylène en C1-C5, un groupe alkylène oxy en C1-C4, un groupe alkylène(oxy)carbonyle en C2-C6 et un groupe carbonyloxy en C2-C5; n est un nombre entier de 1 à 20; et Y est un groupe hydrophile)
PCT/KR2016/001282 2015-03-18 2016-02-05 Procédé de préparation de polymère superabsorbant Ceased WO2016148397A1 (fr)

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KR10-2015-0037502 2015-03-18
KR1020150037502A KR20160112220A (ko) 2015-03-18 2015-03-18 고흡수성 수지의 제조방법

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AR (1) AR104019A1 (fr)
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US12024577B2 (en) 2020-01-20 2024-07-02 Lg Chem, Ltd. Preparation method of super absorbent polymer
US12239956B2 (en) 2019-12-20 2025-03-04 Lg Chem, Ltd. Preparation method of super absorbent polymer composition
US12269009B2 (en) 2019-01-17 2025-04-08 Lg Chem, Ltd. Super absorbent polymer and method for preparing same
US12337294B2 (en) 2019-12-20 2025-06-24 Lg Chem, Ltd. Preparation method of super absorbent polymer composition
US12491495B2 (en) 2021-01-14 2025-12-09 Lg Chem, Ltd. Method for preparing super absorbent polymer

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KR102495827B1 (ko) 2019-06-10 2023-02-06 주식회사 엘지화학 신규한 가교제 화합물 및 이를 이용하여 제조되는 중합체

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Publication number Priority date Publication date Assignee Title
US12269009B2 (en) 2019-01-17 2025-04-08 Lg Chem, Ltd. Super absorbent polymer and method for preparing same
US12239956B2 (en) 2019-12-20 2025-03-04 Lg Chem, Ltd. Preparation method of super absorbent polymer composition
US12337294B2 (en) 2019-12-20 2025-06-24 Lg Chem, Ltd. Preparation method of super absorbent polymer composition
US12024577B2 (en) 2020-01-20 2024-07-02 Lg Chem, Ltd. Preparation method of super absorbent polymer
US12491495B2 (en) 2021-01-14 2025-12-09 Lg Chem, Ltd. Method for preparing super absorbent polymer

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AR104019A1 (es) 2017-06-21
KR20160112220A (ko) 2016-09-28
TW201700501A (zh) 2017-01-01

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