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WO2018151453A1 - Procédé de production d'une résine très absorbante - Google Patents

Procédé de production d'une résine très absorbante Download PDF

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Publication number
WO2018151453A1
WO2018151453A1 PCT/KR2018/001599 KR2018001599W WO2018151453A1 WO 2018151453 A1 WO2018151453 A1 WO 2018151453A1 KR 2018001599 W KR2018001599 W KR 2018001599W WO 2018151453 A1 WO2018151453 A1 WO 2018151453A1
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Prior art keywords
monomer mixture
aqueous monomer
polymerization
oxygen
polymer
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PCT/KR2018/001599
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English (en)
Korean (ko)
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WO2018151453A8 (fr
Inventor
김준규
오재훈
조영빈
장태환
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180014095A external-priority patent/KR102075735B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18754418.4A priority Critical patent/EP3553092B1/fr
Priority to JP2019517066A priority patent/JP6828145B2/ja
Priority to CN201880003985.XA priority patent/CN109843934B/zh
Priority to US16/338,913 priority patent/US10894245B2/en
Publication of WO2018151453A1 publication Critical patent/WO2018151453A1/fr
Publication of WO2018151453A8 publication Critical patent/WO2018151453A8/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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B01J20/267—Cross-linked polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
    • B01J2220/68—Superabsorbents

Definitions

  • the present invention relates to a method for producing a super absorbent polymer having excellent water absorption performance, and more particularly, to a method for producing a super absorbent polymer, which can effectively inhibit the polymerization reaction from starting in a pipe prior to the addition of the polymerization reactor. It is about.
  • Superabsorbent polymer (Super Absorbent Polymer, SAP) is a synthetic polymer material with a can absorb about 500 to 1000 times the water of its own weight, features, developers every SAM (. Super Absorbency Material), AG ( They are named differently, such as Absorbent Gel Material.
  • Such super absorbent polymers have been put into practical use as physiological devices, and are currently used in sanitary products such as paper diapers for children, horticultural soil repair agents, civil engineering, building index materials, seedling sheets, freshness retainers in the food distribution field, and It is widely used as a material for steaming.
  • these super-absorbent resins are widely used in the field of sanitary materials such as diapers and sanitary napkins. Within this sanitary material, the superabsorbent resin is generally included in the state spread in the peel.
  • the content of pulp is reduced, or more so-called pulpless diapers, in which no pil is used at all. Development is underway. As such, the content of pulp may be reduced, or In this case, relatively high absorbent polymers are included in a high proportion, and such superabsorbent polymer particles are inevitably included in the hygienic material in multiple layers.
  • the superabsorbent resin basically needs to exhibit high absorption performance and absorption rate. .
  • Such superabsorbent water paper is made by the method of drying, pulverizing and classifying a hydrogel polymer prepared by cross-polymerizing a monomer containing a salt thereof, or by surface crosslinking again. .
  • an appropriate kind of polymerization initiator or polymerization inhibitor is used, and the progress of polymerization reaction is controlled through the reaction conditions of reaction, and in particular, in order to activate the polymerization, present in the monomer mixture. It is known to remove dissolved oxygen before adding to the polymerization reactor.
  • the water-soluble ethylenically unsaturated carboxylic acid black has to raise the temperature of the neutralized neutralized liquid in order to obtain its salt, in which case the polymerization is initiated in a transfer line such as a pipe rather than a polymerization reactor.
  • a transfer line such as a pipe rather than a polymerization reactor.
  • the polymerization proceeds at a high temperature, it is possible to reduce the amount of polymerization and initiator to be used and to initiate and suppress the polymerization reaction, compared to conventional polymerization methods. It is to provide a method for producing a super absorbent polymer which can be efficiently controlled.
  • a gas containing oxygen in an aqueous monomer mixture comprising a water-soluble ethylenically unsaturated monomer having a neutralized acidic group, a crosslinking agent, and a polymerization inhibitor which inhibits polymerization of the water-soluble ethylenically unsaturated monomer in the presence of oxygen.
  • the polymerization can be carried out at a high temperature, and the amount of the polymerization initiator can be reduced in the polymerization process rather than the conventional polymerization method, and the initiation and suppression of the polymerization reaction can be efficiently controlled. .
  • first and second are used to describe various components, which terms are used only for the purpose of distinguishing one component from other components.
  • Oxygen is added to an aqueous monomer mixture comprising a water-soluble ethylenically unsaturated monomer having a neutralized acidic group, a crosslinking agent, and a polymerization inhibitor that inhibits polymerization of the water-soluble ethylenically unsaturated monomer in the presence of oxygen.
  • a gas comprising;
  • Step D) in the polymerization reactor, crosslinking polymerization of the water-soluble ethylenically unsaturated monomer to form a hydrogel polymer comprising the first crosslinked polymer.
  • Step D) is a step of forming a hydrogel polymer, which is a step of crosslinking and polymerizing an aqueous monomer mixture comprising a water-soluble ethylenically unsaturated monomer having at least a part of which is neutralized with a crosslinking agent and a polymerization initiator.
  • the water-soluble ethylenically unsaturated monomer constituting the first crosslinked polymer may be any monomer commonly used in the preparation of superabsorbent polymers.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by Formula 1:
  • R1 is an alkyl group having 2 to 5 carbon atoms containing an unsaturated bond
  • M 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 acrylic acid, methacrylic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts of these acids. like this.
  • 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 monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2-
  • 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 neutralization degree of the monomer may be from about 40 to about 95 mol%, or from about 40 to about 80 mol%, or from about 45 to about 75 mole 0/0. If the degree of neutralization is too high, polymerization of the monomer may be difficult to proceed due to precipitation of the neutralized monomer. On the contrary, if the degree of neutralization is too low, the absorbing power of the polymer may not be greatly reduced and may exhibit properties such as elastic rubber that is difficult to handle.
  • the present invention is not necessarily limited to the above range, and the range of the degree of neutralization may vary depending on the physical properties of the final superabsorbent polymer.
  • the concentration of the aqueous monomer common compound may be appropriately adjusted in consideration of the polymerization time and banung conditions, preferably from 20 to 90% by weight, or 40 to 65 weight 0/0 days Can you-.
  • This concentration range may be advantageous in order 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 the gel effect phenomenon appearing in the polymerization reaction of a high concentration aqueous solution.
  • the concentration of the monomer is too low, the yield of the super absorbent polymer may be lowered.
  • the concentration of the monomer is too high, some of the monomers may precipitate or process problems may occur, such as when the pulverized efficiency of the polymerized hydrogel polymer is pulverized, and the physical properties of the super absorbent polymer may be reduced.
  • Common ethylenically unsaturated monomers such as acrylic acid and methacrylic acid, generally contain a polymerization inhibitor in order to prevent polymerization from occurring during storage or transportation.
  • Hydroquinone ether-based compounds are commonly used, and specific examples thereof include monomethyl ether of hydroquinone (MEHQ).
  • Polymerization inhibitors are ethylenically unsaturated monomers In contrast, from about lOppmw to about 300ppmw is used, preferably in a content of about 50ppmw to about 250ppmw, or about 150ppmw to about 220ppmw.
  • a polymerization inhibitor Since such a polymerization inhibitor has a polymerization inhibitory effect of an ethylenically unsaturated monomer in the presence of oxygen, it is necessary to maintain a partial pressure of oxygen with a polymerization inhibitor at a constant or higher during the transport or storage of the ethylenically unsaturated monomer. It is necessary to remove the oxygen present in the monomer before starting the polymer polymerization.
  • a thermal polymerization initiator or a photopolymerization initiator may be used depending on the polymerization method.
  • a thermal polymerization initiator is additionally used. Can be.
  • photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, and benzyldimethyl ketal (for example, benzoin ether).
  • benzoin ether dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, and benzyldimethyl ketal (for example, benzoin ether).
  • One or more compounds selected from the group consisting of benzyl dimethyl ketal, acyl phosphine, and alpha-aminoketone can be used.
  • acylphosphine commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used. .
  • thermal polymerization initiators At least one thermal polymerization initiator compound selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide, and ascorbic acid may be used.
  • sodium persulfate Na2S208
  • potassium persulfate Pitassium persulfate
  • Ammonium ammonium persulfate
  • NH4 2S208 ammonium persulfate
  • azo-based initiators include 2,2-azobis- (2-amidinopropane) dihydrochloride (2,2-azobis (2-amidinopropane) dihydrochloride), 2,2-azobis- ( ⁇ , ⁇ -dimethylene) isobutyramidine dihydrochloride (2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2-
  • the polymerization initiator may be added at a concentration of about 0.001 to about 1 part by weight based on 100 parts by weight of the monomer. If the concentration of the polymerization initiator is too low, the polymerization rate may be slow and a large amount of residual monomer may be extracted in the final product, and if the concentration of the polymerization initiator is too high, the polymer chain forming the network may be shortened.
  • the thermal polymerization initiator may be present in an amount of about 0.01 to about 0.5 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer in the present invention.
  • the amount of the thermal polymerization initiator to be used may be The physical properties of the base resin may be affected, and in particular, the water-soluble component content of the base resin may be increased. In addition, when the thermal polymerization initiator is used too little, the efficiency of the hydrogel polymerization may be lowered, and various physical properties of the superabsorbent polymer to be finally produced may be lowered. Is about 0.05 to about 100 parts by weight of the ethylenically unsaturated monomer 0.5 parts by weight can be used.
  • the above-mentioned polymerization initiators may be used in a form initially contained in the aqueous monomer mixture of step A), including a water-soluble ethylenically unsaturated monomer, a crosslinking agent, and a polymerization inhibitor, to remove oxygen from the aqueous monomer mixture.
  • C) may be used in the form of a separate input just before or immediately after the step.
  • the polymerization reaction can be carried out in the presence of a crosslinking agent.
  • the crosslinking agent may be any compound as long as it allows the introduction of a crosslink in the polymerization of the water-soluble ethylenically unsaturated monomer.
  • the crosslinking agent is ⁇ , ⁇ '- methylenebisacrylamide, trimethyl propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di (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) acrylic Rate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri (meth) acrylate, penta Erys tetraacrylate, triarylamine, ethylene glycol diglycidyl ether, prop
  • two polyethyleneglycol diacrylates with different molecular weights are used.
  • a crosslinking agent may be added in an amount of about 0.001 to about 1 part by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. That is, the crosslinking agent is too small If included, the absorption rate of the resin may be lowered and the gel strength may be weakened, which is undesirable. On the contrary, when the crosslinking agent is used too much, the absorbency of the superabsorbent polymer is lowered, which may be undesirable as an absorber.
  • reaction material in such a polymerization reaction may be prepared in the form of an aqueous monomer mixture in which raw materials such as the monomers described above are dissolved in a solvent.
  • a solvent any solvent that can be used may be used without limitation as long as it can dissolve the above-described raw materials.
  • 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 methylethyl Ketones, acetone, methyl amyl ketone cyclonucanonone, cyclopentanone, diethylene glycol monomethyl ether diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbitle, methyl cellosolve acetate, ⁇ , ⁇ -Dimethylacetic acid, or mixtures thereof, and the like can be used.
  • the formation of the hydrogel polymer through polymerization of the aqueous monomer mixture may be performed by a conventional thermal polymerization method.
  • the aqueous monomer mixture may be introduced into a reactor such as a kneader equipped with a stirring shaft, and hot water may be supplied thereto, or the reactor may be heated to thermally polymerize to obtain a hydrogel polymer.
  • the hydrous gel phase polymer discharged to the reactor outlet according to the form of the stirring shaft provided in the reaction vessel may be obtained from particles of several millimeters to several centimeters.
  • the hydrous gel polymer obtained may be obtained in various forms depending on the concentration and the injection speed of the monomer in the injected aqueous monomer mixture, and the hydrogel polymer having a particle size of about 2 to about 50 mm is usually obtained. Can be.
  • the polymerization reaction is added to the polymerization reactor in a state where the temperature of the aqueous monomer mixture further comprising a thickening liquid or various additives is added thereto.
  • the aqueous monomer mixture may be transferred and introduced into the polymerization reactor via a transfer line at a temperature condition of about 40 to about 90 ° C.
  • the polymerization reaction may be started early in the transfer line, which may cause process troubles such as clogging of the pipe.
  • Solubility of water, such as oxygen, in water is very sensitive to silver and pressure, as well as the nature of the gas molecules themselves, such as polarity.
  • oxygen accounts for about 21%, and under this atmospheric composition, at about 20 ° C, about 1 atmosphere, the saturated dissolved oxygen amount per liter of distilled water is about 8.84 mg, but about 40 ° C At 1 atm, the saturated dissolved oxygen content per liter of distilled water is about 6.59 mg.
  • the neutralizing liquid or various additives is further included in the process of producing a super absorbent polymer as in the present application. It becomes an aqueous monomer mixture condition, and by interaction with other components dissolved in water, the solubility of oxygen itself is generally lower than the above range.
  • the saturated dissolved oxygen amount per 1 liter of the aqueous monomer mixture is about 7.5 to about 8 mg at about 20 ° C, about 1 atmosphere, and about 40 ° C, at 1 atmosphere, The amount of saturated dissolved oxygen for 1 liter of the monomer mixture is greatly lowered to about 3.0 to about 4 mg.
  • a gas containing oxygen is optionally injected into a thickening liquid containing the polymerization inhibitor described above, or an aqueous monomer mixture containing such a neutralizing liquid and various additives, and an aqueous monomer mixture in which a gas containing oxygen is injected.
  • the injected oxygen By increasing the activity of the polymerization inhibitor may serve to control the polymerization reaction does not occur during the transfer process.
  • the dissolved oxygen ratio represented by Equation 1 below is greater than about 1.0, about 2.5 or less, preferably about 1.5 or more and 2.5 or less, more preferably, about 1.7 or more Oxygen or a gas containing oxygen (atmosphere, etc.) may be injected to satisfy the range of 2.3 or less.
  • D01 is the amount of dissolved oxygen (mg / L) in the aqueous monomer mixture, measured immediately before injecting the gas containing oxygen into the aqueous monomer mixture,
  • D02 is the amount of dissolved oxygen (mg / L) in the aqueous monomer mixture measured immediately after injecting the gas containing oxygen into the aqueous monomer mixture. .
  • the atmosphere containing oxygen or oxygen is injected into the neutralizing liquid or the aqueous monomer mixture containing the neutralizing liquid and various additives, thereby polymerizing the aqueous monomer mixture having a large increase in the amount of dissolved oxygen.
  • the process shock such as clogging of the pipe.
  • the oxygen-injected aqueous monomer mixture is directly introduced into the polymerization reactor, a polymerization reaction proceeding in the polymerization reactor is suppressed and a reaction efficiency may decrease.
  • the inert gas means a gas which is not reactive to the monomer and various additive components contained in the above-mentioned aqueous monomer mixture, and specifically ,.
  • Group 18 gases such as helium (He), neon (Ne), argon (Ar), carbon monoxide (CO), Carbon dioxide (C0 2 ), nitrogen (N 2 ) and the like may be included, and one or more of these may be used in combination.
  • the inert gas may be injected in the same direction or in the opposite direction as the aqueous monomer mixture to remove oxygen, mixed with the aqueous monomer mixture by a valve, a mixer, or a bubble column, and then discharged. Oxygen contained in the mixture can be removed.
  • the inert gas is preferably injected in the same direction as the aqueous monomer mixture, and may be introduced together with the polymerization reactor. Through this process, oxygen dissolved in the aqueous monomer mixture can be effectively removed.
  • the dissolved oxygen ratio represented by Equation 2 may be about 0.01 or more, or about 0.05 or more, and about 0.2 or less, preferably about 15 or less.
  • the dissolved oxygen ratio represented by the following equation (3) is about ⁇ to about
  • 0.5 preferably about 0.1 or more, or about 0.2 or more, about 0.5 or less, or about 0.4 or less, preferably about 0.3 or less.
  • Equation 1 D01 and D02 are as defined in Equation 1,
  • D03 is the amount of dissolved oxygen in the aqueous monomer mixture (mg / L) measured immediately after removing oxygen from the aqueous monomer mixture.
  • the conventional water content of the hydrogel polymer obtained by the above method may be about 40 to about 80% by weight.
  • water content means the content of water to account for the total weight of the hydrogel polymer minus the weight of the polymer in the dry state. Specifically, In the process of raising the temperature of the polymer through infrared heating and drying, it is defined as a calculated value by measuring the weight loss due to evaporation of water in the polymer.
  • Step E) is a step of drying, pulverizing and classifying the hydrogel polymer prepared by the above-described method to form a base resin powder, wherein the base resin powder and the super absorbent polymer obtained therefrom have a particle diameter of about 150 to about 850. Manufactured and provided to have suitable.
  • the base resin powder and the superabsorbent polymer obtained therefrom have a particle size of about 150 to about 850 mm 3, and the fine powder having a particle size of less than about 150 is less than about 3% by weight.
  • the final superabsorbent polymer prepared may express the above-described physical properties better. On the other hand, it will be described in more detail with respect to the progress of the drying, grinding and classification as follows.
  • the pulverizer used is not limited in configuration, but specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Includes any one selected from the group of grinding machines consisting of cutter mills, disc mills, shred crushers, crushers, choppers and disc cutters Although it is possible, it is not limited to the above-mentioned example.
  • the particle diameter of the hydrogel filler is about 2 mm to about 10 mm. It can be ground as much as possible.
  • the drying temperature of the drying step may be about 50 to about 250 o C. If the drying temperature is less than about 50 o C, the drying time may be too long and the physical properties of the superabsorbent polymer to be finally formed may be lowered.
  • the drying temperature exceeds about 250 o C, only the polymer surface is dried excessively, Fine powder may be generated in a subsequent grinding step, and there is a fear that the physical properties of the superabsorbent polymer to be finally formed are reduced. More preferably, the drying may proceed at a temperature of about 150 to about 200 ° C, more preferably at a temperature of about 160 to about 190 ° C. On the other hand, in the case of drying time may be performed for about 20 minutes to about 15 hours in consideration of process efficiency, but is not limited thereto. As long as it is conventionally used in the drying process, can be selected and used without limitation of the configuration.
  • the drying step may be performed by a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the water content of the polymer after such a drying step may be about 0.05 to about 10 weight 0 /.
  • the step of pulverizing the dried polymer obtained through this drying step is carried out.
  • the polymer powder obtained after the grinding step may have a particle diameter of about 150 to about 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 mill, a roll mill, a disk.
  • a mill or a 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 diameter may be performed.
  • the polymer having a particle size of about 150 to about 850 may be classified and commercialized through a surface crosslinking reaction step to be described later only for the polymer powder having such a particle size.
  • the step F) is a step of crosslinking the surface of the base resin prepared in the step E), and in the presence of a surface crosslinking solution, heat treating the base resin powder to crosslink the surface to form superabsorbent resin particles.
  • the surface crosslinking solution is ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, Diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propane diol, dipropylene glycol, ' polypropylene glycol, glycerin, polyglycerol, butanediol, heptanediol, nucleic acid die, trimethylolpropane, pentaerythritol , Sorbbi, may include one or more surface crosslinking agents selected from the group consisting of calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, calcium chloride, magnesium chloride, aluminum chloride, and iron chloride.
  • ethylene glycol diglycidyl ether can be used.
  • the said surface crosslinking agent about 1 weight part or less with respect to 100 weight part of said base resins.
  • the amount of the surface crosslinking agent used means the total amount thereof when two or more kinds of the surface crosslinking agents are used.
  • the surface crosslinking agent may be used in an amount of about 0.
  • the surface crosslinking solution is water, methanol, ethanol, isopropyl alcohol 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, butyrolactone, carbyl, methyl cellosolve acetate
  • ⁇ , ⁇ -dimethylacetamide may further comprise at least one solvent selected from the group consisting of.
  • water is included.
  • the solvent may be used in about 0.5 to about 10 parts by weight based on 100 parts by weight of the base resin powder.
  • the surface crosslinking liquid may further include aluminum sulfate.
  • the aluminum sulfate may be included in about 0.02 to about 1.5 parts by weight based on 100 parts by weight of the base resin powder.
  • the surface crosslinking liquid may further include an inorganic filler.
  • the inorganic filler may include silica, aluminum oxide, or silicate.
  • the inorganic filler may be included in an amount of about 0.01 to about 0.5 parts by weight based on 100 parts by weight of the base resin powder.
  • the surface crosslinking liquid may further include a thickener.
  • the thickener may be used one or more selected from polysaccharides and hydroxy containing polymers.
  • the polysaccharide gum thickener and cellulose thickener may be used.
  • examples of the gum-based thickener xanthan gum (xanthan gum), Arabic gum (arabic gum), karaya gums (karaya gum), bit i raegeo kaenseu gum (tragacanth gum), Gatti gum (ghatti gum), guar Guar gum, locust bean gum, silylium seed gum, and the like.
  • cellulose-based thickeners include hydroxypropylmethylcellulose, carboxy, and the like.
  • Methyl cellulose, Methylcellose, hydroxymethylcellose, hydroxyethylcellose, hydroxypropylcellose ', hydroxyethylmethylcellose, hydroxymethylpropylcellose, hydroxyethylhydroxypropylcell Rhose, ethyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, etc. are mentioned.
  • specific examples of the hydroxy-containing polymers include polyethylene glycol and polyvinyl alcohol.
  • the surface crosslinking solution and the base resin are put into a reaction tank and mixed, a method of spraying a surface crosslinking solution onto the base resin, and the base resin and the surface crosslinking to a mixer which is continuously operated.
  • the method of supplying and mixing a liquid continuously, etc. can be used.
  • the surface crosslinking may be performed at a temperature of about 100 to about 250 ° C., and may be continuously performed after the drying and grinding step of proceeding at a relatively high temperature. At this time.
  • the surface crosslinking reaction may proceed for about 1 to about 120 minutes, or about 1 to about 100 minutes, or about 10 to about 60 minutes.
  • the polymer particles may be damaged during excessive reaction and thus the physical properties may be deteriorated.
  • the super-absorbent resin according to the present invention centrifugation beam SAT (CRC) for 30 minutes for saline solution (0.9 weight 0/0 aqueous sodium chloride solution) is not less than 30g / g.
  • the measuring method of the centrifugal water holding capacity is specified in the following Examples.
  • the centrifugal water holding capacity is 3 (). 5g / g or more, or 31g / g or more.
  • the super absorbent polymer according to the present invention has a pressurized absorption capacity (0.7 AUP) of 1 g or more for 1 hour under 0.7 psi with respect to physiological saline solution (0.9 weight 0 /. Sodium chloride aqueous solution).
  • the measuring method of the said pressure absorbing power is specified more in the following example.
  • the 0.7 AUP is at least 20 g / g, or at least 8.0 g / g.
  • the superabsorbent polymer according to the present invention has a proportion of particles having a particle diameter of about 150 to about 850 / ⁇ of about 90% or more.
  • In-line Homogenizer (Megatron MT 3000, 4 inlets and 1 outlet) is installed at the upper inlet of single-axis kneader (listed by LIST) that can continuously inject and discharge. , 0.2% ascorbic acid 30g per minute and 0.7% hydrogen peroxide solution 30g per minute, respectively, injecting nitrogen gas into another inlet at a rate of 20L per minute, and rotating the homogenizer at 6,000rpm per minute to mix the solution and gas. The mixed solution and gas inside the homogenizer were introduced into the kneader through the outlet. After adding the neutralizing solution to the kneader, a gel was formed inside the kneader and foaming occurred.
  • the gel was subdivided and discharged out of the kneader by the force given from the rotating body inside, and the size of the gel was 5 mm to 50 mm. This was chopped using a Meat Chopper to further refine the average gel size to 5 mm.
  • the amount of initiator is 100 ascorbic acid and hydrogen peroxide solution described in the above example, and the relative amount is described.
  • Comparative Example 2 0 40 100 Polymer at the outlet of the atmospheric DMS

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Abstract

La présente invention concerne un procédé de production d'une résine très absorbante présentant d'excellentes propriétés d'absorption, et plus particulièrement un procédé de production d'une résine très absorbante dans lequel les problèmes associés à un processus peuvent être évités par la suppression efficace de l'initiation d'une réaction de polymérisation dans une conduite avant l'introduction dans un réacteur de polymérisation.
PCT/KR2018/001599 2017-02-16 2018-02-06 Procédé de production d'une résine très absorbante WO2018151453A1 (fr)

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EP18754418.4A EP3553092B1 (fr) 2017-02-16 2018-02-06 Procédé de production d'une résine très absorbante
JP2019517066A JP6828145B2 (ja) 2017-02-16 2018-02-06 高吸水性樹脂の製造方法
CN201880003985.XA CN109843934B (zh) 2017-02-16 2018-02-06 用于制备超吸收性聚合物的方法
US16/338,913 US10894245B2 (en) 2017-02-16 2018-02-06 Method for preparing superabsorbent polymer

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KR10-2017-0021051 2017-02-16
KR20170021051 2017-02-16
KR1020180014095A KR102075735B1 (ko) 2017-02-16 2018-02-05 고흡수성 수지의 제조 방법
KR10-2018-0014095 2018-02-05

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JP2009543915A (ja) * 2006-07-19 2009-12-10 ビーエーエスエフ ソシエタス・ヨーロピア モノマー溶液の液滴の重合による、高い吸収性を有する後架橋された吸水性ポリマー粒子の製造方法
JP2009543922A (ja) * 2006-07-19 2009-12-10 ビーエーエスエフ ソシエタス・ヨーロピア 高い透過性を有する吸水性ポリマー粒子の重合による製造方法
JP2014205856A (ja) * 2006-07-19 2014-10-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高い透過性を有する吸水性ポリマー粒子
JP2014240501A (ja) * 2006-07-19 2014-12-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ モノマー溶液の液滴の重合による、高い透過性を有する吸水性ポリマー粒子の製造方法
KR20160149238A (ko) * 2014-04-25 2016-12-27 송원산업 주식회사 흡수성 폴리머 입자를 제조하기 위한, 과-중화를 이용한 모노머 처리 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009543915A (ja) * 2006-07-19 2009-12-10 ビーエーエスエフ ソシエタス・ヨーロピア モノマー溶液の液滴の重合による、高い吸収性を有する後架橋された吸水性ポリマー粒子の製造方法
JP2009543922A (ja) * 2006-07-19 2009-12-10 ビーエーエスエフ ソシエタス・ヨーロピア 高い透過性を有する吸水性ポリマー粒子の重合による製造方法
JP2014205856A (ja) * 2006-07-19 2014-10-30 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 高い透過性を有する吸水性ポリマー粒子
JP2014240501A (ja) * 2006-07-19 2014-12-25 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ モノマー溶液の液滴の重合による、高い透過性を有する吸水性ポリマー粒子の製造方法
KR20160149238A (ko) * 2014-04-25 2016-12-27 송원산업 주식회사 흡수성 폴리머 입자를 제조하기 위한, 과-중화를 이용한 모노머 처리 방법

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