WO2021054610A1 - Procédé de préparation de polymère superabsorbant - Google Patents

Procédé de préparation de polymère superabsorbant Download PDF

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Publication number
WO2021054610A1
WO2021054610A1 PCT/KR2020/010614 KR2020010614W WO2021054610A1 WO 2021054610 A1 WO2021054610 A1 WO 2021054610A1 KR 2020010614 W KR2020010614 W KR 2020010614W WO 2021054610 A1 WO2021054610 A1 WO 2021054610A1
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Prior art keywords
super absorbent
absorbent polymer
water
polymer
weight
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PCT/KR2020/010614
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English (en)
Korean (ko)
Inventor
정의석
김규팔
안균혁
김기철
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020200099393A external-priority patent/KR102608042B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US17/285,685 priority Critical patent/US20210317237A1/en
Priority to JP2021518712A priority patent/JP7309255B2/ja
Priority to CN202080005373.1A priority patent/CN113039235B/zh
Priority to EP20862008.8A priority patent/EP3838968A4/fr
Publication of WO2021054610A1 publication Critical patent/WO2021054610A1/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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • 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
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof

Definitions

  • the present invention is capable of suppressing crushing during transport by appropriately controlling the moisture content of the super absorbent polymer by means of water, etc., while suppressing deterioration of physical properties such as generation of large particles or non-uniform moisture content during the hydrolysis process. It relates to a method for producing a resin.
  • Super Absorbent Polymer is a synthetic polymer material that has the ability to absorb moisture of 500 to 1,000 times its own weight, and each developer has a SAM (Super Absorbency Material), AGM (Absorbent Gel). Material) and so on. Since the above-described superabsorbent resin has begun to be put into practical use as a sanitary tool, nowadays, in addition to hygiene products such as paper diapers for children, soil repair agents for horticultural use, water resistant materials for civil engineering and construction, sheets for seedlings, freshness maintenance agents in the food distribution field, It is widely used as a material for poultice.
  • SAM Super Absorbency Material
  • AGM Absorbent Gel
  • super absorbent polymers are widely used in the field of hygiene products such as diapers and sanitary napkins.
  • superabsorbent polymers typically have a form in which fine powders are gathered, and as these fine powders have a uniform particle diameter and a large surface area in the sanitary material, they rapidly absorb a large amount of moisture. Need to be indicated.
  • the super absorbent polymer in the process of manufacturing the super absorbent polymer, there are many cases in which the super absorbent polymer is transferred in order to proceed with a subsequent process or apply to a packaging or sanitary material.
  • the super absorbent polymer has a form in which fine powders are collected, there are many cases where the super absorbent polymer powders physically collide and crush during the resin transfer process. Accordingly, various physical properties such as the overall absorption ability of the super absorbent polymer There is a problem that a decline occurs.
  • the resin powders agglomerate with each other, for example, large particles having a particle diameter larger than 850 ⁇ m ( There were many cases where a large amount of particles that did not pass through the standard body #20) occurred.
  • the generation of such a large amount of large particles may lead to a decrease in properties of the overall superabsorbent polymer, and as a result, it is necessary to additionally remove the large particles by a classification process or the like, resulting in a decrease in the overall productivity of the super absorbent polymer.
  • the water content of the super absorbent polymer can be properly controlled by water, etc. to suppress crushing during transport, while also reducing problems such as generation of large particles during the hydrolysis process.
  • the development of is continuously required.
  • the present invention is capable of suppressing crushing during transport by appropriately controlling the moisture content of the super absorbent polymer by means of a water number, etc., while suppressing degradation of physical properties such as generation of large particles or non-uniform moisture content during the hydrolysis process. It is to provide a method for producing a water absorbent resin.
  • the present invention provides a super absorbent property comprising a base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least partially neutralized acidic groups, and a surface crosslinked layer formed on the surface of the base resin powder by further crosslinking the crosslinked polymer.
  • a base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least partially neutralized acidic groups, and a surface crosslinked layer formed on the surface of the base resin powder by further crosslinking the crosslinked polymer.
  • It provides a method for producing a super absorbent polymer comprising the step of forming a hydrolyzed super absorbent polymer by mixing water and an additive including a carboxylic acid of an aliphatic hydrocarbon having 10 to 30 carbon atoms in the super absorbent polymer particles.
  • the water content of the superabsorbent polymer may be appropriately controlled in the hydrolysis step or the like to suppress crushing or deterioration of physical properties during transport. Furthermore, by the use of the specific additive, it is possible to solve the problem that the physical properties of the super absorbent polymer are deteriorated due to phenomena such as generation of large particles or non-uniform moisture content during the hydrolysis process.
  • the present invention while being able to suppress crushing during transfer of the super absorbent polymer, the decrease in physical properties during the hydrolysis process or decrease in productivity due to the generation of large particles does not appear substantially, so that the super absorbent polymer exhibiting excellent physical properties is highly productive.
  • By manufacturing and transferring it can be preferably applied to the manufacture of various sanitary materials.
  • polymer or “polymer” used in the specification of the present invention means that a water-soluble ethylenically unsaturated monomer is polymerized, and may encompass all ranges of moisture content or particle size.
  • a polymer having a moisture content (moisture content) of about 40% by weight or more, which is in a state before drying after polymerization may be referred to as a hydrogel polymer.
  • “super absorbent polymer” means the polymer or the base resin itself, depending on the context, or an additional process, such as surface crosslinking, fine powder reassembly, drying, grinding, classifying, for the polymer or the base resin, It is used to cover all products made suitable for commercialization through singers, etc.
  • a base resin powder comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least partially neutralized acidic groups, and a surface crosslinked layer formed on the surface of the base resin powder by further crosslinking the crosslinked polymer Providing a super absorbent polymer particle comprising;
  • a method for producing a super absorbent polymer comprising the step of forming a hydrolyzed super absorbent polymer by mixing water and an additive including a carboxylic acid of an aliphatic hydrocarbon having 10 to 30 carbon atoms to the super absorbent polymer particles.
  • an additive has a hydrophobic functional group of a long-chain hydrocarbon in the molecule, and together with a hydrophilic functional group of a carboxylic acid at the terminal.
  • the specific additive includes both the hydrophobic functional group and the hydrophilic functional group of carboxylic acid, the super absorbent polymer particles are evenly dispersed and distributed in the mixed water, so that crushing during transfer of the super absorbent polymer can be more effectively suppressed.
  • the decrease in physical properties during the hydrolysis process or decrease in productivity due to the generation of large particles substantially does not appear.
  • super absorbent polymer particles are prepared. These super absorbent polymer particles are crosslinked, polymerized, and dried according to the manufacturing process and conditions of a general super absorbent polymer. It can be manufactured through processes such as pulverization, classification, and surface crosslinking. Hereinafter, an example of manufacturing super absorbent polymer particles will be described in detail.
  • a monomer composition is formed by mixing each component of a water-soluble ethylenically unsaturated monomer, an internal crosslinking agent, and a polymerization initiator having an acidic group at least partially neutralized.
  • R 1 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.
  • acrylic acid or a salt thereof is used as a water-soluble ethylenically unsaturated monomer, a super absorbent polymer having improved water absorption can be obtained, which is advantageous.
  • the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid, or 2-( Anionic monomers of meth)acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth)acrylamide, N-substituted (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate or polyethylene glycol ( Nonionic hydrophilic-containing monomers of meth)acrylate; And (N,N)-dimethylaminoethyl (meth)acrylate or an amino group-containing unsaturated monomer of (N,N)-dimethylaminopropyl (meth)acrylamide and a quaternary product thereof; Can be
  • the water-soluble ethylenically unsaturated monomer may have an acidic group, and at least a part of the acidic group may be neutralized.
  • the monomer partially neutralized with an alkaline substance such as sodium hydroxide, potassium hydroxide or ammonium hydroxide may 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 precipitates and it may be difficult for the polymerization to proceed smoothly. On the contrary, if the degree of neutralization is too low, the absorbency of the polymer is greatly reduced. It may exhibit properties such as elastic rubber that are difficult to handle.
  • the internal crosslinking agent is a term used to distinguish it from the surface crosslinking agent for further crosslinking the surface of the base resin to be described later, and serves to crosslink and polymerize the unsaturated bonds of the water-soluble ethylenically unsaturated monomers described above.
  • the crosslinking in the above step proceeds without distinction between the surface or the interior, but by the surface crosslinking process of the base resin to be described later, the surface of the finally prepared superabsorbent polymer has a structure crosslinked by a surface crosslinking agent, and the interior is the internal crosslinking agent. It is made of a crosslinked structure by.
  • the internal crosslinking agent any compound may be used as long as it allows the introduction of a crosslinking bond during polymerization of the water-soluble ethylenically unsaturated monomer.
  • the internal crosslinking agent is N,N'-methylenebisacrylamide, trimethylolpropane tri(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylate, ( Poly)propylene glycol di(meth)acrylate, polypropylene glycol (meth)acrylate, butanediol di(meth)acrylate, (poly)butylene glycol di(meth)acrylate, diethylene glycol di(meth) Acrylate, hexanedioldi(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipentaerythrito
  • This internal crosslinking agent may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer.
  • the internal crosslinking agent may be used in an amount of 0.01 parts by weight or more, 0.03 parts by weight or more, or 0.05 parts by weight or more, and 5 parts by weight or less and 3 parts by weight or less based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer.
  • the polymerization initiator may be appropriately selected according to the polymerization method, and when a thermal polymerization method is used, a thermal polymerization initiator is used, when a photopolymerization method is used, a photopolymerization initiator is used, and a hybrid polymerization method (heat and light In the case of using all of the methods), both a thermal polymerization initiator and a photopolymerization initiator can be used.
  • a certain amount of heat is generated by light irradiation such as ultraviolet irradiation, and a certain amount of heat is generated according to the progress of the polymerization reaction, which is an exothermic reaction, and thus a thermal polymerization initiator may be additionally used.
  • the photopolymerization initiator may be used without limitation of its configuration as long as it is a compound capable of forming radicals by light such as ultraviolet rays.
  • photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketone.
  • Ketal examples include acyl phosphine, and alpha-aminoketone ( ⁇ -aminoketone) may be used at least one selected from the group.
  • specific examples of acylphosphine include diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl (2,4,6- Trimethylbenzoyl)phenylphosphineate and the like. More various photoinitiators are well specified in Reinhold Schwalm's book “UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)" p115, and are not limited to the above examples.
  • the photopolymerization initiator may be included in a concentration of 0.0001 to 2.0% by weight based on the monomer composition. If the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow, and if the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be small and physical properties may become uneven.
  • thermal polymerization initiator at least one selected from the group of initiators consisting of persulfate-based initiators, azo-based initiators, hydrogen peroxide and ascorbic acid may be used.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (Potassium persulfate; K 2 S 2 O 8 ), and ammonium persulfate (Ammonium persulfate; (NH 4 )) 2 S 2 O 8 ), etc.
  • examples of azo-based initiators include 2,2-azobis-(2-amidinopropane)dihydrochloride (2,2-azobis(2-amidinopropane) dihydrochloride), 2 ,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride (2,2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride), 2-(carb
  • the thermal polymerization initiator may be included in a concentration of 0.001 to 2.0% by weight based on the monomer composition. If the concentration of the thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, so the effect of the addition of the thermal polymerization initiator may be insignificant. If the concentration of the thermal polymerization initiator is too high, the molecular weight of the super absorbent polymer may be small and physical properties may become uneven. have.
  • the monomer composition may further include additives such as a thickener, a plasticizer, a storage stabilizer, an antioxidant, or a surfactant, if necessary.
  • additives such as a thickener, a plasticizer, a storage stabilizer, an antioxidant, or a surfactant, if necessary.
  • the above-described water-soluble ethylenically unsaturated monomer, an internal crosslinking agent, and a polymerization initiator may be mixed together with a solvent. Therefore, the monomer composition prepared in the above step is in a form dissolved in the solvent, and the content of the solid content in the monomer composition may be 20 to 60% by weight.
  • the solvent that can be used at this time can be used without limitation of its composition as long as the above-described components can be dissolved.
  • the mixing of the above-described components is not particularly limited, and may be performed through a method commonly used in the art, for example, stirring.
  • crosslinking polymerization of the monomer composition is performed to form a hydrogel polymer.
  • the above step may be carried out without any particular limitation of the composition as long as the prepared monomer composition can be crosslinked and polymerized by a method of thermal polymerization, photopolymerization, or hybrid polymerization to form a hydrogel polymer.
  • thermal polymerization when performing thermal polymerization, it may be performed in a reactor having a stirring shaft such as a kneader. In addition, when the thermal polymerization is performed, it may be performed at a temperature of about 80°C or more and less than about 110°C.
  • the means for achieving the polymerization temperature in the above-described range is not particularly limited, and heating may be performed by supplying a heat medium to the reactor or directly supplying a heat source.
  • a heated fluid such as steam, hot air, or hot oil may be used, but the temperature of the heat medium supplied is not limited thereto. You can choose appropriately.
  • the heat source directly supplied may include heating through electricity and heating through gas, but is not limited to the above-described example.
  • the photopolymerization when it is performed, it may be performed in a reactor equipped with a movable conveyor belt, but the polymerization method described above is an example, and the present invention is not limited to the polymerization method described above.
  • a hydrogel polymer discharged to the reactor outlet may be obtained.
  • the hydrogel polymer thus obtained may be obtained in a size of several centimeters to several millimeters, depending on the shape of the stirring shaft provided in the reactor.
  • the size of the resulting hydrogel polymer may vary depending on the concentration and injection speed of the monomer composition to be injected.
  • the form of the hydrogel polymer usually obtained may be a hydrogel polymer on a sheet having a width of the belt.
  • the thickness of the polymer sheet varies depending on the concentration and injection speed of the monomer composition to be injected, but it is preferable to supply the monomer composition so that a sheet-like polymer having a thickness of about 0.5 to about 10 cm can be obtained.
  • the production efficiency is not preferable, and when the thickness of the polymer on the sheet exceeds 10 cm, due to the excessively thick thickness, the polymerization reaction is evenly performed over the entire thickness. It may not happen.
  • the polymerization time of the monomer composition is not particularly limited, and may be adjusted to about 30 seconds to 60 minutes.
  • a typical moisture content of the hydrogel polymer obtained by this method may be about 30 to about 80% by weight.
  • water content refers to a value obtained by subtracting the weight of the dried polymer from the weight of the hydrous gel polymer as the content of water occupied with respect to the total weight of the hydrogel polymer. Specifically, it is defined as a calculated value by measuring the weight loss due to evaporation of moisture in the polymer during drying by raising the temperature of the polymer through infrared heating.
  • the drying condition is a method of increasing the temperature from room temperature to about 180°C and then maintaining it at 180°C.
  • the total drying time is set to 40 minutes including 5 minutes in the temperature raising step, and the moisture content is measured.
  • the hydrogel polymer is dried, pulverized and classified to form a powdery base resin.
  • a process of coarsely pulverizing the hydrogel polymer before drying may be included in order to increase drying efficiency.
  • the grinder used is not limited in configuration, and specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, and cutting Cutter mill, disc mill, shred crusher, crusher, chopper, and disc cutter. However, it is not limited to the above-described example.
  • the particle diameter of the hydrogel polymer may be adjusted to about 0.1 to about 10 mm. Grinding so that the particle diameter is less than 0.1 mm is not technically easy due to the high moisture content of the hydrogel polymer, and a phenomenon of agglomeration between the pulverized particles may occur. On the other hand, when pulverizing so that the particle diameter exceeds 10 mm, the effect of increasing the efficiency of the subsequent drying step may be insignificant.
  • the drying temperature may be about 60°C to about 250°C.
  • the drying temperature is less than about 70° C., the drying time is too long, and when the drying temperature exceeds about 250° C., only the polymer surface is dried excessively, and fine powder may be generated in a subsequent pulverization process.
  • the drying may be performed at a temperature of about 100°C to about 240°C, more preferably about 110°C to about 220°C.
  • drying time it may be performed for about 20 minutes to about 12 hours in consideration of process efficiency and the like. For example, it may be dried for about 10 minutes to about 100 minutes, or about 20 minutes to about 60 minutes.
  • the drying method in the drying step is also commonly used as a drying process of the hydrous gel polymer, it may be selected and used without limitation of its configuration.
  • the drying step may be performed by a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the moisture content of the polymer after such a drying step may be about 0.1 to about 10% by weight.
  • the dried polymer obtained through the drying step is pulverized using a grinder.
  • the pulverizer used to pulverize the powdered base resin to be made of particles having a particle diameter of about 150 ⁇ m to about 850 ⁇ m is specifically, a pin mill, a hammer mill, and a screw. Mill (screw mill), roll mill (roll mill), disk mill (disc mill), may be a jog mill (jog mill), etc., but is not limited to the above-described example.
  • a separate process of classifying the polymer powder obtained after pulverization according to the particle size may be performed.
  • a polymer having a particle diameter of 150 to 850 ⁇ m is classified, and only a polymer powder having such a particle diameter can be produced through a surface crosslinking reaction step.
  • the classified base resin powder has a particle diameter of 150 to 850 ⁇ m, and may include 50% by weight or more of particles having a particle diameter of 300 to 600 ⁇ m.
  • a step of forming a surface crosslinking layer by further crosslinking the surface of the base resin in the presence of a surface crosslinking agent is performed.
  • the step is a step of forming a surface crosslinking layer using a surface crosslinking agent to increase the surface crosslinking density of the base resin, so that the unsaturated bonds of the water-soluble ethylenically unsaturated monomer remaining on the surface without crosslinking are crosslinked by the surface crosslinking agent.
  • a super absorbent polymer having a high surface crosslinking density is formed.
  • the surface crosslinking density that is, the external crosslinking density, is increased by this heat treatment process, while the internal crosslinking density does not change, so that the superabsorbent polymer having a surface crosslinked layer formed thereon has a structure having a higher crosslinking density on the outside than on the inside.
  • a surface crosslinking agent composition including a surface crosslinking agent, an alcohol-based solvent, and water may be used.
  • the surface crosslinking agent included in the surface crosslinking agent composition any surface crosslinking agent that has been conventionally used to manufacture a super absorbent polymer may be used without any particular limitation.
  • the surface crosslinking agent is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 2- One selected from the group consisting of methyl-1,3-propanediol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, tripropylene glycol and glycerol Or more polyols; At least one carbonate-based compound selected from the group consisting of ethylene carbonate and propylene carbonate; Epoxy compounds such as ethylene glycol diglycidyl ether
  • the configuration of the method of mixing the surface crosslinking agent composition with the base resin there is no limitation on the configuration of the method of mixing the surface crosslinking agent composition with the base resin.
  • a method of mixing a surface crosslinking agent composition and a base resin in a reaction tank, or spraying a surface crosslinking agent composition onto the base resin, a method of continuously supplying and mixing the base resin and the surface crosslinking agent composition to a continuously operated mixer, etc. Can be used.
  • the surface crosslinking process may be performed at a temperature of about 80°C to about 250°C. More specifically, the surface crosslinking process may be performed at a temperature of about 100°C to about 220°C, or about 120°C to about 200°C, for about 20 minutes to about 2 hours, or about 40 minutes to about 80 minutes. .
  • the surface of the base resin is sufficiently crosslinked, so that the absorbency under pressure or liquid permeability may be increased.
  • the means for increasing the temperature for the surface crosslinking reaction is not particularly limited. It can be heated by supplying a heat medium or by directly supplying a heat source. At this time, as the type of the heat medium that can be used, a heated fluid such as steam, hot air, or hot oil may be used, but the temperature of the heat medium supplied is not limited thereto. It can be appropriately selected in consideration.
  • the heat source directly supplied may include heating through electricity and heating through gas, but is not limited to the above-described example.
  • super absorbent polymer particles may be manufactured and provided.
  • Such super absorbent polymer particles include, for example, a base resin powder comprising a crosslinked polymer in which a water-soluble ethylenically unsaturated monomer having at least a partly neutralized acidic group is polymerized through an internal crosslinking agent, and the crosslinked polymer is a surface crosslinking agent. It may have a form including a surface crosslinked layer formed on the surface of the base resin powder by being further crosslinked.
  • a carboxylic acid of an aliphatic hydrocarbon having 10 to 30 carbon atoms is used as an additive, and these additives have both a hydrophobic functional group of a long-chain hydrocarbon and a hydrophilic functional group of a carboxylic acid in the molecule. And it is possible to effectively suppress the crushing and agglomeration of the super absorbent polymer during transport.
  • the additive may be a compound in which a carboxylic acid is bonded to the terminal of an aliphatic saturated hydrocarbon such as a linear alkyl group having 12 to 20 carbon atoms, and in a more specific example, stearic acid, lauric acid ) And arachidic acid (Arachidic acid) may be one or more carboxylic acid compounds selected from the group consisting of.
  • the above-described additives are based on the weight of the super absorbent polymer particles so as to effectively suppress the formation of large particles due to the aggregation of the super absorbent polymer particles during the hydrolysis process, and not inhibit the uniform increase of the moisture content due to the hydrolysis process. It may be mixed in an amount of 5 to 20,000ppmw. In a more specific example, the additive may be mixed in an amount of 5 to 1000 ppmw, 10 to 500 ppmw, or 50 to 300 ppmw based on the weight of the super absorbent polymer particles.
  • the additive is used in such a content range, aggregation between super absorbent polymer particles and generation of large particles during the hydrolysis process are more effectively suppressed, while the moisture content of the super absorbent polymer is uniform throughout the desired range due to the hydrolysis process and subsequent drying. Can be controlled.
  • the water is 1 to 10 parts by weight of the super absorbent polymer particles so that water is uniformly mixed with the super absorbent polymer particles in the hydrolysis process so that the moisture content of the final super absorbent polymer can be uniformly controlled as a whole. It is appropriate to mix in an amount of 3 to 8 parts by weight, or 4 to 6 parts by weight.
  • the hydrolysis process of mixing the above-described additive and water may be performed while cooling the surface-crosslinked superabsorbent polymer particles under a temperature of, for example, 40 to 80°C or 45 to 75°C.
  • the step of drying and classifying the hydrolyzing superabsorbent resin may be further performed. While drying the hydrolyzed superabsorbent resin in which water and additives are uniformly mixed in the hydrolysis process, a desired moisture content, for example, a moisture content of 1 to 2.5% by weight may be finally achieved.
  • This moisture content range is an increase compared to the moisture content of about 0.5% by weight or less, or 0.3% by weight or less of the same superabsorbent polymer particles immediately after surface crosslinking, and due to the constant increase in the moisture content, physical crushing is effectively prevented during transport of the superabsorbent polymer. Can be suppressed.
  • Such a drying process can be performed under a drying apparatus and conditions equivalent to those performed in the manufacturing process of the super absorbent polymer particles, and a person skilled in the art can proceed with an appropriate drying time in consideration of the target moisture content.
  • the super absorbent polymer may be further classified.
  • large particles generated in the hydrolysis process for example, particles having a particle diameter of more than 850 ⁇ m and particles having a particle size of less than 150 ⁇ m are removed, and the super absorbent polymer has a particle diameter of 150 to 850 ⁇ m. It can be manufactured to have.
  • the particles having a particle diameter of more than 850 ⁇ m removed in the classification process may be less than 5% by weight, or less than 3% by weight, or 0.1 to 3% by weight based on the total weight of the dried super absorbent polymer. have.
  • a large amount of large particles are still generated during the hydrolysis process, so that particles having a particle diameter of more than 850 ⁇ m removed in the classification process are It may be about 20% by weight or more based on the total weight of the dried super absorbent polymer.
  • the superabsorbent polymer finally prepared by the method according to one embodiment through the above-described drying and classification process when measured for the resin having a particle diameter of 150 to 850 ⁇ m, physiological saline solution (0.9% by weight sodium chloride) Aqueous solution) for 30 minutes centrifugation water retention capacity (CRC) is 30 to 45 g / g, it is possible to maintain excellent absorption performance.
  • the water holding capacity may be measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 241.3, and may be calculated according to the calculation formula A described in Test Examples to be described later.
  • the above-described dried and classified super absorbent polymer may be additionally transferred for application to a subsequent packaging or sanitary material manufacturing process.
  • Such a super absorbent polymer does not substantially cause crushing or deterioration in physical properties due to appropriate control of the moisture content even during the transfer process. Furthermore, since the generation of large particles is also minimized in the hydrolysis process, it can be manufactured to have excellent physical properties and productivity as a whole.
  • the hydrogel polymer was coarsely pulverized with a meat chopper, and dried at 190° C. for 40 minutes using an air-flow oven.
  • a surface crosslinking agent composition which is a mixed solution of 3 g of ultrapure water, 3.5 g of methanol, 0.25 g of 1,3-propanediol, and 0.16 g of oxalic acid, was added, and mixed for 2 minutes. This was heat-treated at 185° C. for 50 minutes to perform surface crosslinking, and then classified to take particles having a particle diameter of 150 to 850 ⁇ m to prepare super absorbent polymer particles.
  • a final product of a super absorbent polymer was obtained in the same manner as in Example 1, except that 0.0250 g of stearic acid was used instead of 0.0250 g of lauric acid.
  • a final product of a super absorbent polymer was obtained in the same manner as in Example 1, except that 0.0250 g of arachidic acid was used instead of 0.0250 g of lauric acid.
  • super absorbent polymer particles were prepared in the same manner as in Example 1. However, the step of administering and mixing the mixed solution of ultrapure water and lauric acid, which was additionally performed in Example 1, and the subsequent drying and classification step, was not performed, and the superabsorbent polymer particles themselves were added to the final of the superabsorbent polymer of Comparative Example 1. It was made into a product.
  • Comparative Example 3 Preparation of super absorbent polymer High water absorption in the same manner as in Example 1, except that 0.0250 g of the polycarboxylic acid copolymer disclosed in Preparation Example 1 of Korean Patent Publication No. 2015-0143167 was used instead of 0.0250 g of lauric acid. The final product of the resin was obtained.
  • a final product of a super absorbent polymer was obtained in the same manner as in Example 1, except that 0.25 g of polyethylene glycol having Mw 600 was used instead of 0.0250 g of lauric acid.
  • the superabsorbent polymer (or base resin powder; hereinafter the same) W 0 (g, about 0.2 g) is uniformly placed in a nonwoven bag and sealed, and the physiology of 0.9% by weight sodium chloride aqueous solution at room temperature. It was immersed in saline. After 30 minutes, the bag was centrifuged and dried at 250 G for 3 minutes, and the mass W 2 (g) of the bag was measured. In addition, after performing the same operation without using a super absorbent polymer, the mass W 1 (g) at that time was measured. Using each of the masses thus obtained, CRC (g/g) was calculated according to the following calculation formula A to confirm the water holding capacity.
  • a super absorbent polymer was classified using a standard mesh of ASTM standard. More specifically, standard mesh bodies having eye sizes of 850 ⁇ m, 600 ⁇ m, 300 ⁇ m, and 150 ⁇ m, respectively, were sequentially stacked, and then 100 g of a super absorbent polymer was put on the top and set in a sieve shaker (AS200). Classification was performed for 10 minutes at Amplitude 1.0mm/g. The superabsorbent polymer remaining between each standard mesh was taken out, weighed, and calculated as a percentage, to calculate the particle size distribution of the superabsorbent polymer.
  • the weight loss due to evaporation of moisture in the superabsorbent polymer was measured and measured as a calculated value.
  • the drying conditions were set to a total drying time of 10 minutes in a manner that the temperature was raised from room temperature to about 140°C and then maintained at 140°C.
  • the moisture content was calculated from the measurement result of the above weight reduction.
  • Comparative Example 1 in which the hydrolysis process was not performed, it is predicted that physical crushing will occur during the subsequent transfer process because the moisture content is low.
  • Comparative Examples 2 to 4 are predicted to be controlled to an appropriate moisture content by the hydrolysis process to suppress crushing during transport, but due to the non-use of additives or the use of other additives such as polycarboxylic acid or polyethylene glycol during the hydrolysis process, large particles are It was confirmed that a number of occurrences occurred, resulting in a decrease in physical properties and a decrease in productivity of the super absorbent polymer.
  • Examples 1 to 3 were found to be able to suppress crushing during transport by appropriate control of the moisture content, while the amount of large particles generated in the hydrolysis process was also significantly reduced.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Absorbent Articles And Supports Therefor (AREA)

Abstract

La présente invention concerne un procédé de préparation de polymère superabsorbant, qui régule de manière appropriée la teneur en eau d'un polymère superabsorbant par l'ajout d'eau, et analogue, et ainsi l'endommagement pendant le transport peut être empêché et la détérioration des propriétés physiques, telles que la génération de macroparticules pendant l'ajout d'eau ou la non-uniformité de la teneur en eau, peut être inhibée.
PCT/KR2020/010614 2019-09-18 2020-08-11 Procédé de préparation de polymère superabsorbant WO2021054610A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US17/285,685 US20210317237A1 (en) 2019-09-18 2020-08-11 Method for Preparing Super Absorbent Polymer
JP2021518712A JP7309255B2 (ja) 2019-09-18 2020-08-11 高吸水性樹脂の製造方法
CN202080005373.1A CN113039235B (zh) 2019-09-18 2020-08-11 用于制备超吸收性聚合物的方法
EP20862008.8A EP3838968A4 (fr) 2019-09-18 2020-08-11 Procédé de préparation de polymère superabsorbant

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KR10-2019-0114791 2019-09-18
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KR1020200099393A KR102608042B1 (ko) 2019-09-18 2020-08-07 고흡수성 수지의 제조 방법

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08120013A (ja) * 1994-10-20 1996-05-14 Nippon Synthetic Chem Ind Co Ltd:The 高吸水性樹脂の製造法
KR20100019416A (ko) * 2007-05-22 2010-02-18 에보니크 스톡하우젠 게엠바하 초흡수제의 약한 혼합 및 코팅 방법
US20130296548A1 (en) * 2006-09-25 2013-11-07 Archer Daniels Midland Company Superabsorbent surface-treated carboxylated polysaccharides and process for producing same
KR20150143167A (ko) 2014-06-13 2015-12-23 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지
KR20160012961A (ko) * 2014-07-25 2016-02-03 에보니크 데구사 게엠베하 점착 방지 가공 조제 및 흡수성 입자 제조에 이들을 이용하는 방법
KR20190069103A (ko) * 2017-12-11 2019-06-19 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법

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JPH08120013A (ja) * 1994-10-20 1996-05-14 Nippon Synthetic Chem Ind Co Ltd:The 高吸水性樹脂の製造法
US20130296548A1 (en) * 2006-09-25 2013-11-07 Archer Daniels Midland Company Superabsorbent surface-treated carboxylated polysaccharides and process for producing same
KR20100019416A (ko) * 2007-05-22 2010-02-18 에보니크 스톡하우젠 게엠바하 초흡수제의 약한 혼합 및 코팅 방법
KR20150143167A (ko) 2014-06-13 2015-12-23 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지
KR20160012961A (ko) * 2014-07-25 2016-02-03 에보니크 데구사 게엠베하 점착 방지 가공 조제 및 흡수성 입자 제조에 이들을 이용하는 방법
KR20190069103A (ko) * 2017-12-11 2019-06-19 주식회사 엘지화학 고흡수성 수지 및 이의 제조 방법

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See also references of EP3838968A4

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