WO2020149691A1 - Super absorbent polymer and preparation method therefor - Google Patents
Super absorbent polymer and preparation method therefor Download PDFInfo
- Publication number
- WO2020149691A1 WO2020149691A1 PCT/KR2020/000852 KR2020000852W WO2020149691A1 WO 2020149691 A1 WO2020149691 A1 WO 2020149691A1 KR 2020000852 W KR2020000852 W KR 2020000852W WO 2020149691 A1 WO2020149691 A1 WO 2020149691A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- super absorbent
- absorbent polymer
- acrylic acid
- chopper
- Prior art date
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/60—Liquid-swellable gel-forming materials, e.g. super-absorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F20/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
- B29B7/428—Parts or accessories, e.g. casings, feeding or discharging means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
- B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
- B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
Definitions
- the present invention relates to a super absorbent polymer and a method for manufacturing the same.
- Super Absorbent Polymer is a synthetic polymer material that has the ability to absorb about 500 to 1,000 times its own weight.Sam (Super Absorbency Material), AGM (Absorbent Gel) for each developer Material).
- the superabsorbent polymer as described above began to be put into practical use as a sanitary tool, and now, in addition to hygiene products such as paper diapers for children, soil repair agents for horticulture, civil engineering, construction index materials, sheet for raising seedlings, freshness preservatives in food distribution, and It is widely used as a material for poultice.
- these superabsorbent resins are widely used in the field of sanitary materials such as diapers and sanitary napkins.
- sanitary materials such as diapers and sanitary napkins.
- pressure may be applied to the sanitary material such as diapers or sanitary napkins according to the weight of the user.
- the superabsorbent polymer applied to hygiene materials such as diapers or sanitary napkins absorbs the liquid
- some liquid absorbed in the superabsorbent polymer is re-wet. And, leakage of urine may occur.
- the conventional super absorbent polymer uses a method of lowering the degree of internal crosslinking and increasing the degree of surface crosslinking.
- the method has an aspect in which the absorption rate is increased, but after the superabsorbent polymer swells with the absorbed liquid, a liquid is present on the surface of the superabsorbent polymer, causing a decrease in wearing comfort and causing skin rash. do.
- the present invention is to provide a superabsorbent polymer having excellent dryness characteristics and a method for manufacturing the same because the absorption rate is fast and elasticity is maintained even in multiple pressurized environments.
- the primary resilience value is 2 g of superabsorbent polymer, swelled in 200 mL of physiological saline (0.9 wt% NaCl) for 1 hour under no pressure, and then loaded into a DMA (Dynamic mechanical analysis) measurement device at room temperature (25°C) and 0.72. It is a modulus (unit: Kpa) of a superabsorbent polymer, measured after being pressed under psi for 5 minutes, after being released from pressure and allowed to stand for 10 minutes,
- the 4th resilience value after measuring the 1st resilience value and pressing again, the process of measuring the resilience value is repeated three more times, and the modulus of the super absorbent polymer is measured 4 times. Kpa).
- the superabsorbent polymer of the present invention As described above, according to the superabsorbent polymer of the present invention and a method for manufacturing the same, it is possible to provide a superabsorbent polymer having excellent physical properties by retaining elasticity even in multiple pressurized environments while having a high absorption rate.
- the superabsorbent polymer of the present invention can be preferably used in hygiene materials such as diapers, thereby exhibiting excellent performance.
- FIG. 1 is a schematic view showing a chopper according to an embodiment of the present invention.
- FIG. 2 is a schematic view showing a chopper according to the prior art.
- FIG. 3 is a schematic view showing a chopper according to the prior art.
- polymer means that the acrylic acid-based monomer is in a polymerized state, and may cover all water content ranges or particle size ranges.
- a polymer having a water content (moisture content) of about 40% by weight or more as a state after drying after polymerization may be referred to as a hydrogel polymer.
- base resin or “base resin powder” is made of a powder by drying and pulverizing the polymer, and means a polymer before performing a surface crosslinking step described later.
- the inventors of the present invention have completed the present invention by concentrating that the gel strength of the hydrogel polymer can be maintained and the absorption rate can be improved by controlling the process of the coarsely crushing step after polymerization of the hydrogel polymer resin.
- the superabsorbent polymer according to an aspect of the present invention is characterized in that the recovery rate of the superabsorbent polymer calculated by Equation 1 below is 85% or more:
- the primary resilience value is 2 g of superabsorbent polymer, swelled in 200 mL of physiological saline (0.9 wt% NaCl) for 1 hour under no pressure, and then loaded into a DMA (Dynamic mechanical analysis) measurement device at room temperature (25°C) and 0.72. It is a modulus (unit: Kpa) of a superabsorbent polymer, measured after being pressed under psi for 5 minutes, after being released from pressure and allowed to stand for 10 minutes,
- the 4th resilience value after measuring the 1st resilience value and pressing again, the process of measuring the resilience value is repeated three more times, and the modulus of the super absorbent polymer is measured 4 times. Kpa).
- the recovery rate is a consideration of an environment in which pressure is applied according to various posture changes, such as a user sitting up, lying down, or lying down when actually using a product such as a diaper containing a super absorbent polymer, and elasticity of the super absorbent polymer under such a pressurized environment It was quantified to quantitatively evaluate the degree of recovery.
- Recovery rate may be 85% or more, or 88% or more, or 90% or more.
- the recovery rate is preferably closer to 100%, and may be, for example, 100% or less, or 98% or less, or 95% or less.
- the superabsorbent polymer of the present invention the primary resilience value of 90 Kpa or more, or 92 Kpa or more, or 93 Kpa or more, 100 Kpa or less, or 99 Kpa or less, or 98 Kpa or less, high initial modulus of elasticity Can be represented.
- the absorption rate measured according to the vortex measurement method may be 40 seconds or less.
- the absorption rate refers to a time when the vortex of the liquid disappears due to the rapid absorption when the superabsorbent resin is added to the physiological saline solution and stirred, which means the rapid absorption capacity of the superabsorbent resin.
- the specific measuring method thereof is more concrete in the following examples.
- the absorption rate of the super absorbent polymer may be 40 seconds or less, or 35 seconds or less, or 30 seconds or less, or 27 seconds or less, or 25 seconds or less, and may be 10 seconds or more, or 15 seconds or more, or 20 seconds or more.
- the superabsorbent polymer may include a base resin comprising an acrylic acid-based monomer having an acidic group at least partially neutralized and a crosslinked polymer of an internal crosslinking agent; And a surface crosslinking layer formed on the base resin by further crosslinking the surface of the base resin in the presence of a surface crosslinking agent.
- the superabsorbent polymer of the present invention as described above is not limited thereto, and may be manufactured according to a manufacturing method described later.
- Method for producing a super absorbent polymer polymerizing a monomer composition comprising an acrylic acid-based monomer having a neutralized acid group, a foaming agent, an internal crosslinking agent and a polymerization initiator, at least partially forming a hydrogel polymer ; Chopping the hydrogel polymer by passing through a chopper including two or more hole plates arranged in series; Drying, grinding and classifying the chopped hydrogel polymer to form a base resin; And in the presence of a surface crosslinking agent, further crosslinking the surface of the base resin powder to form a surface crosslinking layer.
- the method for producing a super absorbent polymer of the present invention in the step of co-grinding after polymerizing the hydrogel polymer, by chopping through a chopper comprising two or more hole plates arranged in series , the gel strength of the hydrogel polymer is maintained by effectively performing coarse grinding without imparting excessive shear force, and the absorption rate can be improved.
- the above method is a method of forming voids only by chemical foaming.
- the superabsorbent polymer particles including voids formed only by chemical foaming have a problem of easily breaking because the strength of the particles becomes weak after drying, and the elasticity is poor. There is this.
- the manufacturing method of the present invention solved the above problems by chopping through a chopper including two or more hole plates arranged in series.
- the method of the present invention does not exclude the use of a foaming agent or surfactant when polymerizing a hydrogel polymer, and additionally performs a two-step chopping step with a small amount of foaming agent while additionally surfactants when polymerizing a hydrogel polymer Can be additionally used.
- the acrylic acid-based monomer constituting the hydrogel polymer may be any monomer commonly used in the production of super absorbent polymers.
- the acrylic acid-based monomer may be a compound represented by Formula 1 below:
- 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 acrylic acid-based monomer may include at least one selected from the group consisting of acrylic acid, methacrylic acid and their monovalent metal salt, divalent metal salt, ammonium salt and organic amine salt.
- the acrylic acid monomer may have an acidic group and at least a portion of the acidic group may be neutralized.
- the acrylic acid-based monomer may be partially neutralized with an alkali material such as sodium hydroxide, potassium hydroxide or ammonium hydroxide.
- the neutralization degree of the acrylic acid-based monomer may be about 40 to about 95 mol%, or about 40 to about 80 mol%, or about 45 to about 75 mol%.
- the range of the neutralization degree can be adjusted according to the final physical properties. However, if the degree of neutralization is too high, the neutralized monomer may be precipitated and polymerization may be difficult to proceed smoothly. On the other hand, if the degree of neutralization is too low, it may exhibit properties such as elastic rubber that is not only poorly absorbed but also difficult to handle. have.
- the concentration of the acrylic acid monomer in the monomer composition may be appropriately adjusted in consideration of polymerization time and reaction conditions, and may be preferably 20 to 90% by weight, or 40 to 65% by weight.
- This concentration range may be advantageous for controlling the grinding efficiency when pulverizing the polymer, which will be described later, while eliminating the need to remove unreacted monomers after polymerization by using the gel effect phenomenon that occurs 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, a part of the monomer may be precipitated or there may be a process problem such as poor crushing efficiency when pulverizing the polymerized hydrogel polymer, and physical properties of the super absorbent polymer may be deteriorated.
- the internal crosslinking agent any compound may be used as long as it allows introduction of crosslinking during polymerization of the acrylic acid monomer.
- the internal crosslinking agent is N,N'-methylenebisacrylamide, trimethylolpropane 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, hexanediol di(meth) )Acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, dipentaerythritol pentaacrylate, glycerin tri(meth)acrylate, pen
- the internal crosslinking agent may be added at a concentration of about 0.001 to 1% by weight relative to the monomer composition. That is, when the concentration of the internal crosslinking agent is too low, the absorption rate of the resin is lowered and the gel strength may be weakened, which is not preferable. Conversely, when the concentration of the internal cross-linking agent is too high, the absorbency of the resin is lowered, which may make it undesirable as an absorber.
- the polymerization initiator may include a polymerization initiator generally used in the production of super absorbent polymers.
- a thermal polymerization initiator or a photo polymerization initiator may be used depending on the polymerization method, and a thermal polymerization initiator may be used.
- a thermal polymerization initiator may be additionally included.
- thermal polymerization initiator one or more compounds selected from the group consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid may be used.
- a persulfate-based initiator sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate (Ammonium persulfate; (NH 4 ) 2 S 2 O 8 ) and the like.
- 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-(carbamoyl azo)isobutyronitrile (2-(carbamoylazo)isobutylonitril), 2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride (2,2-azobis[2-(2-imidazolin-2-yl)propane] dihydrochloride), 4, For example, 4-azobis-(4-cyanovaleric acid) (4,4-azobis-(4-cyanovaleric acid)). More various thermal polymerization initiators are disclosed on page 203 of the Odian book "Principle of
- photo polymerization initiator examples include, for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketal ( One or more compounds selected from the group consisting of Benzyl Dimethyl Ketal, acyl phosphine and alpha-aminoketone may be used.
- acylphosphine a commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide) can be used.
- More various photopolymerization initiators are disclosed on page 115 of Reinhold Schwalm's book "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)", which can be referred to.
- the polymerization initiator may be added in a concentration of about 0.001 to 1% by weight relative to the monomer composition. That is, when the concentration of the polymerization initiator is too low, the polymerization rate may be slow, and residual monomers in the final product may be extracted in large quantities, which is not preferable. Conversely, when the concentration of the polymerization initiator is higher than the above range, the polymer chains forming the network are shortened, and thus the content of the water-soluble component is increased and the pressure absorption capacity is lowered, so that the physical properties of the resin may be deteriorated, which is not preferable.
- the monomer composition comprises a blowing agent.
- the foaming agent foams during polymerization to form pores in the hydrogel polymer to increase the surface area.
- the foaming agent may be a carbonate, for example, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, calcium bicarbonate, calcium Carbonate (calcium bicarbonate), magnesium bicarbonate (magnesiumbicarbonate) or magnesium carbonate (magnesium carbonate) can be used.
- the blowing agent is preferably used at 500 ppmw or less based on the total weight of the acrylic acid monomer.
- the lower limit of the amount of the blowing agent used is not particularly limited, but for effective presentation, for example, 10 ppmw or more, or 50 ppmw or more, or 100 ppmw or more may be used.
- the monomer composition may further include a surfactant to further improve the absorption rate by developing a porous structure of a super absorbent polymer, and the surfactant may include an anionic surfactant or nonionic Surfactants can be used.
- anionic surfactant examples include sodium dodecyl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, dioctyl sodium sulfosuccinate, perfluorooctane sulfonate, perfluorobutane sulfonate, alkyl-aryl ether And at least one selected from the group consisting of phosphate, alkyl ether phosphate, sodium myres sulfate and carboxylate salt.
- nonionic surfactant examples include fatty acid ester, sorbitan trioleate, polyethoxylated sorbitan monooleate (product name: TWEEN 80), sorbitan monooleate (product name: SPAN 80), and sugar ester (product name) : S-570).
- the total amount of the surfactant containing the anionic surfactant and the nonionic surfactant may be included in a concentration of 100 ppmw or less with respect to the total weight of the acrylic acid monomer. . More specifically, 100 ppmw or less, or 70 ppmw or less, and may be included in a concentration of 1 ppmw or more, or 5 ppmw or more, or 10 ppmw or more, or 20 ppmw or more, or 30 ppmw or more.
- concentration of the surfactant is higher than 100 ppmw, other physical properties of the superabsorbent polymer such as pressure absorbing capacity, gel strength, or surface tension may be deteriorated, and if the concentration of the surfactant is too low, addition of surfactant The effect of improving the absorption rate may not be sufficient.
- the gel polymer without the excessive shear force is applied by chopping the hydrogel polymer through a chopper including two or more hole plates arranged in series. Since it is possible to maintain the strength, it is possible to achieve an improvement in absorption rate while supplementing the disadvantages of using a surfactant, such as a decrease in surface tension, including a small amount of 100 ppmw or less, even if it does not contain a surfactant.
- a surfactant such as a decrease in surface tension, including a small amount of 100 ppmw or less
- the monomer composition may further include additives such as a thickener, a plasticizer, a storage stabilizer, and an antioxidant, if necessary.
- additives such as a thickener, a plasticizer, a storage stabilizer, and an antioxidant, if necessary.
- such a monomer composition may be prepared in the form of a solution in which a raw material such as the above-described monomer is dissolved in a solvent.
- a raw material such as the above-described monomer is dissolved in a solvent.
- a usable solvent any material that can dissolve the aforementioned raw materials can be used without limitation of its configuration.
- the solvent includes water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate , Methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate, N,N-dimethylacetamide, or mixtures thereof, and the like can be used.
- the formation of a hydrogel polymer through polymerization of the monomer composition may be performed by a conventional polymerization method, and the process is not particularly limited.
- the polymerization method is largely divided into thermal polymerization and photo polymerization according to the type of polymerization energy source.
- the thermal polymerization is performed, the polymerization method may be performed in a reactor having a stirring axis such as a kneader, and photo polymerization In the case of proceeding, it may proceed in a reactor equipped with a movable conveyor belt.
- a hydrogel polymer may be obtained by introducing the monomer composition into a reactor such as a kneader equipped with a stirring shaft, and supplying hot air to it or heating the reactor to thermally polymerize it.
- a reactor such as a kneader equipped with a stirring shaft
- the hydrogel polymer discharged to the reactor outlet may be obtained as particles of several millimeters to several centimeters.
- the resulting hydrogel polymer can be obtained in various forms depending on the concentration and injection speed of the monomer composition to be injected, and a hydrogel polymer having a particle diameter of 2 to 50 mm (average weight) is usually obtained.
- a hydrogel polymer in the form of a sheet may be obtained.
- the thickness of the sheet may vary depending on the concentration and injection rate of the monomer composition to be injected. In order to ensure the production speed and the like while allowing the entire sheet to be evenly polymerized, it is usually adjusted to a thickness of 0.5 to 5 cm. desirable.
- the normal water content of the hydrogel polymer obtained in this way may be 40 to 80% by weight.
- water content in the present specification refers to a value obtained by subtracting the weight of the polymer in the dry state from the weight of the water-containing gel polymer as a content of moisture to the total weight of the water-containing gel polymer. Specifically, it is defined as a calculated value by measuring the weight loss due to evaporation of moisture in the polymer in the process of raising the temperature of the polymer through infrared heating and drying it.
- the drying condition is a method of raising the temperature from room temperature to about 180°C and then maintaining it at 180°C.
- the total drying time is set to 20 minutes including 5 minutes of the temperature rise step to measure the water content.
- the chopping process is performed by passing the hydrogel polymer through a chopper including two or more hole plates arranged in series.
- Chopper is a device that performs the grinding by pushing the object, that is, through a hole plate (hole plate) through which a plurality of holes (holes) are formed with a certain size by inserting a hydrogel polymer into the inlet
- the extruder used to push the hydrogel polymer may use a single or multiple screw type extruder.
- the superabsorbent polymer is compressed at the front end of the hole plate, and the pressure is released while passing through the hole plate to expand the superabsorbent polymer, that is, hydrogel. Since the deformation of the hydrogel polymer and the gel strength and morphology occurs during the process of compression and expansion, the properties of the polymer after performing the coarse crushing step are changed.
- continuous chopping is performed while shortening the compression and expansion intervals on the hydrogel polymer in the chopping step by connecting the hole plates in series in one chopper, thereby reducing gel strength and reducing elasticity. And it was confirmed that the absorption rate was maintained so that the superabsorbent polymer can exhibit optimized properties.
- the process of coarsely pulverized hydrogel polymer passing through the first hole plate is continuously repeated through the next hole plate, thereby subjecting to a conventional chopping process.
- a superabsorbent polymer having a different resilience and recovery modulus from the superabsorbent polymer particles can be obtained.
- FIG. 1 is a schematic view showing a chopper according to an embodiment of the present invention
- Figure 2 is a schematic view showing a chopper according to the prior art.
- the chopper used in the manufacturing method of the present invention includes two or more hole plates 10a, 10b, and 10c, and the two or more hole plates are connected in series. More specifically, the hydrogel polymer is introduced into the chopper through the inlet 20 and coarsely crushed while being pushed out to the first hole plate 10a by a screw. The hydrogel polymer that passed through the first hole plate (10a) is secondly coarsely crushed while continuously being pushed out to the second hole plate (10b). The hydrogel polymer that has passed through the second hole plate 10b finally passes through the last hole plate 10c and is discharged out of the chopper.
- the chopper is supposed to include three hole plates, but the present invention is not limited to this, and two or more, for example, two to five, or two to four, or two It may include a variety of hole plates such as to three.
- the average diameter of the hole plate when referring to the order of the hole plate closest to the inlet as the first plate, it is desirable to make the average diameter of the hole plate smaller as it moves away from the inlet.
- the average diameter of the holes in the first hole plate is 16 to 18 mm
- the average diameter of the holes in the second hole plate is smaller than this, and may be 12 to 14 mm.
- the average diameter of the holes of the last hole plate for discharging the hydrogel polymer to the outside may be 8 to 10 mm, but the present invention is not limited thereto.
- the hydrogel polymer injected into the chopper through the inlet 20 passes through the hole plate 10a only once and is discharged out of the chopper to perform the next step. do.
- FIG. 3 which shows another conventional chopper
- the hydrogel polymer discharged through the hole plate 10a of the first chopper is second again. It is re-injected into the inlet 40 of the chopper and discharged to the outside of the chopper.
- the hydrogel polymer When the hydrogel polymer is coarsely crushed by passing two or more hole plates in sequence according to the manufacturing method of the present invention as described above, it is smaller due to continuous chopping than the conventional coarse crushing step of chopping using only one hole plate. It is possible to form pores of a size, for example, pores having a diameter of 100 ⁇ m or less.
- the chopping method of the present invention using a chopper continuously comprising two or more hole plates in the chopper as in the present invention may be more advantageous.
- a polycarboxylic acid-based copolymer in the chopping step, may be further added to chop the hydrogel polymer.
- the polycarboxylic acid-based copolymer lowers the load of the chopper due to the lubricating action, thereby inducing uniform pulverization of the polymer, and can also suppress generation of water-soluble components during pulverization. Through this, it is possible to manufacture a super absorbent polymer having a high absorption rate and a high absorption rate at the same time.
- the polycarboxylic acid-based copolymers include alkoxy polyalkylene glycol mono(meth)acrylic acid ester-based monomers (representative examples, methoxypolyethylene glycol monomethacrylate (MPEGMAA), etc.) and (meth)acrylic acid ester-based monomers ( As a typical example, the use of a random copolymer derived from hydrophilic monomers such as (meth)acrylic acid, etc.) may be more advantageous for the expression of the above-described effect.
- the polycarboxylic acid-based copolymer has a weight average molecular weight (Mw) of 500 to 1,000,000 g/mol. More preferably, the weight average molecular weight is 1,000 to 500,000 g/mol, 10,000 to 100,000 g/mol, 20,000 to 90,000 g/mol, 30,000 to 80,000 g/mol, or 40,000 to 70,000 g/mol.
- Mw weight average molecular weight
- the content of the polycarboxylic acid-based copolymer can be appropriately adjusted according to the type of the copolymer or reaction conditions.
- the polycarboxylic acid-based copolymer may be mixed in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the hydrogel polymer. If the content of the polycarboxylic acid-based copolymer is too small, the effect required in the present invention may not be sufficiently expressed. Conversely, when the polycarboxylic acid-based copolymer is used in an excessive amount, the function of the superabsorbent polymer is deteriorated, and thus the absorption characteristics may be deteriorated or the surface tension and powder flow may be deteriorated, which is not preferable.
- the chopped hydrogel polymer is dried, ground and classified to form a base resin.
- the drying temperature may be 50 to 250 °C.
- the drying temperature is less than 50°C, the drying time may be too long, and the physical properties of the superabsorbent polymer to be formed may be deteriorated.
- the drying temperature exceeds 250°C, only the polymer surface is dried excessively, and fine powder may be generated. There is a possibility that the physical properties of the superabsorbent polymer to be formed are lowered.
- the drying may be performed at a temperature of 150 to 200°C, and more preferably at a temperature of 160 to 190°C. Meanwhile, the drying time may be performed for 20 minutes to 15 hours in consideration of process efficiency and the like, but is not limited thereto.
- 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 the drying step may be 0.05 to 10% by weight.
- the polymer powder obtained after the grinding step may have a particle size of 150 to 850 ⁇ m.
- the pulverizer used for crushing to such a particle size is specifically, a ball mill, a pin mill, a hammer mill, a screw mill, a roll mill, or a disc.
- a mill or a jog mill may be used, 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 commercialized through a surface crosslinking reaction step to be described later.
- a superabsorbent polymer is prepared by further crosslinking the surface of the base resin powder to form a surface crosslinking layer.
- the superabsorbent polymer may be prepared by heat-treating the base resin powder to perform surface crosslinking.
- the type of the surface crosslinking agent is not particularly limited.
- the surface crosslinking agent is ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene Carbonate, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propane diol, dipropylene glycol, polypropylene glycol, glycerin, polyglycerin, butanediol, heptanediol, hexanediol trimethylol Propane, pentaerythritol, sorbitol, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, calcium chloride, magnesium chloride, aluminum chloride, and may be one or more compounds selected from the group
- the content of the surface crosslinking agent may be appropriately adjusted according to the type or reaction conditions thereof, and preferably 0.001 to 5 parts by weight based on 100 parts by weight of the base resin.
- the content of the surface crosslinking agent is too low, surface crosslinking may not be properly introduced, and physical properties of the final superabsorbent polymer may be deteriorated.
- the surface crosslinking agent is used in an excessively large amount, the absorbency of the super absorbent polymer may be lowered due to excessive surface crosslinking reaction, which is not preferable.
- the surface crosslinking solution is water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate and N, It may further include one or more solvents selected from the group consisting of N-dimethylacetamide. The solvent may be included in 0.5 to 10 parts by weight based on 100 parts by weight of the base resin.
- the surface crosslinking solution and the base resin are mixed in a reaction tank, a method of spraying a surface crosslinking solution on the base resin, and the surface resin and the surface crosslinking in a continuously operated mixer.
- a method of continuously supplying and mixing the liquid may be used.
- the surface crosslinking may be performed under a temperature of 100 to 250°C, and may be continuously performed after the drying and pulverizing steps proceeding at a relatively high temperature. At this time.
- the surface crosslinking reaction may be performed for 1 to 120 minutes, or 1 to 100 minutes, or 10 to 60 minutes. That is, while inducing a minimum amount of the surface crosslinking reaction, the polymer particles may be damaged during excessive reaction to prevent the physical properties from being deteriorated, and thus the conditions of the surface crosslinking reaction may be performed.
- the superabsorbent polymer having a particle size of 150 to 850 ⁇ m can be 90% by weight or more, or 92% by weight or more, or 95% by weight or more.
- the superabsorbent polymer prepared as described above may exhibit an improved absorption rate, and at the same time, various properties including gel strength may also be maintained.
- the mixed solution prepared above was poured into a Vat-shaped tray (15 cm ⁇ 15 cm wide) installed in a square polymerizer equipped with a light irradiation device at the top and preheated to 80° C. inside. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed from the surface about 20 seconds after the light irradiation time, and that polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation time. Subsequently, the polymerization reaction was performed for an additional 2 minutes, and the polymerized sheet was taken out and cut to a size of 3 cm ⁇ 3 cm.
- the cut sheet was prepared as a crumb. .
- the average particle size (diameter) of the produced flour was 0.2 mm.
- the crumb was dried in an oven capable of controlling the air volume up and down.
- the hot air at 180° C. was allowed to flow from the bottom to the top for 15 minutes, and again from the top to the bottom for 15 minutes so that the water content of the dried powder was about 2% by weight or less. It was dried uniformly.
- the dried powder was pulverized by a grinder and then classified to obtain base resins having a size of 150 to 850 ⁇ m.
- Example 1 a superabsorbent polymer was prepared in the same manner as in Example 1, except that a chopper including three hole plates (average diameters of holes in each hole plate were sequentially 18 mm, 14 mm, and 12 mm) was used.
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that sodium dodecylsulfate was added to the solution C to be 100 ppmw based on the total weight of the acrylic acid.
- Example 2 a super absorbent polymer was prepared in the same manner as in Example 2, except that sodium dodecylsulfate was added to the C solution to be 100 ppmw based on the total weight of the acrylic acid.
- the mixed solution prepared above was poured into a Vat-shaped tray (15 cm ⁇ 15 cm wide) installed in a square polymerizer equipped with a light irradiation device at the top and preheated to 80° C. inside. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed from the surface about 20 seconds after the light irradiation time, and that polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation time. Subsequently, the polymerization reaction was performed for an additional 2 minutes, and the polymerized sheet was taken out and cut to a size of 3 cm ⁇ 3 cm.
- the cut sheet was prepared as a crumb.
- the average particle size (diameter) of the produced flour was 0.4 mm.
- the crumb was dried in an oven capable of controlling the air volume up and down.
- the hot air at 180° C. was allowed to flow from the bottom to the top for 15 minutes, and again from the top to the bottom for 15 minutes so that the water content of the dried powder was about 2% by weight or less. It was dried uniformly.
- the dried powder was pulverized by a grinder and then classified to obtain base resins having a size of 150 to 850 ⁇ m.
- the mixed solution prepared above was poured into a Vat-shaped tray (15 cm ⁇ 15 cm wide) installed in a square polymerizer equipped with a light irradiation device at the top and preheated to 80° C. inside. Thereafter, the mixed solution was irradiated with light. It was confirmed that a gel was formed from the surface about 20 seconds after the light irradiation time, and that polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation time. Subsequently, the polymerization reaction was performed for an additional 2 minutes, and the polymerized sheet was taken out and cut to a size of 3 cm ⁇ 3 cm.
- the cut sheet was manufactured into a crumb.
- the average particle size (diameter) of the produced flour was 0.55 mm.
- the cut sheet was chopped by chopping using a chopper as shown in FIG. 3 (two choppers connected in parallel, and the average diameter of the holes in the hole plates of each chopper in turn is 18 mm, 14 mm). It was prepared as a crumb. The average particle size (diameter) of the produced flour was 0.4 mm.
- the cut sheet was powdered by chopping using a chopper similar to that shown in FIG. 1 (however, two hole plates are included, and the average diameter of the holes in each hole plate is in turn 14 mm, 12 mm). (crumb).
- the average particle size (diameter) of the produced flour was 0.3 mm.
- a super absorbent polymer was prepared according to Example 2 of KR Publication No. 2018-0076272.
- Foaming agent (unit: ppmw)* Surfactant (unit: ppmw)* Chopping method
- Example 1 500 0 Chopping with two hole plates arranged in series in the chopper
- Example 2 500 0 Chopping with three hole plates arranged in series in the chopper
- Example 3 500 100 Chopping with two hole plates arranged in series in the chopper
- Example 4 500 100 Chopping with three hole plates arranged in series in the chopper Comparative Example 1 0 0
- Two-stage chopping with two choppers connected Comparative Example 2 500 0 1-stage chopping Comparative Example 3 500 0
- Two-stage chopping with two choppers connected Comparative Example 4 500 0 3-stage chopping with 3 choppers connected Comparative Example 5 0 0 Chopping with two hole plates arranged in series in the chopper Comparative Example 6 1000 200 1-stage chopping
- blowing agent and surfactant was calculated as the content (unit: ppmw) relative to the total weight of the acrylic acid monomer.
- 2 g of superabsorbent polymer is swelled in 200 mL of physiological saline (0.9 wt% NaCl) for 1 hour under no pressure, and then loaded into a DMA (Dynamic mechanical analysis) measuring device (device name: dynamic mechanical analysis Q800, manufacturer: TA instrument) at room temperature. After pressing for 5 minutes at (25°C) and 0.72 psi, the pressure was released and allowed to stand for 10 minutes, and then the modulus (modulus, unit: Kpa) of the super absorbent polymer was measured to obtain a primary resilience value.
- DMA Dynamic mechanical analysis measuring device
- the absorption rate is 2 g of superabsorbent resin in 50 mL of physiological saline at 23°C to 24°C, and the magnetic bar (8 mm in diameter and 31.8 mm in length) is stirred at 600 rpm to vortex ( vortex) was calculated by measuring the time in seconds.
- Table 2 shows the results measured as described above.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Hematology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
발포제(단위: ppmw)*Foaming agent (unit: ppmw)* | 계면활성제(단위: ppmw)*Surfactant (unit: ppmw)* | 쵸핑 방법Chopping method | |
실시예 1Example 1 | 500500 | 00 | 쵸퍼 내 직렬 배치된 2개의 홀 플레이트로 쵸핑Chopping with two hole plates arranged in series in the chopper |
실시예 2Example 2 | 500500 | 00 | 쵸퍼 내 직렬 배치된 3개의 홀 플레이트로 쵸핑Chopping with three hole plates arranged in series in the chopper |
실시예 3Example 3 | 500500 | 100100 | 쵸퍼 내 직렬 배치된 2개의 홀 플레이트로 쵸핑Chopping with two hole plates arranged in series in the chopper |
실시예 4Example 4 | 500500 | 100100 | 쵸퍼 내 직렬 배치된 3개의 홀 플레이트로 쵸핑Chopping with three hole plates arranged in series in the chopper |
비교예 1Comparative Example 1 | 00 | 00 | 쵸퍼 2개를 연결한 2단 쵸핑Two-stage chopping with two choppers connected |
비교예 2Comparative Example 2 | 500500 | 00 | 1단 쵸핑1-stage chopping |
비교예 3Comparative Example 3 | 500500 | 00 | 쵸퍼 2개를 연결한 2단 쵸핑Two-stage chopping with two choppers connected |
비교예 4Comparative Example 4 | 500500 | 00 | 쵸퍼 3개를 연결한 3단 쵸핑3-stage chopping with 3 choppers connected |
비교예 5Comparative Example 5 | 00 | 00 | 쵸퍼 내 직렬 배치된 2개의 홀 플레이트로 쵸핑Chopping with two hole plates arranged in series in the chopper |
비교예 6Comparative Example 6 | 10001000 | 200200 | 1단 쵸핑1-stage chopping |
1차 레질리언스값(단위:Kpa)1st resilience value (unit: Kpa) | 2차 레질리언스값(단위: Kpa)2nd resilience value (unit: Kpa) | 3차 레질리언스값(단위: Kpa)3rd resilience value (unit: Kpa) | 4차 레질리언스값(단위: Kpa)4th resilience value (unit: Kpa) | Recovery rate (%)Recovery rate (%) | Vortex time(초)Vortex time (seconds) | |
실시예 1Example 1 | 9595 | 9494 | 9292 | 8585 | 8989 | 3333 |
실시예 2Example 2 | 9393 | 9292 | 8989 | 7979 | 8585 | 2424 |
실시예 3Example 3 | 9898 | 9393 | 9090 | 8888 | 9090 | 3030 |
실시예 4Example 4 | 9292 | 9090 | 8585 | 8181 | 8888 | 2323 |
비교예 1Comparative Example 1 | 9393 | 8888 | 8282 | 7575 | 8181 | 5757 |
비교예 2Comparative Example 2 | 7575 | 6767 | 6262 | 5858 | 7777 | 4040 |
비교예 3Comparative Example 3 | 8080 | 6565 | 6060 | 5555 | 6969 | 3232 |
비교예 4Comparative Example 4 | 7373 | 6363 | 5454 | 4040 | 5555 | 2525 |
비교예 5Comparative Example 5 | 9595 | 9292 | 9090 | 8686 | 9191 | 5656 |
비교예 6Comparative Example 6 | 7373 | 7070 | 6464 | 5555 | 7575 | 4141 |
Claims (11)
- 하기 식 1로 계산되는 고흡수성 수지의 회복율(Recovery rate)이 85% 이상인, 고흡수성 수지:The superabsorbent polymer having a recovery rate of 85% or more of the superabsorbent polymer calculated by Equation 1 below:[식 1][Equation 1]Recovery rate (%) = 4차 레질리언스값(resilience value) / 1차 레질리언스값(resilience value) * 100Recovery rate (%) = 4th resilience value / 1st resilience value * 100식 1에서,In equation 1,1차 레질리언스값은, 고흡수성 수지 2g을 무가압하에 1시간 동안 생리 식염수(0.9 wt% NaCl) 200 mL 에 팽윤시킨 후 DMA (Dynamic mechanical analysis) 측정 장치에 로딩하여 상온(25℃) 및 0.72 psi 하에서 5분 동안 가압한 후, 가압을 해제하고 10분 동안 정치시킨 후 측정되는 고흡수성 수지의 모듈러스(modulus, 단위: Kpa)이고, The primary resilience value is 2 g of superabsorbent polymer, swelled in 200 mL of physiological saline (0.9 wt% NaCl) for 1 hour under no pressure, and then loaded into a DMA (Dynamic mechanical analysis) measurement device at room temperature (25°C) and 0.72. It is a modulus (unit: Kpa) of a superabsorbent polymer, measured after being pressed under psi for 5 minutes, after being released from pressure and allowed to stand for 10 minutes,4차 레질리언스값은, 상기 1차 레질리언스값을 측정한 후 다시 가압하여 레질리언스값을 측정하는 과정을 동일하게 3회 더 반복하여 4번째로 측정되는 고흡수성 수지의 모듈러스(modulus, 단위: Kpa)이다.The 4th resilience value, after measuring the 1st resilience value and pressing again, the process of measuring the resilience value is repeated three more times, and the modulus of the super absorbent polymer is measured 4 times. Kpa).
- 제1항에 있어서,According to claim 1,상기 1차 레질리언스값이 90 Kpa 이상인, 고흡수성 수지.The primary resilience value is 90 Kpa or more, super absorbent polymer.
- 제1항에 있어서,According to claim 1,볼텍스(vortex) 측정 방법에 따라 측정한 흡수 속도가 40초 이하인, 고흡수성 수지.A super absorbent polymer whose absorption rate measured according to a vortex measurement method is 40 seconds or less.
- 적어도 일부가 중화된 산성기를 갖는 아크릴산계 단량체, 발포제, 내부 가교제 및 중합 개시제를 포함하는 단량체 조성물을 중합하여 함수겔 중합체를 형성하는 단계; Polymerizing a monomer composition comprising an acrylic acid-based monomer having at least a partially neutralized acid group, a blowing agent, an internal crosslinking agent, and a polymerization initiator to form a hydrogel polymer;상기 함수겔 중합체를, 직렬로 배열된 2개 이상의 홀 플레이트(hole plate)를 포함하는 쵸퍼(chopper)를 통과시켜 쵸핑하는 단계; Chopping the hydrogel polymer by passing through a chopper including two or more hole plates arranged in series;상기 쵸핑한 함수겔 중합체를 건조, 분쇄 및 분급하여 베이스 수지를 형성하는 단계; 및 Drying, grinding and classifying the chopped hydrogel polymer to form a base resin; And표면 가교제 존재 하에, 상기 베이스 수지 분말의 표면을 추가 가교하여 표면 가교층을 형성하는 단계를 포함하는, In the presence of a surface crosslinking agent, comprising the step of further crosslinking the surface of the base resin powder to form a surface crosslinking layer,를 포함하는, 고흡수성 수지의 제조방법.The method of producing a super absorbent polymer comprising a.
- 제4항에 있어서,According to claim 4,상기 홀 플레이트의 평균 직경은 쵸퍼 입구에서 멀어질수록 더 작은, 고흡수성 수지의 제조방법.The average diameter of the hole plate is smaller as the distance from the chopper inlet, the method of producing a super absorbent polymer.
- 제4항에 있어서,According to claim 4,상기 발포제는 소디움 비카보네이트(sodium bicarbonate), 소디움 카보네이트(sodium carbonate), 포타슘 비카보네이트(potassium bicarbonate), 포타슘 카보네이트(potassium carbonate), 칼슘 비카보네이트(calcium bicarbonate), 칼슘 카보네이트(calcium bicarbonate), 마그네슘 비카보네이트(magnesiumbicarbonate) 및 마그네슘 카보네이트(magnesium carbonate)로 이루어진 군에서 선택된 1종 이상을 포함하는, 고흡수성 수지의 제조 방법.The blowing agent is sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, calcium bicarbonate, calcium bicarbonate, magnesium bicarbonate Method for producing a super absorbent polymer comprising at least one selected from the group consisting of carbonate (magnesiumbicarbonate) and magnesium carbonate (magnesium carbonate).
- 제4항에 있어서, 상기 발포제는 상기 아크릴산 단량체의 총 중량에 대하여 500 ppmw 이하로 포함되는, 고흡수성 수지의 제조방법.The method of claim 4, wherein the blowing agent is included in an amount of 500 ppmw or less based on the total weight of the acrylic acid monomer.
- 제4항에 있어서, 상기 단량체 조성물은 계면활성제를 더 포함하는, 고흡수성 수지의 제조방법.The method of claim 4, wherein the monomer composition further comprises a surfactant.
- 제8항에 있어서,The method of claim 8,상기 계면활성제는 소디움 도데실 설페이트, 암모늄 라우릴 설페이트, 소디움 라우레스 설페이트, 디옥틸 소디움 술포숙시네이트, 퍼플루오로옥탄 술포네이트, 퍼플루오로부탄 술포네이트, 알킬-아릴 에테르 포스페이트, 알킬 에테르 포스페이트, 소디움 미레스 설페이트 및 카르복실레이트염으로 이루어진 군에서 선택된 1종 이상을 포함하는, 고흡수성 수지의 제조 방법.The surfactant is sodium dodecyl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, dioctyl sodium sulfosuccinate, perfluorooctane sulfonate, perfluorobutane sulfonate, alkyl-aryl ether phosphate, alkyl ether phosphate , A method for producing a super absorbent polymer comprising at least one selected from the group consisting of sodium myres sulfate and a carboxylate salt.
- 제4항에 있어서,According to claim 4,상기 쵸핑하는 단계에서, 폴리카르복실산계 공중합체를 더 투입하여 쵸핑하는, 고흡수성 수지의 제조방법.In the chopping step, a polycarboxylic acid-based copolymer is further added to chop, and a method for producing a super absorbent polymer.
- 제10항에 있어서,The method of claim 10,상기 폴리카르복실산계 공중합체는 알콕시 폴리알킬렌글리콜모노(메타)아크릴산 에스테르계 단량체 및 (메타)아크릴산 에스테르계 단량체로 이루어진 군에서 선택된 1종 이상을 포함하는, 고흡수성 수지의 제조방법.The polycarboxylic acid-based copolymer comprises an alkoxy polyalkylene glycol mono (meth) acrylic acid ester-based monomer and (meth) acrylic acid ester-based monomer comprising at least one selected from the group consisting of, a method for producing a super absorbent polymer.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/258,660 US20210268475A1 (en) | 2019-01-17 | 2020-01-17 | Super Absorbent Polymer and Method for Preparing Same |
BR112021002909-5A BR112021002909A2 (en) | 2019-01-17 | 2020-01-17 | superabsorbent polymer and method of preparing it |
EP20740914.5A EP3812420B1 (en) | 2019-01-17 | 2020-01-17 | Super absorbent polymer and preparation method therefor |
JP2021518852A JP7233661B2 (en) | 2019-01-17 | 2020-01-17 | SUPER ABSORBENT RESIN AND METHOD FOR MANUFACTURING SAME |
CN202080003843.0A CN112424270B (en) | 2019-01-17 | 2020-01-17 | Superabsorbent polymer and method of making the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20190006228 | 2019-01-17 | ||
KR10-2019-0006228 | 2019-01-17 | ||
KR1020200006215A KR102457690B1 (en) | 2019-01-17 | 2020-01-16 | Super absorbent polymer and preparation method of the same |
KR10-2020-0006215 | 2020-01-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2020149691A1 true WO2020149691A1 (en) | 2020-07-23 |
Family
ID=71613968
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2020/000852 WO2020149691A1 (en) | 2019-01-17 | 2020-01-17 | Super absorbent polymer and preparation method therefor |
Country Status (1)
Country | Link |
---|---|
WO (1) | WO2020149691A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3984711A4 (en) * | 2019-11-21 | 2022-08-24 | LG Chem, Ltd. | Composite chopper for superabsorbent hydrogel |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1987003208A1 (en) | 1985-11-22 | 1987-06-04 | Beghin-Say Sa | Method for preparing a liquid absorbing composition |
WO2011034146A1 (en) * | 2009-09-16 | 2011-03-24 | 株式会社日本触媒 | Method for producing water absorbent resin powder |
KR20150040884A (en) * | 2012-08-01 | 2015-04-15 | 가부시키가이샤 닛폰 쇼쿠바이 | Process for producing polyacrylic acid(salt)-based water-absorbing resin |
KR20170132799A (en) * | 2015-03-31 | 2017-12-04 | 가부시키가이샤 닛폰 쇼쿠바이 | Polyacrylic acid (salt) -sorbable resin powder, process for producing the same, and evaluation method thereof |
KR20180076272A (en) | 2016-12-27 | 2018-07-05 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
KR20180092841A (en) * | 2017-02-10 | 2018-08-20 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
KR20180112110A (en) * | 2010-04-07 | 2018-10-11 | 가부시키가이샤 닛폰 쇼쿠바이 | Method for producing water absorbent polyacrylic acid (salt) resin powder, and water absorbent polyacrylic acid (salt) resin powder |
-
2020
- 2020-01-17 WO PCT/KR2020/000852 patent/WO2020149691A1/en unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1987003208A1 (en) | 1985-11-22 | 1987-06-04 | Beghin-Say Sa | Method for preparing a liquid absorbing composition |
WO2011034146A1 (en) * | 2009-09-16 | 2011-03-24 | 株式会社日本触媒 | Method for producing water absorbent resin powder |
KR20180112110A (en) * | 2010-04-07 | 2018-10-11 | 가부시키가이샤 닛폰 쇼쿠바이 | Method for producing water absorbent polyacrylic acid (salt) resin powder, and water absorbent polyacrylic acid (salt) resin powder |
KR20150040884A (en) * | 2012-08-01 | 2015-04-15 | 가부시키가이샤 닛폰 쇼쿠바이 | Process for producing polyacrylic acid(salt)-based water-absorbing resin |
KR20170132799A (en) * | 2015-03-31 | 2017-12-04 | 가부시키가이샤 닛폰 쇼쿠바이 | Polyacrylic acid (salt) -sorbable resin powder, process for producing the same, and evaluation method thereof |
KR20180076272A (en) | 2016-12-27 | 2018-07-05 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
KR20180092841A (en) * | 2017-02-10 | 2018-08-20 | 주식회사 엘지화학 | Super absorbent polymer and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
ODIAN: "Principle of Polymerization", 1981, WILEY, pages: 203 |
REINHOLD SCHWALM: "UV Coatings: Basics, Recent Developments and New Applications", 2007, ELSEVIER, pages: 115 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3984711A4 (en) * | 2019-11-21 | 2022-08-24 | LG Chem, Ltd. | Composite chopper for superabsorbent hydrogel |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2020145548A1 (en) | Superabsorbent resin and preparation method of same | |
WO2020122442A1 (en) | Method for preparing superabsorbent polymer | |
WO2020149691A1 (en) | Super absorbent polymer and preparation method therefor | |
WO2016159600A1 (en) | Method for preparing superabsorbent resin | |
WO2021071246A1 (en) | Method for producing super absorbent polymer | |
WO2023287262A1 (en) | Preparation method of super absorbent polymer | |
WO2020226385A1 (en) | Super absorbent polymer preparation method and super absorbent polymer | |
WO2020122444A1 (en) | Method for preparing super-absorbent polymer | |
WO2021194202A1 (en) | Super absorbent resin film and preparation method thereof | |
WO2020067705A1 (en) | Method for preparing super absorbent polymer, and super absorbent polymer | |
WO2015084060A1 (en) | Superabsorbent polymer and preparation method therefor | |
WO2022080641A1 (en) | Method for preparing super absorbent polymer | |
KR102457690B1 (en) | Super absorbent polymer and preparation method of the same | |
WO2024111948A1 (en) | Superabsorbent polymer and preparation method therefor | |
WO2021066313A1 (en) | Super absorbent polymer composition and preparation method thereof | |
WO2020149651A1 (en) | Preparation method of super absorbent polymer | |
WO2024106836A1 (en) | Method for preparing super absorbent polymer | |
WO2020122426A1 (en) | Super absorbent polymer and preparation method therefor | |
WO2021066503A1 (en) | Superabsorbent polymer composition and preparation method therefor | |
WO2023106878A1 (en) | Preparation method for super absorbent polymer | |
WO2022131836A1 (en) | Preparation method for super absorbent polymer | |
WO2022154566A1 (en) | Method for preparing super absorbent polymer | |
WO2021054711A1 (en) | Super absorbent polymer and preparation method for same | |
WO2022131835A1 (en) | Method for preparing super absorbent polymer | |
WO2023038340A1 (en) | Preparation method for superabsorbent polymer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20740914 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021518852 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2020740914 Country of ref document: EP Effective date: 20210125 |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112021002909 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112021002909 Country of ref document: BR Kind code of ref document: A2 Effective date: 20210217 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |