WO2016089005A1 - Résine superabsorbante et son procédé de préparation - Google Patents

Résine superabsorbante et son procédé de préparation Download PDF

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WO2016089005A1
WO2016089005A1 PCT/KR2015/011089 KR2015011089W WO2016089005A1 WO 2016089005 A1 WO2016089005 A1 WO 2016089005A1 KR 2015011089 W KR2015011089 W KR 2015011089W WO 2016089005 A1 WO2016089005 A1 WO 2016089005A1
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polymer
meth
superabsorbent polymer
weight
water
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PCT/KR2015/011089
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English (en)
Korean (ko)
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남대우
한장선
이혜민
김동현
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주식회사 엘지화학
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Priority claimed from KR1020150145613A external-priority patent/KR20160067725A/ko
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Publication of WO2016089005A1 publication Critical patent/WO2016089005A1/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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to a super absorbent polymer having excellent solution permeability and a method of preparing the same.
  • a super absorbent polymer is a synthetic polymer material that can absorb about 500 to 1000 times its own weight. It is a SAM (Super Absorbency Material), AGM (Asorbent Gel Material), etc. It is also blowing. Super absorbent resins have been put into practical use as sanitary devices and are now widely used in various materials such as hygiene products such as paper diapers for children, horticultural soil repair agents, civil engineering materials, seedling sheets, and freshness retainers in food distribution. It is used. As a method for producing such a super absorbent polymer, a method by reverse phase suspension polymerization or a solution polymerization is known.
  • the production of superabsorbent polymers through reverse phase suspension polymerization is disclosed, for example, in Japanese Patent Laid-Open Nos. 56-161408, 5,158, JP, 158,209, and the like.
  • the production of superabsorbent polymers through polymerization of aqueous solution is a thermal polymerization method for polymerizing a hydrogel polymer in a kneader equipped with several shafts while breaking and angled, and polymerizing and drying by irradiating UV light to a high concentration of aqueous solution on a belt.
  • the photopolymerization method etc. which perform simultaneously are known.
  • absorption rate which is one of the important physical properties of super absorbent polymer
  • the surface dryness of the product in contact with the skin can be improved by increasing the surface area of the superabsorbent polymer.
  • a method of forming a porous structure on the particle surface of the super absorbent polymer by using a blowing agent has been applied.
  • the general foaming agent cannot form a sufficient amount of porous structure, so that the increase in absorption rate is not large.
  • there is a method of increasing the surface area by reassembling the fine powder obtained in the manufacturing process of the super absorbent polymer to form porous particles of irregular shape.
  • the present invention is to provide a superabsorbent polymer and a method for preparing the same, which have a high water permeability and pressure absorbing ability as well as excellent solution permeability by controlling the degree of surface crosslinking of the base resin.
  • the present invention provides a super absorbent polymer comprising a crosslinked polymer comprising an acidic group and surface-crosslinked a base resin polymerized with a water-soluble ethylenically unsaturated monomer in which at least part of the acidic group is neutralized,
  • the gel strength of the base resin is 4000 to 5000 Pa
  • the gel strength of the crosslinked polymer is 1.4 times or more of the gel strength of the base resin
  • the pressure absorption of 0.7 psi of the crosslinked polymer ⁇ (AUP, g / g) is at least 22
  • And centrifuged beam SAT (CRC, g / g) of the crosslinked polymer is 28 or more, the transmittance of the solution of cross-linked polymer (SFC, 10- 7 cm 1 ⁇ sec / g) is more than 30,
  • the superabsorbent polymer according to the present invention controls the degree of surface crosslinking of a base resin having a gel strength in the above range, such that the gel strength of the crosslinked polymer is compared with that of the base resin.
  • the water-soluble ethylenically unsaturated monomer included in the monomer composition may be any monomer conventionally used for preparing a super absorbent polymer.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by Formula 1:
  • Ri 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 is acrylic acid, methacrylic acid, and
  • It may be at least one selected from the group consisting of monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
  • monovalent metal salts divalent metal salts
  • ammonium salts organic amine salts.
  • the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2- Methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid or 2- (meth) acrylamide-2-methyl propane sulfonic acid, (meth) acrylamide, N-substituted (meth) acrylate, 2-hydrate Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypolyethylene glycol
  • the water-soluble ethylenically unsaturated monomer has an acidic group, at least a portion of the acidic group may be neutralized.
  • those which have been partially neutralized with an alkali substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like 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 may precipitate and polymerization may be difficult to proceed smoothly.
  • the concentration of the water-soluble ethylenically unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of the polymerization time and reaction conditions, preferably 20 to 90% by weight, or 40 to 65% by weight. This concentration range may be advantageous to control the grinding efficiency during the grinding of the polymer to be described later, while eliminating the need for removing the unbanung monomer after the polymerization by using the gel effect phenomenon appearing in the polymerization reaction of the high concentration aqueous solution.
  • the surface crosslinking is a method of increasing the crosslinking density of the surface of the base resin particles, and in particular, in the present invention, the physical properties of the crosslinked polymer are improved by controlling the degree of surface crosslinking of the base resin. Let's do it.
  • the gel strength means the horizontal gel strength of the superabsorbent polymer measured after swelling by absorbing physiological saline solution (0.9% by weight aqueous sodium chloride solution) in the base resin or crosslinked polymer for 1 hour, using a rheometer Can be measured.
  • the pressure absorption capacity (AUP) of 0.7 psi may be represented by the following formula 2:
  • AUP (g / g) [W 4 (g)-W 3 (g)] / W 0 (g)
  • W 0 (g) is the weight of superabsorbent polymer (g) .
  • W 3 (g) is the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer
  • W 4 (g) is the sum of the weight of the water absorbed superabsorbent resin after supplying water to the superabsorbent polymer for one hour under a load (0.7 psi) and the weight of the device capable of loading the superabsorbent polymer. to be.
  • the centrifugal water retention capacity (CRC) for the physiological saline can be expressed according to the following equation 3:
  • W 0 (g) is the weight of superabsorbent polymer (g) .
  • Kg does not use a super absorbent polymer, but uses a centrifuge Device weight measured after dehydration at 250G for 3 minutes,
  • W 2 (g) is the weight of the device, including the superabsorbent polymer, after submerging the superabsorbent polymer for 30 minutes in 0.9 mass% of physiological saline to the silver, followed by dehydration at 250 G for 3 minutes using a centrifuge.
  • the centrifugal water holding capacity (CRC, .g / g) of the crosslinked polymer is 29 or more, more preferably 30 or more.
  • the solution permeability (SFC) is determined by Darcy's law and steady flow method (e.g., "Absorbency", edited by PK Chatter jee, Elsevier 1985, pp. 42-43 and Chemical Engineering, Vol.
  • the super absorbent polymer according to the present invention may be prepared by a manufacturing method comprising the following steps.
  • step 1 Formation of hydrogel polymer (step 1)
  • the method for preparing the superabsorbent polymer includes thermally polymerizing or photopolymerizing a monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator. Polymerizing to form a hydrogel polymer.
  • the water-soluble ethylenically unsaturated monomer included in the monomer composition is as described above.
  • the monomer composition may include a polymerization initiator generally used in the production of superabsorbent polymers.
  • a thermal polymerization initiator or a photopolymerization initiator may be used as the polymerization initiator, depending on the polymerization method.
  • a thermal polymerization initiator may be further included.
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • One or more compounds selected from the group consisting of benzyl dimethyl ketal, acyl phosphine and a -aminoketone can be used.
  • acylphosphine commercially available lucirin TP0, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl benzoyl one trimethyl phosphine oxide) may be used.
  • photopolymerization initiators are disclosed on page 115 of Reinhold Schwalm, "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)", and can be referred to this.
  • the thermal polymerization initiator one or more compounds selected from the group consisting of persulfate-based initiators, azo-based initiators, hydrogen peroxide, and ascorbic acid may be used.
  • sodium persulfate Na 2 S 2 0 8
  • potassium persulfate Pitassium persulfate
  • NH 4 ammonium persulfate
  • azo (Azo) -based initiators are 2,2-azobis- (2-amidinopropane) dihydrochloride (2,2-azobis (2— amidinopropane) dihydrochloride), 2,2-azobis- ( ⁇ , ⁇ —dimethylene) isobutyramimidine dihydrochloride (2,2- azobis- (N, N-dimethyl ene) is obut yr am idi ne dihydrochloride), 2- (carbamoyl azo) isobutyronitrile ( 2- (carbamoylazo) isobutylonitril), 2,2- azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (2, 2- azobis [2- (2-imidazol in-2- yl) propane] dihydrochlor ide), 4,4—azobis -1- (4-cyanovaleric acid) (4,4-320 5- (4 ⁇ £ 1110 31 ⁇ ; acid)) .
  • thermal polymerization initiators are disclosed on page 203 of Odian's book “Principle of Polymerization (Wiley, 1981)", which can be referred to as about 0.001 to 1 weight based on the monomer composition.
  • concentration of the polymerization initiator is too low, the polymerization rate may be slowed down and a large amount of remaining monomer may be extracted in the final product.
  • Too high is not preferable because the polymer chain forming the network is shortened, so that the content of the water-soluble component and the pressure absorption capacity is lowered, such that the physical properties of the resin may be lowered.
  • crosslinking agent for improving the physical properties of the resin
  • the crosslinking agent may be used to internally crosslink the hydrogel polymer, and may be used separately from a crosslinking agent (“surface crosslinking agent”) for crosslinking the surface of the hydrogel polymer.
  • any compound may be used as long as it enables the introduction of crosslinks in the polymerization of the unsaturated monomers
  • the internal crosslinking agent include ⁇ , ⁇ '—methylenebisacrylamide, trimethyl propane tri (meth) acrylate, ethylene glycol Di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol (meth) acrylate, butanediol di (meth) acrylate, butylene glycol die (meth Acrylate, diethylene glycol di (meth) acrylate, nucleic acid die di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) Polyacrylates such as acrylates, dipentaerythrates, pentaacrylates, glycerin tri (meth) acrylates, pen
  • Such internal crosslinking agent may be added at a concentration of about 0.001 to 1% by weight relative to the monomer composition. That is, when the concentration of the internal crosslinking agent is too low, the absorption rate of the resin may be low and the gel strength may be weakened, which is not preferable. On the contrary, when the concentration of the internal crosslinking agent is too high, the absorbing power of the resin may be low, which may be undesirable as an absorber.
  • the monomer composition may further include additives such as thickeners, plasticizers, storage stabilizers, and antioxidants as necessary.
  • the monomer composition may be prepared in the form of a solution in which raw materials such as the aforementioned monomer, polymerization initiator, internal crosslinking agent, and the like are dissolved in a solvent.
  • a solvent any solvent that can be used may be used without limitation as long as it can dissolve the above-described raw materials.
  • the solvent includes water, ethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanedi, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether.
  • the formation of the hydrogel polymer through the polymerization of the monomer composition may be performed by a conventional polymerization method, and the process is not particularly limited.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the type of polymerization energy source.
  • the thermal polymerization the polymerization method may be performed in a reactor having a stirring shaft such as a kneader.
  • the polymerization proceeds, it can be carried out in a semi-unggi equipped with a movable conveyor belt.
  • the monomer composition may be added to a reactor such as a kneader equipped with a stirring shaft, and hot water may be supplied thereto or thermally polymerized by heating the reactor to obtain a hydrogel polymer.
  • the hydrous gel phase polymer discharged to the semi-unggi outlet according to the shape of the stirring shaft provided in the reactor may be obtained in the particles of several millimeters to several centimeters.
  • the resulting hydrogel polymer may be obtained in various forms depending on the concentration and injection rate of the monomer composition to be injected, and a hydrogel polymer having a particle size of 2 to 50 mm 3 can be obtained.
  • the photopolymerization of the monomer composition in a semi-unggi equipped with a movable conveyor belt may be a hydrous gel polymer in the form of a sheet.
  • the thickness of the sheet may vary depending on the concentration and the injection rate of the monomer composition to be injected, in order to ensure the production rate while the entire sheet is evenly polymerized, it is usually adjusted to a thickness of 0.5 to 5 cm desirable.
  • Water-containing gel polymer formed by this method is about 40 to 80 Moisture content in weight percent.
  • the moisture content is a weight of water in the total weight of the hydrogel polymer, and may be a value obtained by subtracting the weight of the dried polymer from the weight of the hydrogel polymer. Specifically, it may be defined as a value calculated by measuring the weight loss due to evaporation of water in the polymer in the process of drying the temperature of the polymer through infrared heating.
  • the drying conditions may be set to 20 minutes, including 5 minutes of the temperature rise step in such a way that the temperature is raised to about 180 ° C and then maintained at 180 ° C. Drying the hydrogel polymer (step 2)
  • the manufacturing method of the super absorbent polymer includes the step of drying the hydrogel-like laminate formed through the above-described steps.
  • the step of pulverizing (coarse grinding) the hydrogel polymer before the drying may be more rough.
  • the grinders available for the coarse grinding include a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting type Examples include a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, a disc cutter, and the like.
  • the coarse grinding may be performed so that the particle size of the hydrogel polymer is 2 to 10 ⁇ .
  • the hydrous gel polymer is preferably pulverized into particles of 10 mm or less.
  • the hydrous gel phase polymer is preferably pulverized into particles of 2 mm or more.
  • the polymer may stick to the surface of the grinder because the polymer has a high water content.
  • the coarsely pulverizing step includes, as necessary, steam, water, surfactants, anti-aggregation agents such as clay or Si ica; Thermal sulfate initiators such as persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid, epoxy crosslinkers, diol crosslinkers, crosslinkers comprising acrylates of difunctional or trifunctional or more than trifunctional groups, and hydroxyl groups.
  • Thermal sulfate initiators such as persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid
  • epoxy crosslinkers diol crosslinkers, crosslinkers comprising acrylates of difunctional or trifunctional or more than trifunctional groups, and hydroxyl groups.
  • Crosslinking agents such as a compound of monofunctional groups, may be added.
  • the drying of the hydrous gel phase polymer immediately after coarse grinding or polymerization may be performed at a temperature of 120 to 250 ° C., or 150 to 200 ° C., or 160 to 180 ° C. It may be defined as the temperature of the heat medium supplied for drying or the temperature inside the drying reactor comprising the heat medium and the polymer in the drying process. That is, when the drying temperature is low and the drying time is long, the physical properties of the final resin may be lowered. In order to prevent this, the drying temperature is preferably 120 ° C or more.
  • drying temperature may be a fine powder generated more in the milling process to be described later is dry only the surface of the function, the gel polymer is higher than necessary, the physical properties of the final resin can be lowered, a drying temperature in order to prevent this, is 250 ° It is preferable that it is C or less.
  • the drying time in the drying step is not particularly limited, but may be adjusted to 20 to 90 minutes under the drying temperature in consideration of process efficiency and the like.
  • the drying method of the drying step can also be commonly used as a drying step of the hydrous gel phase polymer is applicable to the configuration without limitation.
  • the drying step may be a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the polymer dried in this manner may exhibit a water content of about 0.1 to 10% by weight. In other words, if the water content of the polymer is less than 0.1% by weight, it is not advantageous because an increase in the manufacturing cost and degradation of the crosslinked polymer may occur due to excessive drying. In addition, when the water content of the polymer exceeds 10% by weight, defects may occur in subsequent processes, which is not preferable. Grinding the dried polymer (step 3)
  • the manufacturing method of the super absorbent polymer includes the step of pulverizing the polymer dried through the above-described steps.
  • the grinding step may be performed to optimize the surface area of the dried polymer, and may be performed to have a particle diameter of 150 to 850. Mills that can be used to grind to these particle sizes include pin mills, hammer mills, screw mills, roll mills, disc mills and jogs. A jog mill etc. are mentioned, for example.
  • the polymer produced by grinding as described above is referred to as 'base resin' in the present invention, which is distinguished from the 'crosslinked polymer' prepared by crosslinking reaction to be described below.
  • the step of selectively classifying particles having a particle size of 150 to 850 in the polymer powder obtained through the grinding step may be further performed.
  • the manufacturing method of the super absorbent polymer includes the step of surface crosslinking the polymer pulverized through the above-described steps.
  • Surface crosslinking is a method of increasing the crosslinking density of the surface of a resin particle, and the solution comprising a crosslinking agent (surface crosslinking agent) and the pulverized polymer It can be carried out by a method of mixing and crosslinking reaction.
  • the gel strength of the base resin having a gel strength of 4000 to 5000 Pa may be increased by 1.4 times or more, and thus solution permeability (SFC), water retention, and pressure absorption may be improved.
  • SFC solution permeability
  • the gel strength of the base resin is less than 4000 Pa, the solution permeability (SFC) of the crosslinked polymer is lowered.
  • a cross-linking agent contained in the surface cross-linking solution roneun by surface cross-linking as described above comprising a cross-linking agent to increase the gel strength of at least 1.4 times, in particular (C 2 - 4) alkylene carbonates, preferably For example, ethylene carbonate or propylene carbonate can be used.
  • the content of the surface crosslinking agent may be appropriately adjusted according to the type or reaction conditions of the crosslinking agent, and preferably may be adjusted to 0.001 to 5 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the content of the surface crosslinking agent is too low, surface crosslinking may not be properly introduced, and the physical properties of the final resin may be reduced.
  • the surface crosslinking agent is used in an excessively high content, the absorption of the resin may be lowered due to excessive surface crosslinking reaction, which is not preferable.
  • the surface crosslinking solution and the pulverized polymer are mixed in a semi-permanent mixture, a method of spraying the surface crosslinking solution on the pulverized polymer, a pulverized polymer and The method of supplying and mixing the surface crosslinking solution continuously can be used.
  • additional water may be added. Can be. As such water is added together, more even dispersion of the crosslinking agent may be induced, aggregation of the polymer powder may be prevented, and the penetration depth of the surface crosslinking agent into the polymer powder may be further optimized.
  • the amount of water added may be adjusted to 0.5 to 10 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the surface crosslinking reaction step may be performed under a temperature of 100 to 250 ° C, it may be made continuously after the drying and grinding step proceeds to a relatively high temperature. At this time.
  • the surface crosslinking reaction may be performed for 1 to 120 minutes, or 1 to 100 minutes, or 10 to 60 minutes. In other words, in order to induce a minimum surface crosslinking reaction, the polymer particles may be damaged during excessive reaction, thereby preventing the physical properties from deteriorating.
  • the superabsorbent polymer according to the present invention and a method for preparing the same have the characteristics of having excellent solution permeability by controlling the degree of surface crosslinking of the base resin, and exhibiting high water retention and pressure absorption capability.
  • FIG. 1 is a graph showing physical property data of a super absorbent polymer according to an embodiment of the present invention.
  • the resin was sieved through a sieve (30-50 mesh) and weighed 0.5 g, which was then swollen in 50 g of 0.9% NaCl solution for 1 hour. The swollen gel was then spread over a Buchner funnel covered with filter paper to remove the remaining fluids for 3 minutes under vacuum. The gel was stored in a closed container until the test was ready. The gel was sucked into the filter paper so that there was no remaining water between the particles during testing before placing the gel between the rheometer and the parallel plate. Gel strength was measured with a rheometer with 2 g of the swollen gel. At this time, the measurement conditions of the rheometer were as follows. The measured values were taken for 5 minutes and then averaged.
  • Plate Gap Size 2 mm 3; Strain amplitude 1%; Osci lat ion frequency 10 readina / sec; ambient temperature: 22 ° C; plate: 25 mm, TA Instruments-AR series
  • Pressurized absorption capacity was measured by the following method according to the EDANA method WSP 242.2, the European Disposables and Nonwovens Association (EDANA) standard.
  • a stainless steel 400 mesh wire was mounted on the bottom of a 60 mm diameter plastic cylinder.
  • 0.9 g (W 0 ) of the resin was uniformly spread on the wire mesh under conditions of 50% of humidity and room temperature, and a piston was formed thereon which could further uniformly apply a load of 0.7 psi.
  • the piston had an outer diameter of slightly less than 60 mm 3, no gap with the inner wall of the cylinder, and the up and down movement was not disturbed. At this time, the weight W 3 (g) of the apparatus was measured.
  • a 90 mm diameter and 5 mm thick glass filter was placed inside a 150 mm diameter petri dish, and physiological saline consisting of 0.90 wt% sodium chloride was added at the same level as the top surface of the glass filter.
  • physiological saline consisting of 0.90 wt% sodium chloride was added at the same level as the top surface of the glass filter.
  • One sheet of filter paper having a diameter of 90 mm was placed thereon.
  • the measuring device was placed on filter paper and the solution was allowed to absorb under constant load. After 1 hour, the measuring apparatus was lifted up, and the weight W 4 (g) was measured.
  • the AUP was measured by the measurement result as shown in Equation 2 below. '
  • AUP (g / g) [W 4 (g)-W 3 (g)] / W 0 (g)
  • Beam SAT by Mucha Heavy absorption ratio was determined according to European Nonwoven Industry Association (European Disposables and Nonwovens Association,. EDANA) standard EDANA WSP 241.2. Specifically, 0.2 g (W 0 ) of the resin was uniformly placed in a bag made of a nonwoven fabric and sealed, and then immersed in 0.9% physiological saline at room temperature. After 30 minutes, the bag was drained at 250 G for 3 minutes using a centrifuge, and then the mass (g) of the bag was measured. In addition, the time of the mass Kg After the same operation without the use of resin), was measured. From each mass thus obtained, CRC (g / g) was calculated according to the following formula.
  • a phosphorus monomer aqueous solution composition was prepared.
  • the monomer aqueous solution composition was continuously fed into the supply section of the polymerized polymer conveyor belt, and then irradiated with UV light using a UV irradiation apparatus (irradiation amount: 20 mW / ciif), followed by UV polymerization for 2 minutes to form a hydrogel polymer.
  • a UV irradiation apparatus irradiation amount: 20 mW / ciif
  • the hydrogel polymer was transferred to a cutter and cut into 0.2 cm. At this time, the water content of the hydrogel polymer was 47% by weight. Subsequently, the hydrogel polymer was dried at a temperature of 160 ° C. in a hot air dryer for 30 minutes, and the dried hydrogel polymer was pulverized with a pin mill grinder. Subsequently, sieves were used to classify polymers having a particle size (average particle diameter size) of 150 ⁇ to 850 to prepare a base resin. CRC of the prepared base resin was 33 ⁇ 35 g / g, the gel strength was 4500-5000 Pa. Step 2) Preparation of Super Absorbent Resin
  • Resin was prepared using 1,3-propanedi (1, 3-P). Samples were taken at 10 minute intervals during the crosslinking reaction as in Example 1, and the physical properties thereof were shown in FIG. 1 (total 40 minutes). Comparative Example 2
  • Step 2 of Example 1 except that a solution containing 3 g of distilled water, 0.3 g of 4-butanediol and 100 g of base resin was mixed, a superabsorbent polymer was prepared in the same manner as in Example 1. It was. Comparative Example 3
  • Step 2 of Example 1 a superabsorbent polymer was prepared in the same manner as in Example 1, except that 100 g of the base resin was mixed with 3 g of distilled water and 0.3 g of ethylene glycol. Comparative Example 4
  • the CRC of the prepared base resin was 43 g / g, and the gel strength was 3120 Pa.
  • 100 g of the base resin prepared above was mixed with a solution of 3 g of distilled water and 0.4 g of ethylene carbonate, followed by crosslinking reaction at a temperature of 194 ° C. for 40 minutes in a convection oven.
  • the CRC of the prepared base resin was 52 g / g, and the gel strength was 1980 Pa.
  • 100 g of the base resin prepared above was mixed with a solution of 3 g of distilled water and 0.4 g of ethylene carbonate, followed by a crosslinking reaction for 40 minutes at a temperature of 194 ° C. in a convection oven.
  • the physical properties of the Example (red) and Comparative Example (black) were different.
  • the solution permeability of the Example was higher than the comparative example of similar gel strength.
  • the centrifugal water holding capacity of the Example was higher than the comparative example of similar solution permeability, the sum of the centrifugal water holding capacity and the solution permeability of the embodiment (CRC + SFC / 10) It was higher than this comparative example (FIG. 1 (d)). Therefore, it was confirmed that the super absorbent polymer according to the present invention can simultaneously achieve high centrifugal water-retaining ability and solution permeability.

Abstract

Selon une résine super-absorbante et son procédé de préparation de la présente invention, la résine super-absorbante présente non seulement une excellente perméabilité en solution mais peut également présenter une haute capacité de rétention d'eau et un pouvoir absorbant sous pression, par le contrôle du degré de réticulation en surface d'une résine de base.
PCT/KR2015/011089 2014-12-04 2015-10-20 Résine superabsorbante et son procédé de préparation WO2016089005A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0172999 2014-12-04
KR20140172999 2014-12-04
KR1020150145613A KR20160067725A (ko) 2014-12-04 2015-10-19 고흡수성 수지 및 이의 제조 방법
KR10-2015-0145613 2015-10-19

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009161768A (ja) * 2003-08-27 2009-07-23 Nippon Shokubai Co Ltd 表面処理された粒子状吸水性樹脂の製造方法
KR20100014556A (ko) * 2007-03-23 2010-02-10 에보닉 스톡하우젠, 인코포레이티드 높은 투과성의 초흡수성 중합체 조성물
KR20130096152A (ko) * 2010-05-07 2013-08-29 에보닉 스톡하우젠, 엘엘씨 용량이 증가된 미립자형 초흡수성 중합체
WO2014079694A1 (fr) * 2012-11-21 2014-05-30 Basf Se Procédé de production de particules de polymères absorbant l'eau post-réticulées en surface
KR20140130034A (ko) * 2013-04-30 2014-11-07 주식회사 엘지화학 고흡수성 수지

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009161768A (ja) * 2003-08-27 2009-07-23 Nippon Shokubai Co Ltd 表面処理された粒子状吸水性樹脂の製造方法
KR20100014556A (ko) * 2007-03-23 2010-02-10 에보닉 스톡하우젠, 인코포레이티드 높은 투과성의 초흡수성 중합체 조성물
KR20130096152A (ko) * 2010-05-07 2013-08-29 에보닉 스톡하우젠, 엘엘씨 용량이 증가된 미립자형 초흡수성 중합체
WO2014079694A1 (fr) * 2012-11-21 2014-05-30 Basf Se Procédé de production de particules de polymères absorbant l'eau post-réticulées en surface
KR20140130034A (ko) * 2013-04-30 2014-11-07 주식회사 엘지화학 고흡수성 수지

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