WO2017111295A1 - Polymère superabsorbant et son procédé de préparation - Google Patents

Polymère superabsorbant et son procédé de préparation Download PDF

Info

Publication number
WO2017111295A1
WO2017111295A1 PCT/KR2016/012678 KR2016012678W WO2017111295A1 WO 2017111295 A1 WO2017111295 A1 WO 2017111295A1 KR 2016012678 W KR2016012678 W KR 2016012678W WO 2017111295 A1 WO2017111295 A1 WO 2017111295A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
water
weight
super absorbent
base resin
Prior art date
Application number
PCT/KR2016/012678
Other languages
English (en)
Korean (ko)
Inventor
이금형
김기철
박성수
양예솔
성보현
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020160144603A external-priority patent/KR102119813B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/743,841 priority Critical patent/US10995183B2/en
Publication of WO2017111295A1 publication Critical patent/WO2017111295A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • 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
    • 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
    • C08J9/10—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 nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a super absorbent polymer and a method for producing the same. More particularly, the present invention relates to a super absorbent polymer having an improved absorption rate and high gallon density, and a method for 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 super absorbent material (SAM), absorbent gel mater (ALM), etc. Also called. 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 index materials, seedling sheets, and freshness retainers in food distribution. It is used.
  • 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, 57-158209, and 57-198714.
  • the production of superabsorbent polymers through polymerization of aqueous solution is a thermal polymerization method in which a hydrogel polymer is broken and immersed in a half-die with multiple axes, and is polymerized by irradiating ultraviolet light to a high concentration of aqueous solution on a belt.
  • the photopolymerization method etc. which perform simultaneously and drying are known.
  • the rate of absorption which is one of the important physical properties of superabsorbent polymers, is related to the surface dryness of products that touch the skin, such as diapers. Generally this One absorption rate can be improved by increasing the surface area of the superabsorbent polymer.
  • Patent Document 1 Japanese Patent Laid-Open No. 56-161408
  • Patent Document 2 Japanese Patent Laid-Open No. 57-158209
  • Patent Document 3 Japanese Patent Laid-Open No. 57-198714
  • the present invention is to provide a super absorbent polymer having improved absorption rate and high apparent density.
  • the present invention is to provide a method for producing the super absorbent polymer.
  • the base resin powder containing the crosslinked polymer of the water-soluble ethylene-type unsaturated monomer which has the acidic group neutralized at least one part,
  • the base resin powder has the several hole of diameter 1fi or more formed,
  • the said crosslinked polymer contains layered silicate particles dispersed in the crosslinked structure, and has a squeezed density of at least 0.5 g / mt. Ball.
  • the present specification also includes a base resin powder containing a cross-linked polymer of a water-soluble ethylenically unsaturated monomer having at least a portion of neutralized acidic groups, and a plurality of pores of diameter 1 / m or more are formed in the base resin powder,
  • a superabsorbent polymer having a density of 0.55 g / m £ or more and a time for removing vortex generated when stirring 0.9 wt% NaCl solution 50 at 600 rpm at a speed of 54 seconds or less is provided.
  • a water-containing gel polymer is obtained by crosslinking and polymerizing a monomer composition comprising a layered silicate-based particle, a foaming agent, an internal crosslinking agent, and a water-soluble ethylene-based unsaturated monomer having at least part of a neutralized acidic group, and stirred at a speed of 1000 rpm or more.
  • a manufacturing method is provided.
  • the water-containing gel polymer is further crosslinked with a monomer composition comprising a layered silicate-based particle, a blowing agent, an internal crosslinking agent, and a water-soluble ethylenically unsaturated monomer having at least a portion of an acidic group, and stirred at a speed of 1000 rpm or more.
  • the coarsely crushing step is pulverized so as to be 2 kPa to 10 kPa, wherein the coarsely crushing step is provided at a temperature of 50 ° C. or more, and a method for producing a super absorbent polymer which proceeds at a frequency of 15 Hz or more.
  • the hydrogel polymer is further crosslinked with a monomer composition comprising a layered silicate-based particle, a blowing agent, an internal crosslinking agent, and a water-soluble ethylenically unsaturated monomer having at least part of a neutralized acidic group, and stirred at a speed of 1000 rpm or more.
  • a monomer composition comprising a layered silicate-based particle, a blowing agent, an internal crosslinking agent, and a water-soluble ethylenically unsaturated monomer having at least part of a neutralized acidic group, and stirred at a speed of 1000 rpm or more.
  • the base resin powder including cross-linked polymers of ethylenically unsaturated monomers, and the base resin powder having an at least partially neutralized acid has a plurality of pores over a diameter of 1 formation
  • the crosslinked polymer is crosslinked .
  • a superabsorbent polymer containing layered silicate particles dispersed in the structure and having an apparent density of 0.55 g / val or more can be provided.
  • the inventors of the present invention use the above-described superabsorbent polymer, and by using specific layered silicate-based particles, a plurality of micropores can be stably formed in the crosslinked polymer, and the contact area with water increases rapidly.
  • the absorption rate of the absorbent resin can be further improved, and the experiment was confirmed that the superabsorbent polymer having a high apparent density can be prepared through experiments and completed the invention.
  • the super absorbent polymer may include a base resin powder including a cross-linked polymer of a water-soluble ethylenically unsaturated monomer having at least a portion of the acid group.
  • the "crosslinked polymer of water-soluble ethylenically unsaturated monomer” is a hydrogel polymer immediately formed by thermal polymerization or photopolymerization to a composition containing a water-soluble ethylenically unsaturated monomer, as well as a general method for producing a super absorbent polymer.
  • a polymer obtained by drying the hydrogel polymer a polymer obtained by grinding the hydrogel polymer or dried polymer, surface crosslinking It includes both the polymer before the reaction or the polymer after the surface crosslinking reaction, and if the water-soluble ethylenically unsaturated monomer is a polymerized polymerizer, all polymers are included regardless of the form, water content, particle size, surface crosslinking or the like. Can be.
  • the super absorbent polymer of the above embodiment basically includes a polymer obtained by crosslinking polymerization of the water-soluble ethylenically unsaturated monomer as a base resin powder, as in the previous super absorbent polymer.
  • the water-soluble ethylene-based unsaturated monomer acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacrylo Anionic monomers of monoethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, or 2- (meth) acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth) acrylamide, N-substituted (meth) acrylates, 2-hydroxyethyl (meth) acrylates, 2-hydroxypropyl (meth) acrylates, hydroxypolyethylene glycol (meth) acrylates or polyethylene Nonionic hydrophilic-containing monomers of glycol (meth) acrylates; And amino group-containing unsaturated monomers of ( ⁇ , ⁇ ) -dimethylaminoethyl (meth)
  • alkali metal salts such as acrylic acid or salts thereof, for example acrylic acid and / or sodium salts thereof, to which at least a portion of acrylic acid has been amplified, may be used, and such monomers may be used for superabsorbent polymers having superior physical properties. Manufacturing becomes possible.
  • acrylic acid can be neutralized with a basic compound such as caustic soda (NaOH).
  • the crosslinked polymer included in the base resin powder may include a crosslinked structure in which polymer chains of the water-soluble ethylenically unsaturated monomer are crosslinked through a crosslinkable functional group of an internal crosslinking agent.
  • an internal crosslinking agent for introducing the basic crosslinking structure into the crosslinked polymer and the base resin powder any internal crosslinking agent having a crosslinkable functional group, which has conventionally been used in the manufacture of superabsorbent polymers, can be used without any particular limitation.
  • the internal crosslinking agent In order to further improve the polyfunctional acrylate compound having a plurality of ethylene oxide groups can be used as the internal crosslinking agent. More specific examples of such internal crosslinking agents include polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, glycerin triacrylate, unmodified or ethoxylated trimethyl triacrylate (TMPTA), nucleic acid diol diacrylate, And triethylene glycol diacrylate.
  • the base resin powder may have a plurality of pores of 1 or more in diameter, or 1 to 10 kPa, or 1 kPa to 1000 mi.
  • the pores are implemented by a blowing agent added together in the monomer composition, as shown in the method of preparing a superabsorbent polymer, which will be described later.
  • a plurality of pores having a minimum diameter of 1 or more are formed on the base powder. You can see that it is formed.
  • the pores may be present in a plurality of forms, evenly dispersed in the base resin powder.
  • the plurality of pores of diameter 1 m or more contained in the base resin powder may include micropores having a diameter of 10 to 100 urn.
  • the micropores having a diameter of 10 to 100 ⁇ may be formed by adding a blowing agent and inorganic particles together when forming a polymer, as described below. As such micropores are stably formed, the microporosity is increased. The absorption rate of the water absorbent resin can be further improved.
  • the crosslinked polymer contained in the base resin powder may include layered silicate particles dispersed in the crosslinked structure.
  • layered silicate-based particles particles including a metal oxide layer including a metal oxide and unit crystals formed on at least one surface of the metal oxide layer and including a silica layer including silica may be used.
  • the unit crystal refers to a periodic unit of crystalline particles having three-dimensional periodicity, and particles may be formed through repetition of the unit crystal.
  • the unit crystal of the layered silicatetic bib may be formed on at least one surface of the metal oxide layer including the metal oxide and the metal oxide layer, and may include a silica layer including silica. That is, the silica layer is formed on one side or both sides of the metal oxide layer in the unit crystal of the layered silicate particles. Can be.
  • the metal oxide layer and the silica layer may be bonded through a siloxane bond.
  • the siloxane bond means a covalent bond between a silicon atom (Si) and an oxygen atom (0), and more specifically, an oxygen atom included in the metal oxide layer, such as a unit crystal structure shown in FIG. 1.
  • a bond between the metal oxide and the silica layer may be formed through a covalent bond between and silicon atoms included in the silica layer.
  • the metal oxide may exist in a state in which a metal atom and an oxygen atom are bonded to each other, and examples of the metal atom are not particularly limited, and lithium, sodium, potassium, and the like are group 1 or group 2 elements of the periodic table. Beryllium, magnes, and sword.
  • the layered silicate-based particles can stably maintain fine pores in the crosslinked polymer and increase the contact area with water to further improve the absorption rate of the super absorbent polymer.
  • the layered silicate particles may have a light structure having a maximum diameter of 1 ran to 100 ran and a height of O.Olnm to 20 nm, or O.lnm to 20 nm.
  • the lamp structure means a three-dimensional figure in which the upper and lower surfaces are parallel to each other.
  • the specific shape of the light emitting structure is not limited, for example, according to the type of cross section in which the layered silicate particles are cut in a direction parallel to the ground, that is, a cylinder, an ellipse, etc. Etc. can be mentioned.
  • the light emitting structure of the layered silicate particles may be formed by repetition of the unit crystal, and the maximum diameter of the straight section in the columnar structure is a cross section of the layered silicate particles cut in a direction parallel to the ground. It means the largest value among the diameters it can have.
  • the layered silicate particles have a light structure having a maximum diameter of 1 nm to 100 nm and a height of 0.1 nm to 20 nm of the straight section, so that the layered silicate particles in the crosslinked polymer of the embodiment are fine.
  • One particle size not only enables functionality in the crosslinked polymer, but is also formed by the blowing agent in the monomer composition when the crosslinked polymer is formed. It can stabilize the micropores that are.
  • Examples of the layered silicate-based particles are not particularly limited, and examples thereof include hackite (Laponite RD, Laponite XLG, Laponite D, Laponite DF Laponite RS, Laponite XLS, Laponite DS, Laponite S and Laponite JS, etc.). And a more preferred example is Laponite RD.
  • the layered silicate-based particles described above may be included in an amount of 0.01 parts by weight to 30 parts by weight, or 0.01 parts by weight to 5 parts by weight, or 0. 2 parts by weight to 0.1 parts by weight based on 100 parts by weight of the base resin powder. .
  • the degree of formation of fine pores in the crosslinked polymer is optimized, so that the highly absorbent resin of one embodiment may have an improved absorption rate.
  • the super absorbent polymer of the embodiment has an apparent density (Bulk Density, B / D) of 0.55. Or 0.55 g / mi to 1.0 g / mi, or 0.55 g / mi to 0/70 g / al.
  • B / D apparent density
  • the volume of the superabsorbent polymer is relatively high; Increasingly, more storage space is needed, which can reduce storage efficiency.
  • the superabsorbent polymer particles may be stagnant without being smoothly introduced, thereby reducing the efficiency of the process.
  • the super absorbent polymer of the embodiment may have a time for removing the vortex generated when stirring 0.9 wt% NaCl solution 50 at 600 rpm, 60 seconds or less, or 40 seconds to 60 seconds.
  • the superabsorbent polymer may have a water holding capacity of 40 g / g or more, or 40 g / g to 60 g / g of physiological saline measured according to the EDANA WSP 241.2 method.
  • Centrifuge water capacity (CRC) for physiological saline can be measured according to the method of EDANA method WSP 241.2. More specifically, the water retention capacity may be calculated by Equation 1 below after absorbing the superabsorbent polymer in physiological saline over 30 minutes.
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • W g) is the weight of the device measured after dehydration at 250G for 3 minutes using a centrifuge without using the superabsorbent polymer
  • W 2 ( g) is the weight of the device, including the superabsorbent polymer, after submerging the superabsorbent polymer in physiological saline of 0.9 wt.% at room temperature for 30 minutes and then dehydrating it at 250 G for 3 minutes using a centrifuge.
  • the super absorbent polymer of the above-described embodiment may have a particle shape such as spherical or amorphous having a particle diameter of about 850 ⁇ .
  • At least a part comprises a base resin powder containing a cross-linked polymer of a water-soluble ethylenically unsaturated monomer having a neutralized acid group, a plurality of pores of diameter 1 or more is formed in the malleable base resin powder And a superabsorbent polymer having an apparent density of at least 55 g / m £ and removing a vortex generated when stirring 0.9 wt% of NaCl solution 50 at 600 rpm at a speed of 600 rpm can be provided.
  • the monomer composition comprising a layered silicate-based particles, foaming agent, internal crosslinking agent and a water-soluble ethylenically unsaturated monomer having at least a part of the neutralized acid group, stirred at a rate of 1000 rpra or more Crosslinking polymerization to form a hydrogel polymer; And the function of drying, pulverizing, and classifying a gel of the polymer, including the steps of forming a base resin powder, wherein the monomer composition, the concentration of the water-soluble ethylenic unsaturated monomer contained in the water 40 wt% to 60 wt%, and A method for producing a water absorbent resin can be provided.
  • cross-linking polymerization of the monomer composition comprising a water-soluble ethylenically unsaturated monomer having a layered silicate-based particles, a blowing agent, an internal magnetic crosslinking agent and at least a part of the neutralized acid group, and stirred at a speed of 1000 rpm or more to form a hydrogel polymer ; And drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, and drying, pulverizing and classifying the hydrogel polymer to form a base resin powder.
  • the The coarsely pulverizing step may be provided with a method for producing a super absorbent polymer, which proceeds at a frequency of 15 Hz or higher at a temperature of 50 ° C. or higher.
  • cross-polymerizing a monomer—composition comprising a water-soluble ethylenically unsaturated monomer having a layered silicate-based particles, a blowing agent, an internal crosslinking agent and at least a part of a neutralized acidic group, and stirred at a speed of at least 1000 rpm to form a hydrogel polymer.
  • a monomer—composition comprising a water-soluble ethylenically unsaturated monomer having a layered silicate-based particles, a blowing agent, an internal crosslinking agent and at least a part of a neutralized acidic group, and stirred at a speed of at least 1000 rpm to form a hydrogel polymer.
  • drying, pulverizing and classifying the hydrogel polymer to form a base resin powder drying, pulverizing and classifying the hydrogel polymer to form a base resin powder.
  • a coarse grinding step of pulverizing to a particle diameter of 2 to 10 ⁇ , and before or after the coarse crushing step, adding water to a content of less than 20 parts by weight with respect to 100 parts by weight of the hydrogel polymer It can be provided a method for producing a super absorbent polymer further comprising.
  • the layered silicate particles are used together with a conventional blowing agent and an internal crosslinking agent to proceed with the crosslinking polymerization of the water-soluble ethylenically unsaturated monomer, followed by drying according to a general method for preparing a super absorbent polymer.
  • the superabsorbent polymer can be prepared by pulverizing, classifying and surface crosslinking.
  • fine bubbles generated by the blowing agent can be stably maintained by the layered silicate particles.
  • the absorption rate of the superabsorbent polymer to be prepared can be improved more, and the base resin powder having the crosslinked structure already formed by the use of an internal crosslinking agent can be prepared, thereby realizing various physical properties such as excellent water retention.
  • the superabsorbent polymer production method of another embodiment includes a monomer composition comprising a layered silicate-based particle, a blowing agent, an internal crosslinking agent, and a water-soluble ethylenically unsaturated monomer having at least a part of which is neutralized acid group, at least 1000 rpm, or 1000
  • a high shear force can be applied to the monomer composition, so that the base resin powder has a size of several mm to several tens of microseconds. It can suppress the formation of macropores as much as possible, and the diameter is 10 It is possible to distribute a large number of microporous to 100 to 100 IM.
  • the monomer composition is stirred at a speed of 1000 rpm or more, and then 1) the concentration of the water-soluble ethylenically unsaturated monomer contained in the monomer composition is adjusted to 40% by weight to 60% by weight, or 2) the coarse grinding step is 50 ° At a temperature above C, at a frequency of 15 Hz or higher, or 3) by adding water in an amount of less than 20 parts by weight, relative to 100 parts by weight of the hydrogel polymer before or after the coarse grinding step, By reducing the nonuniformity of the particle shape, it is possible to increase the apparent density of the high absorbent resin.
  • the method of preparing the super absorbent polymer includes a layered silicate-based particle, a blowing agent, an internal crosslinking agent, and a water-soluble ethylenically unsaturated monomer having at least a portion of neutralized acidic groups, and a monomer composition stirred at a speed of 1000 rpm or more.
  • Cross-linking polymerization to form a hydrogel polymer ⁇
  • Examples of the method for preparing the monomer composition are not particularly limited, and for example, the layered silicate-based particles, the blowing agent, the internal crosslinking agent, and at least a portion of the water-soluble ethylenically unsaturated monomer having an acidic group neutralized at the same time or sequentially.
  • Examples thereof include a method of mixing with a solvent or the like. More specifically, a first mixture of a water-soluble ethylenically unsaturated monomer and an internal crosslinking agent is prepared, a second mixture of layered silicate particles and a blowing agent is prepared, and then the first mixture and the second mixture are prepared. For example, a method of mixing the same may be mentioned.
  • the monomer composition may be stirred at a speed of 1000 rpm or more, or 1000 rpm to 20000 rpm, or 3000 rpm to 10000 rpm.
  • high shear force can be applied to the monomer composition, it is possible to suppress the formation of macropores of several mm to several tens of millimeters in the size of the base resin powder to the maximum, fine diameter of 10 to loo Multiple pores can be distributed.
  • an example of a method of stirring the monomer composition is not particularly limited, and for example, a method of passing the monomer composition through a high shear force stirring device (dynami c mechani cal system, DMS) may be mentioned.
  • the high shear agitation device (dynami c mechani cal system, DMS) is a pump and Including a stirrer, the motor speed of the pump is 0 to 6000 rpm, the speed of the stirring may be 0 to 20000 rpm.
  • particles including a metal oxide layer containing a metal oxide and a unit crystal formed on at least one surface of the metal oxide layer and including a silica layer containing silica may be used.
  • the unit crystal refers to a periodic unit of crystalline particles having three-dimensional periodicity, and particles may be formed through repetition of the unit crystal.
  • the unit crystal of the layered silicate-based particles may be formed on at least one surface of the metal oxide layer including the metal oxide and the metal oxide layer, and may include a silica layer including silica. That is, the silica layer may be formed on one side or both sides of the metal oxide layer in the unit crystal of the layered silicate particles.
  • the metal oxide layer and the silica layer may be bonded through a siloxane bond (s i loxane).
  • the siloxane (si loxane) bond means a covalent bond between a silicon atom (Si) and an oxygen atom (0), and more specifically, the oxygen included in the metal oxide layer, as shown in the unit crystal structure shown in FIG.
  • a bond between the metal oxide and the silica layer may be formed through a covalent bond between atoms and silicon atoms included in the silica layer. .
  • the metal oxide may be present in a state in which a metal atom and an oxygen atom are bonded to each other, and examples of the metal atom are not particularly limited, and lithium, sodium, potassium, Beryllium, magnesium, calcium and the like.
  • the layered silicate-based particles have a maximum diameter of 1 ran to 100 nm in a straight section, and a height of 0. Olnm to 20 ran, or O. It may have a light structure of 1 nm to 20 nm.
  • the lamp structure means a three-dimensional figure in which the upper and lower surfaces are parallel to each other.
  • the specific shape of the light emitting structure is not limited, for example, according to the type of cross section in which the layered silicate particles are cut in a direction parallel to the ground, that is, a primitive lamp, an ellipse group, etc. Etc. may be mentioned.
  • the light structure of the layered silicate particles is It can be formed through the repetition of the unit crystal, the maximum diameter of the straight cross-section in the lamp structure means the largest value among the diameter that the cross section cut the layered silicate particles in a direction parallel to the ground.
  • the layered silicate-based particles have a maximum diameter of 1 nm to 100 nm in a straight section, and a height of 0.
  • the layered silicate particles in the crosslinked polymer of the embodiment can not only realize functionality in the crosslinked polymer through a fine indenter size, but also when forming the crosslinked polymer. It is possible to stabilize the micropores formed by the blowing agent in the monomer composition.
  • Examples of the layered silicate-based particles are not particularly limited, for example, nuclear lite (Laponi te RD, Laponi te XLG, Laponi te D, Laponi te DF Laponi te RS, Laponi te XLS, Laponite DS, Laponi te S and Laponi te JS and the like), and Laponi te RD is more preferable.
  • nuclear lite Laponi te RD, Laponi te XLG, Laponi te D, Laponi te DF Laponi te RS, Laponi te XLS, Laponite DS, Laponi te S and Laponi te JS and the like
  • Laponi te RD is more preferable.
  • blowing agent examples are not particularly limited, and various blowing agents well known in the art may be used without limitation.
  • blowing agent for example, azodi carbonamide, azodicarboxyamide, benzenesulfonylhydrazide, dinitrosopenta methylenetetramine, toluenesulfonylhydrazide, azobisisobutyronitrile, azo dicarboxylic acid
  • at least one selected from the group consisting of barium and sodium bicarbonate examples of the blowing agent.
  • the step of cross-polymerizing the water-soluble ethylenically unsaturated monomer having at least a part of the neutralized acidic group to form a hydrogel polymer may be carried out in the presence of layered silicate particles, blowing agent and internal crosslinking agent. That is, it may be to polymerize the monomer composition including the layered silicate-based particles, the blowing agent, the internal crosslinking agent, and the water-soluble ethylenically unsaturated monomer having at least one neutralized acidic group.
  • the fine pore even inside the hydrogel polymer is added by adding the layered silicate particles and the blowing agent to the monomer composition for forming the hydrogel polymer. Can be formed.
  • the layered silicate particles, foaming agent, internal crosslinking agent and at least The content of the layered silicate particles may be 1 part by weight to 50 parts by weight based on 100 parts by weight of the blowing agent in the monomer composition including a water-soluble ethylenically unsaturated monomer having a neutralized acidic group.
  • the pore stabilization effect by the layered silicate particles may be reduced to reduce the absorbency of the super absorbent polymer.
  • the concentration of the water-soluble ethylenically unsaturated monomer contained in the monomer composition may be 40% by weight to 60% by weight, or 40% by weight to 50% by weight.
  • the concentration of the monomer is excessively low, the yield of the superabsorbent polymer may be low and problems may occur.
  • the concentration is excessively high, some of the monomer may precipitate or the grinding efficiency of the polymerized hydrogel polymer may be low. Problems may occur in the process and the physical properties of the super absorbent polymer may be reduced.
  • the monomer composition may further include a polymerization initiator generally used in the preparation of a super absorbent polymer.
  • the polymerization initiator may use a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • an additional thermal polymerization initiator may be included. It may be.
  • the photopolymerization initiator may be used without any limitation as long as it is a compound capable of forming radicals by light such as ultraviolet rays.
  • photopolymerization initiators examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketal. Ketal), acyl phosphine and alpha-aminoketone
  • acylphosphine commercially available lucirin TP0, that is, 2,4, 6-trimethyl-benzoyl-trimethyl phosphine ' oxide (2,4,6—trimethyl-benzoyl-trimethyl phosphine oxide) can be used.
  • lucirin TP0 that is, 2,4, 6-trimethyl-benzoyl-trimethyl phosphine ' oxide (2,4,6—trimethyl-benzoyl-trimethyl phosphine oxide
  • a wider variety of photoinitiators is well specified in Reinhold Schwalm lm "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)" pll5, and is not limited to the examples
  • the photopolymerization initiator may be included in a concentration of about 0.01% by weight to about 1.0% by weight based on the monomer composition. When the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow. When the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven.
  • the thermal polymerization initiator may be used at least one selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide and ascorbic acid.
  • persulfate-based initiators include sodium persulfate (Na2S 2 0s), potassium persulfate (K2S208), ammonium persul fate (NH 4 ) 2 S 2 0 8
  • azo initiators include 2, 2-azobis- (2-amidinopropane) dihydrochloride (2, 2- azob is (2-am idi nopr opane) dihydrochlor ide), 2 , 2-Azobis one (N, N_dimethylene) isobutyramidine.
  • Dihydrochloride (2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochlor ide), 2— (carbamoyl azo) isobutyronitrile (2— (carbamoylazo) isobutylonitril), 2, 2-azobis [2 -(2-imidazolin-2-yl) propane] dihydrochloride (2, 2-azob is [2- (2-imi dazo 1 i n-2- yDpropane] dihydrochlor ide), 4,4—azobis (4—Cyanovaleric acid) (4, 4_ azobis- (4-cyanovaleric acid)), etc.
  • thermal polymerization initiators see Odian, Principle of Polymer izat ion (Wi ley, 1981). , p203 is well specified, and is not limited to the example described above.
  • the thermal polymerization initiator may be included in a concentration of about 0.001% to about 0.5% by weight based on the monomer composition. When the concentration of such thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, resulting in thermal polymerization. The effect of the addition of the reagent may be insignificant, and if the concentration of the thermal polymerization initiator is too high, the molecular weight of the superabsorbent polymer may be small and the physical properties may be uneven.
  • the type of the internal crosslinking agent included in the monomer composition is already described above, and the internal crosslinking agent may crosslink the polymerized polymer.
  • the monomer composition may further include additives such as an emulsifier, a thickener, a plasticizer, a storage stabilizer, an antioxidant, and the like, as necessary.
  • additives such as an emulsifier, a thickener, a plasticizer, a storage stabilizer, an antioxidant, and the like.
  • Specific examples of the additives are not particularly limited, and various kinds of known additives may be used without limitation.
  • examples of the emulsifiers include fatty acid esters including sugars, and more specifically, sucrose esters.
  • Raw materials such as the above-mentioned water-soluble ethylene-based unsaturated monomers, silicate-based particles, photopolymerization initiators, thermal polymerization initiators, internal crosslinking agents, and additives may be prepared in the form of a monomer composition solution dissolved in a solvent.
  • the solvent that can be used at this time can be used without limitation in the composition as long as it can dissolve the above-mentioned components, for example, 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, cyclonucleanone, cyclopentanone, diethylene glycol monomethyl ether , Diethylene glycol etheryl ether, toluene, xylene, butyrolactone, carbye, may be used in combination of one or more selected from methyl cellosolve acetate and ⁇ , ⁇ -dimethylacetamide.
  • the solvent may be included in the remaining amount except for the components described above with respect to the total content of the monomer composition.
  • a method of forming a hydrogel by thermal polymerization or photopolymerization of such a monomer composition is also a commonly used polymerization method, in particular There is no limit.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source, and when the thermal polymerization is usually carried out, it can be carried out in a reactor having a stirring axis such as kneader, and when the polymerization proceeds, Although it can proceed in a semi-unggi equipped with a conveyor belt possible, the above-described polymerization method is an example, the present invention is not limited to the above-described polymerization method.
  • a water-containing gel polymer obtained by thermal polymerization by supplying hot air or by heating a reactor according to the shape of the stirring shaft provided in the reactor is a reactor, such as a kneader having a stirring shaft.
  • the hydrogel polymer discharged to the outlet may be in the form of several centimeters to several millimeters.
  • the size of the resulting hydrogel polymer may vary depending on the concentration of the monomer composition to be injected, and the injection speed, etc., a hydrogel polymer having a weight average particle diameter of about 2 mm to 50 mm can be obtained.
  • the form of the hydrogel polymer generally obtained may be a hydrogel polymer on the sheet having a width of the belt.
  • the thickness of the polymer sheet depends on the concentration and the injection speed of the monomer composition to be injected, but it is preferable to supply the monomer composition so that a polymer on a sheet having a thickness of usually about 0.5 cm to about 5 cm can be obtained. Do.
  • the production efficiency is not preferable because it is low, and when the polymer thickness on the sheet exceeds 5 cm, due to the excessively thick thickness, the polymerization reaction is carried over the entire thickness. It may not happen evenly.
  • the water content of the hydrogel polymer obtained by the above method may be 40% by weight to 80% by weight.
  • water content as used throughout the present specification means the amount of water occupied with respect to the total weight of the hydrogel polymer, minus the weight of the polymer in the dry state. Specifically, it is defined as a value calculated by measuring the weight loss due to moisture evaporation in the polymer during the drying process of drying the temperature of the polymer through infrared heating. At this time, dry conditions are maintained at 180 ° C after raising the temperature to about 180 ° C at room temperature In this way, the total drying time is set to 20 minutes, including 5 minutes of temperature rise, and the moisture content is measured.
  • a base resin powder through a process such as drying, grinding and classification, the base resin powder and a super absorbent water obtained therefrom through such a process such as grinding and classification Paper is suitably made and provided to have a particle diameter of about 150 to 850. More specifically, the base resin powder and. At least about 95% by weight or more of the superabsorbent polymer obtained therefrom has a particle diameter of about 150 rni to 850, about
  • the fine powder having a particle diameter of less than 150 may be less than about 3 weight 3 ⁇ 4>.
  • the final manufactured super absorbent polymer may exhibit the above-described physical properties and better liquid permeability.
  • the step of coarsely pulverizing before drying may be further increased to increase the efficiency of the drying step.
  • the coarsely pulverizing step is at least 50 ° C, or 50 ° C to 150 ° C, or 60 ° C to 100 ° C, at least 15 Hz, or 15 Hz to 40 Hz, or 15 Hz to 30 It can proceed at a frequency of Hz.
  • the temperature of the grinding step may be a grinding device, a grinding blade, or a silver of an external heat source, and the frequency may be a vibration frequency of the grinding device or the grinding blade.
  • the superabsorbent polymer production method is less than 20 parts by weight, or 0 parts by weight to 19 parts by weight, or 10 parts by weight to 19 parts by weight based on 100 parts by weight of the hydrogel polymer before or after the coarse grinding step. It may further comprise the step of adding water in the amount of parts.
  • water means ionized water, and when the content of water is 20 parts by weight or more based on 100 parts by weight of the crosslinked polymer, the physical properties of the superabsorbent polymer may be lowered, such as water retention. In addition, the apparent density of the superabsorbent polymer may be reduced, thereby reducing storage efficiency.
  • the pulverizer used is not limited in configuration, specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Any one selected from the group of crushing machines consisting of a cutter mill, a disc mill, a shred crusher, a crusher, a chopper and a disc cutter It may include, but is not limited to the above examples.
  • the coarsely pulverizing step may be pulverized so that the particle size of the hydrogel polymer is about 2 ⁇ to about 10 ⁇ . Grinding to a particle diameter of less than 2 GPa is technically not easy due to the high water content of the ' hydrogel polymer ' , and may also cause aggregation of the pulverized particles with each other. On the other hand, when the particle diameter is more than 10 mm, the effect of increasing the efficiency of the subsequent drying step may be insignificant.
  • the drying temperature of the drying step may be about 150 ° C to about 250 ° C. If the drying temperature is less than about 150 ° C, the drying time may be too long and the physical properties of the final superabsorbent polymer may be lowered. If the drying temperature exceeds about 250 ° C, only the polymer surface may be excessively dried. Fine powder may be generated in a subsequent grinding step, and there is a fear that the physical properties of the superabsorbent polymer to be finally formed are reduced. Therefore, the preferred the drying can proceed at a temperature of about 150 ° C to about 200 ° C.
  • drying time in consideration of the process efficiency, etc., it may proceed for about 20 minutes to about 90 minutes, but is not limited thereto.
  • drying step is also commonly used as a drying step of the hydrogel polymer, can be selected and used without limitation of the configuration. Specifically, the drying step may be performed by hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the water content of the polymer after such a drying step may be about 0.1% by weight to about 10% by weight.
  • the polymer powder obtained after the grinding step has a particle diameter of about 150 mi to about 850 // m can be
  • the grinder used to grind to such a particle size is specifically a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill ) Or a jog mill may be used, but is not limited to the example described above.
  • a separate process of classifying the polymer powder obtained after grinding according to the particle size may be performed.
  • the polymer having a particle size of about 150 / im to about 850 / zm may be classified, and only a polymer powder having such a particle size may be further commercialized through a surface crosslinking reaction step or the like as necessary. Since the particle size distribution of the base resin powder obtained through such a process has already been described above, a detailed description thereof will be omitted.
  • the production method of the other embodiment comprises a layered silicate-based particles, a blowing agent, an internal crosslinking agent and at least a portion of the water-soluble ethylenically unsaturated monomer having a neutralized acid group, crosslinked polymerization of the monomer composition stirred at a speed of 1000 rpm or more To form a hydrogel polymer; And drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, wherein the concentration of the water-soluble ethylenically unsaturated monomer included in the monomer composition is 40 weight 3 ⁇ 4 »to 60 weight 3 ⁇ 4>, Drying, pulverizing, and classifying the hydrogel polymer to form a base resin powder may include a coarse milling step of grinding the particle size of the hydrogel polymer so as to have a particle diameter of 2 kPa to 10 kPa. At a temperature above ° C, a process for producing a super absorbent polymer may be provided that proceeds with a
  • the production method of the other embodiment comprises a layered silicate-based particles, foamed crab, internal cross-linking agent and at least a portion of the water-soluble ethylenically unsaturated monomer having a neutralized acid group, crosslinked polymerization of the monomer composition stirred at a speed of 1000 rpm or more To form a hydrogel polymer; And drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, wherein the concentration of the water-soluble ethylenically unsaturated monomer included in the monomer composition is 40 wt% to 60 wt%, and the hydrogel
  • the particle diameter of the polymer is from 2 ⁇ to 10 ⁇ And coarsely pulverizing the pulverizing step, and before or after the coarse pulverizing step, further comprising adding water in an amount of less than 20 parts by weight, based on 100 parts by weight of the hydrogel polymer. Manufacturing methods may be provided.
  • the production method of the other embodiment comprises a layered silicate-based particles, a blowing agent, an internal crosslinking agent and at least a portion of the water-soluble ethylenically unsaturated monomer having a neutralized acid group, crosslinked polymerization of the monomer composition stirred at a speed of 1000 rpm or more To form a hydrogel polymer; And drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, and drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, the hydrogel polymer Coarse grinding step of grinding so that the particle diameter of 2 to 10 ⁇ , wherein the coarse grinding step proceeds at a frequency of 15 Hz or more, at a temperature of 50 ° C or more, before or after the coarse grinding step, With respect to 100 parts by weight of the hydrogel polymer, a method for preparing a super absorbent polymer may be provided further comprising adding water in an amount of less than 20 parts by weight.
  • the production method of the other embodiment comprises a layered silicate-based particles, foamed crab, internal crosslinking agent and water-soluble ethylene-based unsaturated monomer having at least a portion of the acid group is increased, crosslinking the monomer composition stirred at a speed of 1000 rpm or more Polymerizing to form a hydrogel polymer; And drying, pulverizing and classifying the hydrogel polymer to form a base resin powder, wherein the concentration of the water-soluble ethylenically unsaturated monomer included in the monomer composition is 40 wt% to 60 wt%.
  • Drying, pulverizing and classifying the gel polymer to form a base resin powder includes a coarse pulverizing step of pulverizing the particle diameter of the hydrogel polymer so as to have a particle diameter of 2 kPa to 10 kPa, wherein the co-pulverizing step is 50 ° C. 20 parts by weight, with respect to 100 parts by weight of the hydrogel polymer before or after the coarse grinding step, at a frequency of subphase.
  • a method of preparing a super absorbent polymer may be provided further comprising adding water in a bay amount.
  • the superabsorbent polymer obtained according to the above-described manufacturing method may exhibit very excellent properties with improved physical properties such as water-retaining capacity and absorption rate, and diaper It can exhibit excellent various physical properties that can be suitably used for sanitary products.
  • the super absorbent polymer obtained by the method of preparing the superabsorbent polymer according to another embodiment has an apparent density (Bulk Densi ty, B / D) of 0. or higher, or 0.55 g / m £ to 1.0 Or 0.55 to 0.70.
  • Bulk Densi ty, B / D apparent density
  • 0.55 g / m £ to 1.0 Or 0.55 to 0.70 0.55 g / m £
  • the volume of the superabsorbent polymer is relatively increased, and more storage space is required, thereby reducing storage efficiency.
  • the superabsorbent polymer particles may be stagnant without being smoothly injected, thereby reducing the efficiency of the process.
  • a high absorbent resin having an improved absorption rate and high gallon density, and a manufacturing method thereof.
  • Figure 1 schematically shows the structure of the unit crystal of the layered silicate particles used in the example.
  • Laponite RD 1.6g was added to 155g of ionized water as a silicate type particle
  • a caustic soda solution was prepared by mixing 192 g of ionized water with 661 g of 32% caustic soda (NaOH).
  • the monomer composition was introduced into a supply unit of a polymerization belt composed of a continuously moving conveyor belt, irradiated with ultraviolet light for 1 minute (irradiation amount: 2 mW / ctf) with a UV irradiation device having a 10 mW illuminance, and waited for 2 minutes, 5 cm * After cutting into 5 cm size, 100 g (18.6 phr) of ionized water was added and absorbed to obtain a hydrous gel polymer.
  • a super absorbent polymer was prepared in the same manner as in Example 1, except that ion water was not added when preparing the hydrogel polymer. Compare ⁇ ] 1
  • Super absorbent polymer was prepared in the same manner as in Example 1, except that 195 g (36.7 phr) of ionized water was added to prepare the hydrogel polymer.
  • Comparative Example 2 A superabsorbent polymer was prepared in the same manner as in Example 1, except that 145 g (27.0 phr) of ionized water was added to prepare the hydrogel polymer.
  • a caustic soda solution was prepared by mixing 117 g of ionized water with 624 g of 32% caustic soda (NaOH).
  • the monomer composition was introduced into a supply section of a polymerization vessel consisting of a continuously moving conveyor belt, irradiated with ultraviolet light for 1 minute (irradiation amount: 2 mW / cirf) with a UV irradiation device having a 10 mW illuminance, and waited for 2 minutes, 5 cm * After cutting into 5 cm size, 40 g of ionized water was added and absorbed to obtain a hydrous gel polymer. The hydrogel polymer was transferred to a cutter and then ground at 80 ° C. and 25hz.
  • a caustic soda solution was prepared by mixing 163.4 g of ionized water with 598.5 g of 32% caustic soda (NaOH).
  • the monomer composition was prepared by stirring at 6000 rpm and a stirrer 6900 rpm. At this time, the monomer concentration contained in the monomer composition was 44.0% by weight.
  • Photoinitiator solution was prepared by adding 0.41 g of bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide [IGARCU E 819] to 195.4 g of acrylic acid and mixing for 5 minutes.
  • a caustic soda solution was prepared by mixing 212.9 g of ionized water with 571.2 g of 32% caustic soda (NaOH).
  • the monomer composition was introduced into a supply unit of a polymerizer consisting of a continuously moving conveyor belt, and irradiated with ultraviolet rays for 1 minute (irradiation amount: 2 mW / crf) with a UV irradiation apparatus having a 10 mW illuminance, and then waited for 2 minutes, 5 cm * After cutting into 5 cm size, 40 g of ionized water was added and absorbed to obtain a hydrous gel polymer.
  • the hydrogel polymer was transferred to a cutter and then ground in a 80 ⁇ 25hz condition. Subsequently, the pulverized hydrogel polymer was dried in a hot air dryer at 180 ° C. for 40 minutes, and the dried hydrogel polymer was pulverized with a hammer mill grinder. For example, a sieve is used to classify a polymer having a particle size (average particle size) of 150 to 850, and then to classify a polymer having a particle size (average particle size) of 300 m to 600 mm to obtain a superabsorbent polymer. Prepared. 13 F
  • a high absorbency resin was prepared in the same manner as in Example 3, except that the monomer concentration contained in the monomer composition was adjusted to 39 wt% when the monomer composition was prepared.
  • Laponite RD 1.6g was added to 155g of ionized water as a silicate type particle
  • a caustic soda solution was prepared by mixing 192 g of ionized water with 661 g of 32% caustic soda (NaOH).
  • the monomer composition was introduced into a feeder of a polymerization reactor consisting of a continuously moving conveyor belt, irradiated with ultraviolet light for 1 minute (irradiation amount: 2 mW / ⁇ 2 ) with a UV irradiation device having a 10 mW illuminance, and then waited for 2 minutes, 5 cm * After cutting into 5 cm size 100 g of ionized water was absorbed to obtain a hydrous gel polymer.
  • Laponite RD 1.6g was added to 155g of ionized water as a silicate type particle
  • the monomer composition was introduced into a supply unit of a polymerizer consisting of a continuously moving conveyor belt, irradiated with ultraviolet rays for 1 minute (irradiation amount: 2 mW / cuf) with a UV irradiation apparatus having lOmW illuminance, and then waited for 2 minutes, 5 cm * After cutting into 5cm size, 100g of ionized water was added and absorbed to obtain a hydrous gel polymer.
  • the hydrogel polymer was transferred to a cutter and then ground at 90 ° C. and 15.8 hz. Subsequently, the pulverized hydrogel polymer was dried in a hot air dryer at 180 ° C. for 40 minutes, and the dried hydrogel polymer was pulverized with a hammer mill grinder. Subsequently, a polymer having a particle size (average particle diameter size) of 150 to 850 mm 3 was classified using a sieve, and a polymer having a particle size (average particle size size ) of 300 to 600 mm 3 was again classified to prepare a super absorbent polymer. . Comparison
  • a super absorbent polymer was prepared in the same manner as in Example 6, except that the hydrogel polymer was ground at 90 ° C. and 10 hz.
  • the solution was immersed in a physiological saline solution of 0.9 wt% aqueous sodium chloride solution at room temperature. did. After 30 minutes, the bag was centrifuged and drained at 250 G for 3 minutes, and then the mass W 2 (g) of the bag was measured. Moreover, the mass Wg) at that time was measured after performing the same operation without using resin.
  • W 0 (g) is the initial weight (g) of the super absorbent polymer
  • W g is the weight of the device measured after dehydration at 250 G for 3 minutes using a centrifuge without using a super absorbent polymer
  • W 2 (g) is a device measured by submerging the superabsorbent resin in 0.9 wt% physiological saline at room temperature for 30 minutes and then dehydrating it at 250G for 3 minutes using a centrifuge. It is weight.
  • Experimental Example 2 Water Soluble Component (Extractabl e content, EC)
  • the moisture content was obtained by calculating the weight loss due to moisture evaporation in the process of drying through infrared heating. At this time, the drying condition was set to 20. minutes, including 5 minutes in the temperature rise step in a way that the temperature is maintained at 180 after the temperature is raised to about 180 at room temperature.
  • the superabsorbent polymers obtained in Examples 1 and 2 each had a hanging density of 0.56 g / mi and 0.55 g /, and a comparative example having an apparent density of 0.51 g / l and 0.53 g /, respectively. Compared with the superabsorbent polymers 1 and 2, it was confirmed that the apparent density increased. [Table 2]
  • the superabsorbent polymers obtained in Examples 3 to 5 each had a high apparent density of 0.59 g /, 0.58 g /, and 0.56 g / m £, and each had a apparent density of 0.54 g /. Compared to the super absorbent polymer of 3, the apparent density was confirmed to increase.
  • the superabsorbent resins obtained in Example 6 7 had a high apparent density of 0.60 g / m £ and 0.56 g / ⁇ , respectively, and had a gallon density of 0.54 g / ⁇ . It was confirmed that the apparent density increased compared to the super absorbent polymer.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymerisation Methods In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un polymère superabsorbant présentant un taux d'absorption amélioré et une masse volumique apparente élevée, ainsi que son procédé de préparation.
PCT/KR2016/012678 2015-12-23 2016-11-04 Polymère superabsorbant et son procédé de préparation WO2017111295A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/743,841 US10995183B2 (en) 2015-12-23 2016-11-04 Superabsorbent polymer and preparation method thereof

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2015-0184614 2015-12-23
KR20150184614 2015-12-23
KR1020160144603A KR102119813B1 (ko) 2015-12-23 2016-11-01 고흡수성 수지 및 이의 제조 방법
KR10-2016-0144603 2016-11-01

Publications (1)

Publication Number Publication Date
WO2017111295A1 true WO2017111295A1 (fr) 2017-06-29

Family

ID=59090739

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/012678 WO2017111295A1 (fr) 2015-12-23 2016-11-04 Polymère superabsorbant et son procédé de préparation

Country Status (1)

Country Link
WO (1) WO2017111295A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112135645A (zh) * 2018-06-27 2020-12-25 金伯利-克拉克环球有限公司 纳米多孔超吸收颗粒
RU2777893C2 (ru) * 2018-06-27 2022-08-11 Кимберли-Кларк Ворлдвайд, Инк. Нанопористые сверхвпитывающие частицы

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010072728A (ko) * 1998-08-18 2001-07-31 클림멕 헬무트 케이킹 방지 특성을 갖는 초흡수성 중합체
KR20050036974A (ko) * 2002-08-23 2005-04-20 바스프 악티엔게젤샤프트 초흡수성 중합체 및 그의 제조 방법
KR20110086057A (ko) * 2008-10-20 2011-07-27 에보닉 스톡하우젠, 엘엘씨 점토 함유 초흡수성 중합체, 미립자, 및 그 제조 방법
KR20140107347A (ko) * 2011-12-27 2014-09-04 가부시키가이샤 리브도 코포레이션 흡수성 물품
KR20150067218A (ko) * 2012-10-03 2015-06-17 가부시키가이샤 닛폰 쇼쿠바이 흡수제 및 그의 제조 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20010072728A (ko) * 1998-08-18 2001-07-31 클림멕 헬무트 케이킹 방지 특성을 갖는 초흡수성 중합체
KR20050036974A (ko) * 2002-08-23 2005-04-20 바스프 악티엔게젤샤프트 초흡수성 중합체 및 그의 제조 방법
KR20110086057A (ko) * 2008-10-20 2011-07-27 에보닉 스톡하우젠, 엘엘씨 점토 함유 초흡수성 중합체, 미립자, 및 그 제조 방법
KR20140107347A (ko) * 2011-12-27 2014-09-04 가부시키가이샤 리브도 코포레이션 흡수성 물품
KR20150067218A (ko) * 2012-10-03 2015-06-17 가부시키가이샤 닛폰 쇼쿠바이 흡수제 및 그의 제조 방법

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112135645A (zh) * 2018-06-27 2020-12-25 金伯利-克拉克环球有限公司 纳米多孔超吸收颗粒
CN112135645B (zh) * 2018-06-27 2022-04-12 金伯利-克拉克环球有限公司 纳米多孔超吸收颗粒
RU2777893C2 (ru) * 2018-06-27 2022-08-11 Кимберли-Кларк Ворлдвайд, Инк. Нанопористые сверхвпитывающие частицы

Similar Documents

Publication Publication Date Title
KR101921278B1 (ko) 고흡수성 수지, 및 이의 제조 방법
WO2017164459A1 (fr) Procédé de préparation d'un polymère superabsorbant
KR102119813B1 (ko) 고흡수성 수지 및 이의 제조 방법
WO2011025013A1 (fr) Procédé de fabrication d'une résine capable d'absorber l'eau
KR102069312B1 (ko) 고흡수성 수지의 제조 방법 및 고흡수성 수지
KR101949458B1 (ko) 고흡수성 수지의 제조 방법 및 고흡수성 수지
WO2017159903A1 (fr) Procédé de préparation d'une résine superabsorbante
KR20180087049A (ko) 고흡수성 수지의 제조 방법
WO2016204390A1 (fr) Procédé de fabrication d'une résine superabsorbante
WO2018117548A1 (fr) Procédé de production d'un polymère superabsorbant poreux et polymère superabsorbant poreux
KR102102459B1 (ko) 고흡수성 수지의 제조 방법
WO2018124550A1 (fr) Procédé de production d'une résine poreuse super-absorbante
WO2017131291A1 (fr) Procédé de préparation d'un polymère superabsorbant
KR102452567B1 (ko) 고흡수성 수지 및 이의 제조 방법
CN108350190B (zh) 超吸收性聚合物
WO2018004162A1 (fr) Procédé de préparation d'une résine superabsorbante et résine superabsorbante
WO2016111473A1 (fr) Procédé de préparation de résine super absorbante, et résine super absorbante ainsi préparée
WO2019117541A1 (fr) Polymère superabsorbant et son procédé de préparation
WO2017111295A1 (fr) Polymère superabsorbant et son procédé de préparation
KR20200069717A (ko) 고흡수성 수지의 제조 방법
JP2020505477A (ja) 高吸水性樹脂およびその製造方法
KR102576445B1 (ko) 고흡수성 수지의 제조 방법
WO2017111210A1 (fr) Polymère superabsorbant et son de procédé de préparation
KR20190064978A (ko) 고흡수성 수지 및 이의 제조 방법
WO2018135928A1 (fr) Polymère superabsorbant et son procédé de préparation

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: 16879162

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16879162

Country of ref document: EP

Kind code of ref document: A1