WO2017111210A1 - Polymère superabsorbant et son de procédé de préparation - Google Patents

Polymère superabsorbant et son de procédé de préparation Download PDF

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WO2017111210A1
WO2017111210A1 PCT/KR2016/003888 KR2016003888W WO2017111210A1 WO 2017111210 A1 WO2017111210 A1 WO 2017111210A1 KR 2016003888 W KR2016003888 W KR 2016003888W WO 2017111210 A1 WO2017111210 A1 WO 2017111210A1
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Prior art keywords
polymer
weight
water
solution
layered silicate
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PCT/KR2016/003888
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English (en)
Korean (ko)
Inventor
이금형
김기철
박성수
양예솔
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주식회사 엘지화학
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Priority claimed from KR1020160044324A external-priority patent/KR101921278B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16879078.0A priority Critical patent/EP3252097B1/fr
Priority to US15/557,607 priority patent/US11192088B2/en
Priority to CN201680019001.8A priority patent/CN107406623B/zh
Publication of WO2017111210A1 publication Critical patent/WO2017111210A1/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
    • C08F20/04—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
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape

Definitions

  • the present invention relates to a super absorbent polymer, and a method for producing the same. More specifically, the present invention relates to a highly absorbent resin having an improved absorption rate through micropores formed therein and a method of manufacturing 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 mater (AL) and an absorbent gel mater (ALM). It is also called.
  • Super absorbent ' resins have been put into practical use as sanitary devices, and are currently 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 widely 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 in, for example, 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 absorption rate which is one of the important physical properties of the superabsorbent polymer
  • the surface dryness of the product in contact with the skin In general, this absorption rate can be improved by increasing the surface area of the superabsorbent polymer.
  • Patent Document 1 Japanese Patent Application Publication No. 56-161408
  • Patent Document 2 Japanese Patent Application Publication No. 57-158209
  • Patent Document 3 Japanese Patent Laid-Open No. 57-198714
  • the present invention is to provide a super absorbent polymer having an improved absorption rate through the fine pores formed therein.
  • the present invention is to provide a method for producing the super absorbent polymer.
  • a base resin powder comprising a water-soluble ethylene-based unsaturated monomer cross-linked polymer having at least a part of the neutralized acidic group, a plurality of pores of diameter 1 or more is formed in the base resin powder, Layered silica dispersed in the crosslinked structure A superabsorbent polymer is included which contains particles of particles and has a time of 60 seconds or less for removing the vortex generated when stirring at a speed of 600 rpm in 50 m of a 0.9 wt% NaCl solution.
  • the present disclosure also provides a step of crosslinking and polymerizing a water-soluble ethylenically unsaturated monomer having at least a part of a neutralized acidic group in the presence of layered silicate particles, a blowing agent and an internal crosslinking agent to form a hydrogel polymer; And drying, pulverizing, and classifying the hydrogel polymer to form a base resin powder.
  • At least a part comprises a base resin powder containing a cross-linked polymer of a water-soluble ethylene-based unsaturated monomer having an acidic group, a plurality of pores of diameter 1 or more is formed in the base resin powder
  • the crosslinked polymer includes layered silicate particles dispersed in the crosslinked structure, and a superabsorbent polymer having a time of removing vortex generated when stirring at a speed of 600 rpm at a weight of 0.9 wt. Can be provided.
  • the present inventors can use the above-described superabsorbent polymer, by using a specific layered silicate particles, a number of micropores can be stably formed in the crosslinked polymer, the contact area to water is rapidly increased and superabsorbent Experiments confirmed that the absorption rate of the resin can be further improved and completed the invention.
  • the super absorbent polymer may include a base resin powder including a crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least a portion of neutralized acidic groups.
  • crosslinked polymer of water-soluble ethylenically unsaturated monomer refers to a hydrogel polymer immediately formed by thermal polymerization or photopolymerization to a composition containing a water-soluble ethylenically unsaturated monomer, as well as to a general method for producing a super absorbent polymer.
  • the ethylenically unsaturated monomer is a polymerized polymer, it can be included regardless of its form, water content, particle size, surface crosslinking or the like.
  • 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) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, mesopolyethylene glycol (meth) acrylate 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 of which at least a portion of acrylic acid is neutralized 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.
  • any internal crosslinking agent having a crosslinkable functional group which has been conventionally used in the production of superabsorbent polymers, can be used without particular limitation.
  • a multifunctional acrylate compound having a plurality of ethylene oxide groups may be used as the internal crosslinking agent.
  • Such internal crosslinking agents include polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, glycerin triacrylate, ungalzal or ethylated trimethylol triacrylate (TMPTA), nucleic acid diol diacrylate, And triethylene glycol diacrylate.
  • PEGDA polyethylene glycol diacrylate
  • TMPTA ethylated trimethylol triacrylate
  • nucleic acid diol diacrylate e.glycerin triacrylate
  • TMPTA ethylated trimethylol triacrylate
  • a plurality of pores of diameter 1 / ai or more may be formed in the base resin powder.
  • 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. It can be confirmed that it is formed.
  • the plurality of pores of diameter 1 / or more contained in the base resin powder may include micropores having a diameter of 10 to 100.
  • the micropores having a diameter of 10 to 100 im may be formed by adding a blowing agent and inorganic particles together when forming a polymer, as will be described later. As the micropores are stably formed, the microporosity is increased. The absorption rate of the water absorbent resin can be further improved.
  • the crosslinked polymer included in the base resin powder may include layered silicate particles dispersed in the crosslinked structure.
  • the layered silicate-based particles include a metal oxide layer including a metal oxide and a silica layer formed on at least one surface of the metal oxide layer and include silica. Particles containing unit crystals can 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 worm including a 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 or both surfaces of the metal oxide layer in the unit crystal of the layered silicate particles.
  • the metal oxide layer and the silica layer may be combined through siloxane bonding.
  • the siloxane (si loxane) bond means a covalent bond between a silicon atom (Si) and an oxygen atom (0), and more specifically, an octahedral form, 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 an oxygen atom included in the metal oxide filling of the silicon atom and a silicon atom included in the silica layer of the tetrahydral (Tet rahedra l) form.
  • the metal oxide may exist in a state in which a metal atom and an oxygen atom are combined, 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, magnesium, calcium and the like.
  • the packed silicate-based particles can stably maintain fine pores in the crosslinked polymer, thereby increasing the contact area with water and further improving the absorption rate of the super absorbent polymer.
  • the layered silicate particles have a maximum diameter of 1 nm to 100 nm in straight section, and a height of 0. It may have a light structure of 1 nm to 20 nm.
  • the columnar structure means a three-dimensional shape in which the upper and lower surfaces are parallel to each other. Although the specific shape of the column structure is not limited, for example, depending on the type of cross section in which the layered silicate particles are cut in a direction parallel to the ground, that is, depending on the type of figure represented by the straight cross section, an ellipsoid, etc. , Diversification, and the like.
  • the columnar 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 particles have a maximum diameter of 1 nm to 100 ran in a straight section, and a height of 0.
  • the layered silicate-based particles in the cross-linked polymer of the embodiment can implement functionality in the cross-linked polymer through a fine particle size, as well as monomers when forming the cross-linked polymer. It is possible to stabilize the micropores formed by the blowing agent in the 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, Laponi te DS, Laponi te Te S and Laponi te JS, etc.), 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, Laponi te DS, Laponi te Te S and Laponi te JS, etc.
  • Laponi te RD is more preferable.
  • the layered silicate-based particles described above may be included in an amount of 0.01 parts by weight to 5 parts by weight based on 100 parts by weight of the base resin powder.
  • the degree of formation of micropores in the crosslinked polymer is optimized, so that the superabsorbent polymer of one embodiment may have an improved absorption rate.
  • the superabsorbent polymer of the embodiment has a time for removing vortex generated when stirring at a speed of 600 rpm at 50% of 0.9 wt% NaCl solution at 60 seconds or less, or 40 seconds to 60 seconds, or 50 seconds to It may be 58 seconds.
  • the superabsorbent resin of the embodiment is added to the 0.9 wt.% NaCl solution, and the vortex is absorbed by the superabsorbent polymer. Can be removed.
  • the time to remove the vortex is added to the superabsorbent resin 2.00 g of the embodiment, while stirring 50 ra £ of 0.9% by weight of NaCl solution at 600 rpm using a stirrer, the vortex of the liquid generated by stirring This can be obtained by measuring the time until the vortex disappears and a smooth surface is obtained.
  • a speed of 600 rpm in a NaCl solution 50 of 0.9 wt When added, as the absorption rate of the superabsorbent polymer is slowed down, it may be difficult to realize rapid absorption when applied to a product such as a diaper.
  • the superabsorbent polymer may have a water-retaining capacity of 45 g / g or more, or 45 g / g to 60 g / g for 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 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 250 G for 3 minutes using a centrifuge without using the superabsorbent polymer
  • (g) Is the weight of the device, including the superabsorbent resin, after absorbing the superabsorbent polymer by immersion in 0.9 wt% physiological saline for 30 minutes at room temperature for 30 minutes and then dehydrating it at 250 G for 3 minutes using a centrifuge.
  • the superabsorbent polymer of the above-described embodiment may have a spherical or amorphous particle shape having a particle diameter of about 150 ⁇ ⁇ 850 / m.
  • the step of cross-polymerizing a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized to form a hydrogel polymer and drying, grinding and classifying the hydrogel polymer to form a base resin powder.
  • the layered silicate particles are used together with conventional blowing agents and internal crosslinking agents, to form a water-soluble ethylene-based
  • the crosslinking polymerization of the unsaturated monomer may be carried out, followed by drying, pulverization, classification, surface crosslinking, and the like according to a general manufacturing method of the superabsorbent polymer to prepare a superabsorbent polymer.
  • a general manufacturing method of the superabsorbent polymer to prepare a superabsorbent polymer.
  • 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 of one embodiment may be prepared by the method of preparing the superabsorbent polymer of another embodiment.
  • the method of preparing the superabsorbent polymer includes forming a hydrogel polymer by crosslinking and polymerizing a water-soluble ethylenically unsaturated monomer having at least a part of a neutralized acidic group in the presence of a packed silicate particle, a blowing agent, and an internal crosslinking agent. It may include.
  • particles including a metal oxide layer containing a metal oxide and unit crystals 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 a three-dimensional periodicity, particles may be formed through the repeating of the unit crystal.
  • the unit crystal of the layered silicate 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 or both surfaces 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 (si loxane) bond.
  • the siloxane (si loxane) bond means a covalent bond between a silicon atom (Si) and an oxygen atom (0), and more specifically, as shown in the unit crystal structure shown in FIG. 1, in the form of an octahedral Oxygen atoms contained in the metal oxide layer and tetrahedral silica layer Covalent bonding between the silicon atoms included may form a bond between the metal oxide and the silica layer.
  • the metal oxide may exist in a state where a metal atom and an oxygen atom are combined, and examples of the metal atom are not particularly limited, but lithium, sodium, potassium, and the like are group 1 or group 2 elements of the periodic table. Beryllium, magnesium, calcium and the like.
  • the layered silicate particles may have a structure having a maximum diameter of 1 nm to 100 ran and a height of O.lnm to 20 ran, or O.lnm to 20 ran.
  • the columnar structure means a three-dimensional figure in which the upper and lower surfaces are parallel to each other.
  • the specific shape of the column structure is not limited, for example, depending on the type of cross section in which the layered silicate particles are cut in a direction parallel to the ground, that is, depending on the type of figure represented by the straight cross section, an ellipsoid, etc. Polygonal column etc. are mentioned.
  • the columnar structure of the layered silicate particles may be formed through repetition of the unit crystal, and the maximum diameter of the straight section in the lamp 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 in the crosslinked polymer of the present embodiment are The fine particle size may not only implement functionality in the crosslinked polymer, but also stabilize the fine pores formed by the blowing agent in the monomer composition when the crosslinked polymer is formed.
  • Examples of the layered silicate-based particles are not particularly limited, for example, hackite (Laponite RD, Laponite XLG, Laponite D, Laponite DF, Laponite RS, Laponite XLS, Laponite DS, Laponite S and Laponite JS, etc.).
  • a more preferable example is Laponite RD.
  • 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 And at least one selected from the group consisting of methylenetetramine, toluenesulfonylhydrazide, azobisisobutyronitrile, azo dicarboxylic acid barium and sodium bicarbonate.
  • the step of cross-polymerizing the water-soluble ethylene-based unsaturated monomer having at least a part of the neutralized acid group to form a hydrogel polymer may be carried out in the presence of the layered silicate particles, the blowing agent and the internal crosslinking agent.
  • the fine pores even inside the hydrogel polymer by adding the layered silicate particles and the blowing agent to the monomer composition for forming the hydrogel polymer. Can be formed.
  • the content of the layered silicate particles based on 100 parts by weight of the blowing agent is 1 to 1000 parts by weight, or 1 to 500 parts by weight, or 1 to 100 parts by weight, or 1 to 50 parts by weight. Or, 10 parts by weight to 30 parts by weight.
  • the content of the layered silicate particles is excessively reduced based on the blowing agent content, the pore stabilization effect by the layered silicate particles may be reduced to reduce the absorbency of the super absorbent polymer.
  • the content of the layered silicate particles is excessively increased based on the content of the blowing agent, as the viscosity of the solution in which the layered silicate particles are dispersed rapidly increases, it may be difficult to transfer the superabsorbent polymer manufacturing process.
  • the step of forming the hydrogel polymer more specifically, forming a crab 1 solution containing an internal crosslinking agent and a water-soluble ethylenically unsaturated monomer having at least a part of the neutralized acid group; Forming a crab dilute solution comprising a packed silicate-based particle and a foaming agent; And crosslinking and polymerizing the monomer composition including the first solution and the second solution.
  • At least a part of the internal crosslinking agent may include a water-soluble ethylene-based unsaturated monomer, a layered silicate-based particle, and a blowing agent having a neutralized acidic group, as described above in one embodiment.
  • the content of the internal crosslinking agent is 0.01 weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer Parts to 5 parts by weight.
  • the content of the layered silicate particles is 1 part by weight to 1000 parts by weight or 1 part by weight based on 100 parts by weight of the blowing agent as described above. 500 parts by weight, or 1 part by weight to 100 parts by weight, or 1 part by weight to 50 parts by weight, or 10 parts by weight to 30 parts by weight.
  • the content of the second solution is 1 part by weight to 100 parts by weight relative to 100 parts by weight of the first solution included in the monomer composition. Or, 50 parts by weight to 100 parts by weight, or 80 parts by weight to 100 parts by weight.
  • the first solution, the second solution, and the monomer composition may further each independently include a polymerization initiator generally used for preparing 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 may additionally include a thermal polymerization initiator.
  • 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.
  • acyl phosphine and alpha-aminoketone ((1-& 1 ⁇ 1101 101) may be used.
  • acylphosphine is commercially available. Lucir in TP0, ie, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-trimethylphosphine oxide) can be used. Reinhold Schwa lm, "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)" pll5, as well as, but not limited to, the examples described above.
  • 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 (NasS), potassium persulfate (K2S208), ammonium persulfate (NH 4 ) 2 S 2 0 8 , and the like. .
  • azo initiators examples include 2, 2-azobis- (2-amidinopropane) dihydrochloride (2, 2- azob is (2-am idi nopr opane) dihydrochlor ide), 2, 2- Azobis- (N, N-dimethylene) isobutyramidine dihydrochloride (2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2— (carbamoyl azo) isobutyronitrile (2 -(carbamoylazo) isobutylonitril), 2,2-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride (2,2-azobis [2- (2—imidazolin-2-yDpropane] dihydrochlor ide), 4,4-azobis- (4-cyanovaleric acid) (4,4-azobis- (4-cyanovaleric acid)), etc.
  • Odian's Principle. of Polymer izatonitrile 2, 2-azobis-(
  • 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. If the concentration of the thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, and the effect of adding the thermal polymerization initiator may be insignificant. If the concentration of the thermal polymerization initiator is excessively high, the molecular weight of the superabsorbent polymer is small and the physical properties are uneven. Can be done. In the monomer composition including the first solution and the second solution, the concentration of the water-soluble ethylenically unsaturated monomer includes each of the above-described raw materials and solvents.
  • the concentration of the monomer is too low, the yield of the superabsorbent polymer may be low and there may be a problem in economics.
  • the concentration is too high, some of the monomer may precipitate or the grinding efficiency of the polymerized hydrogel polymer may be low. This may cause problems in the process, and the physical properties of the super absorbent polymer may be reduced.
  • the crab 1 solution, the system 2 solution, and the monomer composition may each independently include additives such as thickeners, plasticizers, preservative stabilizers, antioxidants, and neutralizers, as necessary.
  • the neutralizing agent is added to prevent the pH decrease due to the water-soluble ethylenically unsaturated monomer, it can be used without a great restriction as long as the basic material of pH7 or more.
  • Examples of the neutralizing agent include caustic soda (NaOH) and the like.
  • Examples of the method of adding the neutralizing agent to the monomer composition are not particularly limited, but, for example, a neutralizing agent is added to a crab 1 solution including an internal crosslinking agent and a water-soluble ethylenically unsaturated monomer having at least a partially acidified acidic group, and then layered silicate. A second solution containing system particles and blowing agent can be added.
  • Raw materials such as the above-mentioned water-soluble ethylenically unsaturated monomers, silicate particles, photopolymerization initiators, thermal polymerization initiators, internal crosslinking agents and additives may be added in a dissolved form in a solvent.
  • the solvent that can be used at this time can be used without limitation 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 ethyl ether, toluene, xylene, butyrolactone, carbye may be used in combination of one or more selected from methyl cellosolve acetate and ⁇ , ⁇ -dimethylacetamide.
  • the method of forming a hydrogel by thermal polymerization or photopolymerization of such a monomer composition is not particularly limited as long
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source, when the thermal polymerization is usually carried out, it can be carried out in a semi-unggi having a stirring axis such as kneader, when the photopolymerization, Although it can proceed in a semi-unggi equipped with a movable conveyor belt, the above-described polymerization method is an example, the present invention is not limited to the above-described polymerization method.
  • the water-containing gel polymer obtained by thermal polymerization by supplying hot air or by heating the reactor to a reactor such as a kneader equipped with a stirred shaft may be a semi-unggi machine.
  • the hydrogel polymer discharged to the outlet may be in the form of several centimeters to several millimeters.
  • the size of the hydrogel polymer obtained may vary depending on the concentration and injection speed of the monomer composition to be injected, and a hydrogel polymer having a weight average particle diameter of about 2 mm to about 50 mm 3 can be obtained.
  • the form of the hydrogel polymer generally obtained may be a hydrogel gel polymer on a 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 usually preferable to supply the monomer composition so that a polymer on the sheet having a thickness of about 0.5 cm to about 5 cm can be obtained. Do.
  • the production efficiency is not preferable, and when the polymer thickness on the sheet exceeds 5 cm, due to the excessively thick thickness, the polymerization reaction spreads over the entire thickness. It may not happen evenly.
  • the normal water content of the hydrogel polymer obtained by the above method may be 40 to 80% by weight.
  • water content means the amount of water to account for the total amount of water-containing gel polymer weight minus the weight of the polymer in the dry state.
  • the moisture vapor in the polymer during the process of raising the temperature of the polymer through infrared heating to dry The weight loss along the foot is measured and defined as the calculated value.
  • the drying condition is to increase the temperature to about 180 ° C at room temperature and then maintained at 180 ° C total drying time is set to 20 minutes, including 5 minutes of temperature rise step, the moisture content is measured.
  • the base resin powder may be obtained through drying, pulverization and classification, and the like, and the base resin powder and the super absorbent water obtained therefrom through such a pulverization and classification process.
  • Paper is suitably prepared and provided to have a particle size of about 150 prn to 850. More specifically, at least about 95% by weight or more of the base resin powder and the super absorbent polymer obtained therefrom have a particle size of about 150 rn to 850, and the fine powder having a particle size of less than about 150 urn may be less than about 3% by weight. Can be.
  • 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 pulverizer used is not limited in configuration, and specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Selected from the group of crushing machines consisting of cutter mill, disc mill, shred crusher, hammer mill crusher, crusher, chopper and disc cutter It may include any one, but is not limited to the above-described example.
  • the coarse grinding step may be pulverized so that the particle size of the hydrogel polymer is about 2 mm to about 10 mm 3. Grinding to a particle diameter of less than 2 mm is not technically easy due to the high water content of the hydrogel polymer, and may also cause a phenomenon in which the pulverized particles cross each other. On the other hand, the particle diameter is more than 10 mm In the case of pulverization, the effect of increasing the efficiency of the subsequent drying step may be insignificant.
  • drying is performed on the hydrogel polymer immediately after polymerization, which is coarsely pulverized or not subjected to the coarsely pulverized step.
  • 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 t, only the polymer surface is dried excessively. Fine powder may generate
  • 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 milling step may have a particle diameter of about 150 to about 850 mm 3.
  • the grinder used to grind to such a particle size is specifically a pin mill, hammer mill, screw mill, roU mill, disc mill, A jog mill or a sieve may be used, but is not limited to the example described above.
  • a separate process of classifying the polymer powder obtained after grinding according to the particle diameter may be performed.
  • the polymer having a particle size of about 150 to about 850 is classified, and only a polymer powder having such a particle size may be further commercialized through a surface crosslinking reaction step as necessary. Can be. Since the particle size distribution of the base resin powder obtained through this process has already been described above, further detailed description thereof will be omitted.
  • a super absorbent polymer having an improved absorption rate through micropores formed therein, and a method of manufacturing the same may be provided.
  • Figure 1 schematically shows the structure of the unit crystal of the layered silicate particles used in the example.
  • Figure 2 is a SEM image of the surface of the super absorbent polymer prepared in Example.
  • a caustic soda solution was prepared by mixing 195 g of ionized water with 661 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, irradiated with ultraviolet rays for 1 minute (irradiation amount: 2 mW / ciif) with a UV irradiation device having a 10 mW illuminance, and then waited for 2 minutes, 5 cm * After cutting to 5 cm in size, ion water was added and absorbed to obtain a hydrous gel polymer.
  • Super absorbent polymer was prepared in the same manner as in Example 1, except that 3.2 g of laponite RD and 17.7 g of sodium bicarbonate were not added when the monomer solution was prepared. Compare ⁇ ] 2
  • a superabsorbent polymer was prepared in the same manner as in Example 1, except that 17.7 g of sodium bicarbonate was not added when the monomer solution was prepared. Comparative Example 3
  • a caustic soda solution was prepared by mixing 120 g of ionized water with 653 g of 32% caustic soda (NaOH).
  • the hydrogel polymer was transferred to a cutter and then ground at 25 t: 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 sieve was used to classify a polymer having a particle size (average particle size) of 150 jum to 850 p, and a polymer having a particle size (average particle size) of 300 IM to 600 was classified to prepare a super absorbent polymer. .
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • Kg is the weight of the device measured after dehydration at 250G for 3 minutes using a centrifuge without using a super absorbent polymer
  • W 2 (g) is obtained by submerging and absorbing superabsorbent polymer in 0.9 weight physiological saline solution for 30 minutes at room temperature, dehydrating it at 250G for 3 minutes using a centrifuge, and then measuring the weight of the device including superabsorbent polymer. to be.
  • Experimental Example 2 Extractable content (EC)
  • the absorption rate was 61 seconds, 75 seconds to show, obtained in Examples 1 to 2 using inorganic particles and blowing agent together It was confirmed that the super absorbent polymer had an improved absorption rate of less than 60 seconds. Accordingly, it was confirmed that the superabsorbent polymer of the example in which the blowing agent was added together with the inorganic particles can realize a remarkably improved absorption rate while maintaining an appropriate level of water retention.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
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Abstract

La présente invention concerne un polymère superabsorbant présentant un taux d'absorption amélioré grâce aux micropores qu'il renferme, et son procédé de préparation. Le polymère superabsorbant comprend une poudre de résine de base comprenant un polymère réticulé d'un monomère insaturé à base d'éthylène soluble dans l'eau ayant un groupe acide dont au moins une partie est neutralisée, une pluralité de pores de diamètres de 1 µm ou plus étant formés dans la poudre de résine de base, et le polymère réticulé comprenant des particules de silicate stratifiées dispersées dans sa structure réticulée.
PCT/KR2016/003888 2015-12-23 2016-04-14 Polymère superabsorbant et son de procédé de préparation WO2017111210A1 (fr)

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US15/557,607 US11192088B2 (en) 2015-12-23 2016-04-14 Superabsorbent polymer and method for preparing the same
CN201680019001.8A CN107406623B (zh) 2015-12-23 2016-04-14 超吸收性聚合物及其制备方法

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6610780B1 (en) * 1999-05-26 2003-08-26 Alberta Research Council Inc. Networked polymer/clay alloy
WO2014183987A1 (fr) * 2013-05-15 2014-11-20 Evonik Industries Ag Polymères superabsorbants aux propriétés d'absorption rapide ainsi que leur procédé de production
KR101537565B1 (ko) * 2007-09-27 2015-07-17 에스체아 히기에너 프로덕츠 악티에볼라그 새로운 물리적 형태의 클레이결합된 폴리머 겔, 그들의 형성방법 및 그것의 사용
US20150210825A1 (en) * 2014-01-24 2015-07-30 Baker Hughes Incorporated Enhanced water swellable compositions
KR20150116418A (ko) * 2014-04-07 2015-10-15 에보닉 코포레이션 신속한 흡수를 갖는 초흡수성 중합체

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6610780B1 (en) * 1999-05-26 2003-08-26 Alberta Research Council Inc. Networked polymer/clay alloy
KR101537565B1 (ko) * 2007-09-27 2015-07-17 에스체아 히기에너 프로덕츠 악티에볼라그 새로운 물리적 형태의 클레이결합된 폴리머 겔, 그들의 형성방법 및 그것의 사용
WO2014183987A1 (fr) * 2013-05-15 2014-11-20 Evonik Industries Ag Polymères superabsorbants aux propriétés d'absorption rapide ainsi que leur procédé de production
US20150210825A1 (en) * 2014-01-24 2015-07-30 Baker Hughes Incorporated Enhanced water swellable compositions
KR20150116418A (ko) * 2014-04-07 2015-10-15 에보닉 코포레이션 신속한 흡수를 갖는 초흡수성 중합체

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