WO2017155197A1 - Procédé de préparation d'une résine superabsorbante, et résine superabsorbante - Google Patents

Procédé de préparation d'une résine superabsorbante, et résine superabsorbante Download PDF

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Publication number
WO2017155197A1
WO2017155197A1 PCT/KR2017/000057 KR2017000057W WO2017155197A1 WO 2017155197 A1 WO2017155197 A1 WO 2017155197A1 KR 2017000057 W KR2017000057 W KR 2017000057W WO 2017155197 A1 WO2017155197 A1 WO 2017155197A1
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Prior art keywords
silica particles
polymer
water
superabsorbent polymer
meth
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PCT/KR2017/000057
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English (en)
Korean (ko)
Inventor
윤형기
남대우
이혜민
한장선
서성종
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주식회사 엘지화학
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Priority claimed from KR1020160103024A external-priority patent/KR102075737B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/768,343 priority Critical patent/US10773237B2/en
Priority to CN201780003667.9A priority patent/CN108350189A/zh
Priority to EP17763460.7A priority patent/EP3342801B1/fr
Publication of WO2017155197A1 publication Critical patent/WO2017155197A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/26—Treatment of polymers prepared in bulk also solid polymers or polymer melts
    • C08F6/28—Purification
    • 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
    • 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
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof

Definitions

  • the present invention relates to a superabsorbent polymer and a method for preparing the same while maintaining excellent absorption performance and exhibiting improved liquid permeability, gel strength and absorption rate.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight.As a developer, a super absorbent material (SAM) and an absorbent gel (AGM) They are named differently.
  • SAM super absorbent material
  • AGM absorbent gel
  • Such super absorbent polymers have been put into practical use as physiological tools, and are currently used in sanitary products such as paper diapers for children, horticultural soil repair agents, civil engineering, building index materials, seedling sheets, freshness retainers in food distribution, and It is widely used as a material for steaming.
  • the present invention is to provide a method for producing a super absorbent polymer, which exhibits improved fluid permeability, gel strength, absorption rate, and the like while maintaining excellent absorption performance.
  • the present invention comprises the steps of cross-polymerizing a water-soluble ethylenically unsaturated monomer having at least a part of a neutralized acidic group in the presence of an internal crosslinking agent to form a hydrogel polymer comprising a crosslinked polymer;
  • Surface crosslinking comprising a surface crosslinking agent of alkylene carbonates having 2 to 5 carbon atoms in the presence of hydrophobic silica particles having a contact angle of greater than 10 ° to 150 ° with respect to water and hydrophilic silica particles having a contact angle of 10 ° or less with respect to water. It provides a method for producing a super absorbent polymer comprising the step of surface crosslinking the base resin powder using a liquid.
  • the present invention also provides a resin composition
  • a resin composition comprising: a base resin powder comprising a first crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least part of a neutralized acid group; Formed on the base resin powder, and the first crosslinked polymer A surface crosslinking layer comprising a second crosslinked polymer further crosslinked via a surface crosslinker; And
  • EFFC represented by the following formula 1 is 24 to 28g / g,
  • a super absorbent polymer having a gel strength (G ′) of 9,000 to 15,000 Pa:
  • CRC is the high indicates a centrifugation beam SAT for half an hour for a normal saline solution (0.9 weight 0/0 aqueous sodium chloride solution) of a water-absorbent resin
  • AUP is the super-absorbent resin of the physiological saline (0.9 wt. 0 /.
  • the gel strength (G ′) is the horizontal gel strength of the superabsorbent polymer measured using a rheometer after swelling by absorbing physiological saline solution (0.9 wt. 0 /. Sodium chloride solution) for 1 hour to the superabsorbent polymer. Indicates.
  • a super absorbent polymer according to a specific embodiment of the present invention and a manufacturing method thereof will be described in more detail. However, this is presented as an example of the invention, thereby not limited to the scope of the invention, it is apparent to those skilled in the art that various modifications to the embodiment is possible within the scope of the invention.
  • Surface crosslinking comprising a surface crosslinking agent of alkylene carbonate having 2 to 5 carbon atoms in the presence of hydrophobic silica particles having a contact angle of greater than 10 ° to 150 ° with respect to water and hydrophilic silica particles having a contact angle of 10 ° or less with respect to water
  • a method for producing a super absorbent polymer comprising surface crosslinking the base resin powder using a liquid.
  • the present inventors have super-absorbent resin of the gel strength, barrel-component, and the absorption rate a 'result of continuous studies in order to further improve, and the conditions of the production step of the water-absorbent resin, for example, the type of the internal cross-linking agent to be described later and content of the polymerization Conditions are optimized to obtain a base resin powder having a high gel strength, specific surface crosslinking conditions (e.g., simultaneous or separate use of certain silica particles, more specifically two or more hydrophilic and hydrophobic silica particles upon surface crosslinking, etc.).
  • specific surface crosslinking conditions e.g., simultaneous or separate use of certain silica particles, more specifically two or more hydrophilic and hydrophobic silica particles upon surface crosslinking, etc.
  • the surface having a predetermined level or more on the base resin powder having a high gel strength as the specific silica particles defined in a predetermined contact angle range is used during the surface crosslinking, and the surface crosslinking is carried out under constant temperature raising conditions or the like. It appears that the crosslinking layer can be formed uniformly. This is because the specific silica particles are uniformly included in the crosslinking structure of the surface crosslinking layer to make the crosslinking structure more firm, and the surface crosslinking reaction occurs appropriately around each silica particle under the above elevated temperature conditions during surface crosslinking, thereby providing an appropriate crosslinking structure. It is expected because it can be formed.
  • the surface crosslinking layer may further increase the gel strength of each of the superabsorbent polymer particles, so that the superabsorbent polymer of one embodiment may have high gel strength.
  • the superabsorbent polymer prepared by the method of the embodiment can maintain excellent absorption performance defined by relatively high EFFC (arithmetic mean value of CRC and AUP) as the internal crosslinking structure and the surface crosslinking structure are optimized.
  • the superabsorbent polymer of one embodiment is highly desirable for various sanitary materials, such as ultra-thin diapers with reduced pulp content, as it exhibits excellent absorption performance with significantly improved fluidity, gel strength and absorption rate than previously known. Can be applied.
  • sanitary materials such as ultra-thin diapers with reduced pulp content
  • absorption performance with significantly improved fluidity, gel strength and absorption rate than previously known.
  • Can be applied a method of preparing the super absorbent polymer of one embodiment will be described in more detail.
  • Superabsorbent polymers typically contain a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized in the presence of an internal crosslinking agent, such as, for example, a mixture of acrylic acid and its sodium salt in which at least some carboxylic acid is neutralized with sodium salt or the like. After polymerization, it can be prepared by drying, pulverizing and classifying and surface crosslinking. In a specific example, in the manufacturing method of the embodiment, the superabsorbent polymer crosslinks the monomer in the presence of an internal crosslinking agent to obtain a base resin powder, and then, in the presence of a predetermined surface crosslinking agent and hydrophobic and hydrophilic silica particles. It can be obtained by surface crosslinking the base resin powder.
  • an internal crosslinking agent such as, for example, a mixture of acrylic acid and its sodium salt in which at least some carboxylic acid is neutralized with sodium salt or the like. After polymerization, it can be prepared by drying, pulver
  • a base resin powder having a high gel strength for example, specific silica particles, more specifically hydrophilic and hydrophobic silica particles defined by the contact angle range to water
  • specific silica particles more specifically hydrophilic and hydrophobic silica particles defined by the contact angle range to water
  • the surface crosslinking proceeds using, it was confirmed that a super absorbent polymer having excellent properties and effects as described above can be produced.
  • the following hydrophilic silica particles, more specifically, the hydrophilic and hydrophobic silica particles as follows can be used at the time of surface crosslinking.
  • the manufacturing method when the surface cross-linked more than 10 ° for water and 10 ° or greater than 150 ° or less, and more suitably from 12 ° to 150 ° of the And the hydrophobic silica particles having a contact angle, it is possible to use hydrophilic silica particles having a contact angle of 10 ° or less, or from 1 to 10 ° against water.
  • the superabsorbent polymer prepared by the method of the embodiment may further include hydrophilic silica particles and / or hydrophobic silica particles dispersed on the surface of the base resin powder, for example, on the surface crosslinking layer.
  • the hydrophilic silica particles or the hydrophobic silica particles are dispersed on the surface crosslinking layer means that each of these silica particles are contained / dispersed in the crosslinked structure of the surface crosslinking layer or embedded in the surface of the surface crosslinking layer. It may mean.
  • the hydrophobic silica particles may be included in the surface crosslinking solution and treated as described in more detail below, or may be separately mixed and treated on the base resin powder before the black surface crosslinking.
  • such hydrophobic silica particles may, for example, be present at least in part on the surface of the base resin powder, for example in the surface crosslinking layer, and a portion thereof may be embedded in the surface of the base resin powder.
  • the hydrophilic silica particles may be dispersed on the surface crosslinking layer and present in the crosslinking structure included therein, or a part thereof may be embedded in the surface of the surface crosslinking layer.
  • these hydrophilic and / or hydrophobic silica particles can effectively surround the surface crosslinking liquid. For this reason, it can suppress that a surface crosslinking liquid is absorbed rapidly only to a part of base resin powder locally, and can apply
  • hydrophilic and / or hydrophobic silica particles for improving the liquid permeability are present on at least the surface crosslinking layer, and the surface crosslinking solution is uniformly applied so that the surface crosslinking is uniformly performed on the base resin powder, thereby improving liquid permeability.
  • excellent physical properties can be expressed and maintained for a long time.
  • hydrophobic silica particles at least one of the commercialized hydrophobic silica particles having the above-described contact angle range may be used without any particular limitation, and more preferably, the hydrophobic silica particles may be included in the surface crosslinking solution.
  • particles having a contact angle of more than 10 ° and 50 ° or less may be used in view of dispersibility to the surface crosslinking liquid, or particles having a contact angle of 50 ° to 150 ° or less may be used together with a separate dispersant.
  • the particles having a contact angle of 50 ° to 150 ° or less may be more preferably used in terms of more effective fluid permeability and absorption rate. Can be.
  • the hydrophilic silica particles one or more kinds of commercially available water-dispersible silica particles having a contact angle range of 10 ° or less may be used without any particular limitation.
  • hydrophobic silica particles are trade name: DM30S or
  • Hydrophobic silica particles made of Aerosil or the like can be suitably used.
  • hydrophilic silica particles water-dispersible silica particles made of trade name: ST-O or ST-AK or the like can be used as appropriate, and the liquid permeability and absorption rate of the superabsorbent polymer, etc. Can be further improved.
  • a contact angle with respect to water for separating the hydrophilic and hydrophobic silica particles may be defined as a contact angle with respect to water of each silica particle measured on a glass substrate.
  • the water-soluble ethylenically unsaturated monomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryl Anionic monomers and salts thereof of loylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, or 2- (meth) acrylamide-2-methyl propane sulfonic acid; (Meth) acrylamide, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,
  • acrylic acid or salts thereof such as at least a portion of acrylic acid
  • Alkali metal salts such as neutralized acrylic acid and / or sodium salt thereof may be used, and the use of such monomers enables the production of superabsorbent polymers having better physical properties.
  • the alkali metal salt of acrylic acid 3 ⁇ 4 or the like is used as a monomer, at least a portion of acrylic acid may be neutralized with a basic compound such as caustic soda (NaOH).
  • the internal crosslinking agent for crosslinking polymerization of such monomers includes bis (meth) acrylamide having 8 to 12 carbon atoms, poly (meth) acrylate having 2 to 10 carbon atoms, and poly (meth) having a polyol having 2 to 10 carbon atoms.
  • One or more types selected from the group consisting of allyl ether can be used.
  • the internal crosslinking agent is one selected from the group consisting of polyethylene glycol di (meth) acrylate, polypropyleneoxy di (meth) acrylate, glycerin diacrylate, glycerin triacrylate, and trimethy triacrylate.
  • the poly (meth) acrylate of the above poly can be used suitably.
  • the internal crosslinking agent such as polyethylene glycol di (meth) acrylate is used, an internal crosslinked structure can be optimized and a base resin powder having a high gel strength can be obtained. The water absorbent resin can be obtained more appropriately.
  • the specific internal crosslinking agent is 0.005 mol or more, black is 0.005 to 0.1 mol, or 0.005 to 0.05 mol (black is 0.3 parts by weight relative to 100 parts by weight of acrylic acid) based on 1 mol of unneutralized acrylic acid contained in the monomer. Or 0.3 to 0.6 parts by weight).
  • black is 0.005 to 0.1 mol, or 0.005 to 0.05 mol (black is 0.3 parts by weight relative to 100 parts by weight of acrylic acid) based on 1 mol of unneutralized acrylic acid contained in the monomer. Or 0.3 to 0.6 parts by weight).
  • a base resin powder can be obtained through drying, pulverization, and classification, and the like, and the base resin powder and The superabsorbent polymer obtained is suitably manufactured and provided to have a particle size of 150 to 850 1. More specifically, the base resin powder and And obtained therefrom is at least 95 parts by weight 0 / of the water absorbent resin. This has a particle size of more than 150 to 850 rni, 3 a differential having a particle size of less than 150 parts by weight 0 / less than 0, or 1 to 0.5 is less than 0 wt. /. Can be.
  • the superabsorbent polymer can more properly exhibit the excellent physical properties already described above.
  • the method of preparing a superabsorbent polymer may include forming a hydrogel polymer including a crosslinked polymer by thermally polymerizing or photopolymerizing a monomer composition including a water-soluble ethylenically unsaturated monomer, an internal crosslinking agent, and a polymerization initiator; Drying the hydrogel polymer; Grinding and classifying the dried polymer to form a base resin powder; And surface crosslinking the base resin powder in the presence of the hydrophobic and hydrophilic silica particles using a surface crosslinking solution including a surface crosslinking agent of alkylene carbonate having 2 to 5 carbon atoms.
  • the monomer composition includes a water-soluble ethylenically unsaturated monomer, an internal crosslinking agent and a polymerization initiator, and the type of the monomer is as described above.
  • the concentration of the water-soluble ethylenically unsaturated monomer may be 20 to 60 weight 0 /. Or 40 to 50 weight 0 /. With respect to the total monomer composition including each of the above-described raw materials and solvents. In consideration of polymerization time and reaction conditions, the concentration may be appropriate. However, if 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. On the contrary, if the concentration is too high, a part of the monomer may precipitate or the grinding efficiency of the polymerized hydrogel polymer may be low. Phase problems may occur and the physical properties of the super absorbent polymer may be reduced.
  • the polymerization initiator is generally used for the production of superabsorbent polymers. It will not specifically limit, if it is used.
  • 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 since a certain amount of heat is generated by irradiation of ultraviolet radiation or the like, and a certain amount of heat is generated in accordance with the progress of the polymerization reaction, which is an exothermic reaction, it may further 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.
  • photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketal. Ketal), acyl phosphine and alpha-aminoketone can be used at least one selected from the group consisting of.
  • acylphosphine commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used.
  • a wider variety of photoinitiators are well specified in Reinhold Schwalm's book "UV Coatings: Basics, Recent Developments and New Application (Elsevier 2007)" p1 15, and are not limited to the examples described above.
  • the photopolymerization initiator may be included in a concentration of 0.01 to 1.0 weight 0 /. 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 ascorbine.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K2S 2 O 8 ), and ammonium persulfate ((NH 4 ) 2 S 2 0 8 )
  • azo initiators include 2, 2-azobis- (2-amidinopropane) dihydrochloride (2, 2-azobis (2-amidinopropane) dihydrochloride), 2, 2-azobis -(N, N- Isobutyramidine dihydrochloride (2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2-
  • the thermal polymerization initiator may be included in a concentration of 0.001 to 0.5% by weight based on the monomer composition.
  • concentration of the thermal polymerization initiator is too low, additional thermal polymerization hardly occurs, and the effect of the addition of the thermal polymerization initiator may be insignificant.
  • concentration of the thermal polymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven. have.
  • the type of the internal crosslinking agent included in the monomer composition is the same as described above, and the internal crosslinking agent is included at a concentration of 0.01 to 0.5 weight 0 / ° relative to the monomer composition to crosslink the polymerized polymer. Can be.
  • the internal crosslinking agent is 0.005 moles or more, or 0.005 to 0.1 moles, or 0.005 to 0.05 moles (or 100 parts by weight of acrylic acid) based on 1 mole of unneutralized acrylic acid contained in the monomer. 0.3 parts by weight or more, or 0.3 to 0.6 parts by weight).
  • the monomer composition may further include additives such as thickeners, plasticizers, preservative stabilizers, antioxidants, and the like, as necessary.
  • Raw materials such as the above-mentioned water-soluble ethylenically unsaturated monomers, 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-butanedi, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone 1 selected from cyclonucleanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether toluene, xylene, butyrolactone carbyl, methyl cellosolve acetate and ⁇ , ⁇ -dimethylacetamide, etc. It can use combining a species or more.
  • the solvent may be included in the remaining amount except for the above-described components with respect to the total content of the monomer composition.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the energy source of polymerization, and when the thermal polymerization is usually carried out, the polymerization method may be performed in a reactor having a stirring shaft such as a kneader. Although it can proceed in a reactor with a conveyor belt, the above-described polymerization method is an example, the present invention is not limited to the above-described polymerization method.
  • the hydrogel polymer obtained by supplying hot air to the reactor such as a kneader having a stirring shaft or by heating the reactor is subjected to thermal polymerization, depending on the shape of the stirring shaft provided in the reaction vessel.
  • 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 the injection speed of the monomer composition to be injected, it can be usually obtained a hydrogel polymer having a weight average particle diameter of 2 to 50 mm.
  • the form of the hydrogel polymer usually obtained may be a hydrogel gel polymer on the sheet having the width of the belt.
  • the thickness of the polymer sheet depends on the concentration and the injection rate 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 0.5 to 5 cm can be obtained.
  • the monomer composition is supplied to such an extent that the thickness is too thin, the production efficiency is low, which is not preferable.
  • the polymer thickness on the sheet exceeds 5 cm, the polymerization reaction may not occur evenly over the entire thickness due to the excessively thick thickness.
  • the normal water content of the hydrogel polymer obtained in this way may be a 40 to 80 wt. 0/0.
  • water content means the content of water to account for 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 in the process of raising the temperature of the polymer through infrared heating and drying. At this time, the drying conditions are raised to 18C C at room temperature and maintained at 180 ° C. The total drying time is set to 20 minutes, including 5 minutes of the temperature rise step, the moisture content is measured.
  • 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 Includes any one selected from the group of grinding machines consisting of cutter mills, disc mills, shred crushers, crushers, choppers and disc cutters Although it is possible, it is not limited to the above-mentioned example.
  • the coarse grinding step may be pulverized so that the particle size of the hydrogel polymer is 2 to 15mm.
  • drying is performed on the hydrogel polymer immediately after the polymerization which is coarsely crushed or not subjected to the coarsely crushing step.
  • the temperature may be 150 to 250 ° C. If the drying temperature is less than 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 250 C C, only the polymer surface may be dried excessively. Fine powder may occur in the grinding step, and there is a fear that the physical properties of the superabsorbent polymer to be finally formed decrease. Therefore, preferably, the drying may be performed at a temperature of 150 to 200 ° C, more preferably at a temperature of 160 to 180 ° C.
  • drying time in consideration of the process efficiency, etc., it may proceed for 20 to 90 minutes, but is not limited thereto.
  • the drying method of the drying step is also commonly used as a drying step of the hydrogel polymer, it can be selected and used without limitation of the configuration. Specifically, the drying step may be performed by a method such as 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 to about 10 weight 0 /.
  • the polymer powder obtained after the grinding step may have a particle diameter of 150 to 850 / im.
  • Grinders used to grind to such particle diameters are specifically pin mills, hammer mills, screw mills, mills, disc mills or jogs. A jog mill or the like 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.
  • a polymer having a particle size of 150 to 850 m may be classified, and only a polymer powder having such a particle size may be produced through a surface crosslinking reaction step. Since the particle size distribution of the base resin powder obtained through the above process has already been described above, further detailed description thereof will be omitted.
  • the base resin powder in the presence of a surface crosslinking solution containing the hydrophobic silica particles, the hydrophilic silica particles, and the surface crosslinking agent, the base resin powder may be thermally treated to surface crosslink.
  • the hydrophobic silica particles are first mixed and added to the base resin powder, and then the base resin powder is heat-treated in the presence of a surface crosslinking solution including the hydrophilic silica particles and the surface crosslinking agent. It may also proceed by a method of crosslinking.
  • particles having a contact angle of more than 10 ° and 50 ° or less that is, silica particles exhibiting relatively small hydrophobicity
  • particles having a contact angle of 50 ° to 150 ° or less may be used together with a separate dispersant.
  • any dispersant used to disperse the hydrophobic silica particles in a polar solvent such as a water-soluble solvent can be used without any particular limitation, and for example, a Tween dispersant, a Span dispersant, or a polysaccharide dispersant can be used. .
  • the hydrophobic silica particles may be mixed with the base resin powder in a solid state, and the surface thereof may be subjected to dry treatment. Or a method of mixing.
  • hydrophobic silica particles and hydrophilic silica particles may be used in an amount of 0.0001 to 0.3 parts by weight, or 0.001 to 0.1 parts by weight based on 100 parts by weight of the base resin powder, respectively.
  • the fluid permeability and the absorption rate of a super absorbent polymer can be improved more effectively.
  • the method for adding the surface crosslinking liquid containing the hydrophilic silica particles and the surface crosslinking agent and optionally the hydrophobic silica particles to the base resin powder is not particularly limited.
  • the surface crosslinking liquid, The base resin powder may be mixed in a semi-permanent mixture, or the surface crosslinking solution may be sprayed onto the base resin powder, or the base resin powder and the surface crosslinking solution may be continuously supplied to the mixer to be operated continuously.
  • more suitable examples of the alkylene carbonate having 2 to 5 carbon atoms that can be used as the surface crosslinking agent include ethylene carbonate, propylene carbonate, butylene carbonate, and the like. Of course, it can also be used.
  • the surface crosslinking solution may further include a polycarboxylic acid copolymer disclosed in Korean Patent Application Publication No. 2015-0143167 (Korean Patent Application No. 2014-0072343), and the copolymer may further include the base resin powder. Based on 100 parts by weight, it may be included in the surface crosslinking liquid in an amount of 0.01 to 0.1. According to the use of this specific surface crosslinking liquid, the excellent particle strength, liquid permeability and absorption performance of one embodiment, etc. can be more effectively achieved.
  • the surface crosslinking liquid may further include water and / or methanol as a medium.
  • the surface crosslinking agent and the silica particles can be evenly dispersed on the base resin powder.
  • the content of water and methanol is to 100 parts by weight of the base resin powder for the purpose of inducing even dispersion of the surface crosslinking agent and silica particles, preventing aggregation of the base resin powder and optimizing the surface penetration depth of the surface crosslinking agent. It can be applied by adjusting the addition ratio.
  • the surface crosslinking step 5 minutes to 80 minutes, or 10 minutes to a maximum reaction temperature of 140 ° C to 20 C C, or 150 ° C to 190 ° C with respect to the base resin powder to which the surface cross-linking solution is added
  • the heat treatment may be performed for 70 minutes or 20 minutes to 65 minutes to proceed with the surface crosslinking reaction. More specifically, the surface cross-linking step is the temperature rise to the reaction maximum temperature over 10 minutes to 40 minutes at an initial temperature of 20 ° C to 130 ° C, or 40 ° C to 120 ° C, the maximum temperature is 5 It can be carried out by maintaining the heat treatment for minutes to 80 minutes.
  • the superabsorbent polymer which suitably stratifies the excellent liquid permeability, the absorption rate, etc. can be manufactured by layer reaction of reaction conditions at temperature).
  • the temperature raising means for surface crosslinking reaction is not specifically limited. It can be heated by supplying a heat medium or by directly supplying a heat source.
  • a heat medium such as steam, hot air, or hot oil may be used. Consideration can be made as appropriate.
  • the heat source directly supplied may be a heating method through electricity, a gas heating method, but is not limited to the above-described example.
  • the superabsorbent polymer prepared by the above-described method is a base resin powder comprising a first crosslinked polymer of a water-soluble ethylenically unsaturated monomer having at least a part of the neutralized acid group; A surface crosslinking layer formed on the base resin powder, wherein the first crosslinking polymer comprises a second crosslinking polymer further crosslinked through a surface crosslinking agent; And hydrophilic silica particles dispersed on the surface crosslinking layer and having a contact angle of 10 ° or less with respect to water.
  • Such super-absorbent resin is spread on the surface cross-linked layer, it may further comprise a hydrophobic silica particles having a contact angle of 10 ° or less than 150 ° for water.
  • hydrophilic and / or hydrophobic silica particles may be included in the crosslinked structure in the surface crosslinked layer and dispersed, or may be present in the surface crosslinked layer.
  • Such superabsorbent polymers have hydrophilic and / or hydrophobic silica particles upon surface crosslinking, a base resin powder is prepared under the above-described predetermined conditions, and as the surface crosslinking process proceeds, hydrophilic and / or hydrophobicity on the surface crosslinking layer.
  • the silica particles may have a uniformly dispersed form, and furthermore, may exhibit excellent absorption performance with improved liquid permeability, gel strength and absorption rate.
  • Various physical properties of such a super absorbent polymer may be defined by respective property values described below.
  • the superabsorbent polymer may have a centrifugal water retention capacity (CRC) of 25 to 35 g / g, or 26 to 31 g / g.
  • CRC centrifugal water retention capacity
  • the superabsorbent values obtained by the method of the embodiment may exhibit excellent absorbency under no pressure.
  • the centrifugal water retention capacity (CRC) for the physiological saline can be calculated by the following formula 1 after absorbing the superabsorbent resin in physiological saline over 30 minutes:
  • W 0 (g) is the initial weight of superabsorbent polymer (g)
  • W ⁇ g) is absorbed by immersion in physiological saline for 30 minutes without using superabsorbent resin, and then centrifuge to 250G 3
  • the weight of the device measured after dehydration for a minute, W 2 (g) is absorbed by immersing the superabsorbent resin in physiological saline for 30 minutes at room temperature, and then dehydrated at 250G for 3 minutes using a centrifuge, superabsorbent resin Including the measured device weight.
  • the superabsorbent polymer may have a pressure absorption capacity (AUP) of 24 to 30 g / g, or 24.2 to 27 g / g. As such, the superabsorbent polymer may exhibit excellent absorbency even under pressure.
  • AUP pressure absorption capacity
  • This pressurized absorbent capacity can be calculated according to Formula 2 after absorbing the superabsorbent resin in physiological saline under a pressurization of 0.7 psi over 1 hour:
  • AUP (g / g) [W 4 (g)-W 3 (g)] / W 0 (g)
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • W 3 (g) is the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer
  • W 4 (g ) Is the sum of the weight of the superabsorbent resin and the weight of the device capable of applying a load to the superabsorbent resin after absorbing physiological saline to the superabsorbent resin for 1 hour under a load (0.7 psi).
  • the superabsorbent polymer may have an EFFC of 24 to 28 g / g and a black color of 24.6 to 28 g / g.
  • CRC is the high-centrifuged for half an hour for a normal saline solution (0.9 weight-0 /.
  • Aqueous sodium chloride solution) of a water-absorbent resin exhibits an SAT correction
  • AUP represents the absorption capacity of the pressure for one hour under a 0.7psi for physiological saline solution (0.9 weight 0/0 aqueous sodium chloride solution) of the superabsorbent polymer.
  • the superabsorbent polymer may have excellent absorption performance such as basic absorption and absorption under pressure.
  • a super-absorbent resin mentioned above is induced Saline Flow (SFC) for a physiological saline solution of 30 to 160 1 (T 7 cm 3 s / g, or 85 to 160 10- 7 cm 3 's / g, or 85 To 120 ' 1 (T 7 cm 3' s / g.
  • SFC Saline Flow
  • the superabsorbent polymer may exhibit improved fluid permeability than previously known. This may include silica particles or the like in the surface crosslinking layer.
  • the surface crosslinking layer having a thickness of a predetermined level or more appears to be uniformly formed.
  • SFC physiological saline flow inducibility
  • the above-mentioned super-absorbent resin has such a high saline solution (0.9 weight 0/0 aqueous sodium chloride solution), after swelling by absorbing the horizontal direction, the gel strength of the superabsorbent polymer by using a rheometer for 1 hour, the water-absorbent resin (G When measuring '), the gel strength (G') can be 9,000 to 15,000 Pa, or 9,000 to 13,000 Pa.
  • the horizontal gel strength G ' can better reflect the excellent liquid permeability under the actual use environment of the super absorbent polymer.
  • the liquid permeability of the super absorbent polymer is generally included in sanitary materials such as diapers.
  • it can be determined to be more relevant depending on whether the force applied in the horizontal direction is excellent and whether it exhibits good shape retention and high gel strength.
  • the horizontal gel strength may well reflect the gel strength directly related to the liquid permeability. Can be. Therefore ;
  • the superabsorbent polymer having such a horizontal gel strength G 'satisfying the above-mentioned range exhibits excellent liquid permeability, it has been found that the superabsorbent polymer can be used very favorably in sanitary materials such as diapers.
  • the superabsorbent polymer obtained according to the method of the embodiment maintains excellent water absorption performance such as water retention capacity and pressure absorption capacity, and can achieve improved fluid permeability, gel strength and absorption rate. Therefore, hygiene materials such as diapers, in particular, ultra-thin hygiene materials having a reduced content of the peel can be used as appropriate.
  • a superabsorbent performance such as water-retaining capacity and pressure-absorbing capacity can be maintained excellent, and a superabsorbent polymer can be produced and provided with more improved fluid permeability, gel strength and absorption rate.
  • Such superabsorbent polymers have a high content of sanitary materials, especially diapers, such as diapers. Reduced ultra-thin hygiene and the like can be used as appropriate.
  • a hydrophobic silica particle was used as a coating liquid dispersed in a methylene chloride solvent at a concentration of 5 weight 0 /. After the coating solution was spin coated on the wafer, the contact angle was measured by dropwise dropping water on the coating layer. The measured contact angle is defined as the contact angle of the hydrophobic silica particles with respect to water, and the measured values are shown in Table 1 below.
  • hydrophilic silica particles except that a coating liquid dispersed in water at a concentration of 20 weight 0 /.
  • the particle diameters of the base resin powder and the super absorbent polymer used in the examples and the comparative examples were measured according to the European Disposables and Nonwovens Association (EDANA) standard EDANA WSP 220.3 method.
  • EDANA European Disposables and Nonwovens Association
  • CRC Centrifuge Retention Capacity
  • the resin of Examples and Comparative Examples W 0 (g, about 0.2g) after the insert uniformly in the envelope of the nonwoven fabric is sealed (se al), 0.9 at room temperature. It was immersed in the physiological saline solution which becomes the sodium chloride aqueous solution of the weight of 0 /. After 30 minutes, the envelope was centrifuged and drained at 250 G for 3 minutes, and then the mass W 2 (g) of the envelope was measured. Moreover, after performing the same operation without using resin, the mass W ⁇ g at that time was measured.
  • W 0 (g) is the initial weight (g) of the super absorbent polymer
  • W ⁇ g is the weight of the device measured after immersion in physiological saline for 30 minutes without using a super absorbent polymer, and then dehydrated at 250 G for 3 minutes using a centrifuge,
  • W 2 (g) is the weight of the device, including the super absorbent polymer, after absorbing the superabsorbent polymer in physiological saline at room temperature for 30 minutes and then dehydrating it at 250 G for 3 minutes using a centrifuge.
  • AUP Absorbing under Pressure
  • AUP Absorbency under Pressure
  • a glass filter having a diameter of 125 mm and a thickness of 5 mm was placed on the inside of the petri dish having a diameter of 150 mm, and the physiological saline composed of 0.90 weight 0 / ° sodium chloride was brought to the same level as the upper surface of the glass filter.
  • One sheet of filter paper 120 mm in diameter was loaded thereon.
  • the measuring device was placed on the filter paper and the liquid was absorbed for 1 hour under load. After 1 hour, the measuring device was lifted up and the weight W 4 (g) was measured.
  • AUP (g / g) [W 4 (g)-W 3 (g)] / W 0 (g)
  • W 0 (g) is the initial weight (g) of the superabsorbent polymer
  • W 3 (g) is the sum of the weight of the superabsorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer
  • W 4 (g) is the sum of the weight of the superabsorbent resin and the device weight capable of applying a load to the superabsorbent resin after absorbing physiological saline into the superabsorbent resin for 1 hour under a load (0.7 psi).
  • SFC saline flow conductivity
  • the rheometer is used to identify the shear strain in a linear viscoelastic regime with constant storage modulus and loss modulus at an oscilation frequency of 10 rad / s with increasing shear strain. It was. Generally in a swollen superabsorbent polymer sample, 0.1% shear strain is within the linear viscoelastic state section.
  • the storage modulus and the loss modulus of the superabsorbent polymer swollen for 60 seconds at the shear strain value of the linear viscoelastic state section were measured, respectively.
  • the storage modulus values obtained at this time were averaged to determine the horizontal gel strength.
  • the loss modulus is measured to be a very small value compared to the storage modulus.
  • the monomer composition was irradiated with light for 1 minute, and the polymerization reaction was carried out for 3 minutes by raising the temperature of the glass reaction vessel to 75 ° C.
  • the polymer obtained as a result of the polymerization was passed through a hole having a diameter of about 13 mm using a meat chopper to obtain a crumpled coarse polymer.
  • the polymer in the crumb state was dried in an oven capable of transferring air volume up and down. Specifically, the hot air of 18C C was flowed downwardly upwards for 15 minutes, and further upwards downwards for 15 minutes, thereby uniformly drying the polymer in the crumb state, and the water content of the final dried polymer was about 2% by weight. It adjusted to the following.
  • the dried polymer was pulverized with a grinder and then classified to obtain a base resin powder having a particle size of about 150 to 850.
  • the base resin powder was found to gradually increase in temperature at an initial temperature near 18C C, and was manipulated to reach a reaction temperature of 190 ° C. after 30 minutes. After reaching this reaction maximum temperature, the final prepared superabsorbent polymer sample was taken after further reaction for 65 minutes. After the surface crosslinking process, using a sieve (sieve) A surface crosslinked superabsorbent polymer having a particle diameter of about 150 to 850 was obtained.
  • Example 2 A surface crosslinked superabsorbent polymer having a particle diameter of about 150 to 850 was obtained.
  • Example 1 For 100 g of the base resin powder obtained in the same manner as in Example 1, 0.02 g of hydrophobic silica particles of Aerosil 200, 0.02 g of hydrophilic silica particles of ST-O, 1.5 g of ethylene carbonate, Korean Patent Application Publication No. 2015-0143167 Example 1 except that a surface treatment liquid containing 0.05 g of the polycarboxylic acid copolymer disclosed in Preparation Example 1 of Korean Patent Application No. 2014-0072343 and 4.0 g of water as a solvent was used. A super absorbent polymer was prepared in the same manner.
  • Example 3 After the surface crosslinking process, a surface crosslinked superabsorbent polymer having a particle size of about 150 to 850 was obtained using a sieve.
  • Example 3 a surface crosslinked superabsorbent polymer having a particle size of about 150 to 850 was obtained using a sieve.
  • the particle size is about 150 to about 150 using a sieve.
  • Example 1 For 100 g of the base resin powder obtained in the same manner as in Example 1, 0.02 g of hydrophobic silica particles of Aerosil 200, 0.06 g of hydrophilic silica particles of ST-O, 1.5 g of ethylene carbonate, Korean Patent Application Publication No. 2015-0143167 Example 1 except that a surface treatment liquid containing 0.05 g of the polycarboxylic acid copolymer disclosed in Preparation Example 1 of Korean Patent Application No. 2014-0072343 and 4.0 g of water as a solvent was used. A super absorbent polymer was prepared in the same manner.
  • the particle size is about 150 to about 150 using a sieve.
  • Example 1 For 100 g of the base resin powder obtained in the same manner as in Example 1, except that a surface treatment liquid containing 0.06 g of Aerosil 200 hydrophobic silica particles, 1.5 g of ethylene carbonate, and 4.0 g of water as a solvent was formed and used. was prepared in the same manner as in Example 1.
  • a surface crosslinked superabsorbent polymer having a particle size of about 150 to 850 was obtained using a sieve.
  • the physical properties of CRC, AUP, SFC and gel strength were measured and evaluated for the superabsorbent polymers of Examples 1 to 7, Comparative Examples 1 and 2, and the measured physical properties are shown in Table 2 below.
  • the EFFC value of Equation 1 was calculated from the measured CRC and AUP and shown in Table 2 together.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'une résine superabsorbante, qui conserve une excellente performance d'absorption et fait preuve d'une perméabilité aux liquides et d'un taux absorption des liquides améliorés. La présente invention décrit un procédé de préparation d'une résine superabsorbante qui peut comprendre les étapes suivantes : exécution d'une polymérisation par réticulation sur un monomère éthyléniquement insaturé soluble dans l'eau ayant un groupe acide au moins partiellement neutralisé pour former un polymère hydrogel comprenant un polymère réticulé, en présence d'un agent de réticulation interne ; le séchage, la pulvérisation, et la classification du polymère hydrogel pour former une poudre de résine de base ; et l'exécution de la réticulation de surface sur la poudre de résine de base en utilisant un liquide de réticulation de surface contenant un agent de réticulation de surface d'un carbonate d'alcylène ayant de 2 à 5 atomes de carbone, en présence de particules de silice hydrophobes présentant un angle de contact supérieur à 10 ° et inférieur ou égal à 150 ° par rapport à l'eau et des particules de silice hydrophiles présentant un angle de contact inférieur ou égal à 10 ° par rapport à l'eau.
PCT/KR2017/000057 2016-03-11 2017-01-03 Procédé de préparation d'une résine superabsorbante, et résine superabsorbante WO2017155197A1 (fr)

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US15/768,343 US10773237B2 (en) 2016-03-11 2017-01-03 Method for preparing super absorbent polymer, and super absorbent polymer
CN201780003667.9A CN108350189A (zh) 2016-03-11 2017-01-03 用于制备超吸收性聚合物的方法和超吸收性聚合物
EP17763460.7A EP3342801B1 (fr) 2016-03-11 2017-01-03 Procédé de préparation d'une résine superabsorbante, et résine superabsorbante

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CN114174389B (zh) * 2019-10-07 2024-02-27 株式会社Lg化学 超吸收性聚合物的制备方法

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