WO2020122426A1 - Polymère superabsorbant et son procédé de préparation - Google Patents

Polymère superabsorbant et son procédé de préparation Download PDF

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WO2020122426A1
WO2020122426A1 PCT/KR2019/015056 KR2019015056W WO2020122426A1 WO 2020122426 A1 WO2020122426 A1 WO 2020122426A1 KR 2019015056 W KR2019015056 W KR 2019015056W WO 2020122426 A1 WO2020122426 A1 WO 2020122426A1
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Prior art keywords
polymer
super absorbent
absorbent polymer
fibers
weight
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PCT/KR2019/015056
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English (en)
Korean (ko)
Inventor
최용석
홍연우
신은지
안태빈
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LG Chem Ltd
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LG Chem Ltd
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Priority claimed from KR1020190139625A external-priority patent/KR102603201B1/ko
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to JP2020539707A priority Critical patent/JP7034535B2/ja
Priority to EP19896615.2A priority patent/EP3722353B1/fr
Priority to CN201980010268.4A priority patent/CN111655764A/zh
Priority to US16/968,771 priority patent/US11559784B2/en
Publication of WO2020122426A1 publication Critical patent/WO2020122426A1/fr
Anticipated expiration legal-status Critical
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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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse

Definitions

  • the present invention relates to a super absorbent polymer and a method for manufacturing the same. More particularly, the present invention relates to a method for producing a super absorbent polymer having excellent basic absorption ability and improved absorption rate.
  • Super Absorbent Polymer is a synthetic polymer material that has the ability to absorb about 500 to 1,000 times its own weight, and has started to be put into practical use as a physiological tool. In addition to sanitary products such as gardening, it has been widely used as a material for soil repair agents for gardening, civil engineering, construction water supply materials, sheets for raising seedlings, freshness preservatives in the food distribution field, and poultices.
  • these superabsorbent polymers are widely used in the field of sanitary materials such as diapers and sanitary napkins. For this purpose, it is necessary to exhibit high absorbency for moisture, etc., and absorbed moisture does not come out even under external pressure. It is necessary to exhibit excellent absorption properties. In addition, in recent years, an absorption rate for absorbing and storing a target solution such as moisture more rapidly is further required. Basically, the absorption of the superabsorbent polymer into the aqueous solution occurs at the resin surface, so a method of increasing the surface area of the superabsorbent polymer can be considered to improve the absorption rate. Accordingly, a method for reducing the particle size of the super absorbent polymer or forming a porous structure has been considered as a method for increasing the absorption rate.
  • a method of manufacturing a superabsorbent polymer by adding a blowing agent to form a porous structure in a superabsorbent polymer has been proposed.
  • the higher the content of the blowing agent the absorption rate is improved to a certain level, but due to excessive foaming, the amount of fine powder generated in the super absorbent polymer increases, and there is a problem that the gel strength is lowered.
  • the superabsorbent polymer tends to have reduced basic absorption characteristics as the particle size decreases.
  • the known method has a limitation in improving the absorption rate while maintaining the basic absorption capacity.
  • the present invention is to solve the problems of the prior art as described above, and to provide a method of manufacturing a super absorbent polymer exhibiting improved initial absorption rate while having excellent basic absorption performance such as water retention capacity (CRC).
  • CRC water retention capacity
  • the fiber may be included in 1 to 18 parts by weight based on 100 parts by weight of the hydrogel polymer.
  • the length of the fiber may be 1 to 20 mm.
  • the width of the fiber may be 1 to 100 ⁇ m.
  • water may be further added in at least one of steps c) to e). At this time, the water may be added in 1 to 20 parts by weight based on 100 parts by weight of the hydrogel polymer.
  • the monomer composition may further include a blowing agent.
  • the monomer composition is alkyl sulfate salt (alkyl sulfate salt), alkyl sulfonate salt (alkyl sulfonate salt), alkyl phosphate salt (alkyl phosphate salt), alkyl carbonate salt (alkyl carbonate salt), polyethylene glycol alkyl ester (polyethylene glycol alkyl esters, polypropylene glycol alkyl esters, glucoside alkyl esters, glycerol alkyl esters, and block-copolymers of polyethylene glycol and polypropylene glycol (block- copolymers of polyethylene glycol and polypropylene glycol) may further include one or more foam stabilizers.
  • step g After step g),
  • i) may further include the step of proceeding the surface crosslinking reaction.
  • the surface crosslinking agent is a polyhydric alcohol compound; Epoxy compounds; Polyamine compounds; Halo epoxy compounds; Condensation products of haloepoxy compounds; Oxazoline compounds; Mono-, di- or polyoxazolidinone compounds; Cyclic urea compounds; Polyvalent metal salts; And it may be one or more selected from the group consisting of alkylene carbonate compounds.
  • the surface crosslinking agent may be added in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the mixture.
  • the present invention provides a super absorbent polymer produced by the above manufacturing method.
  • the present invention is a crosslinked polymer in which a water-soluble ethylenically unsaturated monomer is crosslinked and polymerized in the presence of an internal crosslinking agent, and base resin particles comprising at least one fiber among fluff pulp and synthetic polymer fibers;
  • the crosslinked polymer is a super absorbent polymer comprising a surface crosslinking layer further crosslinked via a surface crosslinking agent,
  • the superabsorbent polymer may have a centrifugal water retention capacity (CRC) of 25 to 45 g/g measured according to EDANA method WSP 241.3.
  • CRC centrifugal water retention capacity
  • the superabsorbent polymer may have a pressure absorption capacity (AUL) of 0.3 psi measured according to EDANA method WSP 242.3 of 25 to 40 g/g.
  • AUL pressure absorption capacity
  • the superabsorbent polymer composition is provided.
  • the method for producing a super absorbent polymer according to the present invention it is possible to provide a high quality super absorbent polymer having excellent basic absorbent performance such as centrifugal water retention capacity and exhibiting improved absorbent speed.
  • the manufacturing method of the super absorbent polymer of the present invention is relatively simple because the process steps are high, it is possible to obtain a super absorbent polymer having a high absorption rate.
  • Example 1 is a scanning electron microscope (SEM) photograph of the super absorbent polymer prepared in Example 1.
  • one or more fibers of fluff pulp and synthetic polymer fibers are added in the step of compacting the hydrogel polymer in order to realize an excellent absorption rate while maintaining the basic absorption performance of the super absorbent polymer.
  • the superabsorbent polymer prepared as described above exhibits an improved absorption rate compared to the existing superabsorbent polymer because fibers having excellent absorbent capacity are adsorbed on the surface.
  • the superabsorbent polymer prepared according to the present invention can exhibit a more improved absorption rate while maintaining basic absorbent properties such as water retention capacity.
  • a) a water-soluble ethylenically unsaturated monomer, an internal crosslinking agent, and a polymerization initiator are mixed to prepare a monomer composition.
  • any monomer commonly used in the production of superabsorbent polymers can be used without particular limitation. Any one or more monomers selected from the group consisting of anionic monomers and salts thereof, nonionic hydrophilic-containing monomers and amino group-containing unsaturated monomers and quaternaries thereof can be used.
  • (meth)acrylic acid maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid or 2- Anionic monomers of (meth)acrylamide-2-methyl propane sulfonic acid and salts thereof; (Meth)acrylamide, N-substituted (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate or polyethylene glycol ( Nonionic hydrophilic monomers of meth)acrylate; And an amino group-containing unsaturated monomer of (N,N)-dimethylaminoethyl (meth) acrylate or (N,N)-dimethylaminopropyl (meth)acrylamide, and quaternaries thereof.
  • an acrylic acid or a salt thereof for example, an alkali metal salt such as acrylic acid or a sodium salt thereof may be used, and the use of such a monomer makes it possible to manufacture a super absorbent polymer having better physical properties.
  • an alkali metal salt of acrylic acid is used as a monomer, it can be used by neutralizing acrylic acid with a basic compound such as caustic soda (NaOH).
  • the concentration of the water-soluble ethylenically unsaturated monomer may be about 20 to about 60% by weight, preferably about 40 to about 50% by weight, with respect to the monomer composition containing the raw material and solvent of the superabsorbent polymer, and polymerization It may be an appropriate concentration in consideration of time and reaction conditions. However, if the concentration of the monomer is too low, the yield of the superabsorbent polymer may be low and economic problems may occur. Conversely, if the concentration is too high, a part of the monomer precipitates or the grinding efficiency of the polymerized hydrogel polymer is low. Such problems may occur in the process and physical properties of the super absorbent polymer may be deteriorated.
  • the polymerization initiator used in polymerization in the superabsorbent polymer production method of the present invention is not particularly limited as long as it is generally used for the production of superabsorbent polymers.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • a thermal polymerization initiator may be additionally included.
  • the photopolymerization initiator is a compound capable of forming radicals by light such as ultraviolet rays
  • the composition may be used without limitation.
  • the photopolymerization initiator includes, for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketal. ketal), acyl phosphine, and alpha-aminoketone ( ⁇ -aminoketone).
  • acylphosphine a commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide) can be used.
  • 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide
  • the photopolymerization initiator may be included in a concentration of about 0.01 to about 1.0% by weight relative to the monomer composition. If the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow, and if the concentration of the photopolymerization initiator is too high, the molecular weight of the super absorbent polymer may be small and the properties may be uneven.
  • thermal polymerization initiator one or more selected from the initiator group consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid may be used.
  • the persulfate-based initiator are sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate (Ammonium persulfate; (NH 4 ) 2 S 2 O 8 )
  • examples of the azo-based initiator are 2, 2-azobis-(2-amidinopropane) dihydrochloride (2, 2-azobis (2-amidinopropane) dihydrochloride), 2 , 2-azobis-(N, N-dimethylene)isobutyramidine dihydrochloride (2-azobis-(N,N-dimethylene)isobutyramidine dihydrochloride), 2-(carbamoyl azo)isobutyronit
  • the thermal polymerization initiator may be included in a concentration of about 0.001 to about 0.5% by weight relative to the monomer composition. If the concentration of the thermal polymerization initiator is too low, the additional thermal polymerization hardly occurs, so the effect of the addition of the thermal polymerization initiator may be negligible. If the concentration of the thermal polymerization initiator is too high, the molecular weight of the super absorbent polymer is small and the physical properties may be uneven. have.
  • the internal crosslinking agent while having at least one functional group capable of reacting with the water-soluble substituent of the water-soluble ethylenically unsaturated monomer, a crosslinking agent having at least one ethylenically unsaturated group; Alternatively, a crosslinking agent having two or more functional groups capable of reacting with the water-soluble substituent of the monomer and/or the water-soluble substituent formed by hydrolysis of the monomer may be used.
  • the internal crosslinking agent include bisacrylamide having 8 to 12 carbons, bismethacrylamide, poly(meth)acrylate of polyols having 2 to 10 carbons, or poly(meth)allyl ether of polyols having 2 to 10 carbons, etc. And more specifically, N,N'-methylenebis(meth)acrylate, ethyleneoxy(meth)acrylate, polyethyleneoxy(meth)acrylate, propyleneoxy(meth)acrylate, glycerin diacrylate , Glycerin triacrylate, trimethyrol triacrylate, triallylamine, triaryl cyanurate, triallyl isocyanate, polyethylene glycol, diethylene glycol and propylene glycol.
  • an epoxy compound containing one or more epoxy groups may be used as the internal crosslinking agent.
  • the epoxy compound may further include at least one functional group capable of reacting with the water-soluble ethylenically unsaturated monomer in addition to the epoxy group.
  • Specific examples include polyhydric epoxy compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, or polypropylene glycol diglycidyl ether. Can be lifted.
  • These internal crosslinking agents may be used in combination of two or more, and included in a concentration of about 0.01 to about 0.5% by weight relative to the monomer composition to crosslink the polymerized polymer.
  • the monomer composition may further include additives such as a foaming agent, a foaming stabilizer, a thickener, a plasticizer, a preservative stabilizer, and an antioxidant, if necessary.
  • additives such as a foaming agent, a foaming stabilizer, a thickener, a plasticizer, a preservative stabilizer, and an antioxidant, if necessary.
  • the blowing agent may be used without limitation, inorganic blowing agents and encapsulating blowing agents commonly used in the art.
  • the inorganic blowing agent is calcium carbonate (CaCO 3 ), sodium bicarbonate (NaHCO 3 ), ammonium bicarbonate (NH 4 HCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), ammonium nitrite (NH 4 NO 2 ), hydrogen borohydride
  • CaCO 3 calcium carbonate
  • NaHCO 3 sodium bicarbonate
  • NH 4 HCO 3 ammonium bicarbonate
  • NH 4 HCO 3 ammonium carbonate
  • (NH 4 ) 2 CO 3 ) ammonium nitrite
  • hydrogen borohydride One or more selected from sodium (NaBH 4 ) and sodium carbonate (Na 2 CO 3 ) may be used, but is not limited thereto.
  • the encapsulated foaming agent exists in an encapsulated state during polymerization of the monomer composition, and then foams by heat applied during the drying process described below, thereby forming pores of appropriate size between the polymer structures of the super absorbent polymer, It is possible for the absorbent resin sheet to exhibit the structure of an open pore channel. Therefore, when the foaming agent encapsulated in the monomer composition is included, the absorption rate of the superabsorbent polymer can be further improved, which is preferable.
  • the encapsulated foaming agent may have a structure including a core including a hydrocarbon and a shell surrounding the core and formed of a thermoplastic resin.
  • the encapsulated foaming agent has different expansion characteristics depending on the weight and diameter of the components constituting the core and the shell, and can be expanded to a desired size by controlling it, and can control the porosity of the superabsorbent polymer sheet.
  • the expansion characteristics of the encapsulated blowing agent in order to determine whether pores of a desired size are formed, it is necessary to first grasp the expansion characteristics of the encapsulated blowing agent.
  • the form in which the foaming agent encapsulated in the superabsorbent polymer is foamed may vary depending on the manufacturing conditions of the superabsorbent polymer, so it is difficult to define it as one form. Therefore, by first foaming the encapsulated foaming agent in the air, the expansion ratio and size can be checked to confirm whether it is suitable for forming desired pores.
  • the encapsulated foaming agent may have an average diameter of 5 to 50 ⁇ m, or 5 to 30 ⁇ m, or 5 to 20 ⁇ m, or 7 to 17 ⁇ m. When the encapsulated foaming agent exhibits such an average diameter, it can be judged to be suitable for achieving an appropriate porosity.
  • the method of manufacturing the superabsorbent polymer sheet according to the present invention It can be judged to be suitable for forming a suitable open pore structure.
  • the hydrocarbons constituting the core of the encapsulated blowing agent are n-propane, n-butane, iso-butane, cyclobutane, n-pentane, iso-pentane, cyclopentane, n-hexane, iso-hexane, cyclohexane, n- It may be one or more selected from the group consisting of heptane, iso-heptane, cycloheptane, n-octane, iso-octane and cyclooctane.
  • hydrocarbons having 3 to 5 carbon atoms are suitable for forming pores of the size described above, and iso- Butane may be the most suitable.
  • thermoplastic resin constituting the shell of the encapsulated foaming agent is formed from at least one monomer selected from the group consisting of (meth)acrylate, (meth)acrylonitrile, aromatic vinyl, vinyl acetate, vinyl halide, and vinylidene halide. It can be a polymer. Among them, a copolymer of (meth)acrylate and (meth)acrylonitrile may be most suitable for forming pores of the size described above.
  • the encapsulated blowing agent may contain 10 to 30% by weight of hydrocarbons based on the total encapsulated blowing agent weight. It may be most suitable to form an open pore structure within this range.
  • the encapsulated foaming agent may be prepared and used, or a commercialized foaming agent satisfying the above-described conditions may be used.
  • the content of the encapsulating foaming agent may be 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, and more preferably 0.1 to 1 part by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. If the content of the encapsulated foaming agent is too small, the open pore structure may not be properly formed, and if it is contained too much, the porosity may be too high, so that the strength of the super absorbent polymer may be weak, so the content range is preferable in this respect. Can be.
  • the monomer composition may further include a foaming stabilizer.
  • the foam stabilizer is an alkyl sulfate salt, an alkyl sulfonate salt, an alkyl phosphate salt, an alkyl carbonate salt, and a polyethylene glycol alkyl ester. ), polypropylene glycol alkyl ester, glucoside alkyl ester, glycerol alkyl ester, block-copolymers of polyethylene glycol and polypropylene glycol glycol and polypropylene glycol) or mixtures thereof.
  • the alkyl group is not particularly limited, and may be a straight chain, branched chain or cyclic alkyl group having 1 to 30 carbon atoms.
  • the foaming stabilizer may be included in a concentration of about 0.0001 to 0.1% by weight or about 0.001 to 0.1% by weight in 100% by weight of the monomer composition to improve the foaming efficiency of the foaming agent to form a crosslinked polymer having an appropriate pore structure.
  • Raw materials such as the water-soluble ethylenically unsaturated monomer, photopolymerization initiator, thermal polymerization initiator, internal crosslinking agent, and additives described above may be prepared in the form of a solution of a monomer composition dissolved in a solvent.
  • the solvent that can be used at this time can be used without limitation of its 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, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol Ethyl ether, toluene, xylene, butyrolactone, carbitol, methyl cellosolve acetate and N,N-dimethylacetamide can be used in combination.
  • the solvent may be included in the remaining amount excluding the above-mentioned components with respect to the total content of the monomer composition.
  • the monomer composition is thermally polymerized or photopolymerized to prepare a hydrogel polymer.
  • the thermal polymerization or photopolymerization method of the monomer composition is not particularly limited as long as it is a commonly used polymerization method.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source, and in general, when performing thermal polymerization, it can be carried out in a reactor having a stirring axis such as a kneader, and when performing photopolymerization, it is movable Although it may be carried out in a reactor equipped with a conveyor belt, the polymerization method described above is an example, and the present invention is not limited to the polymerization method described above.
  • a hydrogel polymer obtained by thermal polymerization by supplying hot air or heating a reactor to a reactor such as a kneader having a stirring shaft is used as a reactor outlet, depending on the type of the stirring shaft provided in the reactor.
  • the discharged hydrogel polymer 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 2 to 50 mm can be usually obtained.
  • the shape of the hydrogel polymer usually obtained may be a hydrogel polymer on a sheet having a belt width.
  • the thickness of the polymer sheet varies depending 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 about 0.5 to about 5 cm can be obtained.
  • the monomer composition is supplied to such an extent that the thickness of the polymer on the sheet is too thin, production efficiency is low, which is undesirable.
  • the thickness of the polymer on the sheet exceeds 5 cm, due to the excessively thick thickness, the polymerization reaction does not occur evenly over the entire thickness. It may not.
  • the normal water content of the hydrogel polymer obtained in this way may be about 40 to about 80% by weight.
  • water content refers to a value obtained by subtracting the weight of the polymer in a dry state from the weight of the hydrogel polymer as the content of moisture to the total weight of the hydrogel polymer. Specifically, it is defined as a calculated value by measuring the weight loss due to evaporation of water in the polymer during the drying process by raising the temperature of the polymer through infrared heating.
  • the drying condition is a method of raising the temperature from room temperature to about 180°C and then maintaining it at 180°C.
  • the total drying time is set to 20 minutes including 5 minutes of the temperature rise step to measure the water content.
  • the used grinder is not limited in configuration, but specifically, a vertical cutter (Vertical pulverizer), a turbo cutter (Turbo cutter), a turbo grinder (Turbo grinder), a rotary cutting mill (Rotary cutter mill), cutting Cutter mill, disc mill, shred crusher, crusher, chopper, and disc cutter
  • a vertical cutter Very pulverizer
  • turbo cutter Turbo cutter
  • Turbo grinder turbo grinder
  • rotary cutting mill Rotary cutting mill
  • cutting Cutter mill disc mill
  • shred crusher crusher
  • chopper chopper
  • disc cutter rotary cutting mill
  • step c) may be performed so that the particle diameter of the hydrogel polymer is about 2 to about 20 mm.
  • Coarse pulverization with a particle diameter of less than 2 mm is not technically easy due to the high water content of the hydrogel polymer, and there may also be a phenomenon in which the particles are aggregated with each other.
  • the particle size is roughly crushed to more than 20 mm, the effect of increasing the efficiency of the drying step to be performed later may be insignificant.
  • the fibers adsorbed on the surface of the hydrogel polymer particles may be incorporated into the particles by the chopper. Accordingly, at least a portion of the fibers are mixed in a form penetrating the inside of the particles of the base resin, and fibers may be distributed both inside and outside the base resin particles. As described above, the fibers distributed inside and outside of the base resin serve to absorb the surrounding moisture rapidly through the capillary action and transfer it to the polymer. Therefore, the superabsorbent polymer prepared according to the present invention can exhibit an improved initial absorption rate.
  • such fibers are easy to apply to the process and are not only inexpensive, but also harmless to the human body, and according to the present invention, it is possible to manufacture a superabsorbent polymer that is human-friendly and excellent in absorbency in a simple and economical manner.
  • the fluff pulp is a cellulose fluff pulp, but may be wood fluff pulp such as softwood kraft paper, broadleaf kraft pulp, but is not limited thereto, and fluff pulp used for absorbent articles may be used without limitation.
  • the synthetic polymer fiber may be at least one selected from the group consisting of nylon, polypropylene, polyethylene, polyester, polyacrylonitrile, polyvinyl chloride, polyvinyl alcohol, polyacrylate, and acetate.
  • Such a synthetic polymer fiber is excellent in hygroscopicity, and it is easy to control the width or length of the fiber, so it is possible to easily control the physical properties of the super absorbent polymer.
  • the fiber may be preferably used having a length of 1 to 20 mm.
  • the fiber may preferably have a width of 1 to 100 ⁇ m. If the length of the fiber exceeds the above range or the width is too wide, a load may occur in the process of compacting the water-containing gel polymer and the fiber, and it is difficult to adsorb the fiber inside and outside the base resin particles, so that the super absorbent polymer is It can be difficult to evenly distribute the fibers.
  • the length of the fiber is too short or the width is too narrow, the effect of improving the properties of the super absorbent polymer may be insignificant, so it is preferable to satisfy the above range.
  • the surface crosslinking solution can be more evenly applied regardless of the particle size variation of the base resin particles in the subsequent surface crosslinking step, the surface crosslinking efficiency can be further increased.
  • the adsorption rate deviation with the small particles may be reduced due to the adsorbed fibers. Therefore, regardless of the particle size of the base resin, the degree of application of the surface crosslinking solution becomes uniform, and the variation in crosslinking degree decreases, thereby improving the overall physical property balance of the superabsorbent polymer produced.
  • the length of the fibers may be 2 mm or more, or 3 mm or more, and 15 mm or less, or 10 mm or less.
  • the fiber having an average length of 3 to 10 mm may be preferably used.
  • the average length of the fibers can be derived by randomly selecting 100 fibers, measuring the length of individual fibers, and calculating the average value thereof.
  • the width of the fiber may be 10 ⁇ m or more, 15 ⁇ m or more, 30 ⁇ m or more, or 50 ⁇ m or more, and 90 ⁇ m or less, or 80 ⁇ m or less.
  • the content of the fiber may be 1 part by weight or more, 3 parts by weight or more, or 5 parts by weight or more, and 18 parts by weight or less, 15 parts by weight or less, or 10 parts by weight or less based on 100 parts by weight of the hydrogel polymer. If the fiber is less than 1 part by weight based on 100 parts by weight of the hydrogel polymer, the effect of improving the absorption rate due to the inclusion of the fiber cannot be secured, and if it exceeds 18 parts by weight, the centrifugal water retention capacity (CRC) of the superabsorbent polymer produced is Basic absorption performance such as pressurized absorption capacity (AUL) and absorption rate may be lowered, and a problem that mechanical load increases in the step of compacting the hydrogel polymer may occur.
  • AUL pressurized absorption capacity
  • steps d) and e) may be repeated 2 to 5 times.
  • steps d) and e) may be repeated 2 to 5 times.
  • the same amount of fibers can be added for each repetition for smooth mixing, but it is preferable that the total content of the added fibers is within the above range.
  • water may be further added in at least one of the steps c) to e). Adding an appropriate amount of water to the step of compacting the hydrogel polymer can lower the load of the grinder, the hydrogel polymer can be more evenly compacted, and accordingly the particle size of the hydrogel polymer can be easily adjusted.
  • the water may be distilled water, and the amount of water added in each step is not particularly limited, but may be, for example, 1 to 20 parts by weight based on 100 parts by weight of the hydrogel polymer.
  • the hydrogel polymer containing fibers it is preferable that the particle size is in the range of 1 to 15 mm. In the particle size range, the efficiency of the drying step may be increased.
  • the drying temperature of the drying step may be about 150 to about 200 °C.
  • the drying temperature is less than 150°C, the drying time is too long and there is a fear that the physical properties of the superabsorbent resin to be formed are lowered.
  • the drying temperature exceeds 200°C, only the polymer surface is dried excessively, and a subsequent grinding process is performed. In the fine powder may be generated, there is a fear that the physical properties of the superabsorbent polymer to be formed finally decreases. Therefore, preferably, the drying may be performed at a temperature of about 150 to about 200°C, more preferably at a temperature of about 160 to about 180°C.
  • process efficiency and the like may be considered, but may be performed for about 20 minutes to about 1 hour, but is not limited thereto.
  • the drying method of the drying step may also be selected and used without limitation, as long as it is commonly used as a drying process for the hydrogel polymer. Specifically, the drying step may be performed by a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the moisture content of the polymer after the drying step may be about 0.1 to about 10% by weight.
  • the polymer powder obtained after the grinding step may have a particle size of about 150 to about 850 ⁇ m.
  • the pulverizer used for pulverizing to such a particle size is specifically, a pin mill, a hammer mill, a screw mill, a roll mill, a disc mill or a jog. A mill may be used, but the present invention is not limited to the examples described above.
  • the polymer powder obtained after pulverization is generally classified according to particle size.
  • it may be subjected to a step of classifying particles having a particle diameter of less than about 150 ⁇ m, particles having a diameter of about 150 to about 850 ⁇ m, and particles having a particle diameter of greater than 850 ⁇ m.
  • the method for preparing a super absorbent polymer of the present invention may further include h) adding a surface crosslinking agent to the mixture obtained after step g), and i) progressing a surface crosslinking reaction.
  • the surface crosslinking step is a step of forming a superabsorbent polymer having improved physical properties by inducing a crosslinking reaction on the surface of the mixture, that is, a polymer containing fibers on the surface, in the presence of a surface crosslinking agent.
  • a surface crosslinking layer (surface modification layer) is formed on the surface of the pulverized polymer particles.
  • the surface crosslinking agent is applied to the surface of the superabsorbent polymer particles, so that the surface crosslinking reaction occurs on the surface of the superabsorbent polymer particles, which improves the crosslinkability on the surface of the particles without substantially affecting the inside of the particles. Therefore, the surface-crosslinked superabsorbent polymer particles have a higher degree of crosslinking near the surface than from the inside.
  • any surface crosslinking agent that has been used in the manufacture of super absorbent polymers can be used without any limitation. More specific examples thereof, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2-hexanediol, 1,3-hexanediol, 2-methyl- One or more polyols selected from the group consisting of 1,3-propanediol, 2,5-hexanediol, 2-methyl-1,3-pentanediol, 2-methyl-2,4-pentanediol, tripropylene glycol and glycerol ; At least one carbonate-based compound selected from the group consisting of ethylene carbonate and propylene carbonate; Epoxy compounds such as ethylene glycol diglycidyl ether; Oxazoline compounds such as oxazolidinone; Polyamine compounds; Oxazoline
  • the surface crosslinking agent may be used in an amount of about 0.01 to 5 parts by weight based on 100 parts by weight of the mixture obtained in step g).
  • the content range of the surface crosslinking agent By adjusting the content range of the surface crosslinking agent to the above-described range, it is possible to provide a super absorbent polymer exhibiting excellent water absorption properties.
  • the surface crosslinking agent may be dry mixed with the mixture obtained in step g) or may be added in the form of a surface crosslinking solution.
  • Water, methanol, ethanol, propylene glycol, and combinations thereof may be used as the solvent of the surface crosslinking solution, but are not limited thereto.
  • a polyvalent metal salt, an inorganic filler, a thickener, and the like may be further included as necessary.
  • These additives may be dry mixed with the mixture obtained in step g), or in the form added to the surface crosslinking solution.
  • the polyvalent metal salt may further include, for example, at least one selected from the group consisting of aluminum salts, more specifically aluminum sulfates, potassium salts, ammonium salts, sodium salts, and hydrochloride salts.
  • the liquid permeability of the superabsorbent polymer produced by the method of one embodiment can be further improved.
  • the polyvalent metal salt may be added to the surface crosslinking solution together with the surface crosslinking agent, and may be used in an amount of 0.01 to 4 parts by weight based on 100 parts by weight of the base resin.
  • the inorganic filler may include silica, aluminum oxide, or silicate.
  • the inorganic filler may be included in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the base resin powder.
  • Such an inorganic filler can act as a lubricant to improve the application efficiency of the surface crosslinking solution on the surface of the super absorbent polymer, and further improve the liquid permeability of the prepared super absorbent polymer.
  • a thickener may be further included.
  • a thickener may be further included.
  • one or more selected from polysaccharides and hydroxy-containing polymers may be used as the thickener.
  • the polysaccharide a gum-based thickener and a cellulose-based thickener may be used.
  • the gum-based thickener examples include xanthan gum, arabic gum, karaya gum, tragacanth gum, ghatti gum, guar gum (guar gum), locust bean gum (locust bean gum) and silylium seed gum, and the like
  • specific examples of the cellulose-based thickener include hydroxypropyl methyl cellulose, carboxymethyl cellulose, and methyl cellulose , Hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxyethylmethylcellulose, hydroxymethylpropylcellulose, hydroxyethylhydroxypropylcellulose, ethylhydroxyethylcellulose and methylhydroxypropylcellulose You can.
  • specific examples of the hydroxy-containing polymer include polyethylene glycol and polyvinyl alcohol.
  • the surface crosslinking reaction may be performed by heating the mixture of the pulverized hydrogel polymer, the surface crosslinking agent, and the fibers to raise the temperature.
  • the surface crosslinking step may be performed by heating at a temperature of 185°C or higher, preferably 185 to about 230°C, for about 10 to about 90 minutes, preferably about 20 to about 70 minutes. If the crosslinking reaction temperature is less than 185 °C or the reaction time is too short, there may be a problem that the surface crosslinking agent does not sufficiently react with the hydrogel polymer, and if it exceeds 230 °C or the reaction time is too long, the hydrogel polymer decomposes and physical properties Degradation problems may occur.
  • the heating means for the surface crosslinking reaction is not particularly limited.
  • the heating medium may be supplied or a heat source may be directly supplied to heat.
  • a heated fluid such as steam, hot air, and hot oil may be used, but the present invention is not limited to this, and the temperature of the heat medium supplied is the means of the heat medium, the rate of temperature increase, and the temperature increase. It can be appropriately selected in consideration of the target temperature.
  • the heat source directly supplied may include a heating method through electricity or a gas, but the present invention is not limited to the above-described example.
  • a surface modification layer may be formed on the surface of the polymer.
  • the superabsorbent polymer prepared according to the manufacturing method of the present invention exhibits an improved absorption rate as it includes at least one fiber among fluff pulp and synthetic polymer fibers.
  • the water-soluble ethylenically unsaturated monomer is a crosslinked polymer crosslinked in the presence of an internal crosslinking agent, and base resin particles comprising at least one fiber of fluff pulp and synthetic polymer fibers; And it is formed on the surface of the base resin particles, the cross-linking polymer is a super absorbent polymer comprising a surface cross-linking layer further cross-linked through a surface cross-linking agent, at least a portion of the fiber penetrates the interior of the base resin particles A superabsorbent polymer that is incorporated is provided.
  • the superabsorbent polymer of the present invention includes fibers having excellent hygroscopicity in the process of compacting a hydrogel polymer during base resin production, and fibers can be evenly distributed inside and outside the base resin on the particles. Accordingly, the superabsorbent polymer of the present invention has excellent basic absorption performance such as water retention capacity and pressure absorption capacity, and can exhibit improved absorption speed and liquid permeability.
  • the superabsorbent polymer has a water retention capacity (CRC) measured according to EDANA method WSP 241.3 of about 25 g/g or more, 28 g/g or more, or about 30 g/g or more, and about 45 g/g. Or less, 40 g/g or less, or about 35 g/g or less.
  • CRC water retention capacity
  • the superabsorbent polymer has a pressure absorption capacity (AUL) of 0.3 psi measured according to EDANA method WSP 242.3 of 25 g/g or more, or 27 g/g or more, and 40 g/g or less, or 30 g/g or less. Can be.
  • AUL pressure absorption capacity
  • the superabsorbent polymer is added to 2 g of superabsorbent polymer in 50 mL of physiological saline at 23°C to 24°C, and a magnetic bar (8 mm in diameter and 31.8 mm in length) is stirred at 600 rpm to obtain vortex.
  • the vortex time measured in seconds until disappearance, may be 50 seconds or less, or 45 seconds or less.
  • the lower the absorption rate, the better, and the lower limit is not limited, but may be, for example, 10 seconds or more, or 20 seconds or more.
  • superabsorbent polymer particles includes a fluff pulp and one or more fibers of synthetic polymer fibers, at least a portion of the fiber is provided with a superabsorbent polymer composition that penetrates through the interior of the superabsorbent polymer particles.
  • the superabsorbent polymer composition in the superabsorbent polymer composition, a part of the fibers are present outside the superabsorbent polymer particles, and some are present in a state embedded in the superabsorbent polymer particles. Accordingly, the superabsorbent polymer composition of the present invention can exhibit an improved absorption rate compared to a composition in which a superabsorbent polymer and hygroscopic fiber are simply mixed.
  • a photopolymerization reaction was performed on the monomer aqueous solution composition to obtain a polymerized sheet.
  • the polymerized sheet was taken out and cut to a size of 3 cm X 3 cm, and then chopping was performed using a meat chopper.
  • a meat chopper hole size 16 mm, speed 60 Hz
  • 5 parts by weight of distilled water with respect to 100 parts by weight of hydrogel polymer, and each fiber in Table 1 below It was added according to the content described in 1 (expressed as parts by weight compared to 100 parts by weight of the gel-like polymer), and again minced to a meat chopper (hole size 16 mm, speed 60 Hz).
  • 5 parts by weight of distilled water was sprayed onto the compacted hydrogel polymer, followed by compaction with a meat chopper (hole size 16 mm, speed 60 Hz) to prepare a crumb.
  • the crumb was dried in an oven capable of transferring air volume up and down.
  • the hot air at 185° C. was uniformly dried by flowing from bottom to top for 15 minutes and from top to bottom for 15 minutes, and after drying, the water content of the dried body was set to 2% or less. After drying, it was crushed with a grinder, and then divided into 10 minutes with Amplitude 1.5 mm (classification mesh combination: #20 / #30 / #50 / #100) and each classification (10% / 65% / 22% / 3 %) was collected to obtain a base resin powder having a particle diameter of about 150 ⁇ m to 850 ⁇ m.
  • a superabsorbent polymer was prepared in the same manner as in Example 1, except that fibers were not added in the process of compacting the hydrogel polymer.
  • Example 1 To 100 parts by weight of the superabsorbent polymer of Comparative Example 1, 5 parts by weight of fluff pulp used in Example 1 was added and mixed to prepare a superabsorbent polymer composite in which a superabsorbent polymer and fluff pulp were simply mixed.
  • the pressure absorption capacity of 0.3 psi of each resin was measured according to EDANA method WSP 242.3. In the measurement of the pressure absorption capacity, the resin classifier for the CRC measurement was used.
  • a 400 mesh wire mesh made of stainless steel was mounted on a cylindrical bottom of a plastic having an inner diameter of 25 mm.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside the petri dish of 150 mm in diameter, and the physiological saline composed of 0.9 wt% sodium chloride was brought to the same level as the top surface of the glass filter.
  • a sheet of filter paper having a diameter of 90 mm was placed thereon. The measuring device was mounted on a filter paper, and the liquid was absorbed for 1 hour under a load. After 1 hour, the measuring device was lifted, and the weight W5 (g) was measured.
  • the absorption rate of each resin was measured in seconds according to the method described in International Patent Publication No. 1987-003208.
  • the absorption rate is 2 g of superabsorbent resin in 50 mL of physiological saline at 23°C to 24°C, and the magnetic bar (8 mm in diameter and 31.8 mm in length) is stirred at 600 rpm to vortex. It was calculated by measuring the time until (vortex) disappears in seconds.
  • the average length of the fiber is the average value of the length derived by randomly selecting 100 fibers.
  • the superabsorbent polymer prepared according to the present invention is superior in basic physical properties such as CRC and AUL, but the pulp fiber is simple in Comparative Example 1 that does not contain fibers and the superabsorbent resin previously prepared as described above. It can be seen that it shows a significantly improved absorption rate compared to the mixed comparative example 2.

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Abstract

L'invention concerne un procédé de préparation d'un polymère superabsorbant. Plus particulièrement, l'invention concerne un procédé de préparation d'un polymère superabsorbant capable de préparer un polymère superabsorbant qui présente un taux d'absorption amélioré tout en conservant d'excellentes propriétés d'absorption fondamentale telles qu'une capacité de rétention centrifuge.
PCT/KR2019/015056 2018-12-11 2019-11-07 Polymère superabsorbant et son procédé de préparation Ceased WO2020122426A1 (fr)

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JP2020539707A JP7034535B2 (ja) 2018-12-11 2019-11-07 高吸水性樹脂およびその製造方法
EP19896615.2A EP3722353B1 (fr) 2018-12-11 2019-11-07 Polymère superabsorbant et son procédé de préparation
CN201980010268.4A CN111655764A (zh) 2018-12-11 2019-11-07 超吸收性聚合物及其制备方法
US16/968,771 US11559784B2 (en) 2018-12-11 2019-11-07 Superabsorbent polymer and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN111748057A (zh) * 2020-07-09 2020-10-09 重庆工商大学 一种通过复合引发体系合成阿拉伯树胶高聚物的方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111748057A (zh) * 2020-07-09 2020-10-09 重庆工商大学 一种通过复合引发体系合成阿拉伯树胶高聚物的方法

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