WO2017155173A1 - Procédé de préparation d'une résine hautement absorbante, et résine hautement absorbante - Google Patents

Procédé de préparation d'une résine hautement absorbante, et résine hautement absorbante Download PDF

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WO2017155173A1
WO2017155173A1 PCT/KR2016/010375 KR2016010375W WO2017155173A1 WO 2017155173 A1 WO2017155173 A1 WO 2017155173A1 KR 2016010375 W KR2016010375 W KR 2016010375W WO 2017155173 A1 WO2017155173 A1 WO 2017155173A1
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fine powder
polymer
weight
super absorbent
aqueous solution
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PCT/KR2016/010375
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English (en)
Korean (ko)
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임종두
김영삼
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주식회사 엘지화학
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Priority claimed from KR1020160101900A external-priority patent/KR101853401B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP16893687.0A priority Critical patent/EP3333198B1/fr
Priority to US15/765,092 priority patent/US10920023B2/en
Priority to CN201680057846.6A priority patent/CN108137725B/zh
Publication of WO2017155173A1 publication Critical patent/WO2017155173A1/fr
Priority to US17/126,816 priority patent/US11492451B2/en

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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
    • C08J3/02—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
    • 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

Definitions

  • the present invention relates to a super absorbent polymer and a method for preparing the same. More specifically, the present invention relates to a superabsorbent polymer and a method for preparing the finely divided powder assembly having improved granular strength and exhibiting excellent absorption properties.
  • Super Absorbent Polymer is from 500 to 500
  • the absorption mechanism of the superabsorbent polymer is an interaction between the penetration pressure due to the difference in electrical attraction force of the charge of the polymer electrolyte, the affinity between water and the polymer electrolyte, the expansion of the molecule due to the repulsive force between the polymer electrolyte ions, and the expansion inhibition due to crosslinking. Is ruled by That is, the absorbency of the absorbent polymer depends on the affinity and molecular expansion described above, and the rate of absorption depends largely on the penetration pressure of the absorbent polymer itself.
  • Korean Patent Publication No. 2014-0063457 discloses a step of preparing a fine powder reassembly using only fine powder and base resin without additives.
  • a method of preparing a superabsorbent polymer including the polymer is disclosed, there is a problem in that the physical properties of the finely divided reassembly are lower than that of the base resin and the process is complicated and the efficiency is lowered.
  • the fine powder that is inevitably generated in the manufacturing process of the super absorbent polymer has a method of adding a fine powder during the polymerization in order to solve this as a factor of lowering the physical properties of the product, but this method induces non-uniform polymerization or by scattering light There is a problem that interferes with the physical properties. Therefore, a method of reassembling fine powder using a separate reassembler has been developed. This method is a method of mixing fine powder and water at a predetermined ratio to make large particles.
  • the problem with this technique is that due to the small particle size of the fine powder, the absorption rate is increased and the water is unevenly mixed, resulting in non-uniformity of the entire reassembly, thereby producing a non-uniform size and strength reassembly, while incomplete drying of hard particles. Due to the damage to the device during the crushing and the weakly reassembled particles had a problem of reducing the performance of the reassembly because it is easily crushed and returned to the fine powder.
  • the present invention is to solve the problems of the prior art as described above, the superabsorbent polymer comprising a fine powder reassembly having excellent assembly strength but does not cause a drop in physical properties such as water retention capacity (CRC) or pressure absorption capacity (AUP) And to provide a method for producing the same.
  • CRC water retention capacity
  • AUP pressure absorption capacity
  • It provides a method for producing a super absorbent polymer comprising the step of mixing the fine powder aqueous solution and the coarsely pulverized hydrogel polymer to prepare a fine powder reassembly.
  • Superabsorbent polymer comprising surface-crosslinked finely divided powder reassembled by mixing sodium hydroxide with respect to fine powder having an acidic group and polymerizing a water-soluble ethylenically unsaturated monomer in which at least part of the acidic group is neutralized and having a particle size of less than 150.
  • the water holding capacity (CRC) measured according to the EDANA method WSP 241.3 is 33.0 to 39.0 g / g;
  • AUP Absorption Capacity
  • a superabsorbent polymer having a water absorption rate of 100 seconds or less by Vortex is provided.
  • the fine powder content is regrinded by using an additive during fine powder reassembly to improve the assembly strength. Can be reduced.
  • the reassembly process is carried out by mixing fine powder in the hydrous gel phase polymer, so the process step is relatively simple, so the efficiency is high, and the absorption rate is High reassembly can be obtained.
  • Method for producing a super absorbent polymer the step of thermally polymerizing or photopolymerizing a monomer composition comprising a water-soluble ethylenically unsaturated monomer and a polymerization initiator to obtain a hydrogel polymer; Coarsely pulverizing the hydrogel polymer; Drying and grinding the coarsely pulverized hydrogel polymer to classify it into fine powder having a particle size of less than 150 and normal particles having a particle size of 150 to 850; Preparing a fine powder aqueous solution by mixing the fine powder, water, and additives; And mixing the finely divided aqueous solution with the coarsely pulverized hydrogel polymer to produce a finely divided reassembly.
  • polymer or “polymer” means that the water-soluble ethylenically unsaturated monomer is in a polymerized state and may cover all water content ranges, all particle size ranges, all surface crosslinking states, or processing states. Number have.
  • the water content (moisture content) of about 40 parts by weight 0 / I to the drying condition after the polymerization. May refer to one polymer functions as a gel-like polymer.
  • the polymer whose particle diameter is less than 150 can be called "fine powder".
  • Superabsorbent polymer also means, according to the context, the polymer itself »or in a state suitable for commercialization by further processing such as surface crosslinking, fine powder reassembly, drying, grinding, classification, etc., for the polymer. It is used to encompass everything.
  • a hydrogel or photopolymerization is performed on a monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator to form a hydrogel polymer.
  • the monomer composition which is a raw material of the super absorbent polymer includes a water-soluble ethylenically unsaturated monomer and a polymerization initiator.
  • the water-soluble ethylene-based unsaturated monomer can be used without any limitation any monomers commonly used in the production of superabsorbent polymer. 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 quaternized compounds thereof can be used.
  • acrylic acid may be neutralized with a basic compound such as caustic soda (NaOH).
  • the concentration of the water-soluble ethylenically unsaturated monomers, said high from about 20 to about 60 weight 0/0, preferably for a monomer composition containing a source material and a solvent of the water-absorbent resin is about 40 to about 50 weight 0/0 It may be made to an appropriate concentration in consideration of the polymerization time and reaction conditions. However, when 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, when the concentration is too high, some of the monomer may be precipitated or the grinding efficiency of the polymerized hydrogel polymer may be low. Etc. may cause problems in the process and may decrease the physical properties of the super absorbent polymer.
  • the polymerization initiator used in the polymerization in the method for producing a super absorbent polymer of the present invention is not particularly limited as long as it is generally used for producing the super absorbent polymer.
  • the polymerization initiator may use a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • a thermal polymerization initiator since a certain amount of heat is generated by irradiation such as ultraviolet irradiation, 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 may be used.
  • acylphosphine commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used. .
  • photoinitiators see Rein old Schwalm, "UV Coatings: Basics, Recent Developments and New.” Application (Elsevier 2007) "pi 15, and is not limited to the above example.
  • the photopolymerization initiator may be included in a concentration of about 0.01 to about 1.0 wt% based on the monomer composition. If the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow. If the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven.
  • the thermal polymerization initiator may be used at least one selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide and ascorbic acid.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 O s ), potassium persulfate (K 2 S 2 0 8 ), and ammonium persulfate (NH 4 ).
  • examples of the azo (Azo) initiator include 2, 2-azobis- (2-amidinopropane) dihydrochloride (2, 2- azobis (2-amidinopropane) dihydrochloride), 2 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride
  • the thermal polymerization initiator may be included in a concentration of about 0.001 to about 0.5% by weight based on the monomer composition.
  • 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 monomer composition may further include an internal crosslinking agent as a raw material of the super absorbent polymer.
  • the crosslinking agent include at least one functional group capable of reacting with the water-soluble substituent of the water-soluble ethylenically unsaturated monomer and having at least one ethylenically unsaturated group; Or the crosslinking agent which has 2 or more functional groups which can react with the water-soluble substituent of the said monomer, and / or the water-soluble substituent formed by hydrolysis of the monomer can be used.
  • the internal crosslinking agent examples include bisacrylamide having 8 to 12 carbon atoms, bismethacrylamide, poly (meth) acrylates having 2 to 10 carbon atoms, or poly (meth) allyl ether having a polyol having 2 to 10 carbon atoms. These etc.
  • acrylate, glycerin triacrylate, trimethol triacrylate, triallylamine, triarylcyanurate, triallyl isocyanate, polyethylene glycol, diethylene glycol and propylene glycol can be used.
  • Such an internal crosslinking agent may be included at a concentration of about 0.01 to about 0.5 weight 0 / ° based on the monomer composition to crosslink the polymerized polymer.
  • the monomer composition of the super absorbent polymer may further include additives such as thickeners, plasticizers, storage 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-described components, for example, water, ethanol ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol propylene glycol Ethylene glycol monobutyl ether propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate methyl ethyl ketone, acetone, methyl amyl ketone, cyclonucleanone, cyclopentanone diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene , Xylene Butyllactone, carby, methyl cellosolve acetate, and one or more selected from ⁇ , ⁇ -dimethylacetamide and the like can be used in combination.
  • 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 polymerization energy source, 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 be carried out in a semi-unggi equipped 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 thermal polymerization by supplying hot air or by heating the reaction machine may have a half-stirrer such as a kneader having a stirring shaft.
  • the hydrogel polymer discharged to the mandrel outlet may be in the form of several centimeters to several millimeters.
  • the size of the water-containing gel polymer obtained may vary depending on the concentration and the injection speed of the monomer composition to be injected, the water-containing gel polymer having a weight average particle diameter of 2 to 50 mm can be obtained.
  • the form of the hydrogel polymer generally obtained may be a hydrogel gel polymer on a sheet having a width of the belt.
  • the thickness of the polymer sheet depends on the concentration and the injection speed of the monomer composition to be injected, but it is usually preferable to supply the monomer composition so that a polymer on the sheet having a thickness of about 0.5 to about 5 cm can be obtained.
  • the normal water content of the hydrogel polymer obtained by the above method is about 40 to about 80 weight percent.
  • water content throughout the present specification is the amount of water to account for the total weight of the hydrous gel phase polymer dried at the weight of the hydrogel polymer. It means the value obtained by subtracting the weight of the polymer in the 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 drying the temperature of the polymer through infrared heating. At this time, the drying conditions are raised to a temperature of about 180 ° C at room temperature and then maintained at 180 ° C. The total drying time is set to 20 minutes, including 5 minutes of temperature rise step, the moisture content is measured.
  • the hydrogel polymer is coarsely ground.
  • 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 about 2 to about 20mm.
  • Coarse pulverization of less than 2 mm in particle size is not technically easy due to the high water content of the hydrogel polymer, and may also cause agglomeration of pulverized particles with each other.
  • coarsely pulverizing more than 20mm the effect of increasing the efficiency of the subsequent drying step may be insignificant.
  • the drying temperature of the drying step may be about 150 to about 250 ° C. If the drying temperature is less than 150 ° C., the drying time is too long and there is a risk that the physical properties of the superabsorbent polymer to be formed is lowered, if the drying temperature exceeds 250 ° C, only the polymer surface is dried too much, Fine powder may occur in the grinding process, and there is a fear that the physical properties of the superabsorbent polymer to be finally formed decrease.
  • the drying is at a temperature of about 150 to about 200 ° C., Preferably at a temperature of about 160 to about 180 ° C.
  • drying time in consideration of the process efficiency, etc., it may proceed for about 20 to about 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% by weight.
  • the polymer powder obtained after the grinding step may have a particle diameter of about 150 to about 850! M. Mills used to grind to such particle diameters are specifically pin mills, hammer mills, screw mills, mills, disc mills or jogs. Although a jog mill or the like may be used, the present invention is not limited to the above-described example.
  • the polymer powder obtained after grinding is generally classified according to the particle size.
  • the particles are classified into particles having a particle size of less than about 150, particles of about 150 to about 850, and particles having a particle size of more than 850 mm 3.
  • finely divided particles having a particle size of less than a certain particle size, that is, less than about 150 / m are referred to as superabsorbent polymer fine powder, SAP fine powder or fine powder (fines, fine powder), having a particle diameter of about 150 to about 850 Particles that are / m are called normal particles.
  • the fine powder may be generated during a polymerization process, a drying process, or a pulverization step of a dried polymer.
  • the fine powder is difficult to handle and exhibits a gel blocking phenomenon. It is desirable to exclude them from inclusion or to reuse them to be normal particles.
  • the fine powder may be subjected to a reassembly process in which the fine particles are formed to have a normal particle size.
  • a reassembly process is performed in which the fine particles are coarse in a wet state in order to increase the coarse strength.
  • the reassembly process may cause too large reassembly lumps, which may cause problems during the operation of the process. It is often broken into fine powder again.
  • the fine powder reassembly thus obtained has lower physical properties such as water-retaining capacity (CRC) and pressure-absorbing capacity (AUP) than normal particles, resulting in deterioration of the quality of the super absorbent polymer.
  • CRC water-retaining capacity
  • AUP pressure-absorbing capacity
  • a fine powder reassembly is prepared by mixing a finely divided hydrogel polymer having a particle size of less than 150 to prepare a fine powder reassembly.
  • the fine powder, water, and additives are mixed to prepare a fine powder aqueous solution, and thus the fine powder aqueous solution and the coarsely pulverized hydrogel polymer are mixed to prepare a fine powder reassembly.
  • the additives included in the fine powder solution include sodium hydroxide, a crosslinking agent, and a thermal polymerization initiator.
  • the sodium hydroxide (NaOH) may be included as about 1 to about 10 parts by weight 0/0, preferably about 2 to about 8 parts by weight 0/0, preferably about 2 to about 6% by weight relative to the differential solution and the differential member assembly May contribute to the improvement of water retention (CRC).
  • the crosslinking agent forms a crosslinked structure between the fine particles and serves to improve granulation strength.
  • Crosslinking agents that can be used include polyethylene glycol diacrylate (PEGDA), nucleic acid-1,6-di diacrylate (hexane-l, 6-diol diacrylate, HDD A), and ethoxylated trimethyl propane.
  • PEGDA polyethylene glycol diacrylate
  • nucleic acid-1,6-di diacrylate hexane-l, 6-diol diacrylate, HDD A
  • ethoxylated trimethyl propane ethoxylated trimethyl propane.
  • Acrylate ethoxylated trimethylolpropane triacrylate, ETTA
  • EC ethylene carbonate
  • the crosslinking agent may be included in an amount of about 1 to about 0.5 parts by weight, preferably about 0.2 to about 0.4 parts by weight, based on 100 parts by weight of the fine powder. When the crosslinking agent is included in the above weight part range, it may exhibit high assembly strength and physical properties.
  • the thermal polymerization initiator is assembled by inducing further polymerization of the fine powder It serves to improve strength.
  • thermal polymerization initiators that can be used include sodium persulfate, potassium persulfate, and the like, and preferably sodium persulfate.
  • the thermal polymerization initiator may include about 0.1 to about 0.5 parts by weight, preferably about 0.1 to about 0.3 parts by weight, based on 100 parts by weight of the fine powder. When the thermal polymerization initiator is included in the above weight part range, high assembly strength and physical properties may be exhibited.
  • the fine powder aqueous solution includes water so that the fine powder can be reassembled in a wet state, wherein the amount of water included is about 100 to about 300 parts by weight, preferably about 100 to about 200 parts by weight based on 100 parts by weight of the fine powder. Can be added.
  • the fine powder aqueous solution may further include porous particles.
  • the porous particles may be silica particles having a BET specific surface area of about 300 to about 1500 m 2 / g and a porosity of about 50% or more, for example, about 50 to about 98%. have.
  • the porous particles may have a superhydrophobicity with a contact angle with respect to water of 125 ° or more, preferably 140 ° or more, more preferably 145 ° or more.
  • the fine powder aqueous solution may further include a porous particle as described above, thereby further performing fine powder reassembly, thereby further improving permeability and pore strength of the fine powder reassembled product.
  • the porous particles may include about 0.01 to about 0.4 parts by weight, preferably about 0.05 to about 2 parts by weight, based on 100 parts by weight of the fine powder. When the porous particles are included in the weight part range, it may exhibit high assembly strength and improved permeability.
  • the above-mentioned additives and optionally porous particles are added to the fine powder to prepare a fine powder aqueous solution.
  • the heated additive can be manufactured by mixing fine powder with aqueous solution. By mixing the fine powder in the heated additive aqueous solution as described above it can exhibit a more improved foam strength.
  • a fine powder reassembly is prepared by mixing the prepared fine powder aqueous solution and the coarsely pulverized hydrogel polymer.
  • the coarsely pulverized hydrogel polymer means that the hydrous gel polymer obtained by thermal polymerization or photopolymerization of the monomer composition described above is first ground in a form of lumps having a large particle size before drying.
  • the particle size of the milled crude function polymer gel is from about 2 to may be about 20mm, before drying because the water content is from about 40 to about 80 weight 0/0 of the hydrogel state.
  • a finely divided aqueous solution is mixed with the coarsely pulverized hydrogel polymer to form a fine powder reassembly, and thus the finely divided reassembly is maintained at a similar level with the high physical strength of the original hydrogel polymer.
  • High quality fine powder reassembly can be obtained.
  • the coarsely pulverized hydrogel polymer may be mixed in an amount of about 50 to about 500 parts by weight, preferably about 50 to about 300 parts by weight, based on 100 parts by weight of fine powder contained in the fine powder solution. have.
  • the coarsely pulverized hydrogel polymer may exhibit high assembly strength and improved physical properties.
  • the method for adding the finely divided aqueous solution to the coarsely pulverized hydrogel polymer is not limited in its configuration.
  • the finely divided aqueous solution and the coarsely pulverized hydrous gel polymer are mixed in a semi-aperture, or the finely divided aqueous solution and the coarsely pulverized hydrous gel polymer are mixed in a semi-permanent mixture such as a mixer.
  • the method of supplying continuously and mixing etc. can be used.
  • the obtained fine powder reassembly may further comprise the step of drying, grinding and classifying.
  • Drying the fine powder reassembly may be performed for 20 to 90 minutes at a temperature of 150 to 250 ° C.
  • a temperature raising means for drying in the above there is no limitation in the structure.
  • supply the heat medium or electricity Although it can heat directly by means, etc., this invention is not limited to the above-mentioned example.
  • Specific heat sources that may be used include steam, electricity, ultraviolet rays, infrared rays, and the like, and a heated thermal fluid may be used.
  • the dried fine powder reassembly may be ground to have a particle size of about 150 to about 850.
  • Mills used to grind to such particle diameters are specifically pin mills, hammer mills, screw mills, mills, disc mills or jogs. Although a jog mill or the like may be used, the present invention is not limited to the above-described example.
  • the fine powder reassembly obtained according to the production method of the present invention has a high foaming strength with a low ratio of re-crushing into fine powder after the reassembly and drying and grinding step as described above.
  • the reassembled polymer obtained according to the preparation method of the present invention has a weight ratio of fine powder having a particle size of 150 m or less after grinding, for example, less than about 15% by weight of the total fine powder reassembly, preferably about 10 Less than%, more preferably less than about 7%.
  • the finely divided reassembly obtained after grinding may be classified into particles having a particle size of less than about 150, particles of about 150 to about 850 ⁇ , and particles having a particle size of more than 850 depending on the particle size.
  • the classified fine powder reassembly may be performed alone or in combination with other normal particles to perform a surface crosslinking process.
  • Surface crosslinking is the step of increasing the crosslink density near the surface of the superabsorbent polymer particles with respect to the crosslink density inside the particles.
  • the surface crosslinking agent is applied to the surface of the super absorbent polymer particles.
  • this reaction occurs on the surface of the superabsorbent resin particles, which improves the crosslinkability on the surface of the particles without substantially affecting the interior of the particles.
  • the surface crosslinked superabsorbent resin particles thus have a higher degree of crosslinking in the vicinity of the surface than in the interior.
  • the surface crosslinking agent is not limited as long as it is a compound capable of reacting with the functional group of the polymer.
  • Polyhydric alcohol compounds as the surface crosslinking agent; Epoxy compounds; Polyamine compounds; Haloepoxy compound; Condensation products of haloepoxy compounds; Oxazoline compounds; Mono-, di- or polyoxazolidinone compounds; Cyclic urea compounds; Polyvalent metal salts; And it may be used one or more selected from the group consisting of alkylene carbonate compounds.
  • examples of the polyhydric alcohol compound include mono-, di-, tri-, tetra- or polyethylene glycol, monopropylene glycol, 1,3-propanediol, dipropylene glycol, 2,3,4-trimethyl-1,3 -Pentanediol, polypropylene glycol, glycerol, polyglycerol, 2-butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6- nucleic acid diol And 1, 1 or more selected from the group consisting of 1,2-cyclonucleodimethane can be used.
  • ethylene glycol diglycidyl ether and glycidol may be used as the epoxy compound, and as polyamine compounds, ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylenepentamine, pentaethylene nucleoamine , At least one selected from the group consisting of polyethyleneimine and polyamide polyamine can be used.
  • epichlorohydrin epichlorohydrin, epibromohydrin and ⁇ -methyl epichlorohydrin can be used.
  • a mono-, di-, or a polyoxazolidinone compound 2-oxazolidinone etc. can be used, for example.
  • alkylene carbonate compound ethylene carbonate etc. can be used. These may be used alone or in combination with each other.
  • the amount of the surface crosslinking agent to be added may be appropriately selected depending on the kind of the surface crosslinking agent to be added or the reaction conditions, but it is usually from about ⁇ to about 5 parts by weight, preferably about 0.01 to about 1 part by weight of the polymer loo. 3 parts by weight, more preferably from about 0.05 to about 2 parts by weight can be used have.
  • the content of the surface crosslinking agent is too small, the surface crosslinking reaction hardly occurs, and when 100 parts by weight of the polymer is more than 5 parts by weight, the excessive absorption of the surface crosslinking reaction may result in deterioration of absorbing ability and physical properties. .
  • the surface crosslinking reaction and drying can occur simultaneously by heating the polymer particles to which the surface crosslinking agent is added.
  • 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 heated fluid such as steam, hot air, and hot oil may be used, but the present invention is not limited thereto, and the temperature of the heat medium to be supplied is a means of heating medium, a temperature increase rate, and a temperature increase. It may be appropriately selected in consideration of the target temperature.
  • the heat source directly supplied may be a heating method through electricity, a heating method through a gas, but the present invention is not limited to the above examples.
  • the superabsorbent polymer prepared by the above-described method is prepared by mixing sodium hydroxide with respect to fine powder having a particle size of less than 150 in a polymer including an acidic group and polymerizing a water-soluble ethylenically unsaturated monomer in which at least a part of the acidic group is neutralized.
  • a superabsorbent polymer having surface-crosslinked finely divided reassembly, the water-retaining capacity (CRC) measured according to EDANA method WSP 241.3 is 33.0 to 39.0 g / g; EDANA Law WSP
  • the polymer comprises an acidic group and polymerized a water-soluble ethylene-based unsaturated monomer in which at least a portion of the acidic group is neutralized. The same as exemplarily described in the method for preparing a gel polymer.
  • the fine powder refers to particles having a particle diameter of less than 150 / zm in the polymer, regardless of the step or surface crosslinking occurs the fine powder, all of the superabsorbent resin
  • the process for example, a polymerization process, a drying process, the pulverization process of the dried polymer, the surface crosslinking process, etc. can include all.
  • the fine powder reassembly may be reassembled by mixing sodium hydroxide with respect to fine powder, or may be reassembled by adding more crosslinking agent, thermal polymerization initiation, or porous particles in addition to sodium hydroxide. More detailed description of the crosslinking agent, thermal polymerization initiation, or porous particles is as described above in the method for preparing a super absorbent polymer.
  • the sodium hydroxide may be included in an amount of about 0.1 to about 20 parts by weight, or about 1 to about 15 parts by weight, or about 1 to 10 parts by weight, based on 100 parts by weight of the fine powder. When the sodium hydroxide is included in the weight range, it may contribute to high assembly strength, improved permeability and water retention.
  • the fine powder may be reassembled by mixing the coarsely pulverized hydrogel polymer. More detailed description of the mixing with the coarsely pulverized hydrogel polymer is as described above in the preparation method of the super absorbent polymer.
  • the superabsorbent polymer surface-crosslinked with the reassembled finely divided granules has a water retention (CRC) of about 33.0 to about 39.0 g / g, or about 34.0 to about 38.0 g / g, measured according to EDANA WSP 241.3. Can be.
  • the 0.7 psi pressurized absorbent capacity (AUP) measured according to the EDANA method WSP 241.3 may be from about 20.0 to about 25.0 g / g, or from about 21.0 to about 25.0 g / g.
  • the superabsorbent polymer may have an absorption rate of about 100 seconds or less, or about 95 seconds or less based on a vortex method.
  • a vortex method 50 ml saline was added to a 100 ml beaker with a magnetic stir bar, the stirring speed of the magnetic stir bar was set at 600 rpm using a stirrer, and 2.0 g of superabsorbent polymer was added to the stirred saline.
  • the lower limit of the absorption rate is not particularly limited but may be about 20 seconds or more, or about 30 seconds or more.
  • the monomer mixture was placed on a continuously moving conveyor belt, and irradiated with ultraviolet light (irradiation amount: 2 mW / cm 2 ) to undergo UV polymerization for 2 minutes to obtain a hydrous gel polymer.
  • ultraviolet light irradiation amount: 2 mW / cm 2
  • the hydrogel polymer was pulverized with a meat chopper (hole size 8 mm) to obtain a coarsely pulverized hydrogel polymer. It was dried for 2 hours in a hot air dryer at 170 ° C, crushed by a pin mill grinder and classified into a standard mesh of ASTM standard.
  • An additive aqueous solution comprising 1,500 ppm of sodium persulfate (SPS), 3,000 ppm of polyethylene glycol diacrylate (PEGDA), 1,000 ppm of silica aerogel (Silica Aerogel, AeroZelTM, JIOS) and 3% by weight of sodium hydroxide was prepared.
  • the additive aqueous solution was heated to 8 (rc.
  • a super absorbent polymer was prepared in the same manner as in Example 1, except that 250 g of fine powder and 750 g of a coarsely pulverized hydrogel polymer were used. Comparative Example 1
  • Surface crosslinking comprising 100 g of particles having a classified particle diameter of 150 ⁇ or more and less than 850 // m, containing 0.2 g of poly (ethylene glycol) diglycidyl ether, 3 g of methane, 5 g of water, and silica aerogel (AeroZelTM, JIOS) O.Olg After mixing with the solution, a surface crosslinking reaction was performed for 50 minutes at a temperature of 180 ° C to obtain a final superabsorbent polymer.
  • the absorbency under pressure was measured for each of the superabsorbent polymers prepared in Examples 1 to 2 and Comparative Example 1.
  • the measurement of the absorbency under pressure was based on the EDANA method WSP 241.3. 0.9 g of the particle size 300 to 600 / ⁇ sample of the prepared superabsorbent polymer was put in a cylinder defined by EDANA, and a pressure of 0.7 psi was applied to the piston and weight. After that, the amount of 0.9% saline solution absorbed for 60 minutes was measured.

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Abstract

La présente invention concerne une résine hautement absorbante et son procédé de production. Plus particulièrement, la présente invention concerne un procédé de préparation d'une résine hautement absorbante capable de produire des particules fines réassemblées qui conservent d'excellentes propriétés physiques.
PCT/KR2016/010375 2016-03-11 2016-09-13 Procédé de préparation d'une résine hautement absorbante, et résine hautement absorbante WO2017155173A1 (fr)

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EP16893687.0A EP3333198B1 (fr) 2016-03-11 2016-09-13 Procédé de préparation d'une résine hautement absorbante
US15/765,092 US10920023B2 (en) 2016-03-11 2016-09-13 Manufacturing method of super absorbent polymer and super absorbent polymer
CN201680057846.6A CN108137725B (zh) 2016-03-11 2016-09-13 超吸收性聚合物的制造方法和超吸收性聚合物
US17/126,816 US11492451B2 (en) 2016-03-11 2020-12-18 Manufacturing method of super absorbent polymer and super absorbent polymer

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KR10-2016-0029840 2016-03-11
KR20160029840 2016-03-11
KR1020160101900A KR101853401B1 (ko) 2016-03-11 2016-08-10 고흡수성 수지의 제조 방법, 및 고흡수성 수지
KR10-2016-0101900 2016-08-10

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JP2013034942A (ja) * 2011-08-08 2013-02-21 Nippon Shokubai Co Ltd 粒子状吸水剤の製造方法
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CN112839993A (zh) * 2019-09-18 2021-05-25 株式会社Lg化学 用于制备超吸收性聚合物的方法
CN112839993B (zh) * 2019-09-18 2023-04-11 株式会社Lg化学 用于制备超吸收性聚合物的方法

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