WO2016085152A1 - Procédé de préparation de résine superabsorbante et résine superbsorbante ainsi préparée - Google Patents

Procédé de préparation de résine superabsorbante et résine superbsorbante ainsi préparée Download PDF

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WO2016085152A1
WO2016085152A1 PCT/KR2015/012000 KR2015012000W WO2016085152A1 WO 2016085152 A1 WO2016085152 A1 WO 2016085152A1 KR 2015012000 W KR2015012000 W KR 2015012000W WO 2016085152 A1 WO2016085152 A1 WO 2016085152A1
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polymer
weight
super absorbent
glycol
absorbent polymer
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PCT/KR2015/012000
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English (en)
Korean (ko)
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이용훈
안태빈
한장선
서성종
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주식회사 엘지화학
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Priority claimed from KR1020150155892A external-priority patent/KR101745679B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/302,845 priority Critical patent/US9976003B2/en
Priority to EP15863575.5A priority patent/EP3112383A4/fr
Priority to CN201580021684.6A priority patent/CN106459236B/zh
Publication of WO2016085152A1 publication Critical patent/WO2016085152A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to a method for producing a super absorbent polymer having excellent absorption characteristics such as water holding capacity and pressure absorbing capacity, but having a fast absorption rate and high permeability.
  • a super absorbent polymer is a synthetic polymer material that can absorb about 500 to 1,000 times its own weight. It is a super absorbent mater (AL) and an absorbent gel mater (ALM). It's also called. Super absorbent resins have been put into practical use as sanitary devices, and are now widely used in sanitary products such as paper diapers for children, horticultural soil repair agents, civil engineering materials, seedling sheets, and fresheners in food distribution. It is used.
  • As a method for producing such a super absorbent polymer a method by reverse phase suspension polymerization or a solution polymerization is known. Among them, the production of superabsorbent polymers through reverse phase suspension polymerization is disclosed, for example, in Japanese Patent Laid-Open Nos.
  • the production of superabsorbent polymers through polymerization of aqueous solution is a thermal polymerization method for polymerizing a hydrogel polymer in a kneader equipped with several shafts while breaking and angled, and polymerizing and drying by irradiating UV light to a high concentration of aqueous solution on a belt.
  • the photopolymerization method etc. which perform simultaneously are known.
  • the rate of absorption one of the important properties of superabsorbent polymers, is related to the surface dryness of products that touch the skin, such as diapers. In general, this absorption rate can be improved by increasing the surface area of the superabsorbent polymer.
  • a method of forming a porous structure on the particle surface of the super absorbent polymer by using a blowing agent has been applied.
  • the general foaming agent cannot form a sufficient amount of porous structure, so that the increase in absorption rate is not large.
  • the absorption rate of the superabsorbent polymer can be improved through this method, there is a limit that the water retention capacity (CRC) and the pressure absorption capacity (AUP) of the resin are relatively lowered.
  • CRC water retention capacity
  • AUP pressure absorption capacity
  • the present invention is to provide a method for producing a super absorbent polymer having a fast absorption rate and high transmittance.
  • the present invention provides a method for producing a super absorbent polymer comprising the following steps:
  • Water-containing gel polymer by thermally polymerizing or photopolymerizing a monomer composition comprising a water-soluble ethylenically unsaturated monomer, a polymerization initiator, and a polycarboxylic acid copolymer having a repeating unit represented by the following Formulas 1-a and 1-b. Forming a step ,
  • R 1 , R 2 and R 3 are each independently hydrogen or an alkyl group having 1 to 6 carbon atoms
  • R 0 is an oxyalkylene group having 2 to 4 carbon atoms
  • M 1 is hydrogen or a monovalent metal or nonmetal ion
  • X is -C00-, an alkyloxy group having 1 to 5 carbon atoms or an alkyldioxy group having 1 to 5 carbon atoms
  • n 1 to 100
  • n is an integer from 1 to 1000
  • p is an integer of 1 to 150, and when p is 2 or more, -R repeated two or more times may be the same or different from each other.
  • Superabsorbent polymers are evaluated for their water-retaining capacity (CRC), pressure-absorbing capacity (AUP), and permeability (SFC) as important physical properties. Especially, articles using superabsorbent polymers, such as diapers, are becoming thinner. It is important to have a high transmittance.
  • CRC water-retaining capacity
  • AUP pressure-absorbing capacity
  • SFC permeability
  • articles using superabsorbent polymers, such as diapers are becoming thinner. It is important to have a high transmittance.
  • the polycarboxylic acid-based copolymer is used to polymerize the hydrous gel phase polymer, and the polycarboxylic acid-based copolymer reduces the internal crosslinking reaction rate during the polymerization, so that the water-containing gel polymer having a uniform network structure and low water-soluble component is used.
  • Manufacture it is possible to obtain a powder having a uniform surface and a wide surface area when grinding the hydrogel.
  • step 1 Formation of hydrogel polymer (step 1)
  • the method of preparing the super absorbent polymer includes thermally polymerizing or photopolymerizing a monomer composition including a water-soluble ethylenically unsaturated monomer, a polymerization initiator, and a polycarboxylic acid-based copolymer to form a hydrogel polymer.
  • the polycarboxylic acid-based copolymer defined above is used together.
  • the polycarboxylic acid copolymer is alkoxy Polyalkylene glycol mono (meth) acrylic acid ester monomers (typically, mesospecific polyethylene glycol monomethacrylate (MPEGMM, etc.)) and
  • the use of random copolymers derived from hydrophilic monomers such as (meth) crylic acid ester monomers (typically, (meth) acrylic acid, etc.) may be more advantageous for the expression of the effects described above. And, in order that the effect of adding the polycarboxylic acid-based copolymer can be better expressed, it is preferable that the polycarboxylic acid-based copolymer has a weight average molecular weight of 500 to 1,000, 000.
  • the content of the polycarboxylic acid-based copolymer may be appropriately adjusted according to the type or reaction conditions of the copolymer, preferably can be adjusted to 0.001 to 5 parts by weight based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. . If the polycarboxylic acid copolymer and the content is too low, the effect required in the present invention may not be sufficiently expressed. On the contrary, when the polycarboxylic acid-based copolymer is used in an excessive amount, it is not preferable because the function of the superabsorbent polymer may be degraded and thus the absorption characteristics may be degraded, or the surface tension and the powder flowability may be reduced.
  • the content of the polycarboxylic acid copolymer is 0.01 part by weight, 0.1 part by weight, 0.2 part by weight, or 0.3 part by weight or more based on 100 parts by weight of the water-soluble ethylenically unsaturated monomer. 4 parts by weight or less, 3 parts by weight or less, 2 parts by weight or less, or 1 part by weight or less.
  • the water-soluble ethylenically unsaturated monomer included in the monomer composition may be any monomer conventionally used for preparing a super absorbent polymer.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by the following formula (3):
  • R4 is an alkyl group having 2 to 5 carbon atoms containing an unsaturated bond
  • M 2 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
  • the monomer is acrylic acid, methacrylic acid, and
  • the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, or 2- (meth).
  • the water-soluble ethylenically unsaturated monomer has an acidic group, at least a portion of the acidic group may be neutralized.
  • those which have been partially neutralized with an alkali substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like may be used.
  • the degree of neutralization of the monomer may be 40 to 95 mol%, or 40 to 80 mol% or 45 to 75 mol%.
  • the range of the degree of neutralization may vary depending on the final physical properties, but if the degree of neutralization is too high, the neutralized monomer may precipitate and polymerization may be difficult to proceed smoothly.
  • the concentration of the water-soluble ethylene-based unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of the polymerization time and reaction conditions, preferably 20 to 90% by weight, or 40 to 65% by weight. This concentration range may be advantageous in order to control the grinding efficiency during the grinding of the polymer to be described later, while eliminating the need for removing the unbanung monomer after polymerization by using the gel effect phenomenon appearing in the polymerization reaction of the high concentration aqueous solution. However, when the concentration of the monomer is too low, the yield of the super absorbent polymer may be lowered.
  • the monomer composition may include a polymerization initiator generally used in the production of superabsorbent polymer.
  • the polymerization initiator include thermal polymerization initiator or a photopolymerization initiator may, be used in accordance with the polymerization method.
  • a thermal polymerization initiator may be further included.
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyl
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyl
  • One or more compounds selected from the group consisting of benzyl dimethyl ketal, acyl phosphine and a-aminoketone can be used.
  • acyl phosphine examples include commercially available luci r in TP0, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2, 4, 6—tr imethyl—benzoyl ⁇ tr imethyl phosphine oxide). Can be used.
  • a wider variety of photopolymerization initiators are disclosed on page 115 of Reinhold Schwa lm, "UV Coat ings: Basi cs, Recent Developments and New Appli- cation (El sevier 2007)".
  • the thermal polymerization initiator one or more compounds selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide, and ascorbic acid may be used.
  • the persulfate-based initiators include sodium persulfate (Na 2 S 2 0 8 ), potassium persulfate (K 2 S 2 0 8 ), ammonium persulfate (NH 4 ) 2 3 ⁇ 40 8 ) and the like.
  • azo (Azo) based initiators include 2,2-azobis-eu (2-amino, Dino propane) dihydrochloride (2, '2-azobis (2-amidinopropane) dihydrochlor ide), 2, 2-azobis- ( ⁇ , ⁇ -dimethylene) isobutyramimidine dihydrochloride (2, 2- azob i s- (N, Nd i me t hy 1 ene) i sobut yr am idi ne dihydrochlor ide), 2-
  • Such a polymerization initiator may be added at a concentration of about 0.001 to 1% by weight based on the monomer composition.
  • concentration of the polymerization initiator is too low, the polymerization rate may be slow and a large amount of residual monomer may be extracted in the final product.
  • concentration of the polymerization initiator is too high, it is not preferable because the polymer chain constituting the network is shortened, so that the content of the water-soluble component is increased and the pressure absorption capacity is lowered.
  • the monomer composition contains a crosslinking agent ( "internal crosslinking agent, i") to improve the physical properties of the composition according to the polymerization of the water-soluble ethylenically unsaturated monomer may be further included.
  • the crosslinking agent is for internal crosslinking of the hydrogel polymer, wherein the hydrogel phase.
  • Crosslinking the Surface of the Polymer Can be used separately from the crosslinking agent ("surface crosslinking agent").
  • surface crosslinking agent any compound may be used as long as it enables the introduction of a crosslink in the polymerization of the water-soluble ethylenically unsaturated monomer.
  • the internal crosslinking agent is ⁇ , ⁇ '-methylenebisacrylamide, trimethyl propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) acrylate, propylene glycol di (meth Acrylate, polypropylene glycol (meth) acrylate, butanediol di (meth) acrylate butylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, nucleic acid diol di (meth) acryl Triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri (meth) acrylate, penta Erys tetraacrylate, triarylamine, ethylene glycol digly Ether, but is not propylene glycol di (meth)
  • Such internal crosslinking agent may be added at a concentration of about 0.001 to 1% by weight relative to the monomer composition. That is, when the concentration of the internal crosslinking agent is too low, the absorption rate of the resin may be lowered and the gel strength may be weakened, which is not preferable. On the contrary, when the concentration of the internal crosslinking agent is too high, the absorbing power of the resin may be low, which may be undesirable as an absorber.
  • the monomer composition may further include additives such as thickeners, plasticizers, storage stabilizers, antioxidants, and the like, as necessary.
  • the monomer composition may be prepared in the form of a solution in which raw materials such as the aforementioned monomer, polymerization initiator, internal crosslinking agent, and the like are dissolved in a solvent.
  • raw materials such as the aforementioned monomer, polymerization initiator, internal crosslinking agent, and the like are dissolved in a solvent.
  • any solvent that can be used may be used without limitation as long as it can dissolve the above-described raw materials.
  • solvent 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, cyclonucleone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene butyrolactone, carbyle, methyl cellosolve acetate , N, N-dimethylacetamide, or a combination thereof may be used.
  • the formation of the hydrogel polymer through the polymerization of the monomer composition may be performed by a conventional polymerization method, and the process is not particularly limited.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the type of polymerization energy source, when the thermal polymerization is carried out in a reactor having a stirring shaft such as kneader, photopolymerization When proceeding can be carried out in a semi-ungki equipped with a movable conveyor belt.
  • the monomer composition may be added to a reactor such as a kneader equipped with a stirring shaft, and a hydrogel polymer may be obtained by supplying hot air thereto or by heating and heating the reaction reactor.
  • the hydrous gel polymer discharged to the outlet of the counterunggi according to the shape of the stirring shaft provided in the counterunggi may be obtained from particles of several millimeters to several centimeters.
  • the resulting hydrogel polymer may be obtained in various forms according to the concentration and injection speed of the monomer composition to be injected, and a hydrogel polymer having a particle size of 2 to 50 kPa can be obtained.
  • the photopolymerization of the monomer composition in the reaction vessel equipped with a movable conveyor belt sheet A hydrous gel phase polymer of the form can be obtained.
  • the thickness of the sheet may vary depending on the concentration and the injection speed of the monomer composition to be injected, in order to ensure the production rate, while the entire sheet is polymerized evenly, it is usually adjusted to a thickness of 0.5 to 5 cm desirable.
  • the hydrogel polymer formed in this manner may exhibit a water content of about 40 to 80% by weight.
  • the moisture content is a weight of water in the total weight of the hydrogel polymer, and may be a value obtained by subtracting the weight of the dried polymer from the weight of the hydrogel polymer. Specifically, it may be defined as a value calculated by measuring the weight loss due to evaporation of water in the polymer in the process of raising the temperature of the polymer through infrared heating.
  • the drying conditions may be set to 20 minutes including a 5 minute increase in the degree of drying in a manner of increasing the temperature to about 180 ° C at room temperature and maintained at 180 ° C. Drying the hydrogel polymer (step 2)
  • the method of preparing the super absorbent polymer includes drying the hydrogel polymer formed through the above-described steps.
  • the step of grinding (coarsely pulverizing) the hydrogel polymer before the drying may be more rough.
  • the grinder that can be used for the coarse grinding includes a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting type Examples include a cutter mill, a disc mill, a shred crusher, a crusher, a chopper, a disc cutter, and the like.
  • the coarse grinding may be performed so that the particle diameter of the hydrogel polymer is 1 to 10 mm.
  • the hydrous gel polymer is preferably pulverized into particles of 10 mm or less.
  • the hydrous gel phase polymer is preferably pulverized into particles of 1 mm or more.
  • the coarsely pulverizing step includes, as necessary, steam, water, surfactants, fine-flocculation inhibitors such as clay or Si 1 i ca; persulfate initiator, azo initiator, hydrogen peroxide, and ascor
  • a crosslinking agent such as a thermal polymerization initiator such as hydrochloric acid, an epoxy crosslinking agent, a diol crosslinking agent, a crosslinking agent including a bifunctional or trifunctional or higher polyfunctional acrylate, or a monofunctional compound including a hydroxyl group may be added. .
  • the drying for the hydrous gel phase polymer immediately after the coarse grinding or polymerization may be performed at a temperature of 120 to 250 ° C, or 150 to 200 ° C, or 160 to 180 ° C (wherein the temperature is Can be defined as the temperature of the heat medium supplied for drying or the silver inside the drying reactor comprising the polymer and the heat medium in the drying process. That is, when the drying temperature is low due to a low drying temperature, physical properties of the final resin may be lowered. In order to prevent this, the drying temperature is preferably at least i2crc.
  • the drying temperature when the drying temperature is higher than necessary, only the surface of the hydrous gel polymer may be dried to increase the generation of fine powder in the pulverization process described later, and the physical properties of the final resin may be lowered. In order to prevent this, the drying temperature is 25CTC or less. It is preferable. At this time, the drying time in the drying step is not particularly limited, but may be adjusted to 20 to 90 minutes under the drying temperature in consideration of process efficiency and the like. In addition, if the drying method of the drying step can also be commonly used as a drying step of the hydrous gel phase polymer, its configuration can be applied without limitation.
  • the drying step may be a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the polymer dried in this manner may exhibit a water content of about 0.1 to 10% by weight. In other words, if the water content of the polymer is less than 0.1% by weight, it is not advantageous because an increase in manufacturing cost and degradation of the crosslinked polymer may occur due to excessive drying. In addition, when the water content of the polymer exceeds 10% by weight, defects may occur in subsequent processes, which is not preferable. Grinding the dried polymer (step 3)
  • the manufacturing method of the super absorbent polymer includes the step of pulverizing the polymer dried through the above-described steps.
  • the grinding step is to optimize the surface area of the dried polymer, the particle diameter of the pulverized polymer is 150 to 850 May be carried out as desired. Mills that can be used to grind to these particle sizes include pin mills, hammer mills, screw mills, roll mills, disc mills and jogs. A jog mill etc. are mentioned, for example.
  • the step of selectively classifying particles having a particle size of 150 to 850 in the polymer powder obtained through the grinding step may be further performed. Surface crosslinking reaction of the ground polymer (step 4)
  • the manufacturing method of the super absorbent polymer includes the step of surface crosslinking the polymer pulverized through the above-described steps.
  • Surface crosslinking is a method of increasing the crosslinking density of the surface of the resin particles, and may be performed by mixing and crosslinking the pulverized polymer with a solution containing a crosslinking crab (surface crosslinking agent).
  • the kind of crosslinking agent (surface crosslinking agent) contained in the surface crosslinking solution is not particularly limited.
  • the surface crosslinking agent may be ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene carbonate, ethylene glycol, diethylene glycol, propylene glycol,.
  • the content of the surface crosslinking agent may be appropriately adjusted according to the type or reaction conditions of the crosslinking agent, and preferably may be adjusted to 0.001 to 5 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the content of the surface crosslinking agent is too low, the surface crosslinking may not be properly introduced, and the physical properties of the final resin may decrease.
  • the surface crosslinking agent is used in an excessively high content, the absorbency of the resin may be lowered due to excessive surface crosslinking reaction, which is not preferable.
  • the method of mixing the surface crosslinking solution and the pulverized polymer in a semi-permanent mixture the method of spraying the surface crosslinking solution to the pulverized polymer, the pulverized polymer and Method of mixing by supplying the surface crosslinking solution continuously And the like can be used.
  • water may be additionally added when the surface crosslinking solution is added. As such water is added together, more even dispersion of the crosslinking agent may be induced, aggregation of the polymer powder may be prevented, and the penetration depth of the surface crosslinking agent into the polymer powder may be further optimized.
  • the amount of water added may be adjusted to 0.5 to 10 parts by weight based on 100 parts by weight of the pulverized polymer.
  • the surface crosslinking reaction step may be performed under a temperature of 100 to 25CTC, it may be made continuously after the drying and grinding step proceeds to a relatively high temperature. At this time.
  • the surface crosslinking reaction may be performed for 1 to 120 minutes, or 1 to 100 minutes, or 10 to 60 minutes. That is, in order to induce a minimum surface crosslinking reaction, the polymer particles may be damaged during excessive reaction, and thus the physical properties of the surface crosslinking reaction may be reduced.
  • a super absorbent polymer having a low amount of coarse part i cles and fine powder (f ine part i cl es), having excellent absorption characteristics such as water retention and pressurized absorption, but having a high absorption rate and high permeability, can be prepared.
  • a superabsorbent polymer having high absorption rate and high permeability while having excellent absorption characteristics such as water-retaining capacity and pressure-absorbing capacity is prepared. can do.
  • a polycarboxylic acid copolymer was prepared in the same manner as in Preparation Example 2, except that triethane was neutralized with an aqueous sodium hydroxide solution instead of an aqueous amine solution. Obtained (weight average molecular weight 40,000) Production Example 4
  • methoxy polyethylene glycol monomethacrylate (about 50 moles of an average added mole number of ethylene oxide (E0)), 49.8 parts by weight of methacrylic acid, water 50 parts by weight of a mixed aqueous monomer solution, 5 parts by weight of 3-mercaptopropionic acid, 30 parts by weight of a mixed solution, and 80 parts by weight of an aqueous solution of ammonium persulfate at a concentration of 3% by weight were continuously added at a uniform rate for 4 hours.
  • methoxy polyethylene glycol monomethacrylate about 50 moles of an average added mole number of ethylene oxide (E0)
  • methacrylic acid water 50 parts by weight of a mixed aqueous monomer solution, 5 parts by weight of 3-mercaptopropionic acid, 30 parts by weight of a mixed solution, and 80 parts by weight of an aqueous solution of ammonium persulfate at a concentration of 3% by weight were continuously added at a uniform rate for 4 hours.
  • a polycarboxylic acid copolymer was obtained in the same manner as in Preparation Example 4, except that the polymerization reaction was completed in the same manner as in Preparation Example 4, except that the reaction was neutralized with an aqueous solution of triethanolamine at a concentration of 30 wt% for about 1 hour (weight average molecular weight 45 , 000).
  • Preparation Example 6 A polycarboxylic acid copolymer was obtained in the same manner as in Preparation Example 4, except that the polymerization reaction was completed in the same manner as in Preparation Example 4, except that the reaction was neutralized with an aqueous solution of triethanolamine at a concentration of 30 wt% for about 1 hour (weight average molecular weight 45 , 000).
  • the monomer composition was prepared by adding (neutralization degree of acrylic acid monomer: 70 mol%).
  • the monomer composition was supplied to a 5 L twin arm kneader having a sigma-shaped shaft, and nitrogen gas was added for 30 minutes while maintaining the temperature at 65 ° C. to remove oxygen dissolved in the aqueous solution.
  • the finely divided gel was spread about 30 mm thick on a stainless wire gauze having a pore size of 600 / mm 3 and dried in a 150 ° C. hot air oven for 4 hours.
  • the dry polymer thus obtained was pulverized using a pulverizer and classified into a standard mesh of ASTM standard to obtain an absorbent resin powder having a particle size of 150 to 850.
  • 100 g of the water-absorbent resin powder was mixed evenly while adding 0.3 g of ethylene carbonate (surface crosslinking agent), and a surface crosslinking solution containing 3 g of water and 3 g of water, followed by drying in an 18 CTC hot air oven for 30 minutes.
  • the dried powder was classified into a standard mesh of ASTM standard to obtain a super absorbent polymer having a particle size of 150 urn to 850.
  • Example 2
  • a superabsorbent polymer was obtained in the same manner as in Example 1, except that the polycarboxylic acid copolymer according to Preparation Example 3 was used instead of Preparation Example 1.
  • Example 4
  • a superabsorbent polymer was obtained in the same manner as in Example 1, except that polyethylene glycol (PEG-200) was added in the same amount instead of the polycarboxylic acid copolymer according to Preparation Example 1. Comparative Example 3
  • a super absorbent polymer was obtained in the same manner as in Example 1, except that 1 g of sodium bicarbonate was added instead of the polycarboxylic acid copolymer according to Preparation Example 1.
  • the water holding capacity of the above Examples and Comparative Examples was measured. That is, the resin W (g) (about 0.2 g) obtained through the examples and the comparative examples was uniformly placed in a bag made of a nonwoven fabric and sealed, and then impregnated with physiological saline (0.9 weight) at room temperature. 3, the water was removed from the bag for 3 minutes using a centrifugal separator and the bag weight W2 ( g ) was measured, and the mass Wl (g) was measured after the same operation without using a resin. Using each mass obtained, CRC ( g / g) was computed according to the following formula.
  • the pressure absorption capacity was measured for the resins of the above Examples and Comparative Examples. That is, a stainless steel 400 mesh wire mesh was mounted on the bottom of a plastic cylinder having an inner diameter of 60 mm 3. Under conditions of room temperature and humidity of 50% Evenly spread the absorbent resin W (g) (about 0.90g) on the wire mesh
  • Pistons capable of evenly applying a load of 4.83 kPa (0.7 psi)
  • the weight Wa (g) of the apparatus was measured.
  • a 90 mm diameter and 5 mm thick glass filter was placed inside a 150 mm diameter petri dish and the physiological saline consisting of 0.90 weight 3 ⁇ 4> sodium chloride was brought to the same level as the top surface of the glass filter.
  • One filter with a diameter of 90 mm was loaded thereon.
  • the measuring device was placed on the filter paper and the liquid was absorbed for 1 hour under load. After 1 hour, the measuring device was lifted up and the weight Wb (g) was measured. And the pressure absorption capacity (g / g) was computed from said Wa and Wb by following Formula.
  • AUP (g / g) ⁇ Wb-Wa ⁇ / W
  • the superabsorbent polymers according to the examples were found to have a higher water permeability (SFC) and a higher absorption rate than the resin of Comparative Example 1, having a water retention capacity and a pressurized absorption capacity.
  • SFC water permeability
  • Comparative Example 2 the physical properties as in Example were not expressed, and in the case of using a foaming agent that generates gas during polymerization as in Comparative Example 3, absorption rate and permeability were At the same time, the results were not satisfied. Therefore, it was confirmed that the superabsorbent polymer having a high absorption rate and high permeability at the same time according to the manufacturing method according to the present invention could be prepared.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne un procédé de préparation d'une résine superabsorbante. Le procédé de préparation d'un superabsorbant selon la présente invention peut produire une résine superabsorbante, qui présente une vitesse d'absorption rapide et une perméabilité élevée tout en présentant d'excellentes caractéristiques d'absorption, telles que la capacité de rétention d'eau et un pouvoir absorbant sous pression, par l'utilisation d'un copolymère à base d'un poly(acide carboxylique) au moment de la polymérisation d'un polymère en phase de gel hydraté.
PCT/KR2015/012000 2014-11-27 2015-11-09 Procédé de préparation de résine superabsorbante et résine superbsorbante ainsi préparée WO2016085152A1 (fr)

Priority Applications (3)

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US15/302,845 US9976003B2 (en) 2014-11-27 2015-11-09 Method for preparing super absorbent polymer and super absorbent polymer prepared therefrom
EP15863575.5A EP3112383A4 (fr) 2014-11-27 2015-11-09 Procédé de préparation de résine superabsorbante et résine superbsorbante ainsi préparée
CN201580021684.6A CN106459236B (zh) 2014-11-27 2015-11-09 用于制备超吸收性聚合物的方法和由此制备的超吸收性聚合物

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KR10-2014-0167735 2014-11-27
KR20140167735 2014-11-27
KR10-2015-0155892 2015-11-06
KR1020150155892A KR101745679B1 (ko) 2014-11-27 2015-11-06 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지

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WO2018117390A1 (fr) * 2016-12-23 2018-06-28 주식회사 엘지화학 Résine superabsorbante et procédé pour sa préparation

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JPH09503954A (ja) * 1994-08-01 1997-04-22 レオナルド パールスタイン 高性能な高吸収材料及びそれを含む吸収用品
JP2003534407A (ja) * 2000-05-25 2003-11-18 ビーエーエスエフ アクチェンゲゼルシャフト 表面処理された高吸水性ポリマー粒子
KR20140025083A (ko) * 2012-08-21 2014-03-04 주식회사 엘지화학 폴리카르본산계 공중합체를 포함하는 시멘트 조성물의 첨가제 및 이를 포함하는 시멘트 조성물
KR20140063401A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지의 제조방법
KR20140133470A (ko) * 2013-05-09 2014-11-19 주식회사 엘지화학 고흡수성 수지의 제조방법

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JPH09503954A (ja) * 1994-08-01 1997-04-22 レオナルド パールスタイン 高性能な高吸収材料及びそれを含む吸収用品
JP2003534407A (ja) * 2000-05-25 2003-11-18 ビーエーエスエフ アクチェンゲゼルシャフト 表面処理された高吸水性ポリマー粒子
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Publication number Priority date Publication date Assignee Title
WO2018117390A1 (fr) * 2016-12-23 2018-06-28 주식회사 엘지화학 Résine superabsorbante et procédé pour sa préparation
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US12053757B2 (en) 2016-12-23 2024-08-06 Lg Chem, Ltd. Super absorbent polymer and method for producing same

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