WO2016104962A1 - Polymère superabsorbant et procédé de préparation - Google Patents

Polymère superabsorbant et procédé de préparation Download PDF

Info

Publication number
WO2016104962A1
WO2016104962A1 PCT/KR2015/012664 KR2015012664W WO2016104962A1 WO 2016104962 A1 WO2016104962 A1 WO 2016104962A1 KR 2015012664 W KR2015012664 W KR 2015012664W WO 2016104962 A1 WO2016104962 A1 WO 2016104962A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
superabsorbent polymer
meth
water
glycol
Prior art date
Application number
PCT/KR2015/012664
Other languages
English (en)
Korean (ko)
Inventor
장태환
허성범
김미영
김민규
Original Assignee
주식회사 엘지화학
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020150140933A external-priority patent/KR102011926B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US15/104,485 priority Critical patent/US9901904B2/en
Priority to EP15864314.8A priority patent/EP3075760A4/fr
Priority to CN201580003275.3A priority patent/CN105934451B/zh
Publication of WO2016104962A1 publication Critical patent/WO2016104962A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • 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
    • 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 superabsorbent polymer having excellent gel bed permeability (GBP) and sut ion power and a method for producing the same.
  • GBP gel bed 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 (SAM) and an absorbent gel mater (ALM). It is also called.
  • SAM super absorbent mater
  • ALM absorbent gel mater
  • Super absorbent polymers have been put into practical use as sanitary devices and are now widely used in various materials such as hygiene products such as paper diapers for children, horticultural soil repair agents, civil engineering materials, seedling sheets, and freshness retainers in food distribution. It is 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, for the production of super absorbent polymers through reverse phase suspension polymerization, for example, see Japanese Patent Application Laid-Open No. 56-161408.
  • the production of superabsorbent polymer resin by aqueous solution polymerization is a thermal polymerization method for polymerizing while breaking and cooling the hydrogel polymer in a kneader equipped with several shafts, and polymerizing and drying by irradiating UV light to a high concentration aqueous solution on a belt.
  • the photopolymerization method etc. which perform simultaneously are known.
  • Important performances of sanitary devices, such as diapers, include intake time and wet back.
  • the permeability is also important to enable efficient diffusion of the absorbed material into the superabsorbent polymer used therein, and the improvement in suction power that can pull ur ine from the pulp to improve the dryness of the diaper. It is important.
  • a method of increasing the internal crosslinking strength and gel strength of a super absorbent polymer or coating silica or inorganic particles on a surface thereof is known.
  • the suction force it is necessary to lower the internal crosslinking degree of the super absorbent polymer and to reduce the content of silica or inorganic particles on the surface.
  • the present invention is to provide a super absorbent polymer having excellent suct ion power and gel bed permeability.
  • the present invention is to provide a method for producing the super absorbent polymer. [Measures of problem]
  • this invention provides the following superabsorbent polymer.
  • a surface comprising a crosslinked polymer of a water-soluble ethylenically unsaturated monomer containing an acidic group and at least a portion of the acidic group neutralized, and a surface formed on the base resin, wherein the base resin further crosslinked
  • the salt absorbed by 1 g of the superabsorbent polymer for 5 minutes is 13 mL / g or more
  • the gel bed transmittance (GBP) is 41 darcy or more. Water absorbent resin.
  • the permeability is important to enable efficient diffusion of the absorbed material into the superabsorbent polymer used therein, and the gel bed permeability (gel bed permeabi li ty).
  • the gel bed permeability gel bed permeabi li ty
  • a method of coating silica or inorganic particles on the surface of a super absorbent polymer is known to increase gel bed permeability.
  • the gel bed permeability of the superabsorbent polymer can be improved, but as the coating amount increases, there is a problem in that the pressure absorption capacity and the suction power, which are other important characteristics of the superabsorbent polymer, are lowered.
  • the present invention when coating the silica particles on the surface of the superabsorbent resin, as described below, to increase the surface crosslink density of the superabsorbent resin, the superabsorbent polymer with improved suction force as well as gel bed transmittance and pressure absorption capacity, the superabsorbent polymer with improved suction force as well as gel bed transmittance and pressure absorption capacity It has the feature of providing. 1 g of the superabsorbent polymer absorbed for 5 minutes (suet ion power; SP) can be measured by the following method.
  • the value of the amount of saline (SP) measured according to the above is preferably 13.2 mL / g or more, 13.4 mL / g or more, 13.6 mL / g or more, 13.8 mL / g or more, 14.0 mL / g, at least 14.2 mL / g, at least 14.4 mL / g, at least 14.6 mL / g, at least 14.8 mL / g, or at least 15.0 mL / g. Can be.
  • the present invention also provides a superabsorbent polymer in the superabsorbent polymer of (1), wherein the gel bed transmittance (GBP) of the superabsorbent resin is 41 darcy or more.
  • the gel bed permeability (GBP) is expressed as "darcy" which is the CGS unit for permeability.
  • 1-Darcy is, if the two pressures of the cross section of the solid-state difference of 1 atmosphere and a viscosity of 1 cps fluid 1 cm 3 of the through cross-sectional thickness of 1 cm and the cross sectional area 1 on 2 the transmittance of the solid to flow within one second, a transmittance Has the same units as the area since there is no SI unit for the transmittance, and m 2 is used.
  • 1 Darcy is equal to about 0.98692 X 10 ⁇ 12 in 2 or about 0.98692 X 10 "8 cuf. How to measure this gel bed permeability are set forth in U.S. Patent Publication US 7, 179, 851 call.
  • the gel bed Permeability is a measure of the permeability of a swelling bed of gel particles (eg, surface treated absorbent material or superabsorbent material prior to surface treatment), especially under conditions referred to as a "free swelling" state.
  • Gel bed permeability (GBP) of the superabsorbent polymer according to the invention is preferably at least 45 darcy, at least 50 darcy, at least 55 darcy, at least 60 darcy, at least 65 darcy, at least 70 darcy, at least 75 darcy, at least 80 darcy, More than 85 darcy, more than 90 darcy, more than 95 darcy, more than 100 darcy, more than 105 darcy, more than 110 darcy, more than 115 darcy, or more than 120 darcy, and the higher the gel bed transmittance, the higher the physical properties of the superabsorbent polymer.
  • the present invention also provides a superabsorbent polymer (1) or (2), wherein the superabsorbent polymer has a pressure absorption capacity (AUL) of 0.9 psi of at least 17.3 g / g.
  • AUL pressure absorption capacity
  • the pressure absorption capacity (AUL) of 0.9 psi may be represented by the following formula 1.
  • AUL (g / g) [Wb (g)-Wa (g)] / Mass of superabsorbent polymer (g)
  • Wa (g) is the sum of the weight of the super absorbent polymer and the weight of the device capable of applying a load to the superabsorbent polymer (g),
  • Wb (g) is the sum of the weight of the water absorbed superabsorbent resin after supplying the water to the superabsorbent polymer for 60 minutes under a load (0.9 psi) and the weight of the device capable of applying a load to the superabsorbent polymer ( g).
  • 0.9 psi of pressure-absorbing capacity (AUL) of the superabsorbent polymer according to the present invention is preferably 17.5 g / g or more, 18.0 g / g or more, 18.5 g / g or more, 19.0 g / g or more, 19.5 g / g or more , 20.0 g / g or more, 20.5 g / g or more, 21.0 g / g or more, or 21.5 g / g or more.
  • the water-soluble ethylenically unsaturated monomer may be any monomer commonly used in the preparation of the superabsorbent polymer.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by Formula 1:
  • 3 ⁇ 4 is an alkyl group having 2 to 5 carbon atoms containing an unsaturated bond
  • M 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
  • the water-soluble ethylenically unsaturated monomer is acrylic acid, methacrylic acid, monovalent metal salts of these acids, divalent metal salts, It may be at least one selected from the group consisting of ammonium salts and organic amine salts.
  • the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethane sulfonic acid, 2-methacryloylethanesulfonic acid, 2— (meth) acryloylpropanesulfonic acid, or
  • 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, 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. On the contrary, if the degree of neutralization is too low, the absorbency of the polymer may be greatly reduced. It can exhibit the same properties as elastic rubber, which is difficult to handle.
  • the surface crosslinking increases the crosslinking density of the resin particle surface. As a method, the crosslinking agent and surface crosslinking method used for this are mentioned later. Manufacturing method of super absorbent polymer
  • the present invention provides a method for preparing a super absorbent polymer, comprising the steps of:
  • step 1 Formation of hydrogel polymer (step 1)
  • the method of preparing the superabsorbent polymer includes thermally polymerizing or photopolymerizing a monomer composition including a water-soluble ethylenically unsaturated monomer and a polymerization initiator to form a hydrogel polymer.
  • the water-soluble ethylenically unsaturated monomer included in the monomer composition is as described above.
  • the concentration of the water-soluble ethylenically unsaturated monomer in the monomer composition may be appropriately adjusted in consideration of polymerization time and reaction conditions, preferably 20 to 90 weight%, or 40 to 65 weight%.
  • This concentration range may be advantageous to control the grinding efficiency during the grinding of the polymer to be described later, while eliminating the need for removing uncoated monomer after the polymerization by using a gel effect phenomenon occurring in the polymerization reaction of a high concentration aqueous solution.
  • concentration of the monomer when the concentration of the monomer is too low, the yield of the super absorbent polymer may be lowered.
  • concentration of the monomer if the concentration of the monomer is too high, some of the monomer may be precipitated, or the grinding efficiency may be reduced during the pulverization of the polymerized hydrogel polymer, and the physical properties of the super absorbent polymer may be reduced.
  • the monomer composition may include a polymerization initiator generally used in the production of superabsorbent polymer.
  • a thermal polymerization initiator or a photopolymerization initiator may be used depending on the polymerization method.
  • a thermal polymerization initiator since a certain amount of heat is generated by ultraviolet irradiation or the like, and a certain amount of heat is generated in accordance with the progress of the polymerization reaction, which is exothermic reaction, a thermal polymerization initiator may be further included.
  • the photoinitiator for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • benzoin ether dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl
  • benzyl dimethyl ketal acyl phosphine and alpha-aminoketone
  • the specific lucirinTPO That is, 2,4 ⁇ 6_trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide) can be used.
  • thermo polymerization initiator at least one compound selected from the group consisting of a persulfate initiator, an azo initiator, hydrogen peroxide, and ascorbic acid may be used, and specifically, as the persulfate initiator, sodium per sulfate; 2 s 2 0 8), potassium persulfate (potassium persulfate; ⁇ 2 3 ⁇ 40 8 ), ammonium persulfate (ammonium persulfate; (NH 4) . the like are exemplified 2 s 2 0 8) in addition, azo (azo) As a system initiator
  • thermal polymerization initiators A wider variety of thermal polymerization initiators is disclosed on page 203 of the Odian book “Principle of Polymer izat ion (ffi ley, 1981)", which may be referred to.
  • a polymerization initiator may be added at a concentration of about 0.001 to 1% by weight based on the monomer composition. In other words, when the concentration of the polymerization initiator is too low, the polymerization rate may be slow and a large amount of remaining monomer may be extracted in the final product.
  • the monomer composition may further include a crosslinking agent ("internal crosslinking agent”) for improving the physical properties of the resin by polymerization of the water-soluble ethylenically unsaturated monomer.
  • the crosslinking agent is for internal crosslinking of the hydrogel polymer, and may be used separately from a crosslinking agent ("surface crosslinking agent”) for crosslinking the surface of the hydrogel polymer.
  • any internal crosslinking agent having a crosslinkable functional group which has conventionally been used in the preparation of a super absorbent polymer, may be used without any particular limitation.
  • a polyfunctional acrylate compound having a plurality of ethylene oxide groups may be used as the internal crosslinking agent. More specific examples of such internal crosslinkers include polyethylene glycol diacrylate (PEGDA), glycerin diacrylate, glycerin triacrylate, unmodified or ethoxylated trimethylol triacrylate (TMPTA), nucleic acid diol diacrylate, and And at least one selected from the group consisting of triethylene glycol diacrylate.
  • the internal crosslinking agent may be added at a concentration of about 0.001 to 1 weight 3 ⁇ 4 with respect 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 low 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 absorptivity 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, and antioxidants 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.
  • the solvent includes 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, ⁇ , ⁇ -dimethylacetamide, or a combination thereof.
  • 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, and when the thermal polymerization is performed, the polymerization may be performed in a semi-unggi machine having a stirring shaft such as a kneader. When the polymerization proceeds, it can be carried out in a semi-unggi equipped with a movable conveyor belt.
  • a hydrogel polymer may be obtained by adding the monomer composition to a reaction vessel such as a kneader equipped with a stirring shaft and supplying hot air thereto or by heating the reactor to thermally polymerize it.
  • a reaction vessel such as a kneader equipped with a stirring shaft and supplying hot air thereto or by heating the reactor to thermally polymerize it.
  • the hydrous gel phase polymer discharged to the reactor outlet depending on the shape of the stirring shaft provided in the reactor may be obtained in the 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.
  • a hydrous gel polymer in the form of a sheet in the case of performing the light polymerization of the monomer composition in a semi-unggi equipped with a movable conveyor belt can be obtained a hydrous gel polymer in the form of a sheet.
  • 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 evenly polymerized, it is usually adjusted to a thickness of 0.5 to 5 cni 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 increase 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 5 minutes of the temperature rise step in such a way that the temperature is raised to about 18 (C and then maintained at 180 ° C in phase silver. Drying the hydrogel polymer Steps to Step (Step 2)
  • the manufacturing method of the super absorbent polymer includes drying the hydrogel polymer formed through the above-described steps.
  • the step of pulverizing (coarse grinding) the hydrogel polymer before the drying may be more rough.
  • the grinders available for the coarse grinding include a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mi 11, a cutting machine. Examples thereof 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 2 to 10 mm.
  • the hydrous gel polymer is preferably pulverized into particles of 10 mm or less.
  • the hydrous gel polymer is preferably pulverized into particles of 2 GPa or more.
  • the polymer may stick to the surface of the grinder because the polymer has a high water content.
  • the coarsely pulverizing step may include, as necessary, steam, water, surfactants, anti-flocculation agents such as clay or silica; Thermal polymerization initiators such as persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid, epoxy crosslinkers, diol crosslinkers, crosslinkers comprising acrylates of difunctional or trifunctional or more than trifunctional groups, and hydroxyl groups.
  • Thermal polymerization initiators such as persulfate initiators, azo initiators, hydrogen peroxide, and ascorbic acid
  • epoxy crosslinkers diol crosslinkers, crosslinkers comprising acrylates of difunctional or trifunctional or more than trifunctional groups, and hydroxyl groups.
  • Crosslinking agents such as a compound of monofunctional groups, may be added.
  • the drying of the coarsely pulverized black polymer for the hydrous gel phase immediately after 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 Can be defined as the silver content of the heat medium supplied for drying or the temperature inside the drying reactor which contains the heat medium and the polymer in the drying process.). That is, when the drying temperature is low and the drying time is long, physical properties of the final resin may be lowered. In order to prevent this, the drying temperature is preferably 12 CTC or more. In addition, when the drying temperature is higher than necessary, only the surface of the hydrogel polymer may be dried to increase the generation of fine powder in the grinding process described later. The physical properties may be reduced, in order to prevent this, the drying temperature is preferably 250 ° C or less.
  • 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.
  • the drying method of the drying step can also be commonly used as a drying step of the hydrous gel phase polymer is applicable to the configuration 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 weight 3 ⁇ 4.
  • step 3 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 performed.
  • the grinders that can be used to grind to these particle diameters include pin mills, hammer mills, screw mi 11s, roll mills and disc mills.
  • a jog mill may be used, and in order to manage the physical properties of the super absorbent polymer to be finalized, particles having a particle size of 150 to 850 are selectively classified 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 a solution containing a crosslinking agent (surface crosslinking agent) and the pulverized polymer.
  • a crosslinking agent surface crosslinking agent
  • a compound having two or more epoxy rings is used as the crosslinking agent (surface crosslinking agent) contained in the surface crosslinking solution.
  • the epoxy ring may react with the carboxyl group present on the surface of the superabsorbent polymer.
  • the crosslinking agent may form a multi-crosslinking structure on the surface of the superabsorbent polymer. Surface crosslinking density can be raised. Thereby, the gel bed permeability of the super absorbent polymer can be improved.
  • the compound having two or more epoxy rings may be a compound represented by the following formula (2).
  • 3 ⁇ 4 is ( 3 alkylene.
  • the content of the surface crosslinking agent may be appropriately adjusted according to the type of the crosslinking agent or the reaction conditions, and preferably 0.001 to 5 parts by weight based on 100 parts by weight of the pulverized polymer. If 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 be degraded. The absorption of the resin can be rather low, which is undesirable.
  • silica may be used together to perform a surface crosslinking reaction. When the silica particles are used together, silica particles may be coated on the surface of the superabsorbent polymer.
  • the gel bed permeability of the superabsorbent polymer may be improved by coating the silica particles, but the pressure absorption capacity (AUL) and the suction force ( suct ion power) tends to decrease.
  • AUL pressure absorption capacity
  • suct ion power suct ion power
  • the surface crosslinking reaction since the surface crosslinking reaction is performed with the compound having two or more epoxy rings, it has an improved gel bed permeability due to the use of silica, and also has a pressure absorbing capacity (AUL) and a suction power (suet i on power). It can be improved.
  • AUL pressure absorbing capacity
  • suction power suet i on power
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propane die, dipropylene glycol, polypropylene glycol, glycerin, polyglycerol, butanedi, heptanediol and nucleic acid die. All trimethyl can be mentioned propane, pentaerythritol, and sorbbi.
  • the surface cross-linking solution and the pulverized polymer in a semi-permanent mixture a method of spraying the surface cross-linking solution to the pulverized polymer, a pulverized polymer in a continuously operated mixer And a method of continuously supplying and mixing the surface crosslinking solution and the like can be used.
  • water may be additionally added when the surface crosslinking solution is added.
  • the addition of water together may lead to more even dispersion of the crosslinking agent : prevention of agglomeration of the polymer powder, and more optimized penetration depth of the surface crosslinker into the polymer powder.
  • 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. have.
  • the surface crosslinking reaction step is preferably performed at a temperature of 170 to 250 ° C. If less than 170 ° C. surface crosslinking of the superabsorbent polymer by the compound having two or more epoxy rings does not occur sufficiently.
  • the surface crosslinking reaction may proceed for more than 50 minutes. That is, in order to induce a minimum surface crosslinking reaction and to prevent excessive reactions from damaging polymer particles and deteriorating physical properties, the surface crosslinking reaction may be performed under the conditions of the aforementioned surface crosslinking reaction. Can be. In addition, the reaction may be performed in 120 minutes or less, 100 minutes or less, or 60 minutes or less.
  • the superabsorbent polymer according to the present invention is excellent in gel bed transmittance (GBP) and suction power (suct i on power), and can be usefully used as a material for sanitary devices such as diapers.
  • FIG. 1 is a schematic diagram showing an example of an apparatus for measuring the pressure absorption rate for the super absorbent polymer according to an embodiment of the present invention.
  • GBP gel bed transmittance
  • FIG.3 and FIG.4 is a schematic diagram which shows an example of the gel bed transmittance measurement cylinder and mesh arrangement, respectively.
  • Figure 5 shows an example of a measuring device of Suct i on Power according to an embodiment of the present invention.
  • Example 1-2 After drying, the resultant was pulverized with a pulverizer and classified to prepare a base resin by selecting 150 to 850 urn in size. Thereafter, for 100 g base resin, 3% water, 3% methane, 0.1% epoxy compound (Ethyleneglycol diglycidyl ether), silica ⁇ 6! " After mixing by adding 0 ⁇ 12000.06%, reacting for 1 hour while raising the temperature from 170 ° C to 195 ° C, and after crushing, the surface diameter of 150 ⁇ 850 ⁇ by the sieve A super absorbent polymer was obtained Example 1-2
  • Example 1-3 Superabsorbent polymer was prepared in the same manner as in Example 1-1, except that 0.08% silica Aerosil was applied during surface crosslinking.
  • Example 1-3
  • Example 1-4 Superabsorbent polymer was prepared in the same manner as in Example 1-1, except that 0.10% silica Aerosil was applied during surface crosslinking.
  • Example 1-4 Example 1-4
  • Example 1-5 Superabsorbent polymer was prepared in the same manner as in Example 1-1, except that 0.14% silica Aerosil was applied during surface crosslinking.
  • Example 1-6
  • Example 2-1 Superabsorbent polymer was prepared in the same manner as in Example 1-1, except that 0.16% silica Aerosil was applied during surface crosslinking.
  • Example 2-1 Example 2-1
  • Example 2-2 After drying, the resultant was pulverized with a pulverizer and classified to prepare a base resin by selecting 150 to 850 sizes. Subsequently, for 100 g base resin, 3% of water, 3% of methanol, 0.1% of an epoxy compound (Ethyleneglycol diglycidyl ether), After mixing with silica ⁇ 0 ⁇ 12000.06%, the mixture was reacted for 1 hour while increasing the silver content from 170 ° C to 195 ° C, and then ground to a particle size of 150 to 850 using a sieve after grinding. A super absorbent polymer was obtained.
  • Example 2-2 Example 2-2
  • Superabsorbent polymer was prepared in the same manner as in Example 2-1, except that 10.04% of silica Aerosi was applied during surface crosslinking.
  • Example 2-3
  • Example 2-1 except that 0.06% silica Aerosil was applied at the surface cross-linking
  • a super absorbent polymer was prepared in the same manner.
  • Example 2-4
  • Super absorbent polymer was prepared in the same manner as in Example 2-1, except that 0.08% silica Aerosi l was applied during surface crosslinking.
  • Example 2-5
  • a super absorbent polymer was prepared in the same manner as in Example 2-1, except that silica Aerosi 10% was applied during surface crosslinking.
  • Example 2-6
  • a super absorbent polymer was prepared in the same manner as in Example 2-1, except that silica AerosIL 12% was applied during surface crosslinking. Comparative Example 1-1
  • Super absorbent polymer was prepared in the same manner as in Example 1-1, except that the reaction temperature was 120 ° C. during surface crosslinking. Comparative Example 1-2
  • a superabsorbent polymer was prepared in the same manner as in Example 1-1, except that the reaction temperature was 12 CTC and the silica was applied at 0.08%. Comparative Example 1-3
  • the superabsorbent polymer was prepared in the same manner as in Example 1-1, except that the reaction temperature was 120 ° C. during surface crosslinking, and silica Aerosil 0.1% was applied. Comparative Example 2-1
  • Super absorbent polymer was prepared in the same manner as in Example 2-1, except that the reaction temperature was 120 ° C. during surface crosslinking.
  • the super absorbent polymer was prepared in the same manner as in Example 2-1, except that the reaction silver was set at 120 ° C and 0.04% silica Aerosi l was applied during surface crosslinking.
  • Test apparatus 28 includes a sample vessel (typically labeled 30) and a piston (typically labeled 35).
  • the piston 35 comprises a cylindrical LEXANR shaft 38 with a central cylindrical hole 40 drilled below the longitudinal axis of the shaft. Both ends of the shaft 38 are machined to provide the upper and lower ends (indicated by 42 and 46, respectively).
  • the weight (indicated by 48) is above one end 42 and has a cylindrical hole 48a that is drilled through at least a portion of its center.
  • the circular piston head 50 is located above the other end 46 and has a central inner ring of seven holes (60 each of which has a diameter of about 0.95 cm) and 14 holes (54 each of which are about 0.95 cm in diameter). Having a central outer ring).
  • the holes 54, 60 are drilled from the top to the bottom of the piston head 50.
  • the piston head 50 also has a cylindrical hole 62 drilled in its center to receive the end 46 of the shaft 38.
  • Has The lower portion of the piston head 50 may also be covered with a biaxially stretched 400 mesh stainless steel screen 64.
  • the sample vessel 30 includes a cylinder 34 and a 400 mesh stainless steel skinned screen 66, which is taut biaxially stretched and attached to the lower end of the cylinder.
  • the superabsorbent polymer sample (designated 68 in FIG. 3) is supported on the screen 66 inside the cylinder 34 during the test.
  • the cylinder 34 may be perforated with a transparent LEXANR rod or equivalent material or cut into a lexan tube or equivalent material, having an inner diameter of about 6 cm (eg, a cross-sectional area of about 28.27 cm 2 ) and a wall thickness of about 0.5 cm, about 10 cm in height.
  • a drain hole (not shown) is formed in the sidewall of the cylinder 34 at a height of about 7.8 cm above the screen 66 to drain liquid from the cylinder, and at a fluid level of sample vessel build up at about 7.8 cm above the screen 66. Keep it.
  • the piston head 50 is machined from a lexan rod or equivalent material and has a height of approximately 16 mm and a diameter of a predetermined size and still slides freely while fitting it to the minimum wall space inside the cylinder 34.
  • the shaft 38 is machined from a lexan rod or equivalent material and has an outer diameter of about 2.22 cm and an inner diameter of about 0.64 cm.
  • the shaft upper end 42 is about 2.54 cm in length and about 1.58 cm in diameter, thereby forming an annular shoulder 47 to support the weight 48.
  • the annular weight 48 has an inner diameter of about 1.59 on Then, it slides to the upper end 42 of the shaft 38 and is present on the annular shoulder 47 formed thereon.
  • the annular weight 48 can be made of stainless steel or of another suitable material that is corrosion resistant in the presence of a test solution that is 0.9 wt% sodium chloride in distilled water.
  • the combined weight of the piston 35 and the annular weight 48 corresponds to approximately 596 g, which means that the pressure applied to the absorbent structure sample 68 is about 0.3 ps i or about 20.7 g / for a sample area of about 28.27 cm 2 . It's cipher.
  • the sample vessel 30 generally resides on a 16 mesh rigid stainless steel support screen (not shown).
  • the sample vessel 30 has a support having a diameter substantially the same as the cylinder 34 such that the support ring does not restrict flow from the bottom of the vessel. Stay on the ring (not shown). Freedom .
  • a piston 35 with a weight 48 disposed thereon is placed in the hollow sample vessel 30 and from the bottom of the weight 48 to the top of the cylinder 34. The height of is measured with a caliper with suitable measurement accuracy up to 0.01 mm 3.
  • the same piston 35 and weight 48 should be used for the measurement when the superabsorbent polymer sample 68 is water swelled after saturation.
  • the sample to be tested is made from superabsorbent material particles, which are prescreened through a US standard 30 mesh screen and held on a US standard 50 mesh screen.
  • the three test samples thus comprise particles ranging in size from about 300 to about 600.
  • the particles can be prescreened manually or automatically.
  • About 2.0 g of sample is placed in sample vessel 30, and then the vessel is immersed in test solution for a period of about 60 minutes in the absence of piston 35 and weight 48 to saturate the sample and swell the sample without limiting load. .
  • the piston 35 and weight 48 are placed over the saturated sample 68 in the sample vessel 30, and then the sample vessel 30, the piston 35, the weight 48 and the sample 68 ) Is removed from the solution.
  • the thickness of the saturated sample 68, the same clipper or instrument used previously again measuring the height from top of using (provided that the zero point is unchanged from the initial height measurement) ", the cylinder 34 from a lower portion of the increase (48) Is determined by.
  • the height measurement difference obtained by the measurement of the hollow sample vessel 30, the piston 35 and the height 48 is subtracted from the height measurement obtained after the saturation of the sample 48.
  • the value obtained is the thickness or height ("H") of the swelling sample.
  • Permeability measurements are initiated by delivering a flow of test solution to a sample vessel 30 having a saturated sample 68, a piston 35, and a weight 48 therein. Adjust the flow rate of the test solution into the vessel so that a fluid height of about 7.8 cm is placed on the bottom of the sample vessel. Keep it. The amount versus time of solution passing through sample 68 is determined gravimetrically. The data point is that the fluid level is about 7.8 cm. If kept stable at height, collect every second for at least 20 seconds. The flow rate Q through the swelling sample 68 is measured in g / s' by a linear least squares approximation of the fluid g through the sample 68 versus the time in seconds. The transmittance (darcy) is calculated according to the following formula (3).
  • K is the transmittance (cuf)
  • Q is the flow rate (g / velocity)
  • H is the height of the sample (cm)
  • Mu is the liquid viscosity (approximately in the test solution used in the poi seK test) 1 cps)
  • A is the cross-sectional area for the liquid flow (cuf)
  • Rho is the liquid density (g / cuf) (for the test solution used in the test)
  • P is hydrostatic pressure (dynes / cuf) (typically About 3, 923 dynes / cuf). The hydrostatic pressure is calculated by the following equation.
  • Rho is the liquid density (g / cuf)
  • g is the weight acceleration, typically 981 cm / sec 2
  • h is the fluid height (e.g. 7.8 cm for the permeability test described herein).
  • Absorbency under Load (AUL) of 0.9 psi was measured by the following method. First, a stainless steel 400 mesh wire was mounted on the bottom of a plastic cylinder having an inner diameter of 25 mm 3. Piston which can evenly spread superabsorbent resin W 0 (g, 0. 16 g) on wire mesh under normal temperature and humidity 5 and give a load of 5. 1 kPa (0.9 ps i) evenly on it. (pi ston) is slightly smaller than the outer diameter of 25 ⁇ , is not the same as the inner wall of the cylinder, and the up and down movement is not disturbed. The weight of the device W 3 (g) was measured.
  • a glass filter with a thickness of 5 mm3 was placed inside a petri dish of 150 mm diameter with a diameter of 90 mm, and a physiological saline consisting of 0.90 wt% sodium chloride was made at the same level as the upper surface of the glass filter.
  • One sheet of filter paper having 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.
  • AUL (g / g) [W 4 (g)-W 3 (g).] / W 0 (g)
  • W 0 (g) is the weight of the absorbent resin (g) .
  • W 3 (g) is the sum of the weight of the absorbent resin and the weight of the device capable of applying a load to the absorbent resin
  • W 4 (g) is the sum of the weight of the absorbed water absorbed resin after supplying the absorbent resin with water for 1 hour under lowering (0.9 ps i) and the weight of the device capable of applying a load to the absorbent resin.
  • SP was measured by the measuring apparatus as shown in FIG. Specifically, brine (0.9% NaCl) was filled to the right side of the measuring instrument to a 0 mL scale of a glass tube having an inner diameter of 20 mm 3. On the left side of the measuring instrument, a 50 mm cylindrical funnel bottom is equipped with a 100 micrometer gl ass fil ter, evenly spraying 1.0 g of superabsorbent polymer on the gl ass fil ter under conditions of 50 ° C and 23 ° C. It was. While spraying the super absorbent polymer, the burette of the burette of the measuring instrument was opened, and the amount of salt (g) absorbed by 1 g of the super absorbent polymer was measured for 5 minutes. The measurement results are shown in Tables 1 and 2 below. Table 1

Landscapes

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

Abstract

La présente invention concerne un polymère superabsorbant et son procédé de préparation. Selon la présente invention, le polymère superabsorbant présente une excellente perméabilité de lit de gel (GBP) et un excellent pouvoir aspirant, et est par conséquent utile en tant que matériau pour un produit hygiénique tels que des couches.
PCT/KR2015/012664 2014-12-22 2015-11-24 Polymère superabsorbant et procédé de préparation WO2016104962A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/104,485 US9901904B2 (en) 2014-12-22 2015-11-24 Superabsorbent polymer and preparation method thereof
EP15864314.8A EP3075760A4 (fr) 2014-12-22 2015-11-24 Polymère superabsorbant et procédé de préparation
CN201580003275.3A CN105934451B (zh) 2014-12-22 2015-11-24 超吸收性聚合物及其制备方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR10-2014-0186252 2014-12-22
KR20140186252 2014-12-22
KR10-2015-0140933 2015-10-07
KR1020150140933A KR102011926B1 (ko) 2014-12-22 2015-10-07 고흡수성 수지 및 이의 제조 방법

Publications (1)

Publication Number Publication Date
WO2016104962A1 true WO2016104962A1 (fr) 2016-06-30

Family

ID=56150937

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2015/012664 WO2016104962A1 (fr) 2014-12-22 2015-11-24 Polymère superabsorbant et procédé de préparation

Country Status (1)

Country Link
WO (1) WO2016104962A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155591A1 (fr) 2017-02-22 2018-08-30 株式会社日本触媒 Feuille absorbant l'eau, feuille allongée absorbant l'eau, et article absorbant

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56161408A (en) 1980-05-19 1981-12-11 Kao Corp Production of water-absorbing resin
JPS57158209A (en) 1981-03-25 1982-09-30 Kao Corp Production of bead-form highly water-absorbing polymer
JPS57198714A (en) 1981-05-29 1982-12-06 Sumitomo Chem Co Ltd Production of hydrogel
US7179851B2 (en) 2003-09-05 2007-02-20 Kimberly-Clark Worldwide, Inc. Damage-resistant superabsorbent materials
KR20110111943A (ko) * 2010-04-06 2011-10-12 주식회사 엘지화학 표면개질된 흡수성수지
KR20140063400A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지
JP5504334B2 (ja) * 2010-03-12 2014-05-28 株式会社日本触媒 吸水性樹脂の製造方法
KR20140107491A (ko) * 2011-12-30 2014-09-04 에보닉 코포레이션 초흡수성 중합체 및 가교제 조성물에 대한 공정
KR20140125420A (ko) * 2012-02-17 2014-10-28 가부시키가이샤 닛폰 쇼쿠바이 폴리아크릴산(염)계 흡수성 수지 및 그의 제조 방법

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56161408A (en) 1980-05-19 1981-12-11 Kao Corp Production of water-absorbing resin
JPS57158209A (en) 1981-03-25 1982-09-30 Kao Corp Production of bead-form highly water-absorbing polymer
JPS57198714A (en) 1981-05-29 1982-12-06 Sumitomo Chem Co Ltd Production of hydrogel
US7179851B2 (en) 2003-09-05 2007-02-20 Kimberly-Clark Worldwide, Inc. Damage-resistant superabsorbent materials
JP5504334B2 (ja) * 2010-03-12 2014-05-28 株式会社日本触媒 吸水性樹脂の製造方法
KR20110111943A (ko) * 2010-04-06 2011-10-12 주식회사 엘지화학 표면개질된 흡수성수지
KR20140107491A (ko) * 2011-12-30 2014-09-04 에보닉 코포레이션 초흡수성 중합체 및 가교제 조성물에 대한 공정
KR20140125420A (ko) * 2012-02-17 2014-10-28 가부시키가이샤 닛폰 쇼쿠바이 폴리아크릴산(염)계 흡수성 수지 및 그의 제조 방법
KR20140063400A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ODIAN: "Principle of Polymerization", 1981, WILEY, pages: 203
REINHOLD SCHWALM: "UV Coatings: Basics, Recent Developments and New Applications", 2007, ELSEVIER, pages: 115
See also references of EP3075760A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018155591A1 (fr) 2017-02-22 2018-08-30 株式会社日本触媒 Feuille absorbant l'eau, feuille allongée absorbant l'eau, et article absorbant

Similar Documents

Publication Publication Date Title
KR102011926B1 (ko) 고흡수성 수지 및 이의 제조 방법
JP6321805B2 (ja) 高吸水性樹脂の製造方法
JP6443998B2 (ja) 高吸水性樹脂
JP6592461B2 (ja) 高吸水性樹脂
WO2017164459A1 (fr) Procédé de préparation d'un polymère superabsorbant
EP3018149B1 (fr) Procédé de préparation d'une résine superabsorbante
JP7039105B2 (ja) 高吸水性樹脂およびその製造方法
EP3196231A1 (fr) Résine hautement absorbante et son procédé de préparation
EP3290447B1 (fr) Procédé de préparation d'un polymère superabsorbant
EP3241861A1 (fr) Polymère superabsorbant
WO2018110760A1 (fr) Polymère superabsorbant et son procédé de préparation
KR20170057705A (ko) 고흡수성 수지의 제조 방법
JP2021506989A (ja) 高吸水性樹脂およびその製造方法
JP2021518874A (ja) 高吸水性樹脂およびその製造方法
WO2018124404A1 (fr) Polymère superabsorbant et son procédé de préparation
JP2021534314A (ja) 高吸水性樹脂の製造方法および高吸水性樹脂
KR102069313B1 (ko) 고흡수성 수지의 제조 방법 및 고흡수성 수지
EP3424991B1 (fr) Polymère superabsorbant et procédé de préparation associé
JP7080539B2 (ja) 高吸水性樹脂の製造方法
EP3342802B1 (fr) Polymère superabsorbant et procédé pour sa préparation
JP6949111B2 (ja) 高吸水性樹脂およびその製造方法
WO2016104962A1 (fr) Polymère superabsorbant et procédé de préparation
WO2015088200A1 (fr) Procédé de préparation d'une résine super-absorbante
WO2015016643A1 (fr) Polymère superabsorbant
KR102614036B1 (ko) 고흡수성 수지의 제조 방법 및 고흡수성 수지

Legal Events

Date Code Title Description
REEP Request for entry into the european phase

Ref document number: 2015864314

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2015864314

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 15104485

Country of ref document: US

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15864314

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE