WO2019004653A1 - Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé - Google Patents

Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé Download PDF

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Publication number
WO2019004653A1
WO2019004653A1 PCT/KR2018/007028 KR2018007028W WO2019004653A1 WO 2019004653 A1 WO2019004653 A1 WO 2019004653A1 KR 2018007028 W KR2018007028 W KR 2018007028W WO 2019004653 A1 WO2019004653 A1 WO 2019004653A1
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Prior art keywords
meth
acrylate
weight
polymer
powder
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PCT/KR2018/007028
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English (en)
Korean (ko)
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WO2019004653A8 (fr
Inventor
김태희
양세우
황지영
김기철
Original Assignee
주식회사 엘지화학
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Priority claimed from KR1020180071073A external-priority patent/KR102215025B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2019506089A priority Critical patent/JP6789375B2/ja
Priority to US16/341,804 priority patent/US11028237B2/en
Priority to EP18822675.7A priority patent/EP3502168B1/fr
Priority to CN201880003995.3A priority patent/CN109863194B/zh
Publication of WO2019004653A1 publication Critical patent/WO2019004653A1/fr
Publication of WO2019004653A8 publication Critical patent/WO2019004653A8/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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a method for producing a highly water absorbent resin and a superabsorbent resin obtained by such a method, which are basically excellent in absorption performance and capable of not only reducing heat loss in a pulverization regeneration step but also improving productivity.
  • Super Absorbent Polymer is a superabsorbent polymer
  • the above-mentioned superabsorbent resin has begun to be put to practical use as a sanitary article, and nowadays, in addition to sanitary articles such as diapers for children, it is used for agricultural and horticultural soil repairing materials, indexing materials for construction, seedling- And as a material for fomentation and the like.
  • Such a superabsorbent resin can be generally prepared into a powdery phase by preparing a hydrogel polymer by a polymerization process of a monomer, pulverizing and drying and then classifying the base resin powder to prepare a base resin powder, followed by surface treatment.
  • pulverization of the hydrous gel is a process necessary for producing a superabsorbent resin in the form of powder or particles. In this process, fine particles having a size less than the reference size are generated.
  • the normal superabsorbent resin may be about 150 to 850 / in or about 300 to 500 / ⁇ in the production process.
  • Polyacrylic acid (PAA Particles) It is called "differential”. Since the fine powder of such a superabsorbent resin occurs at about 10 to 15% of the total resin product, it is necessary to re-assemble them to improve the productivity.
  • the above-mentioned fine powder acts as one of the factors of productivity deterioration, and in particular, there is a heat loss which occurs upon re-assembling the fine powder of the superabsorbent resin.
  • the present invention can reduce the heat loss generated during the reassembling of the fine particles during the manufacturing process of the conventional superabsorbent resin .
  • Absorbing resin which can efficiently recycle fine particles and improve the productivity of a superabsorbent resin having excellent physical properties and a superabsorbent resin obtained therefrom.
  • the present invention relates to a method for crosslinking a water-soluble ethylenically unsaturated monomer having at least partly acidified groups, in the presence of an internal cross-linking agent, by cross-linking a water-soluble ethylenically unsaturated monomer having an acidified group at least partially formed to form a hydrous gel polymer comprising the first cross-linking polymer;
  • the fine powder is reassembled in the presence of a powdery polymer binder Providing a pulverizer assembly
  • the present invention also relates to a base resin powder comprising a first crosslinked polymer of a water soluble ethylenically unsaturated monomer having at least partly neutralized acidic groups;
  • the weight average molecular weight refers to the weight average molecular weight (unit: g / mol) in terms of polystyrene measured by the GPC method.
  • a detector such as a known analyzer and a Refract ive Index Detector and an analyzing column can be used.
  • Temperature conditions, solvent, and f low rate can be applied. Specific examples of the measurement conditions include a temperature of 35 ° C, THF (tetrahydrofuran) and f low rate of 1 mL / min.
  • the method comprising the steps of: recovering fine powder after classification of the dried product of the hydrogel polymer; Reassembling the fine powder in the presence of a polymer binder in the form of a powder to provide a fine powder compact; And fusing the finely divided microspheres with the hydrous gel polymer before drying.
  • the present invention after the dry blend of the fine particles and the powdery polymer binder is carried out, the fine powder compact can be formed even if only the short heat treatment is performed. Therefore, the present invention can improve both workability and productivity.
  • the specific polymeric binder used in the present invention is polyethylene oxide .
  • the polymer binder is superior to the known compounds such as polypropylene glycol, Hereinafter, a method for producing a superabsorbent resin including a fine particle reassembling step of the present invention in one embodiment will be described in more detail.
  • the method for producing a superabsorbent resin according to the present invention comprises: crosslinking a water-soluble ethylenically unsaturated monomer having an acidic group at least partially neutralized in the presence of an internal crosslinking agent to form a hydrogel polymer comprising a first crosslinked polymer; Gel-grinding the hydrogel polymer; Drying the gel-pulverized hydrogel polymer, pulverizing and classifying the dried gel of the hydrogel polymer to form a base resin powder; And forming a superabsorbent resin particle by surface cross-linking in the presence of the surface cross-linking agent while heat-treating the base resin powder.
  • the fine powders are recovered after the drying, pulverization and classification, and the recovered fine powders are subjected to a re-granulation process and then subjected to a step of the gel- , And can be used for producing the base resin powder through the subsequent series of steps.
  • the 'first crosslinked polymer 1' means that the water-soluble ethylenically unsaturated monomer described above is cross-linked polymerized in the presence of an internal crosslinking agent, and the 'base resin powder' means a material containing such crosslinked polymer.
  • second crosslinked polymer &quot refers to the surface of the first crosslinked polymer.
  • the surface cross-linking agent will be described later.
  • the fineness of the superabsorbent resin referred to in the present invention may contain less than 150 smaller than the average particle diameter and fine powder.
  • the " one superabsorbent resin” referred to in the present specification refers to a base resin powder comprising a gel-crosslinked polymer of a water-soluble ethylene-vinyl saturated monomer having at least partially neutralized acidic groups; And a superabsorbent resin formed on the base resin powder, wherein the super-absorbent resin includes a surface crosslinked layer containing a crab crosslinked polymer in which the crosslinked U-crosslinked polymer is additionally crosslinked via a surface crosslinking agent. Accordingly, in the present invention, the fine powder is recovered and reused for the production method of the superabsorbent resin.
  • the above manufacturing method will be described in more detail.
  • the step of forming the hydrogel polymer, the step of forming the base resin powder, and the step of treating the surface of the base resin powder may be carried out according to a method described later.
  • the hydrogel polymer is obtained according to the production process of the superabsorbent resin, followed by gel pulverization, followed by drying, pulverization and classification.
  • a method for recovering a dried gel of a functional gel polymer Reassembling the fine powder in the presence of a polymer binder in the form of a powder to provide a fine powder compact; And comminuting the finely divided microspheres with the hydrogel polymer before drying.
  • the providing of the fine pulverulent assembly has an average particle size of less than 150.
  • polymer binder in the form of powder are dried and dissolved in a non-solvent, and then heat-treated to re-assemble the fine powder.
  • the binder used in the fine particle reassembling should be free of organic solvents and harmful substances, have no harmfulness to human body, have no volatile detection substance, can reduce heat loss of 5% or more in water content, , Tm or Tg below the process temperature, and low cost.
  • the present invention uses a powdery polymer binder capable of exhibiting excellent performance even without using a solvent.
  • the powdery polymer binder is characterized by using a poly (ethylene oxide) powder having a weight average molecular weight of 100, 000 to 600, 000 g / ri.
  • the polyethylene oxide powder may have a surface area larger than that of the water-soluble polymer Therefore, a high binding effect can be exhibited and a water-free process is possible.
  • the binder powder When the binder powder is used in a low molecular weight range close to 100,000, increasing the binder content, reassembling temperature and reassembling time can further improve the reassembling efficiency.
  • the content of the powdery polymer binder may be preferably about 50 to 100 parts by weight based on 100 parts by weight of the fine powder.
  • the reassembly can be performed at a temperature of 105 ° C to 180 ° C for 5 minutes to 10 minutes.
  • the binder powder when used in a high molecular weight range close to the 600,000 range of the weight average molecular weight of 100,000 to 600,000 g / mol, the binder content, The CRC can be further improved.
  • the content of the powdery polymer binder may preferably be about 10 to 25 parts by weight based on 100 parts by weight of the fine powder.
  • the reassembly can also be performed at a temperature of 105 ° C to 180 ° C for 5 minutes to 10 minutes.
  • the binding cohesive force can be relatively increased by increasing the binder content .
  • the polyethylene oxide powder is used in a state of being dry and in a state of being in common with the fine powder, the water consumption (water content) used in the conventional microfine reassembling can be reduced, and heat loss generated when water is dried can be reduced.
  • the heat treatment is preferably performed at 105 ° C to 180 ° C for 10 minutes to 20 minutes. If the heat treatment temperature is lower than 105 ° C, the re-assembly efficiency is lowered. If the heat treatment temperature is higher than 180 ° C, the heat loss may be increased without increasing the re-assembly efficiency. If the heat treatment time is less than 10 minutes, there is a problem that the re-assembly efficiency is lowered. If the heat treatment time is longer than 20 minutes, there is a problem that heat loss is increased without increasing the re-assembly efficiency.
  • the powdery polymer binder may be used in an amount of 1 to 100 parts by weight based on 100 parts by weight of the fine powder. More preferably, the polymer binder is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the fine powder.
  • the weight is 100 parts or more significantly the CRC value falling problem.
  • the pulverization assembly may be additionally added to the hydrogel polymer before the drying, more specifically, between the just before and after the gel pulverization step, and the drying step.
  • the pulverulent re-assembly according to the present invention may be incorporated in an amount of 10 to 30 parts by weight, or 15 to 28 parts by weight, based on 100 parts by weight of the hydrogel polymer before drying. Due to the addition of such a fine pulverizing agent, the inner surface area of the base resin powder and the superabsorbent resin can be widened, and the superabsorbent resin can exhibit a further improved absorption rate. In addition, the strength of the base resin powder and the superabsorbent resin can be controlled within an appropriate range by the introduction of the finely pulverized material within the above-mentioned content range, and the physical properties of one embodiment can be more effectively achieved.
  • the re-assembled fine powder may be pulverized using a hammer mill or a ball mill, and classified, and the re-assembly efficiency of each grain size may be measured.
  • the re-assembly efficiency is evaluated according to the degree of pulverization and classification, but the method is not limited. For example, in the case of refinement of the finely granulated powder by about 3 to 7 stages, the ratio of the particle size of the fine powder having an average particle diameter of less than 150 / rni is classified according to the size The re-assembly efficiency can be evaluated.
  • the fineness re-assembly efficiency can be 14 to 76%, and the present invention can be variously adjusted in its range.
  • the centrifugal separation performance (CRC) of the fine pulverized material of the present invention for 30 minutes in physiological saline (0.9 wt / 3> sodium chloride aqueous solution) is 9 g / g or more, preferably 9.7 g / .
  • the productivity can be improved by further performing the step of mixing with the hydrogel polymer before drying.
  • the centrifugal separation capacity (CRC) of the above-mentioned microdispersant for physiological saline can be calculated by the following equation 1 after the microdispersed product is absorbed into physiological saline over 30 minutes:
  • W 0 (g) is the initial weight (g) of the finely divided assembly
  • Kg is the weight measured after impregnation of the nonwoven fabric bag without pulverization into the physiological saline solution for 30 minutes and then dehydration for 3 minutes at 250G using a centrifuge.
  • W 2 (g) is the weight measured after impregnating the nonwoven fabric bag containing the fine pulverized material in physiological saline solution at room temperature for 30 minutes and then dehydrating at 250 G for 3 minutes using a centrifuge.
  • a hydrogel polymer containing a crab crosslinked polymer can be prepared through crosslinking polymerization of a monomer composition containing a water-soluble ethylenically unsaturated monomer in the presence of an internal crosslinking agent.
  • the water-soluble ethylenically unsaturated monomer may be any monomer conventionally used in the production of a superabsorbent resin.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by the following Formula 1:
  • M 1 is a hydrogen atom, a monovalent or divalent metal, an ammonium group or an organic amine salt.
  • the monomer may be at least one selected from the group consisting of acrylic acid, methacrylic acid, and monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts of these acids.
  • acrylic acid or a salt thereof is used as the water-soluble ethylenically unsaturated monomer, it is advantageous to obtain a highly water-absorbent resin having improved water absorption.
  • the monomer may be selected from the group consisting of maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2- Meth) acrylamide-2-methylpropanesulfonic acid and salts thereof; (Meth) acrylamide, N-substituted (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
  • Non-ionic hydrophilic-containing monomers such as methoxypolyethylene glycol (meth) acrylate or polyethylene glycol (meth) acrylate; And unsaturated monomers containing amino groups of (N, N) -dimethylaminoethyl (meth) acrylate or (N, N) -dimethylaminopropyl (meth) acrylamide and quaternary products thereof Can be used.
  • the water-soluble ethylenically unsaturated monomer may have an acidic group and at least a part of the acidic group may be neutralized.
  • the monomer is partially neutralized with an alkali substance such as sodium hydroxide, potassium hydroxide, ammonium hydroxide or the like.
  • the neutralization degree of the monomer may be 40 to 95 mol%, or 40 to 80 mol%, or 45 to 75 mol%.
  • the degree of neutralization may vary depending on the final physical properties. However, if the degree of neutralization is too high, the neutralized monomer may precipitate and polymerization may not proceed smoothly. On the other hand, if the degree of neutralization is too low, It can exhibit properties similar to elastic rubber which is difficult to handle.
  • the monomer composition may include a polymerization initiator generally used in the production of a superabsorbent resin.
  • a polymerization initiator generally used in the production of a superabsorbent resin.
  • a thermal polymerization initiator or a photopolymerization initiator may be used depending on the polymerization method.
  • a certain amount of heat is generated and a certain amount of heat is generated in accordance with the progress of the polymerization reaction which is an exothermic reaction, so that a thermal polymerization initiator may further be included.
  • photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, benzyldimethyl At least one compound selected from the group consisting of benzyl dimethyl ketal, acyl phosphine and a-aminoketone may be used.
  • acylphosphine lucyrin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide, may be used .
  • a variety of photopolymerization initiators are disclosed in Reinhold Schwarz, "UV Coatings: Basics, Recent Developments and New Applications" (Elsevier 2007), page 115, which is incorporated herein by reference.
  • thermal polymerization initiator at least one compound selected from the group consisting of a persulfate-based initiator, an azo-based initiator, hydrogen peroxide, and ascorbic acid may be used.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), ammonium persulfate (NH 4 ) 2 S 2 0 8 ).
  • Azo-based initiators include 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis- (1 2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2-azobis
  • Such a polymerization initiator may be used in an amount of from about 0.001 to 1 % ≪ / RTI > by weight. That is, if the concentration of the polymerization initiator is too low, the polymerization rate may be slowed and the remaining monomer may be extracted in the final product in a large amount, which is not preferable. On the contrary, when the concentration of the polymerization initiator is too high, the chain of the polymer forming the network is shortened, and the physical properties of the resin may be lowered, such that the content of the water-soluble component is increased and the pressure absorption capacity is lowered.
  • the monomer composition includes a crosslinking agent (" internal crosslinking agent ”) for improving the physical properties of the resin by polymerization of the water-soluble ethylenically unsaturated monomer.
  • the cross-linking agent is for cross-linking the hydrogel polymer, and can be used separately from the " surface cross-linking agent "
  • the above-mentioned two or more internal crosslinking agents for example, a poly (meth) acrylate-based first internal crosslinking agent and an allyl (meth)
  • a hydrogel polymer having a gel strength of higher gel strength for example, a gel strength of not less than lOOOOPa, or llOOOPa or more, or not less than 120000Pa, and particularly not limited to 50,000Pa or less, or 40,000Pa or less, or 38,000Pa or less can be obtained have.
  • trimethyl is preferably used in combination with at least one member selected from the group consisting of propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, diethylene glycol di (meth) acrylate, butane diol di (meth) acrylate, butylene glycol di (meth) acrylate, diethylene glycol di di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di-penta the EPO Li pentaacrylate, glycerin tri (meth) acrylate and penta a tetraacrylate erythro At least one selected from the group consisting of .
  • the internal crosslinking agent allyl methacrylate, allylacrylate and the like can be used.
  • the first internal cross-linking agent may be used in an amount of 0.4 to 1 part by weight based on 100 parts by weight of the entire monomer composition including the internal cross-linking agent and the monomer, 0.5 to 0.9 parts by weight of black, 0.6 to 0.8 parts by weight of black, and the second internal cross-linking agent may be added in an amount of 0.008 to 0.5 parts by weight, or 0.01 to 5 parts by weight per 100 parts by weight of the entire monomer composition, 0.1 part by weight, and black in an amount of 0.01 to 0.05 part by weight.
  • the monomer composition may further contain additives such as a thickener, a plasticizer, a storage stabilizer, and an antioxidant, if necessary.
  • additives such as a thickener, a plasticizer, a storage stabilizer, and an antioxidant, if necessary.
  • Such a monomer composition may be prepared in the form of a solution in which a raw material such as the above-mentioned monomer, polymerization initiator, internal cross-linking agent, etc. is dissolved in a solvent.
  • usable solvents may be used without limitation of the constitution as long as they can dissolve the above-mentioned raw materials.
  • the solvent include water, ethane, ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl But are not limited to, ether acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, N, N-dimethylacetamide, or a mixture thereof can be used.
  • the formation of the hydrogel polymer through polymerization of the monomer composition can be carried out by a conventional polymerization method, and the process is not particularly limited.
  • the polymerization method is divided into thermal polymerization and photopolymerization depending on the type of polymerization energy source.
  • the polymerization may proceed in a reactor having a stirring axis such as a kneader, It is possible to proceed in a reactor equipped with a movable conveyor belt. ' .
  • the hydrogel polymer can be obtained by charging the monomer composition into a semipermeable vessel such as a kneader equipped with a stirring shaft, and supplying hot air thereto or by heating the reactor to heat-polymerize.
  • a semipermeable vessel such as a kneader equipped with a stirring shaft
  • the hydrogel polymer discharged to the reactor outlet depending on the shape of the stirring shaft provided in the reactor can be obtained as particles of several millimeters to several centimeters.
  • the hydrogel polymer can be obtained in a variety of forms depending on the concentration and the injection rate of the monomer composition to be injected, and a hydrogel polymer having a normal (weight average) particle diameter of 2 to 50 mm is obtained.
  • a hydrogel polymer in the form of a sheet can be obtained when photopolymerization is carried out on the monomer composition in a reactor equipped with a movable conveyor belt.
  • the thickness of the sheet may vary depending on the concentration and the injection rate of the monomer composition to be injected. In general, the thickness of the sheet is adjusted to 0.5 to 10 cm in order to ensure uniform polymerization of the entire sheet, desirable.
  • the hydrogel polymer formed by such a method may have a water content of 38 to 60 wt%, or 40 to 55 wt%.
  • the water content may be the weight of water in the total weight of the hydrogel polymer, which is the weight of the hydrogel polymer minus the weight of the polymer in the dry state.
  • a step of gel-grinding the hydrogel polymer is carried out.
  • the hydrogel polymer may be subjected to at least one grinding step.
  • the hydrogel polymer is capable of performing primary and secondary pulverization.
  • the pulverizer to be used is not limited in its constitution, but it may be a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary pulverizer a crusher, a chopper, and a disc cutter, which are selected from the group consisting of a cutter mill, a cutter mill, a disc mill, a shred crusher, a crusher, a chopper and a disc cutter.
  • the present invention is not limited to the above-described example.
  • the hydrogel polymer when the hydrogel polymer is secondarily pulverized, a disk-shaped cutter may be used in the first pulverization process, and a chopper equipped with a screw may be used in the second pulverization process.
  • a chopper crusher hot water can be injected.
  • the gel pulverization of the hydrogel polymer can be performed so that the diameter of the hydrogel polymer ranges from 0.1 mm to 10 mm. That is, in order to increase the drying efficiency, the hydrogel polymer is preferably pulverized into particles having a size of 10 or less. However, since excessive agglomeration may occur during pulverization, it is preferable that the hydrogel polymer is gel-pulverized into particles having a size of 0.1 mm or more.
  • hydrogel polymer may stick to the surface of the gel pulverizer.
  • steam, water, surfactant, anti-caking agent for example, c l ay, s i l i ca, etc.
  • a cross-linking agent containing an acrylate of a bifunctional group or a polyfunctional group having three or more functional groups, a cross-linking agent containing a hydroxyl group, a cross-linking agent containing a hydroxyl group, a cross-linking agent containing a hydroxyl group, Etc. may be added to the hydrogel polymer.
  • the gel-pulverized hydro gel polymer is dried, and the dried product of the hydro gel polymer is pulverized and classified to form a base resin powder having an average particle diameter of 150 to 850.
  • the base resin powder is moved to the surface cross-linking step, and the fine powder is recovered to perform a fine particle reassembling process. Then, the fine powder compact is again introduced into the step of mixing with the hydrogel polymer before drying, Thereby forming a resin powder.
  • the base resin powder of the present invention can be produced by a process that further includes a finely divided re-assembly according to the above-described method.
  • the gel-pulverized hydrogel polymer can be dried first.
  • the drying may be carried out at a temperature of 120 to 250 ° C, preferably 140 to 20 ° C, more preferably 150 to 190 ° C.
  • the drying temperature may be the temperature of the heating medium supplied for drying, or the temperature of the heating medium and the polymer in the drying process. Can be defined as the temperature inside the drying reactor that contains it. If the drying temperature is low and the drying time is long, the process efficiency is lowered. To prevent this, the drying temperature is preferably 120 ° C or more. In addition, if the drying temperature is higher than necessary, the surface of the hydrogel polymer is excessively dried, and the generation of fine powder may be increased in the subsequent grinding step, and the physical properties of the final resin may be lowered. To prevent this, 250 ° C or lower.
  • the drying time in the drying step is not particularly limited, in consideration of the physical properties of the process efficiency and the resin, to 20 minutes under the drying temperature
  • the drying can be carried out by using a conventional medium, for example, by supplying hot air to the pulverized hydrogel polymer, infrared irradiation, microwave irradiation, ultraviolet irradiation, or the like.
  • drying is preferably carried out so that the dried polymer has a moisture content of about 0.1 to 10% by weight. That is, when the water content of the dried polymer is 0.1 wt% or more, the increase of the manufacturing cost due to excessive drying and the degradation of the crosslinked polymer may occur, which is not preferable. And, if the water content of the dried polymer is 10 weight or more, it may occur in a subsequent step, which is undesirable.
  • the dry polymer can be pulverized, whereby the particle size and surface area of the polymer can be adjusted to an appropriate range.
  • the pulverization can be carried out such that the particle diameter of the pulverized polymer is 150 to 850 / m.
  • a pin mill, a hammer mill and a screw mill are conventionally used as a mill, a disc mill, a jog mill a jog mill or the like may be used.
  • the step of selectively classifying particles having a particle diameter of 150 to 850 in the polymer particles obtained through the above-mentioned pulverization step may be further performed.
  • the base resin powder is produced through the above-mentioned classification step, the base resin powder is heat-treated in the presence of the surface cross- It is possible to form the superabsorbent resin particles by crosslinking.
  • the surface crosslinking induces a crosslinking reaction on the surface of the base resin powder in the presence of a second crosslinking agent (surface crosslinking agent).
  • a surface modifying layer (surface crosslinking layer) is formed on the surface of the base resin powder .
  • the surface cross-linking may be carried out, for example, by a method of cross-linking a solution containing the second cross-linking agent (surface cross-linking agent) with the base resin powder.
  • the surface cross-linking agent is a compound capable of reacting with the functional group of the polymer, and may be an alkylene carbonate compound or a polyhydric alcohol compound, preferably an alkylene carbonate having 2 to 5 carbon atoms. More preferably, ethylene carbonate can be used as the surface cross-linking agent.
  • silica (silica) or clay may be further used.
  • an acidic compound or a polymer may be further added.
  • the content of the surface cross-linking agent may be appropriately controlled according to the type of cross-linking agent, reaction conditions, etc., and preferably 0.001 to 5 parts by weight based on 100 parts by weight of the base resin powder. If the content of the surface cross-linking agent is too low, the surface modification may not be performed properly, and the physical properties of the final resin may be deteriorated. On the contrary, when an excessive amount of surface cross-linking agent is used, the basic absorption ability of the resin may be deteriorated due to excessive surface cross-linking reaction, which is not preferable.
  • the surface cross-linking step may include a method in which a surface cross-linking liquid containing the surface cross-linking agent is mixed with a base resin powder in a reaction tank, a method of spraying a surface cross-linking liquid containing a surface cross-linking agent on a base resin powder, Base resin powder, and surface cross-linking liquid are continuously supplied and mixed, and the like.
  • water may be added additionally when the surface cross-linking agent is added.
  • uniform dispersion of the surface cross-linking agent can be induced, clustering of the base resin powder is prevented,
  • the penetration depth of the surface cross-linking agent to the powder can be further optimized.
  • the amount of water to be added together with the surface cross-linking agent may be adjusted to 0.5 to 10 parts by weight based on 100 parts by weight of the base resin powder.
  • the surface cross-linking step can be conducted at a temperature of 100 to 250 ° C.
  • the surface cross-linking may be conducted for 1 minute to 120 minutes, preferably 1 minute to 100 minutes, more preferably 10 minutes to 80 minutes. That is, the surface cross-linking step may be carried out under the above-described conditions in order to prevent the polymer particles from being damaged due to excessive reaction while inducing minimal surface cross-linking reaction.
  • a base resin powder comprising: a water-soluble ethylenically unsaturated monomer having at least partially neutralized acid groups; And a surface cross-linked layer formed on the base resin powder, wherein the crab cross-linked polymer comprises a second cross-linked polymer that is additionally cross-linked through a surface cross-linking agent,
  • a superabsorbent resin having a centrifugal separation performance (CRC) of 30 g / g to 45 g / g may be provided.
  • the superabsorbent resin of one embodiment can exhibit excellent absorption magnification while satisfying all of the required basic physical properties.
  • the superabsorbent resin can exhibit excellent liquid-permeability as the surface of the base resin powder is cross-linked and the surface cross-linked layer is included.
  • the superabsorbent resin of one embodiment produced according to the above-described method may have an average particle size of about 150 to 850, or about 300 to 500.
  • at least 95% by weight of the base resin powder and the superabsorbent resin containing the base resin powder may have a particle diameter of 150 to 850, and the fine powder having a particle diameter of less than 150 may be less than 3% by weight.
  • water is not used in the process of re-assembling fine particles of a superabsorbent resin, heat loss due to the water drying process is reduced, and specific polymer binder powder It is possible to provide a method of manufacturing a superabsorbent resin with improved productivity while maintaining excellent absorption performance by using re-assembling of the fine powder by using the above-
  • FIG. 1 is a scanning electron micrograph of a microfibrillated assembly used in Examples 8 and 9 of the present invention.
  • a continuous manufacturing apparatus composed of a polymerization process, a hydrogel pulverization process, a drying process, a pulverization process, a classification process, a surface cross-linking process, a submerging process, a classification process and a transportation process connecting each process Respectively.
  • Step 2 Function gel polymer grinding step
  • the hydrogel polymer was first cut with a cutter to an average size of about 300 mm or less, and then put into a chopper together with the finely pulverized product, followed by secondary pulverization.
  • the fine pulverized material used was the fine pulverized material prepared in the following step 5, and the charging ratio was 20 parts by weight based on 100 parts by weight of the hydrogel polymer.
  • step 2 the pulverized hydrogel polymer was dried in a drier capable of airflow transfer up and down.
  • a hot air of 180 ° C was flowed upward from below for 15 minutes and then flowed downward from above for 15 minutes so that the water content of the dried powder was not more than about 2% Lt; / RTI >
  • the hydrogel polymer dried in step 3 was pulverized by a pulverizer and classified to obtain a base resin having a size of 150 to 850. .
  • the fine particles as the polymer particles having a particle diameter of less than 150 m were collected through the above-mentioned ' classification, and then the fine pulverized material was prepared according to the following step 5 and used as the fine pulverized material of step 2 described above.
  • microfibrillator assembly moisture content 0% microfibrillated
  • the PEO powder was used while varying its content based on 100 parts by weight of the whole fine powder. That is, the PEO powders were classified into Examples 1 to 8 using 1, 5, 10, 15, 25, 50, 75 and 100 weight parts, respectively.
  • the stirrer was equipped with stirring means and temperature adjusting means.
  • Step 6 After completion of the drying process, heat treatment was carried out at 105 ° C for 10 minutes to prepare a fine pulverized product. (Step 6)
  • a superabsorbent resin was prepared in the same manner as in Example 8, except that the heat treatment temperature was changed to 180 ° C in the fine particle reassembling step of step 5 above. Comparative Example 1
  • a superabsorbent resin was prepared in the same manner as in Example 1, except that 10 g (water content: 10%) of a polypropylene glycol aqueous solution was used based on 100 parts by weight of the fine powder in the above step 5.
  • the average particle size of the fine powder compacts of Examples 8 and 9 was measured using a scanning electron microscope and is shown in Fig.
  • the pulverization and classification of the pulverized and pulverized fine pulverized products of Examples 1 to 8 were conducted according to the following Table 1, and the re-assembly efficiency and the CRC were measured, and the results are shown in Table 2. That is, the pulverized re-assembly of the examples was pulverized using a hammer mill or a ball mill, and classified into three or seven stages using a mesh, and the re-assembly efficiency and CRC were measured.
  • the re-assembly efficiency can be measured according to the following formula: have.
  • Comparative Example 1 satisfied a certain level of re-assembly efficiency and CRC. However, since it has a high moisture content, it is troublesome to perform a separate drying process. In addition, Comparative Example 2 required a drying process even though the water content was low, and in particular, it was inefficient because it could not exhibit the re-assembly effect.
  • the centrifugal separation capacity (CRC) was measured according to the EDANA WSP 241.3 standard.
  • the high absorbency resin Wo '(g, about 0.2 g) was uniformly put in an envelope made of a nonwoven fabric and sealed, and then immersed in physiological saline solution of 0.9 wt% aqueous solution of sodium chloride at room temperature. After using a centrifugal separator the bag after 30 minutes, leave for 3 minutes to dry 250G was measured weight W 2 '(g) of the bag. Further, after the same operation was performed without using a superabsorbent resin, the mass' (g) at that time was measured. Using the thus obtained masses, the CRC (g / g) of the superabsorbent resin was calculated according to the following equation (4) to confirm the maintenance performance.
  • Example 1 of the present invention exhibits a physical property equal to or higher than that of Comparative Example 2, and particularly superior in basic absorption performance defined by CRC.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé permettant de préparer une résine superabsorbante, et une résine superabsorbante obtenue par ledit procédé, le procédé comprenant : la mise en œuvre d'un mélange à sec d'une poudre fine et d'un liant polymère spécifique en phase poudre au moment du réassemblage de la poudre fine générée pendant un procédé de fabrication d'une résine superabsorbante, le procédé n'exigeant donc pas une étape de séchage à l'état humide traditionnellement exigée après réassemblage de la poudre fine, et pouvant ainsi réduire la perte de chaleur, améliorer la productivité et donner une résine superabsorbante, dont toutes les propriétés basiques d'absorption sont excellentes.
PCT/KR2018/007028 2017-06-30 2018-06-21 Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé WO2019004653A1 (fr)

Priority Applications (4)

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JP2019506089A JP6789375B2 (ja) 2017-06-30 2018-06-21 高吸水性樹脂の製造方法およびこのような方法で得られた高吸水性樹脂
US16/341,804 US11028237B2 (en) 2017-06-30 2018-06-21 Method for preparing superabsorbent polymer and superabsorbent polymer prepared thereby
EP18822675.7A EP3502168B1 (fr) 2017-06-30 2018-06-21 Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé
CN201880003995.3A CN109863194B (zh) 2017-06-30 2018-06-21 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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CN113929166A (zh) * 2021-09-08 2022-01-14 五池（珠海）日化科技有限公司 一种可凝固废液的抑菌除臭剂及其制备方法和应用

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KR20140063457A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이로부터 제조되는 고흡수성 수지
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CN111848856A (zh) * 2020-07-28 2020-10-30 山东诺尔生物科技有限公司 一种高吸水树脂细粉粘合剂及其制备方法
CN113929166A (zh) * 2021-09-08 2022-01-14 五池（珠海）日化科技有限公司 一种可凝固废液的抑菌除臭剂及其制备方法和应用

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