WO2019083211A1 - Procédé de préparation d'un polymère superabsorbant - Google Patents

Procédé de préparation d'un polymère superabsorbant

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Publication number
WO2019083211A1
WO2019083211A1 PCT/KR2018/012127 KR2018012127W WO2019083211A1 WO 2019083211 A1 WO2019083211 A1 WO 2019083211A1 KR 2018012127 W KR2018012127 W KR 2018012127W WO 2019083211 A1 WO2019083211 A1 WO 2019083211A1
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WO
WIPO (PCT)
Prior art keywords
polymer
monomer
particle diameter
polymer particles
resin
Prior art date
Application number
PCT/KR2018/012127
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English (en)
Korean (ko)
Other versions
WO2019083211A9 (fr
Inventor
김무곤
이상기
남혜미
이창훈
김태윤
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 KR1020180121994A external-priority patent/KR102566942B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP18871353.1A priority Critical patent/EP3546503B1/fr
Priority to US16/474,850 priority patent/US11407848B2/en
Priority to JP2019529927A priority patent/JP6806903B2/ja
Priority to CN201880012410.4A priority patent/CN110312755B/zh
Publication of WO2019083211A1 publication Critical patent/WO2019083211A1/fr
Publication of WO2019083211A9 publication Critical patent/WO2019083211A9/fr

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Classifications

    • 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
    • C08F20/04—Acids, Metal salts or ammonium salts thereof
    • C08F20/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention provides a method for producing a superabsorbent resin which enables production of a superabsorbent resin capable of exhibiting an excellent absorption rate including a uniform porous structure through a simple and economical process.
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing moisture of about 500 to 1,000 times its own weight.
  • SAM super absorbent polymer
  • Such a superabsorbent resin has started to be put into practical use as a sanitary article, and nowadays, in addition to sanitary articles such as diapers for children, there are currently used soil repair agents for horticultural use, index materials for civil engineering and construction, sheets for seedling growing, freshness- And it is widely used as a material for fomentation and the like.
  • a method for producing a water-soluble ethylenically unsaturated monomer comprising crosslinking a water-soluble ethylenically unsaturated monomer having at least partially neutralized acid groups in the presence of an internal crosslinking agent to form a hydrogel polymer comprising a first crosslinked polymer;
  • a method for producing a superabsorbent resin in which foam polymerization is carried out in the presence of polymer particles having an average particle diameter of 10 to 200 zm obtained in the classification step and an anionic surfactant.
  • foam polymerization is carried out in the presence of polymer particles having an average particle diameter of 10 to 200 zm obtained in the classification step and an anionic surfactant.
  • the fine powder obtained in the classification step that is, the synthetic resin particle having a particle diameter of 10 to 200 is used as a kind of foaming agent in the crosslinking polymerization for producing a superabsorbent resin
  • the active agent is used as a foam and a tablet. It has been confirmed that as the foaming polymerization proceeds by using such a fine powder and an anionic surface active agent, homogeneous pores are formed in the base resin powder and the superabsorbent resin obtained through the crosslinking polymerization and the subsequent steps, which are uniform in the particle diameter of the fine powder.
  • the superabsorbent resin having a uniform porous structure is produced as compared with the prior art using the blowing agent or the like, the superabsorbent resin can exhibit a higher absorption rate and further, The disadvantages of the conventional techniques such that the absorption rate is made nonuniform may be solved, and the superabsorbent resin particles may exhibit a uniformly uniform absorption rate as a whole.
  • the manufacturing process of the superabsorbent resin particularly, the fine powder generally obtained in the classifying process, and the general anionic surfactant can be used without expensive additive such as capping foaming agent, Absorbing resin in which the structure is stably introduced, the process cost of the entire superabsorbent resin can be largely lowered, and a superabsorbent resin having an excellent absorption rate can be obtained through a simplified process.
  • the production method of one embodiment and the superabsorbent resin obtained thereby will be described in more detail. .
  • the first crosslinked polymer The constituent water-soluble ethylenically unsaturated monomers may be any monomers conventionally used in the production of superabsorbent resins.
  • the water-soluble ethylenically unsaturated monomer may be a compound represented by the following Formula 1:
  • Ri 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 monomer may be at least one member selected from the group consisting of (meth) acrylic acid, and monovalent (alkali) metal salts, bivalent metal salts, ammonium pseudo and organic amine salts of these acids.
  • (meth) acrylic acid and / 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.
  • Examples of the monomers include maleic anhydride, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2- methacryloylethanesulfonic acid, 2- (meth) acryloylpropanesulfonic acid, 2- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, methoxypoly (meth) acrylate, (N, N) -dimethylaminoethyl (meth) acrylate, (N, N) -dimethylaminopropyl (meth) acrylamide, and the like 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 55 to 95 mol%, or 60 to 80 mol%, or 65 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 internal crosslinking agent and the polymer particles (fine powder) having an average particle diameter of 10 to 150 / dish obtained in the classifying process to be described later and 10 to 200 / rni, and the anionic surfactant,
  • the water-soluble ethylenically unsaturated monomer is as described above. Further, the above monomer composition, the concentration of the water-soluble ethylenically unsaturated monomer may be appropriately adjusted in consideration of the polymerization time and banung conditions, preferably from 20 to 90 parts by weight 0 /., Or 40 to 65 weight 0 /. Day . Such a concentration range may be advantageous for controlling the grinding efficiency at the time of pulverization of a polymer described below, while eliminating the need to remove the unpaired monomer after polymerization by utilizing the gel effect phenomenon occurring in the polymerization reaction of a high concentration aqueous solution. However, if the concentration of the monomer is excessively low, the yield of the superabsorbent resin may be lowered.
  • the concentration of the monomer is excessively high, a part of the monomer may precipitate or the pulverization efficiency may be lowered upon pulverization of the polymer gel, and the physical properties of the superabsorbent resin may be deteriorated.
  • the internal crosslinking agent any compound can be used as long as it allows the introduction of crosslinking in the polymerization of the water-soluble ethylenically unsaturated monomer.
  • the internal cross-linking agent is selected from the group consisting of N, N'-methylenebisacrylamide, trimethylol propane tri (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol (meth) (Meth) acrylate, butylene diol di (meth) acrylate, butylene diol di (meth) acrylate, diethylene glycol di (meth) acrylate, ) Acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipentaerythritol pentaacrylate, glycerin tri , Pentaerythritol is reacted with
  • Such an internal cross-linking agent may be added at a concentration of about 0.001 to 1% by weight based on the monomer composition. That is, when the concentration of the internal cross-linking agent is too low, the absorption rate of the resin may be lowered and the gel strength may be weakened. On the contrary, when the concentration of the internal cross-linking agent is too high, the absorption power of the resin is lowered, which may be undesirable as an absorber.
  • the polymer particles having a particle size of 150 may be contained in an amount of 0.1 to 5 parts by weight, or 0.5 to 3 parts by weight, or 0.7 to 2.5 parts by weight, based on 100 parts by weight of the monomer.
  • the superabsorbent resin can be removed.
  • the anionic surfactant may include sodium dodecyl sulfate, ammonium lauryl sulfate, sodium laureth sulfate, dioctyl sodium sulfosuccinate, perfluorooctanesulfonate, perfluorobutane At least one selected from the group consisting of sulfonates, alkyl-aryl ether phosphates, alkyl ether phosphates, sodium missesulfate and carboxylate salts may be used. In addition, various anionic surfactants may be used.
  • Such anionic surfactant enables the porous structure to be better formed through the foaming polymerization using the fine powder, and stabilizes such a porous structure.
  • the superabsorbent resin can exhibit a higher absorption rate.
  • Such anionic surfactant may be used in an amount of 0.002 to 0.05 parts by weight based on 100 parts by weight of the monomer and 0.005 to 0.02 parts by weight of black. This makes it possible to obtain a superabsorbent resin in which a uniform porous structure is suitably introduced to exhibit a further improved absorption rate while suppressing deterioration of other physical properties.
  • the monomer composition for example, a monomer aqueous solution may contain the above-mentioned monomer, internal cross-linking agent, polymer particles having a particle diameter of 10 to 200 and anionic
  • the surfactant may further comprise at least one additive selected from the group consisting of a polyvalent metal salt, a photo initiator, a thermal initiator, and a polyalkylene glycol-based polymer.
  • Such additives can be used to further improve the liquid permeability of the superabsorbent resin (such as polyvalent metal salt or polyalkylene glycol-based polymer), or to improve the physical properties of the superabsorbent resin by facilitating crosslinking polymerization.
  • the superabsorbent resin such as polyvalent metal salt or polyalkylene glycol-based polymer
  • the above-mentioned additives may be used in an amount of 2000 ppmw or less, 0 to 2000 ppmw, black silver or 10 to 1000 ppmw, black silver or 50 to 500 ppmw, based on 100 parts by weight of the monomer, depending on their respective roles. As a result, properties such as liquid permeability or absorption performance of the superabsorbent resin can be further improved.
  • polyethylene glycol, polypropylene glycol, and the like can be used as the polyalkylene glycol-based polymer.
  • any polymerization initiator generally used in the production of a superabsorbent resin may be used.
  • 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,
  • An initiator may be used together to produce a superabsorbent resin having a better absorption rate and various physical properties.
  • the 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.
  • the persulfate-based initiator and sodium sulfate sodium persulfate; Na2S 2 0 8
  • potassium persulfate Pot persulfate
  • ammonium persulfate Ammonium persulfate; (NH 4) 2 S 2 0 8 ).
  • Azo-based initiators include 2,2-azobis (2-amidinopropane) dihydrochloride, 2,2-azobis- (N, N-dimethylene isobutyramidine dihydrochloride, 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride,
  • photo polymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, At least one compound selected from the group consisting of benzyl dimethyl ketal, acyl phosphine and alpha-aminoketone may be used.
  • acylphosphine a commonly used lucyrin TPO, i.e., 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used .
  • a variety of photopolymerization initiators are disclosed in Reinhold Schwalm, "UV Coatings: Basics, Recent Developments and New Applications," at page 15, page 15.
  • Such an initiator may be added in an amount of 500 ppmw or less based on 100 parts by weight of the monomer. 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. Conversely, if the concentration of the polymerization initiator is higher than the above range, the chain of the polymer forming the network becomes shorter, and the physical properties of the resin may be lowered, such that the content of the water-soluble component becomes higher and the pressure absorption capacity becomes lower.
  • 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 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 examples 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 ether Acetate, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, Diethylene glycol monomethyl ether, diethylene glycol ethyl ether, diene, xylene, butyrolactone, carbide, methylsalosolve acetate, N, N-dimethylacetamide, or a mixture thereof have.
  • the monomer composition having the above-mentioned form of an aqueous solution or the like can be controlled so that the initial temperature has a temperature of 30 to 60 ° C, and light energy or heat energy is applied thereto to form a crosslinking polymerization.
  • Formation of hydrogel polymer through cross-linking polymerization of such monomer composition can be performed 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 semi-woven machine provided with a movable conveyor belt.
  • the monomer composition may be introduced into a semipermeable vessel such as a kneader equipped with a stirring shaft .
  • the hydrogel polymer can be obtained by supplying hot air thereto or by heat-polymerizing the monolith.
  • the hydrogel polymer discharged to the reactor outlet according to the shape of the stirring shaft provided in the semi-cylindrical tower can be obtained as particles of several millimeters to several centimeters.
  • the resulting hydrogel polymer can be obtained in various forms depending on the concentration and the injection rate of the monomer composition to be injected, and a hydrogel polymer having a particle diameter of 2 to 50 mm (weight average) can be obtained.
  • a hydrogel polymer in the form of a sheet can be obtained.
  • the thickness of the sheet may vary depending on the concentration and the injection rate of the monomer composition to be injected. In order to ensure the uniformity of the entire sheet and to secure the production rate, the thickness of the sheet is usually adjusted to 0.5 to 5 cm desirable.
  • the water content of the hydrogel polymer obtained in the same method may be 40 to 80 parts by weight 0 /.
  • &quot moisture content " refers to the amount of moisture occupied by the total functional gel polymer weight, Quot; means the value obtained by subtracting the weight of the polymer in the state. Specifically, it is defined as a value calculated by measuring the weight loss due to moisture evaporation in the polymer in the process of raising the temperature of the polymer through infrared heating.
  • the drying condition is a method of raising the temperature from room temperature to about 180 ° C and then keeping it at 180 ° C, and the total drying time is set to 20 minutes including 5 minutes of the temperature raising step, and water content is measured.
  • the hydrogel polymer may be dried and pulverized. Prior to such drying, the step of first pulverizing the hydrous gel polymer to produce a hydrous gel polymer having a small average particle diameter may be carried out first.
  • the hydrogel polymer can be pulverized to 1.0 mm to 2.0 mm.
  • the pulverizer to be used in the coarse pulverization is not limited in its constitution, but may be a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, A crusher, a cutter mill, a disc mill, a shred crusher, a crusher, a chopper and a disc cutter. But it is not limited to the example described above.
  • the coarse pulverization can be performed in a plurality of cycles according to the particle size.
  • the hydrogel polymer may be subjected to first crude pulverization with an average particle size of about 10 mm, second crude pulverization with an average particle diameter of about 5 mm, and then third-stage pulverization with the above-mentioned particle size.
  • the hydrogel polymer can be dried.
  • This drying temperature may be between 50 and 250 ° C. If the drying temperature is lower than 50 ° C, the drying time becomes excessively long and the physical properties of the ultrafine water-absorbent resin to be finally formed may deteriorate. If the drying temperature exceeds 250 ° C, There is a possibility that the physical properties of the superabsorbent resin finally formed are lowered. More preferably, the drying can be carried out at a temperature of 150 to 200 ° C, more preferably at a temperature of 160 to 190 ° C. On the other hand, the drying time may be 20 minutes to 15 hours in consideration of process efficiency and the like, but is not limited thereto.
  • the drying step can be selected and used without limitation of its constitution.
  • the drying step can be carried out by hot air supply, infrared irradiation, microwave irradiation, ultraviolet irradiation, or the like.
  • the increased water content of the polymer after such drying phase can be from 0.05 to 10 parts by weight 0 /.
  • the polymer powder obtained after the pulverization step may have a particle diameter of 150 to 850.
  • the pulverizer used for crushing with such a particle diameter is specifically a ball mill, a pin mill, a hammer mill, a screw mill, a roll mill, A disc mill, a jog mill, or the like may be used, but the present invention is not limited to the above examples.
  • a separate process of classifying the polymer powder obtained after pulverization according to the particle size may be performed.
  • the pulverized polymer can be classified into polymer particles having a particle size of at least 10-150 / m, polymer particles having a particle size of 150-200, and polymer particles having a particle size of 200-850 have. Part of the polymer particles having a particle size of 10 to 150 / m and all of the polymer particles having a particle size of 150 to 200 are selected and the fine particles containing them are subjected to the cross- Recycle it, and use it as a kind of foaming agent. As described above, it is possible to provide a superabsorbent resin having a uniform porous structure and an improved and yet uniform absorption rate.
  • the remaining polymer particles other than these fine particles for example, the remainder of the polymer particles having a particle diameter of 150-200 / m, and all of the polymer particles having a particle diameter of 200-850, To form a base resin powder.
  • the base resin powder having such a particle diameter that is, a particle diameter of 150 to 50 nm, can be produced through a surface cross-linking reaction step described later.
  • the step of cross-linking the surface of the base resin powder may include a step of cross-linking the surface of the base resin powder by heat treatment of the base resin powder in the presence of a surface cross- Resin can be produced.
  • the kind of the surface cross-linking agent contained in the surface cross-linking liquid is not particularly limited.
  • the surface cross-linking agent may be selected from ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, But are not limited to, ethylene carbonate, ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, tetraethylene glycol, propanediol, dipropylene glycol, polypropylene glycol, glycerin, polyglycerin, butanediol, heptanediol, Propane, pentaerythritol, sorbic acid, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, calcium chloride, magnesium chloride, aluminum chloride and iron chloride.
  • the content of the surface cross-linking agent may be appropriately adjusted according to the type thereof, the conditions of the reaction, 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, surface cross-linking may not be properly introduced, and the physical properties of the final superabsorbent resin may be deteriorated. On the contrary, if the surface cross-linking agent is used in an excessive amount, absorption of the superabsorbent resin may be lowered due to excessive surface cross-linking reaction, which is not preferable.
  • the surface cross-linking solution may be 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, Methylene chloride, methyl ethyl ketone, acetone, methyl amyl ketone, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, Butylolactone, carboxy, methylcellosolve acetate, and N, N-dimethylacetamide.
  • the solvent may be included in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the base resin.
  • the surface cross-linking solution may further include a thickener. If the surface of the base resin powder is further crosslinked in the presence of the thickening agent, deterioration of physical properties can be minimized even after the pulverization.
  • a thickening agent at least one selected from a polysaccharide and a hydroxy-containing polymer may be used.
  • the polysaccharide may be a gum-based thickener, a salicylose-based thickener, or the like.
  • Specific examples of the gum series thickener include xanthan gum, arabic gum, karaya gum, tragacanth gum, ghatti gum, guar gum, guar gum, locust bean gum, and psyllium seed gum.
  • Examples of the cellulose-based thickener include hydroxypropyl methylcellulose, carboxymethyl cellulose, Cellulose, methyl salicylose,. Hydroxymethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, hydroxypropylmethylcellulose, Ethylcellulose, and methylhydroxypropylcellulose, and the like.
  • specific examples of the hydroxy-containing polymer include polyethylene glycol and polyvinyl alcohol.
  • the surface cross-linking may be carried out at a temperature of 100 to 250 ° C, and may be continuously performed after the drying and crushing step which proceeds at a relatively high temperature. At this time.
  • the surface cross-linking reaction may be carried out for 1 to 120 minutes, or 1 to 100 minutes, or 10 to 60 minutes. That is, the surface cross-linking reaction may be carried out in order to prevent the degradation of the physical properties of the polymer particles during the excessive migration while inducing the minimum surface cross-linking reaction.
  • the superabsorbent resin prepared as described above can have a bulk density of 0.55 to 0.65 g / ml, or 0.57 to 0.64 g / ml, as a uniform porous structure is introduced.
  • the absorption rate measured according to the Vortex measurement method may be 30 to 53 seconds, or 33 to 50 seconds, or 35 to 48 seconds.
  • the absorption rate refers to the time for which the vortex of the liquid disappears due to rapid absorption when the superabsorbent resin is added to the physiological saline solution and stirred. This means a rapid absorption capacity of the superabsorbent resin.
  • the concrete measurement method thereof will be further specified in the following examples.
  • the superabsorbent resin has a centrifugal separation capacity (CRC) of 28 to 35 g / g or 30 to 33 g / g measured according to the EDANA method WSP 241.3 and a pore volume of 0.9 psi measured according to EDANA method WSP 242.3 And a pressure absorption capacity (AUL) of 16 to 23 g / g, or 17 to 20 g / g.
  • CRC centrifugal separation capacity
  • AUL pressure absorption capacity
  • the superabsorbent resin has an average particle diameter of 300 to 600. Also preferably includes a super-absorbent resin and the particle diameter of the water-absorbent resin is 300 to 600 m according to the invention to 45 to 85 parts by weight 0 /. Further, preferably, a superabsorbent resin having a particle size of 300 or less in the superabsorbent resin
  • 15 comprises by weight 0 /. Above.
  • the fountain solution prepared in Step 1 was poured into a Vat-shaped tray (15 cm x 15 cm wide) equipped with a light irradiation device on the top and a square polymerizer whose interior was preheated to 8 C C. Thereafter, the mixed solution was irradiated with light. It was confirmed that the gel was formed from the surface after about 20 seconds from the light irradiation point, and it was confirmed that polymerization reaction occurred simultaneously with foaming after about 30 seconds from the light irradiation point. Then, continue the polymerization for an additional 2 minutes. And the polymerized sheet was taken out and cut into a size of 3 cm x 3 cm. Then, the cut sheet was made into a crump by chopping using a meat chopper. The average particle size of the crump produced was 1.5 mm.
  • Step 3 the crump prepared in the above step 2 was dried in an oven capable of controlling the airflow in the up and down directions.
  • the hot air of 18CTC was allowed to flow upward from below for 15 minutes and then flow downward from above for 15 minutes to make the crump uniform so that the water content of the dried powder was less than about 2% Lt; / RTI >
  • the dried powder was pulverized by a pulverizer and classified to obtain a base resin having a size of 150 to 850 IM.
  • the remaining polymer particles of the base resin powder having a particle diameter of 10 to 150 / were used by recycling to the above-mentioned step 1.
  • Step 3 Of the polymer particles of the base resin powder having a particle size of 10 to 150 ⁇ ) obtained in Step 3 described below was added to the aqueous monomer solution. 5 g (170 ppmw) of sodium dodecylsulfate solution (D-1 solution) diluted with water to 2% was prepared as a surfactant. Further, 30 g of a sodium persulfate solution (D-2 solution) diluted with water to 4% was prepared. When the temperature of the fusing solution was cooled to about 45 ° C, D-1 and D-2 solutions previously prepared were injected into the fusing solution and fused.
  • D-1 solution sodium dodecylsulfate solution
  • D-2 solution sodium persulfate solution
  • a superabsorbent resin was prepared in the same manner as in Example 1 except that sodium dodecylsulfate solution (D-1 solution) was not used in step 1. Comparative Example 3
  • step 1 a superabsorbent resin was prepared in the same manner as in Example 2, except that sodium dodecylsulfate solution (D-1 solution) was not used.
  • D-1 solution sodium dodecylsulfate solution
  • the absorption rate (black vortex time) was determined by adding 2 g of superabsorbent resin to 50 ml_ of physiological saline at 23 ° C to 24 ° C and changing the magnetic bar (diameter 8 mm, length 31.8 mm) to 600 rpm And the time until the disappearance of the vortex by stirring was calculated in seconds.
  • the pressure absorption capacity of 9 psi of each resin was measured according to EDANA method WSP 242.3.
  • a 400 mesh wire mesh made of stainless steel was attached to the bottom of a cylindrical plastic having an inner diameter of 25 mm.
  • the piston capable of uniformly spreading the water absorbent resin W 0 (g) (0.16 g) on the wire net under uniform temperature and humidity of 50% and uniformly applying a load of 0.9 psi thereon is slightly smaller than the outer diameter of 25 mm.
  • the inner wall of the cylinder is free from cracks and the up and down movement is prevented from being disturbed.
  • the weight W 3 (g) of the device was measured.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside a Petro dish having a diameter of 150 mm and a physiological saline solution composed of 0.9% by weight sodium chloride was made to have the same level as the upper surface of the glass filter. And a filter paper having a diameter of 90 mm was placed thereon.
  • the measuring device was placed on a filter paper, and the solution was absorbed under a load for 1 hour. After one hour, the measuring device was lifted and its weight W 4 (g) was measured.
  • the pressure absorption capacity (g / g) was calculated by using the obtained masses according to the following equation.
  • AUL (g / g) [ W 4 (g) - W 3 (g)] / W 0 (g) shows the measurement results are shown below in Table 1 as described above.

Abstract

La présente invention concerne un procédé de préparation d'un polymère superabsorbant permettant, par un procédé simple et économique, la préparation d'un polymère superabsorbant pouvant présenter un excellent taux d'absorption par le fait de comprendre une structure poreuse uniforme. Le procédé de préparation de polymère superabsorbant comprend les étapes consistant à : former un polymère d'hydrogel comprenant un premier polymère réticulé par réalisation d'une polymérisation par réticulation sur un monomère éthyléniquement insaturé soluble dans l'eau présentant des groupes acides dont au moins une partie sont neutralisés, en présence d'un agent de réticulation interne ; sécher et pulvériser le polymère d'hydrogel ; former une poudre de résine de base présentant un diamètre de 150-850 µm par classification du polymère pulvérisé en particules de polymère présentant un diamètre d'au moins 10-150 µm, en particules de polymère présentant un diamètre de 150-200 µm et en particules de polymère présentant un diamètre de 200-850 µm ; et réticuler en surface la poudre de résine de base, dans l'étape de polymérisation par réticulation, une polymérisation par moussage étant effectuée en présence d'un tensioactif anionique et des particules de polymère présentant un diamètre de 10-200 µm, qui sont obtenues dans l'étape de classification.
PCT/KR2018/012127 2017-10-27 2018-10-15 Procédé de préparation d'un polymère superabsorbant WO2019083211A1 (fr)

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EP18871353.1A EP3546503B1 (fr) 2017-10-27 2018-10-15 Procédé de préparation d'un polymère super absorbant
US16/474,850 US11407848B2 (en) 2017-10-27 2018-10-15 Method for preparing super absorbent polymer
JP2019529927A JP6806903B2 (ja) 2017-10-27 2018-10-15 高吸水性樹脂の製造方法
CN201880012410.4A CN110312755B (zh) 2017-10-27 2018-10-15 超吸收性聚合物的制备方法

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