WO2017078369A1 - Procédé de préparation d'un polymère superabsorbant - Google Patents

Procédé de préparation d'un polymère superabsorbant Download PDF

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WO2017078369A1
WO2017078369A1 PCT/KR2016/012461 KR2016012461W WO2017078369A1 WO 2017078369 A1 WO2017078369 A1 WO 2017078369A1 KR 2016012461 W KR2016012461 W KR 2016012461W WO 2017078369 A1 WO2017078369 A1 WO 2017078369A1
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Prior art keywords
polymer
fine powder
weight
water
super absorbent
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PCT/KR2016/012461
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English (en)
Korean (ko)
Inventor
김동현
한장선
남대우
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주식회사 엘지화학
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Priority claimed from KR1020160142887A external-priority patent/KR101960043B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN201680006819.6A priority Critical patent/CN107207745B/zh
Priority to EP16862385.8A priority patent/EP3225649B1/fr
Priority to US15/540,705 priority patent/US10086362B2/en
Publication of WO2017078369A1 publication Critical patent/WO2017078369A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules

Definitions

  • the present invention relates to a method for producing a super absorbent polymer. More specifically, the present invention relates to a method for producing a super absorbent polymer having a high fine powder cohesive strength. [Technique to become background of invention]
  • Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight.
  • SAP Super Absorbent Polymer
  • Such super absorbent polymers have been put into practical use as physiological tools, and are currently used in gardening, soil repair agents, civil engineering, building index materials, seedling sheets, food fresheners in addition to hygiene products such as paper diapers for children, and It is widely used as a material for steaming.
  • a method for producing such a super absorbent polymer a method by reverse phase suspension polymerization or a method by aqueous solution polymerization is known.
  • Reverse phase suspension polymerization is disclosed in, for example, Japanese Patent Laid-Open No. 56-161408, Japanese Patent Laid-Open No. 158209, Japanese Patent Laid-Open No. 57-198714, and the like.
  • a thermal polymerization method of breaking and staggering a polymerization gel in a kneader having several shafts and a photopolymerization method of simultaneously performing polymerization and drying by irradiating ultraviolet rays or the like on a belt with a high concentration of aqueous solution Etc. are known.
  • the hydrous gel polymer obtained through the polymerization reaction as described above is generally pulverized through a drying process and then marketed as a powder product.
  • f ines having a particle size of less than about 150 ⁇ may be generated during the cutting, grinding and powdering of the dried polymer. It is considered undesirable in hygiene articles including infant diapers and adult incontinence devices because the superabsorbent polymer particles prepared including the fine powder may exhibit physical properties that have been transferred or degraded prior to use when applied to the product. Therefore, the reassembling process of excluding the fine powder in the final resin product or aggregating the fine powder to a normal particle size is often performed, and the coagulation strength of the reassembled polymer is often broken down into fine powder again.
  • the present invention relates to a method for producing a superabsorbent polymer having improved permeability without increasing water retention capacity or pressure absorption capacity by increasing the foaming strength of the fine powder reassembly.
  • the present invention comprises the steps of thermal polymerization ' or photopolymerization to the monomer composition comprising a water-soluble ethylenically unsaturated monomer and a polymerization initiator to form a hydrogel polymer; Drying the hydrogel polymer; Pulverizing the dried polymer; Classifying the ground polymer into fine powder having a particle size of less than 150 m and a polymer having a particle size of 150 to 850 IM depending on the particle size; 50 to 200 parts by weight of mixed water of 5 to 30 ° C.
  • a step of thermally polymerizing or photopolymerizing a monomer composition comprising a water-soluble ethylenically unsaturated monomer and a polymerization initiator to form a hydrogel polymer; Drying the hydrogel polymer; Pulverizing the dried polymer; Classifying the pulverized polymer into fine powder having a particle size of less than 150 IM and a polymer having a particle size of 150 to 850 depending on the particle size; Reassembling by mixing 50 to 200 parts by weight of water at a temperature of 5 to 30 ° C with respect to 100 parts by weight of fine powder having a particle diameter of 150 im or less; And a surface crosslinking of the polymer having a particle diameter of 150 to 850 m and the fine powder reassembly, may be provided.
  • the monomer composition which is a raw material of the super absorbent polymer includes a water-soluble ethylenically unsaturated mono
  • the water-soluble ethylenically unsaturated monomer may be used without any limitation any monomers commonly used in the production of superabsorbent polymers. Any one or more monomers selected from the group consisting of anionic monomers and salts thereof, nonionic hydrophilic-containing monomers and amino group-containing unsaturated monomers and quaternized compounds thereof can be used. _
  • alkali metal salts such as acrylic acid or salts thereof, for example acrylic acid or sodium salts thereof, may be used.
  • acrylic acid or salts thereof for example acrylic acid or sodium salts thereof
  • the use of such monomers enables the production of superabsorbent polymers having better physical properties.
  • acrylic acid may be neutralized with a basic compound such as caustic soda (NaOH).
  • the concentration of the water-soluble ethylenically unsaturated monomer may be about 20 to about 60% by weight, preferably about 40 to about 50% by weight, based on the monomer composition including the raw material and the solvent of the superabsorbent polymer.
  • the concentration may be appropriate in consideration of time and reaction conditions. However, when the concentration of the monomer is too low, the yield of the superabsorbent polymer may be low and there may be a problem in economics. On the contrary, when the concentration is too high, some of the monomer may be precipitated or the grinding efficiency of the polymerized hydrogel polymer may be low. Etc. may cause problems in the process and may decrease the physical properties of the super absorbent polymer.
  • the polymerization initiator is not particularly limited as long as it is generally used for the production of superabsorbent polymers, and may be a thermal polymerization initiator or a photopolymerization initiator according to UV irradiation depending on the polymerization method.
  • the photopolymerization method since a certain amount of heat is generated by irradiation of ultraviolet radiation or the like, and a certain amount of heat is generated in accordance with the progress of the polymerization reaction, which is an exothermic reaction, it may further include a thermal polymerization initiator.
  • the photopolymerization initiator may be used without any limitation as long as it is a compound capable of forming radicals by light such as ultraviolet rays.
  • acyl phosphine for example, benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenylglyoxylate, benzyldimethyl ketal (Benzyl Dimethyl Ketal), acyl phosphine and One or more selected from the group consisting of alpha-aminoketone may be used.
  • acylphosphine commercially available lucirin TP0, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-tr imethyl phosphine oxide) 3 ⁇ 4- can be used.
  • lucirin TP0 that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide (2,4,6-trimethyl-benzoyl-tr imethyl phosphine oxide) 3 ⁇ 4- can be used.
  • lucirin TP0 2,4,6-trimethyl-benzoy
  • the photopolymerization initiator may be included in a concentration of about 0.01 to about 1.0 wt% based on the monomer composition. When the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow. When the concentration of the photopolymerization initiator is too high, the molecular weight of the superabsorbent polymer may be low and the physical properties may be uneven.
  • the thermal polymerization initiator may be used at least one selected from the group consisting of persulfate initiator, azo initiator, hydrogen peroxide and ascorbic acid.
  • persulfate-based initiators include sodium persulfate (Na 2 S 2 0 8 ), potassium persulfate (K 2 S 2 0 8 ), ammonium persulfate (NH 4 ) 2 S2 (3 ⁇ 4)
  • azo initiators include 2, 2-azobis- (2-amidinopropane) dihydrochloride (2, 2-azob is (2-am idi nopr opane) dihydrochlor ide) : 2, 2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride (2, 2-azobis- (N, N—dimethyl ene) i sobuty rami dine dihydrochloride), 2— ( Carbamoyl azo) isobutyronitrile (2-
  • the thermal polymerization initiator may be included in a concentration of about 0.001 to about 0.5% by weight based on the monomer composition.
  • the concentration of this thermal polymerization initiator When too low, additional thermal polymerization hardly occurs, so that the effect of the addition of the thermal polymerization initiator may be insignificant.
  • the concentration of the thermal polymerization initiator is too high, the molecular weight of the superabsorbent polymer may be small and the physical properties may be uneven.
  • the monomer composition may further include an internal crosslinking agent as a raw material of the super absorbent polymer.
  • the internal crosslinking agent include a crosslinking agent having at least one ethylenically unsaturated group while having at least one functional group capable of reacting with the water-soluble substituent of the water-soluble ethylenically unsaturated monomer;
  • a crosslinking agent having two or more water-soluble substituents and / or functional groups capable of reacting with the water-soluble substituents formed by hydrolysis of the monomers may be used.
  • the internal crosslinking agent examples include bisacrylamide having 8 to 12 carbon atoms, bismethacrylamide, poly (meth) acrylate having 2 to 10 carbon atoms or poly (meth) allyl ether having 2 to 10 carbon atoms. More specifically, N, ⁇ '- methylenebis (meth) acrylate, ethyleneoxy (meth) acrylate, polyethyleneoxy (meth) acrylate, propyleneoxy (meth) acrylate, glycerin diacrylate Glycerol triacrylate, trimethy triacrylate, triallylamine, triaryl cyanurate, triallyl isocyanate, polyethylene glycol, diethylene glycol and propylene glycol may be used.
  • Such an internal crosslinking agent may be included in a concentration of about 0.01 wt% to about 0.5 wt% based on the monomer composition to crosslink the polymerized polymer.
  • the monomer composition of the superabsorbent polymer production method of the embodiment may further include additives such as a thickener, a plasticizer, a storage stabilizer, an antioxidant, and the like, as necessary.
  • Raw materials such as the above-mentioned water-soluble ethylenically unsaturated monomers, photopolymerization initiators, thermal polymerization initiators, internal crosslinking agents and additives may be prepared in the form of a monomer composition solution dissolved in a solvent.
  • the solvent that can be used at this time can be used without limitation in the composition as long as it can dissolve the above-mentioned components, for example, 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, cyclo 1 type selected from nucleanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbyl, methyl salosolve acetate, and N, N-dimethylacetamide
  • the above can be used in combination.
  • the solvent may be included in the remaining amount except for the above-described components with respect to the total content of the monomer
  • the method of forming a hydrogel polymer by thermally polymerizing or photopolymerizing such a monomer composition is not particularly limited as long as it is a commonly used polymerization method.
  • the polymerization method is largely divided into thermal polymerization and photopolymerization according to the polymerization energy source, and when the thermal polymerization is usually carried out, it can be carried out in a semi-unggi with a stirring shaft such as kneader, when the polymerization proceeds, Although it can proceed in a semi-unggi equipped with a conveyor belt possible, the above-described polymerization method is an example, the present invention is not limited to the above-described polymerization method.
  • the hydrogel polymer obtained by thermal polymerization by supplying hot air or by heating the reaction vessel may be a semi-ungker, such as a kneader having a stirring shaft, according to the shape of the stirring shaft provided in the reactor.
  • the hydrogel polymer discharged to the outlet may be in the form of several centimeters to several millimeters.
  • the size of the water-containing gel polymer obtained may vary depending on the concentration and the injection speed of the monomer composition to be injected, it can be obtained a water-containing gel polymer having a weight average particle diameter of 2 to 50 kPa.
  • the form of the hydrogel polymer generally obtained may be a hydrogel gel polymer on a sheet having a width of the belt.
  • the thickness of the polymer sheet depends on the concentration and the injection speed of the monomer composition to be injected, but it is usually preferable to supply the monomer composition so that a polymer on the sheet having a thickness of about 0.5 to about 5 cm is obtained.
  • the water content of the hydrogel polymer obtained by the above method may be about 30 to about 70 wt%, preferably about 40 to about 60 wt%.
  • water content as used throughout the present specification means the content of the water to the total weight of the water-containing gel polymer subtracted from the weight of the water-containing gel polymer minus the weight of the dry polymer. 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 and drying. At this time, the drying conditions are raised to a temperature of about 180 ° C at room temperature and then maintained at 18 CTC, the total drying time is set to 20 minutes, including 5 minutes of temperature rise step, the moisture content is measured.
  • the pulverizer used is not limited in configuration, but specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Any one selected from the group of crushing machines consisting of cutter mills, disc mills, shred crushers, crushers, choppers and disc cutters Although it is possible, it is not limited to the above-mentioned example.
  • the grinding step may be pulverized so that the particle size of the hydrogel polymer is about 2 to about 10mm. Grinding to a particle diameter of less than 2 ⁇ s is not technically easy due to the high water content of the hydrogel polymer, and may also cause agglomeration between the milled particles. On the other hand, when the particle size is pulverized in excess of 10 ⁇ , the effect of increasing the efficiency of the subsequent drying step is insignificant. Drying is performed on the hydrous gel polymer immediately after the polymerization as described above or not subjected to the grinding step. At this time, the drying temperature of the drying step may be about 150 to about 250 ° C.
  • the drying temperature is less than 150 ° C, the drying time may be too long and the physical properties of the final superabsorbent polymer may be lowered. If the drying temperature is higher than 250 ° C, only the polymer surface is dried excessively. Fine powder may occur in the grinding process, and there is a fear that the physical properties of the superabsorbent polymer to be finally formed decrease.
  • the drying may be carried out at a temperature of about 150 to about 20 CTC, more preferably at a silver degree of about 160 to about 180 ° C.
  • drying time in consideration of the process efficiency, etc., it may proceed for about 20 to about 90 minutes, but is not limited thereto.
  • the drying method of the drying step is also commonly used as a drying step of the hydrogel polymer, it can be selected and used without limitation of the configuration. Specifically, the drying step may be performed by a method such as hot air supply, infrared irradiation, microwave irradiation, or ultraviolet irradiation.
  • the water content of the polymer after the drying step may be about 0.1 to about 10% by weight.
  • the dried polymer obtained through such a drying step is pulverized, which is distinguished from the coarse pulverizing step which is pulverized to 2 to about 10 mm 3, and the polymer powder obtained after the pulverizing step has a particle diameter of about 850 im or less.
  • the grinder used to grind to such a particle size may specifically be a pin mill, hammer mill, screw mill, roll mill, disc mill or A jog mill or the like may be used, but the present invention is not limited to the above-described example.
  • the polymer obtained after grinding is classified into fine powder having a particle size of less than 150 im and a polymer having a particle size of about 150 to about 850 depending on the particle size.
  • Fine particles having a particle size below a certain particle size, ie less than about 150 im, are referred to as superabsorbent polymer fine powder, polymer fine powder, SAP fine powder or fine powder (fines, fine powder).
  • the fines can be generated during the polymerization process, the drying process or the grinding of the dried polymer, When included, it is difficult to handle and exhibits a gel blocking phenomenon, thereby deteriorating physical properties. Therefore, it is preferable to exclude them from the final resin product or reuse them to become normal particles.
  • the water of 5 to 30 ° C may be mixed about 50 to 200 parts by weight with respect to 100 parts by weight of fine powder, the reassembly step is carried out in a wet state to increase the cohesive strength of the reassembly.
  • the higher the water content the higher the cohesive strength of the fine powder, but during the reassembly process, too large reassembly lumps or partly water-containing reassembly lumps (jelly balls) are formed and subsequent crushing processes are operated. Problems can arise.
  • the water content is low, the reassembly process is easy, but the foaming strength is low, and after reassembly, the powder is often crushed again.
  • the reaction may proceed by adding low temperature water of about 5 to 30 ° C to form a wet state in which the fine powder has the above-mentioned water content.
  • low temperature water of about 5 to 30 ° C
  • the rate of fungization after the drying and grinding process is reduced compared to the case of using high temperature water of about 60 ° C or more.
  • the water of 5 to 30 ° C was mixed with the fine powder by using a mist (mis st), spray nozzle (spray) device and the like can be wet.
  • mist mist
  • spray nozzle spray nozzle
  • the fine powder may be reassembled in a wet state having a water content of about 40 to 60 wt%.
  • the fine powder and water are mixed at an appropriate ratio, the fine powder may be wetted at a water content of about 40 to 60 wt%, and reassembled in this state, thereby preparing a fine powder reassembly having a higher coarse strength.
  • surface-crosslinking is carried out by mixing the above-mentioned polymer with a particle size of 150 to 850; ⁇ and a fine powder reassembly.
  • the polymer having a particle size of 150 to 850 urn is derived from the step of classifying the pulverized polymer according to the particle size, the range of the normal particle size range
  • the powder reassembly which corresponds to a polymer, refers to a reassembly which has been reassembled by the above-described method of fine powder having a particle diameter of less than 150 ⁇ derived in the classification step.
  • the fine powder reassembly may be used in a state derived from the fine powder reassembling process, or may be used in a state in which the fine powder reassembly is dried, pulverized and classified.
  • the drying, pulverizing and classification process of the fine powder reassembly can be applied without any limitation in the process of drying, pulverizing and classifying the hydrous gel polymer described above. .
  • the polymer having a particle size of 150 to 850 and the fine powder reassembly may be mixed at a weight ratio of about 6: 4 to 8: 2.
  • the mixing ratio there is no particular restriction on the mixing ratio, but as the ratio of the reassembly of the powder increases, the physical properties are reduced compared to the case of using only a polymer having a normal particle size range. It is preferable not to exceed the above.
  • the surface crosslinking step is to increase the crosslinking density near the surface of the superabsorbent polymer particles in relation to the crosslinking density inside the particles.
  • the surface crosslinking agent is applied to the surface of the super absorbent polymer particles.
  • this reaction occurs on the surface of the superabsorbent resin particles, which improves the crosslinkability on the surface of the particles without substantially affecting the interior of the particles.
  • the surface crosslinked superabsorbent resin particles thus have a higher degree of crosslinking in the vicinity of the surface than in the interior.
  • the surface crosslinking agent is not limited as long as it is a compound capable of reacting with the functional group of the polymer.
  • the surface crosslinking agent may be a polyhydric alcohol compound; Epoxy compounds; Polyamine compounds; Haloepoxy compound; Condensation products of haloepoxy compounds; Oxazoline compounds; Mono-, di- or polyoxazolidinone compounds; Cyclic urea compounds; Polyvalent metal salts; And it may include one or more selected from the group consisting of alkylene carbonate compounds.
  • examples of the polyhydric alcohol compound include mono-, di-, tri-, tetra- or polyethylene glycol, monopropylene glycol, 1,3-propanedi, dipropylene glycol, 2,3,4-trimethyl-1, 3 -Pentanedi, polypropylene glycol, glycerol, polyglycerol, 2-butene-1, 4-diol, 1,4-butanediol, 1, 3-butanedi, 1, 5-pentanedi, 1, 6-nucleic acid Di, and 1, 2-cyclohexane dimethane can be used 1 or more types chosen from the group which consists of.
  • Ethylene glycol diglycidyl ether and glycidol may be used as the epoxy compound, and polyamine compounds may be ethylene diamine, diethylene triamine, triethylene tetraamine, tetraethylenepentamine, or pentaethylene nucleoamine. , At least one selected from the group consisting of polyethyleneimine and polyamide polyamine can be used.
  • epichlorohydrin, epibromohydrin, and (alpha)-methyl epichlorohydrin can be used as a halo epoxy compound.
  • 2-oxazolidinone etc. can be used as a mono-, di-, or a polyoxazolidinone compound.
  • alkylene carbonate compound ethylene carbonate or the like may be used.
  • At least one alkylene carbonate compound in the surface crosslinking agent in order to minimize the formation of coarse particles after the surface crosslinking and increase the surface crosslinking efficiency, it is preferable to include at least one alkylene carbonate compound in the surface crosslinking agent, and more preferably ethylene carbonate may be used.
  • the amount of the surface crosslinking agent to be added may be appropriately selected depending on the kind or reaction conditions of the surface crosslinking agent to be added, but it is usually about 0.001 to 100 parts by weight based on 100 parts by weight of the polymer having a particle diameter of 150 to 850 im About 5 parts by weight, preferably about 0.01 to about 3 parts by weight, more preferably about 0.05 to about 2 parts by weight can be used.
  • the surface crosslinking may be a surface crosslinking reaction for 10 minutes to 100 minutes at a temperature of 150 ° C to 300 ° C. That is, the surface crosslinking reaction may be performed by heating a mixture of a polymer having a particle size of 150 to 850 to which a surface crosslinking agent is added and the fine powder reassembly, and drying may be performed together.
  • the temperature raising means for surface crosslinking reaction is not specifically limited. It can be heated by supplying a heat medium or by directly supplying a heat source.
  • a heated fluid such as steam, hot air, or hot oil may be used.
  • the present invention is not limited thereto, and the silver content of the heat medium to be supplied is a means of heating medium, a temperature rising rate, and a temperature increase. It may be appropriately selected in consideration of the target temperature.
  • the heat source directly supplied may be a heating method through electricity, a gas heating method, the present invention is not limited to the above examples.
  • the superabsorbent polymer having improved permeability can be prepared without increasing the water retention capacity or the pressurized absorbent capacity by increasing the foaming strength of the fine powder reassembly.
  • FIG. 1 is a scanning electron microscope (SEM) photograph of Preparation Example 1.
  • a fine powder reassembled product was obtained in the same manner as in Production Example 1, except that 40 g of cold water was sprayed with mi 40 g of fine powder of 150! M or less.
  • a fine powder reassembled product was obtained in the same manner as in Preparation Example 1, except that 50 g of hot water was sprayed while mixing 40 g of fine powder of 150 im or less.
  • a fine powder reassembled product was obtained in the same manner as in Preparation Example 1, except that 40 g of fine powder of 150 im or less was injected with mi xi ng and 40 g of hot water was sprayed.
  • Comparative Production Example 3 A ⁇ reassembled product was obtained in the same manner as in Preparation Example 1, except that 40 g of a powder of 150 m or less was added with a spray of hot water 30 g.
  • the monomer composition was irradiated with ultraviolet light for 1 minute with a 10 mV UV lamp light source in a chamber having an internal temperature of 80 ° C., and polymerization reaction was performed in a non-light source state for 2 minutes. After the polymerization reaction was cut into particles of 10 kPa or less using a meat chopper, and dried at 180 ° C. for 30 minutes using a hot air dryer. Thereafter, the resultant was ground and classified to obtain a super absorbent base resin having a particle diameter of 150 to 850.
  • Superabsorbent polymer was obtained in the same manner as in Example 1, except that the surface crosslinking was performed at 180 ° C. for 60 minutes. Comparative Example 1
  • a super absorbent polymer was obtained in the same manner as in Example 1, except that 70 g of the base resin of Example 1 and 30 g of the fine powder reassembly of Comparative Example 1 were mixed and subjected to surface crosslinking at 180 ° C. for 40 minutes.
  • a super absorbent polymer was obtained in the same manner as in Example 1, except that 70 g of the base resin of Example 1 and 30 g of the fine powder reassembly of Comparative Preparation Example 1 were mixed and subjected to surface crosslinking at 180 ° C. for 60 minutes.
  • the superabsorbent polymer was obtained in the same manner as in Example 1, except that the surface recrosslinking was carried out at 180 ° C. for 40 minutes using 100 g of the base resin of Example 1 without mixing the fine powder reassembly.
  • a superabsorbent polymer was obtained in the same manner as in Example 1, except that the fine powder reassembled was not mixed and surface crosslinking was performed at 180 ° C. for 60 minutes using 100 g of the base resin of Example 1.
  • the resin W (g) (about O. lg) obtained in Examples and Comparative Examples was uniformly sealed in a nonwoven fabric bag, and then immersed in 0.9% by mass of physiological saline at room temperature. After 30 minutes, the envelope was centrifuged and drained at 250 G for 3 minutes, and then the mass W2 (g) of the envelope was measured. Moreover, after carrying out the same operation without using resin, the mass W1 (g) at that time was measured. Using each mass obtained, CRC (g / g) was computed according to the following formula.
  • the water-soluble components were measured in the same manner as the procedure disclosed in the EDANA method WSP 270.2 and listed in Table 3.
  • the neutralization degree referred to in the present invention is a neutralization value calculated by an equation calculated at the time of measuring the aqueous component.
  • Runner electron microscopy (SEM) images of fine powder reassembly 1 to 3 are photographs of the fine powder reassembles according to Preparation Examples 1 to 2 and Comparative Preparation Example 3, respectively, with a scanning electron microscope (SEM).
  • XT2plus equipment from Text Analyzer was used to measure the force of the superabsorbent polymer single particles at a constant speed of 0.01 mm / s into a cylinder of 8 mm in diameter. As the device descends, the force of the superabsorbent polymer increases gradually, and when a certain amount is exceeded, crushing occurs. At this time, the maximum force that the particles endure is defined as crushing strength (kg 'Force), and after 10 measurements, a normal distribution curve is drawn. The average was obtained after excluding%. And this average value is described in Table 3.
  • a simple method of measuring Absorbency Under Pressure is as follows.
  • a stainless steel 400 mesh wire mesh was mounted on the bottom of a 60-mm inner plastic cylinder.
  • the piston which can evenly spray 0.90 g of the absorbent resin onto the wire mesh under the condition of room temperature and humidity of 5 OT, and further give a lowering of 4.83 kPa (0.7 ps i) on it, has an outer diameter of 60 kPa. It is slightly smaller and has no gaps with the inner wall of the cylinder, and the up and down movement is not disturbed. At this time, the weight Wa (g) of the apparatus was measured.
  • a glass filter having a diameter of 90 mm and a thickness of 5 mm was placed inside a petri dish having a diameter of 150 mm 3, and the physiological saline consisting of 0.90 weight> sodium chloride was set to 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. Put the measuring device on the filter paper and load the liquid Absorbed for 1 hour. After 1 hour, the measuring device was lifted and the weight Wb (g) was measured.
  • AUP (g / g) [Wb (g)-Wa (g)] / mass of absorbent resin (g)
  • SFC physiological saline flow inducible refers to the permeability of 0.69% by weight aqueous sodium chloride solution to an absorbent resin under a 2.07 kPa load and is measured in accordance with the SFC test method described in US Pat. No. 5669894 and listed in Table 4.
  • Examples 1 to 2 have a high solution permeability (SFC) value because the assembly strength of the fine powder reassembly is increased to decrease the amount of particle size down during transport, grinding, and surface crosslinking, thereby maintaining pores.
  • SFC solution permeability

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  • Dispersion Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un polymère superabsorbant. Plus spécifiquement, selon la présente invention, le procédé de préparation d'un polymère superabsorbant comprend les étapes suivantes : formation d'un polymère de type hydrogel par polymérisation thermique ou photopolymérisation d'une composition monomère contenant un monomère à insaturation éthylénique soluble dans l'eau et un initiateur de polymérisation ; séchage du polymère de type hydrogel ; réduction en poudre du polymère séché ; classification selon le diamètre, du polymère réduit en poudre en poudre fine ayant un diamètre inférieur à 150 µm et polymère ayant un diamètre de 150 à 850 μm ; mise en œuvre d'une regranulation par voie humide par mélange de 50 à 200 parties en poids d'eau à 5 à 30 °C pour 100 parties en poids de la poudre fine ayant un diamètre inférieur à 150 μm ; et mise en œuvre d'une réticulation superficielle par mélange du polymère ayant un diamètre de 150 à 850 µm et de la poudre fine regranulée, pour obtenir ainsi un polymère superabsorbant à haute force cohésive en poudre fine.
PCT/KR2016/012461 2015-11-03 2016-11-01 Procédé de préparation d'un polymère superabsorbant WO2017078369A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201680006819.6A CN107207745B (zh) 2015-11-03 2016-11-01 超吸收性聚合物的制备方法
EP16862385.8A EP3225649B1 (fr) 2015-11-03 2016-11-01 Procédé de préparation d'un polymère superabsorbant
US15/540,705 US10086362B2 (en) 2015-11-03 2016-11-01 Preparation method of super absorbent polymer

Applications Claiming Priority (4)

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KR10-2015-0153879 2015-11-03
KR20150153879 2015-11-03
KR10-2016-0142887 2016-10-31
KR1020160142887A KR101960043B1 (ko) 2015-11-03 2016-10-31 고흡수성 수지의 제조 방법

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EP3502168A4 (fr) * 2017-06-30 2019-10-09 LG Chem, Ltd. Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé

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KR20140063457A (ko) * 2012-11-15 2014-05-27 주식회사 엘지화학 고흡수성 수지의 제조 방법 및 이로부터 제조되는 고흡수성 수지
KR20140145810A (ko) * 2013-06-14 2014-12-24 주식회사 엘지화학 고흡수성 수지의 제조 방법
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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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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3502168A4 (fr) * 2017-06-30 2019-10-09 LG Chem, Ltd. Procédé de préparation d'une résine superabsorbante, et résine superabsorbante obtenue par ce procédé
US11028237B2 (en) 2017-06-30 2021-06-08 Lg Chem, Ltd. Method for preparing superabsorbent polymer and superabsorbent polymer prepared thereby

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