WO2015046992A1 - 고흡수성 수지의 제조 방법 - Google Patents
고흡수성 수지의 제조 방법 Download PDFInfo
- Publication number
- WO2015046992A1 WO2015046992A1 PCT/KR2014/009115 KR2014009115W WO2015046992A1 WO 2015046992 A1 WO2015046992 A1 WO 2015046992A1 KR 2014009115 W KR2014009115 W KR 2014009115W WO 2015046992 A1 WO2015046992 A1 WO 2015046992A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- polymer
- water
- producing
- photopolymerization
- superabsorbent polymer
- Prior art date
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- 239000002689 soil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical compound C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- 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
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08F6/00—Post-polymerisation treatments
- C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
-
- 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
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
- C08L101/14—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
Definitions
- the present invention relates to a method for producing a super absorbent polymer. More specifically, the present invention relates to a method for preparing a super absorbent polymer comprising a two stage polymerization step.
- Super Absorbent Polymer is a synthetic polymer material capable of absorbing water of 500 to 1,000 times its own weight.As a developer, super absorbent material (SAM) and absorbent gel (AGM) They are named differently. Such super absorbent polymers have been put into practical use as physiological devices, and are currently used in sanitary products such as paper diapers for children, horticultural soil repair agents, civil engineering, building index materials, seedling sheets, freshness retainers in food distribution, and It is widely used as a material for steaming.
- the superabsorbent polymer as described above may be generally prepared as a powdery product by polymerizing the resin monomer and drying and pulverizing it.
- the polymerization of the monomers in the process of preparing such a super absorbent polymer is an important step in determining the physical properties of the resin.
- a method by reverse phase suspension polymerization, a method by thermal polymerization, a method by photopolymerization and the like are known.
- a method by photopolymerization there exists a method of polymerizing a monomer composition by putting a monomer composition for resin on a belt, and irradiating light from the upper part.
- the irradiation amount is not constant depending on the depth of the monomer composition, the degree of polymerization may be uneven depending on the position.
- the polymerization composition proceeds excessively due to the large amount of light irradiation on the upper portion of the monomer composition located close to the light source, and the lower portion of the monomer composition located far from the light source is insufficient in polymerization. Components that are not fully made and not polymerized may remain. In this case, the physical properties of the super absorbent polymer may decrease.
- the amount of light or the light irradiation time may vary depending on the position of the monomer composition solution. In this case, the process may be complicated and the process time may increase, resulting in decreased productivity.
- an object of the present invention is to provide a method for producing a super absorbent polymer having improved physical properties, including a two-step polymerization step.
- the present invention comprises the steps of photopolymerization at a silver degree of 30 to 55 ° C for a monomer composition comprising a water-soluble ethylene-based unsaturated monomer, a thermal polymerization initiator and a photopolymerization initiator; Thermal polymerization and photopolymerization at a temperature of 55 to 120 ° C. to form a hydrogel polymer; And it provides a method for producing a super absorbent polymer comprising the step of drying the hydrogel polymer.
- the manufacturing method of the superabsorbent polymer of the present invention it is possible to produce a superabsorbent polymer having a high water absorption capacity and a low water-soluble component content.
- Method for producing a super absorbent polymer of the present invention comprises the steps of photopolymerization at a temperature of 30 to 55 ° C for a monomer composition comprising a water-soluble ethylenically unsaturated monomer, a thermal polymerization initiator and a photopolymerization initiator; Step to form a hydrogel polymer by thermal polymerization and photopolymerization at a temperature of 55 to 120 ° C); And drying the hydrogel polymer.
- the monomer composition which is a raw material of the super absorbent polymer includes a water-soluble ethylenically unsaturated monomer and a polymerization initiator.
- 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.
- acrylic acid it can be used by neutralizing with a basic compound such as caustic soda (NaOH).
- the concentration of the water-soluble ethylenically unsaturated monomer in which the subject from about 20 to about 60 weight 0/0, preferably from about 40 to about 50% by weight based on the monomer composition containing a source material and a solvent of the water-absorbent resin, and In consideration of the polymerization time, the reaction conditions and the like, the concentration may be appropriate.
- the high surface concentration of the monomer is too low, a low yield of the water-absorbent resin may be a problem in economical efficiency, whereas the concentration of "a too high surface grinding during grinding efficiency of the function gel polymer partially precipitated or polymerization of the monomers as low It may cause process problems such as appearing, and the physical properties of the super absorbent polymer may decrease.
- the polymerization method is largely followed by thermal polymerization and photopolymerization depending on the polymerization energy source.
- the reaction stage may vary depending on the polymerization method such as progressing in a reaction vessel equipped with a movable conveyor belt.
- a hydrogel polymer obtained by thermal polymerization and polymerization by supplying hot air or by heating a reactor according to the shape of the stirring shaft provided in the reaction vessel is provided in a reaction vessel such as a kneader having a stirring shaft.
- the hydrogel polymer discharged to the reaction vessel 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, a water-containing gel polymer having a weight average particle diameter of 2 to 50 mm can be obtained.
- the form of the hydrous gel polymer generally obtained may be a hydrous 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 preferable to supply the monomer composition so that a polymer on the sheet is usually obtained having a thickness of about 0.5 to about 5 cm.
- the monomer composition is supplied to such an extent that the thickness of the polymer on the sheet is too thin, the production efficiency is low, which is not preferable.
- the polymer thickness on the sheet exceeds 5 cm, due to the excessively thick thickness, the polymerization reaction may not occur evenly over the entire thickness.
- both thermal polymerization and photopolymerization are performed in a semi-unggi equipped with a conveyor belt.
- the polymerization reaction for polymerizing the ethylenically unsaturated monomer is exothermic reaction. Therefore, even if the reaction is started by lowering the temperature of the monomer composition initially, as the reaction proceeds, the temperature of the monomer composition gradually rises to a high temperature state. Therefore, in the case of thermal polymerization, a low temperature thermal polymerization initiator capable of initiating reaction at low temperature and a high temperature thermal polymerization initiator which initiates reaction in a high temperature state after the middle of the reaction are mixed in order to start the reaction at an early stage. use.
- the temperature is difficult to control as the reaction proceeds, so that the decomposition rate of the thermal polymerization initiator in the monomer composition is changed. Not constant and wide distribution. Will appear. This can lead to a decrease in the physical properties of the final super absorbent polymer.
- thermopolymerization is performed at a temperature of about 30 to about 55 ° C with respect to the monomer composition.
- the action of the thermal polymerization initiator may be excluded and the photopolymerization reaction may proceed at a constant rate. If too low, than the temperature range, the US and the polymer concerned is caused, it is not preferable because it is too high, thermal polymerization in excess of 55 ° C can occur.
- the light source that can be used in the photopolymerization step is not particularly limited, and an ultraviolet light source known to cause photopolymerization reaction may be used without particular limitation.
- an ultraviolet light source known to cause photopolymerization reaction
- light having a wavelength of about 200 to about 400 nm UV light source such as Xe lamp, mercury lamp or metal halide lamp can be used.
- the photopolymerization step may be performed for about 5 seconds to about 10 minutes at an intensity of about 0.1 mw / cm 2 to about 1 kw / cm 2 . If the intensity and time of the light applied to the photopolymerization reaction is too small or short, the polymerization reaction may not occur in a large amount, and if the polymerization reaction is too large or long, the quality of the superabsorbent polymer may be degraded.
- the silver composition of the monomer composition increases, and when the temperature of the monomer composition reaches about 55 ° C., the thermal polymerization proceeds further by the action of the thermal polymerization initiator.
- the temperature of the second step in which the thermal polymerization and the photopolymerization are performed may be about 55 to about 120 ° C, or about 60 to about 120 ° C. However, at this temperature, thermal polymerization may be superior to photopolymerization.
- a separate heat source can be further used so that the monomer composition can reach a temperature suitable for thermal polymerization.
- the heat source may be used without any particular limitation, and for example, a method such as hot air, microwave irradiation, and near infrared irradiation may be used.
- the polymerization initiator used in the polymerization includes both a thermal polymerization initiator and a photopolymerization 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.
- photopolymerization initiator examples include benzoin ether, dialkyl acetophenone, hydroxyl alkylketone, phenyl glyoxylate, and benzyl dimethyl ketal. Ketal), acyl phosphine (alpha) and one or more selected from the group consisting of alpha -aminoketone can be used.
- acylphosphine commercially available lucirin TPO, that is, 2,4,6-trimethyl-benzoyl-trimethyl phosphine oxide can be used.
- More photoinitiators are well documented in Reinhold Schwalm's book "UV Coatings: Basics, Recent Developments and New Application (Elsevier 20 (X7)" pi 15). It is not limited.
- the photopolymerization initiator may be included in a concentration of about 0.002 to about 0.2 0/0 with respect to the monomer composition. If the concentration of the photopolymerization initiator is too low, the polymerization rate may be slow. If 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 ), and ammonium persulfate (NH 4 ).
- azo initiators examples include 2, 2-azobis- (2-amidinopropane) dihydrochloride, 2, 2-azobis (2-amidinopropane) dihydrochloride, 2 2,2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride), 2-azobis- (N, N-dimethylene) isobutyramidine dihydrochloride
- sodium persulfate Na 2 S 2 0 8
- potassium persulfate K 2 S 2 0 8
- ammonium persulfate (NH 4 ) 2 S 2 0 8 )
- Persulfate initiators such as these, can be used.
- the thermal polymerization initiator is from about 0.01 to about about the monomer composition
- the monomer composition may further include an internal crosslinking agent as a raw material of the super absorbent polymer.
- the internal crosslinking agent examples 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; Black can use the crosslinking agent which has 2 or more functional groups which can react with the water-soluble substituent of the said monomer, and / or the water-soluble substituent formed by hydrolysis of the monomer.
- the internal crosslinking agent examples include bisacrylamide having 8 to 12 carbon atoms, bismethacrylamide, poly (meth) acrylate having 2 to 10 carbon atoms, poly (meth) allyl ether having 2 to 10 carbon atoms, and the like. More specifically, N , N ,-methylenebis (meth) acrylate, ethyleneoxy (meth) acrylate, polyethyleneoxy (meth) acrylate, propyleneoxy (meth) acrylate, glycerin diacrylate , Glycerin 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 super absorbent polymer may further include additives such as thickeners, plasticizers, preservative stabilizers, antioxidants 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 configuration as long as it can dissolve the above-described 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, cyclonucanonone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol ethyl ether, toluene, xylene, butyrolactone, carbyl, methyl cellosolve acetate and One or more types selected from ⁇ , ⁇ -dimethylacetamide and the like 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 composition.
- Typical water content of the hydrogel polymer obtained in this manner may be about 40 to about 80% by weight.
- the "water content” as used throughout the present specification means the content of the water to account for the total amount of 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 drying the temperature of the polymer through infrared heating. At this time, the drying conditions are raised to a temperature of about 180 ° C at room temperature and maintained at 180 ° C. The total drying time is set to 20 minutes, including 5 minutes of the silver rising step, the water content is measured.
- the pulverizer used is not limited in configuration, specifically, a vertical pulverizer, a turbo cutter, a turbo grinder, a rotary cutter mill, a cutting machine Includes any one selected from the group of grinding 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 pulverizing step may be crushed back to about 2 to about 10mm particle diameter of the hydrogel polymer.
- the drying temperature of the drying step may be about 150 to about 250 ° C. If 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.
- the drying silver exceeds 250 ° C., only the polymer surface is dried too much, which is formed later. Fine powder may occur in the grinding step, 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 200 ° C, more preferably at a silver degree of about 160 to about 180 ° C.
- 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 such a drying step may be about 0.1 to about 10% by weight.
- the polymer powder obtained after the grinding step may have a particle diameter of about 150 to about 850 mm 3.
- Grinders used to grind to such particle diameters are specifically pin mills, hammer mills, screw mills, mills, disc mills or jogs. A jog mill or the like may be used, but the present invention is not limited to the above-described example.
- a separate process of classifying the polymer powder obtained after grinding according to the particle size may be performed.
- a polymer having a particle size of about 150 to about 850 may be classified, and only a polymer powder having such a particle size may be produced through a surface crosslinking reaction step.
- a surface crosslinking reaction is performed by adding a surface crosslinking agent to the pulverized polymer.
- Surface crosslinking is the step of increasing the crosslink density near the surface of the superabsorbent polymer particles with respect to the crosslink 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 be used 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-propanediol, dipropylene glycol, 2,3,4-trimethyl— 1,3 -Pentanediol, polypropylene glycol, glycerol, polyglycerol, 2 -butene-1,4-diol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanedi, 1,6- nucleic aciddi And at least one selected from the group consisting of 1,2-cyclonucleic acid dimethane.
- 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 epichlorohydrin, epibromohydrin and ⁇ -methyl epichlorohydrin
- a mono-, di-, or a polyoxazolidinone compound 2xoxazolidinone etc. can be used, for example.
- an alkylene carbonate compound ethylene carbonate etc. can be used. These may be used alone or in combination with each other.
- it is preferable to use including 1 or more types of polyhydric alcohol compounds among these surface crosslinking agents More preferably, C2-C10 polyhydric alcohol compounds can 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 additional surface crosslinking agent, but is generally about 0.001 to about 5 parts by weight, preferably about 0.01 to about 100 parts by weight of the polymer. 3 parts by weight, more preferably about 0.05 to about 2 parts by weight may be used.
- the content of the surface crosslinking agent is too small, the surface crosslinking reaction hardly occurs, and if 100 parts by weight of the polymer is more than 5 parts by weight, the phenomenon of absorption and physical properties may occur due to the progress of the excessive surface crosslinking reaction.
- the surface crosslinking agent and the polymer powder may be mixed in a semi-permanent mixture, or a method of spraying the surface crosslinking agent on the polymer powder, a method of continuously supplying the polymer and the surface crosslinking agent to the mixer to be operated continuously, and the like may be used.
- the surface crosslinking agent When the surface crosslinking agent is added, water may be further mixed and added together. When water is added, there is an advantage that the surface crosslinker can be evenly dispersed in the polymer. At this time, the amount of water added is about 1 to about 100 parts by weight of the polymer for the purpose of inducing even dispersion of the surface crosslinking agent and preventing aggregation of the polymer powder and optimizing the surface penetration depth of the crosslinking agent.
- 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, and hot oil may be used, but the present invention is not limited thereto, and the silver of the heat medium to be supplied is a means of heating medium, a rate of temperature increase, 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 super absorbent polymer obtained according to the preparation method of the present invention may exhibit an effect of high water holding capacity and high pressure absorbing capacity and low content of water-soluble components.
- the super absorbent polymer prepared according to the preparation method of the present invention has a water holding capacity of about 34 g / g to about 37 g / g measured according to the EDANA method WSP 241.2, and measured according to the method of the EDANA method WSP 242.2.
- One pressure-absorbing capacity is about 24 g / g to about 27 g / g, showing excellent water retention and pressure absorption capacity.
- the water-soluble ingredient is about 11 to about 13% by weight, indicating a low water-soluble ingredient content.
- the monomer composition was prepared by adding phosphine oxide O.Olg, 0.18 g of sodium persulfate as a thermal polymerization initiator, and 0.30 g of polyethylene glycol diacrylate as a crosslinking agent.
- the monomer composition was maintained at 40 ° C using a thermostat, injected into a rotating belt in the form of a biaxial silicon belt, and irradiated with ultraviolet light for 60 seconds at an intensity of 10 mW using a mercury UV lamp light source located on the top of the belt.
- the reactor was installed with a hot air and a thermal insulation device to maintain the internal temperature at 90 ° C so that the reaction reaction can occur smoothly.
- the obtained gel-type resin was cut with a cutter to have a volume average particle diameter of 10 mm, dried at 40CTC for 40 minutes in a hot air drier, and then pulverized using a rotary mixer and classified to a particle size of 150 to 850 using a particle size distribution analyzer. Resin was prepared.
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that the initial temperature of the monomer composition was maintained at 50 ° C. using an anti-silver bath.
- Example 3 the initial temperature of the monomer composition was maintained at 50 ° C. using an anti-silver bath.
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that the initial temperature of the monomer composition was maintained at 35 ° C. using a thermostat.
- Example 4 the initial temperature of the monomer composition was maintained at 35 ° C. using a thermostat.
- Example 1 superabsorbent by the same method as in Example 1, except that 0.005 g of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide was used. Resin was prepared.
- Example 5
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that lucirin TPO O.Olg was used instead of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide.
- lucirin TPO O.Olg was used instead of diphenyl (2,4,6-trimethylbenzoyl) -phosphine oxide.
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that 0.07 g of sodium persulfate was used. Comparative Example 1
- Example 1 the initial temperature of the monomer composition was
- Example 1 the initial temperature of the monomer composition was
- Example 1 a super absorbent polymer was prepared in the same manner as in Example 1, except that the internal temperature of the reaction vessel was maintained at 50 ° C.
- the pressure absorption capacity measurement method was in accordance with the EDANA method WSP 242.2. Specifically, 0.9 g of a super absorbent polymer of 850 to 150 / is evenly distributed in a cylinder defined by the EDANA method, pressurized with a piston and a pressure of 21 g / cm 2 , and then absorbed with 0.9% saline solution for 1 hour. The pressure absorbing capacity was calculated as the amount.
- the measurement of the water-soluble component was based on the EDANA method 270.2. Specifically, the superabsorbent polymer lg was placed in a 250 mL Erlenmeyer flask and eluted for 18 hours in 200 mL of 0.9% saline solution. Filter the eluted solution with a filter paper (No. 4), filter out the gel, and analyze the content by taking only the part dissolved in 9% saline solution. The weight ratio of the eluted superabsorbent resin to the weight of the superabsorbent polymer before elution was determined. The amount of water-soluble ingredient was determined.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP14848361.3A EP3006470A4 (en) | 2013-09-30 | 2014-09-29 | PROCESS FOR THE PREPARATION OF SUPER ABSORBENT RESIN |
JP2016545696A JP6277282B2 (ja) | 2013-09-30 | 2014-09-29 | 高吸水性樹脂の製造方法 |
US14/917,235 US9701763B2 (en) | 2013-09-30 | 2014-09-29 | Method for preparing super absorbent polymer |
CN201480044792.0A CN105452306B (zh) | 2013-09-30 | 2014-09-29 | 用于制备超吸收性聚合物的方法 |
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KR1020130116757A KR101680829B1 (ko) | 2013-09-30 | 2013-09-30 | 고흡수성 수지의 제조 방법 |
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US10285866B2 (en) | 2015-01-16 | 2019-05-14 | Lg Chem, Ltd. | Super absorbent polymer |
KR101880218B1 (ko) * | 2015-11-06 | 2018-07-20 | 주식회사 엘지화학 | 고흡수성 수지의 제조 방법 및 이를 통해 제조된 고흡수성 수지 |
KR102191462B1 (ko) * | 2017-08-22 | 2020-12-15 | 주식회사 엘지화학 | 고흡수성 수지 시트의 제조 방법 및 이로부터 제조된 고흡수성 수지 시트 |
KR102577709B1 (ko) * | 2018-01-16 | 2023-09-11 | 주식회사 엘지화학 | 고흡수성 수지의 제조 방법 |
CN110358017A (zh) * | 2019-07-03 | 2019-10-22 | 合肥聚合辐化技术有限公司 | 一种提高丙烯酸乳液性能的方法 |
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EP3006470A1 (en) | 2016-04-13 |
KR101680829B1 (ko) | 2016-11-29 |
TW201525009A (zh) | 2015-07-01 |
JP6277282B2 (ja) | 2018-02-07 |
EP3006470A4 (en) | 2016-11-09 |
CN105452306A (zh) | 2016-03-30 |
US20160208022A1 (en) | 2016-07-21 |
US9701763B2 (en) | 2017-07-11 |
KR20150037277A (ko) | 2015-04-08 |
TWI572619B (zh) | 2017-03-01 |
JP2016532001A (ja) | 2016-10-13 |
CN105452306B (zh) | 2018-06-08 |
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