WO2010040466A1 - A continuous process for the production of a superabsorbent polymer - Google Patents
A continuous process for the production of a superabsorbent polymer Download PDFInfo
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- WO2010040466A1 WO2010040466A1 PCT/EP2009/007037 EP2009007037W WO2010040466A1 WO 2010040466 A1 WO2010040466 A1 WO 2010040466A1 EP 2009007037 W EP2009007037 W EP 2009007037W WO 2010040466 A1 WO2010040466 A1 WO 2010040466A1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
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- 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
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
Definitions
- the present invention relates to a continuous process for the production of a superabsorbent polymer.
- the preparation of water-absorbent polymers is, for example, summarized in "Modern Superabsorbent Polymer Technology" F. L. Buchholz and AT. Graham, Wiley-VCH, 1998, or in Ullmann's Encyclopedia Industrial Chemistry, 6 th ed. vol. 35 pp 73-103.
- the preferred preparation process is the solution or gel polymerization.
- a monomer mixture is prepared which is discontinuously neutralized and then transferred into the polymerization reactor and is then discontinuously or continuously polymerized to form a polymer gel which is in case of a stirred polymerization comminuted.
- the polymer gel is subsequently dried, ground and sieved and optionally a surface treatment is applied.
- the solution or gel polymerization is a free radical polymerization process this process is susceptible to the presence of oxygen.
- oxygen is known to inhibit the polymerization reaction.
- the presence of oxygen can create numerous problems since it makes the controlled start and progress of the polymerization difficult due to inhibition and chain termination reactions.
- the monomer solution is saturated with oxygen and that by feeding the monomer solution into the reactor an undesired high amount of dissolved oxygen is introduced into the polymerization process.
- US-A-4,656,232 discloses a method for the polymerization of ⁇ , ⁇ -ethylenically unsaturated monomers to produce a superabsorbent resin by forwarding the aqueous monomer solution and an inert gas, each in the form of a continuous flow, toward the site of polymerization, spouting either of the two flows or fluids through a nozzle parallelly into the other flow thereby creating forced contact between the aqueous monomer solution and the inert gas and effecting substantial removal of dissolved oxygen from the aqueous monomer solution before the aqueous monomer solution reaches the site of polymerization.
- the aqueous monomer solution from which the dissolved oxygen has been removed is then admixed with the polymerization initiator and then subjected to polymerization in an atmosphere of inert gas.
- Inert gas is exemplified by nitrogen, carbon dioxide, argon, methane and ethane.
- WO-A-01 /38402 relates to a continuous process for the preparation of a superabsorbent polymer.
- the dissolved oxygen is removed from the monomer solution prior to transfer of the monomer solution into the reactor by directing an inert gas either cocurrently or countercurrently through the monomer solution whereby an appropriate admixing between the liquid phase and the gas phase can be achieved by valve, static or dynamic mixers or by a bubble column.
- the thereby inertized monomer solution is directed together with an inert gas stream through the reactor. Consequently, WO-A-01 /38402 discloses the use of inert gas in two different stages of the process.
- First dissolved oxygen is removed from the monomer solution by applying an inert gas stream and then second the monomer solution is directed through the reactor together with an inert gas stream.
- Preferred inert gases are noble gases, like argon, carbonmonoxide, carbondioxide, sulfurhexafluoride, or mixtures of those gases. Only with respect to creating an inert gas stream within the reactor the possibility of creating the inert gas partially or completely by chemical reaction in the reactor, i.e. the mixing kneader, is disclosed. But in WO-A-01 /38402 the use of nitrogen as inert gas when inertizing the monomer solution, as well as for the inert gas stream through the reactor is used. This is also evident from the examples in WO-A-01 /38402.
- WO-A-03/022896 discloses with specific reference to the examples the deoxygenation of the monomer mixture with a nitrogen stream creating a bubble column.
- the use of carbonates is only disclosed as a neutralizing agent in order to adjust the desired degree of neutralization of the monomer solution.
- EP-B-688 340 with reference to the examples discloses a process for the preparation of superabsorbent polymers by preparing a monomer mixture in a beaker and thus under ambient atmosphere. Neutralization is performed by adding a solution of sodium carbonate in water with stirring. Thus, when preparing the neutralized monomer solution the aqueous solution is still saturated with dissolved oxygen. In the examples, in order to remove the dissolved oxygen, the monomer mix is sparged with nitrogen for one hour. Thus, the carbonate is used solely for neutralization purposes without any effect on the removal of dissolved oxygen.
- a process for producing a water-absorbent resin capable of fast water absorption is known.
- the purpose of that process is to produce a sponge-like gel in order to obtain a fast water absorption.
- This is achieved by polymerizing a foam, i.e. a monomer solution containing dispersed inert gas bubbles.
- a foam i.e. a monomer solution containing dispersed inert gas bubbles.
- all the examples in that reference contain an emulsifier in the aqueous monomer solution in order to stabilize the foam.
- the monomer solution is deoxygenated and then inert gas, especially nitrogen bubbles, are formed.
- the inert gas bubbles in the foam that is subjected to polymerization are substantially free of oxygen which is in line with the teaching that polymerization is conducted in presence of the dispersed inert gas bubbles.
- the presence of oxygen in the dispersed inert gas bubbles would create the above problems related to inhibition and chain termination.
- the aqueous monomer solution is deoxygenated prior to the start of the free-radical polymerization reaction. Thereby a considerable effort has been taken to ensure a preferably complete deoxygenation.
- complicated mixing devices are necessary to ensure intimate mixing between the inert gas and the aqueous monomer mixture.
- a similar teaching is disclosed in US 5,314,420.
- Another problem of complete deoxygenation of the monomer mixture is that prior to the controlled start of the radical polymerization reaction, due to the lack of any inhibitor, it is difficult to avoid premature start of the polymerization within the monomer mixture, for example, in transfer lines.
- the problem is particularly pronounced in continuous polymerization processes since premature start of the polymerization reaction will result in the formation of gel prior to the entry of the monomer solution into the reactor resulting in fowling and blocking of transfer or offgas lines. Especially in continuous processes this will influence flow rates and the whole process has to be periodically shut down for cleaning purposes.
- WO-A-2007/028748 addresses this problem and suggests to include into the monomer solution 0.001 to 0.016 wt% of a polymerization inhibitor and that at least 50 volume percent of the used inert gas for inertization of the monomer solution is transferred together with the inertized monomer solution into the polymerization reactor.
- polymerization inhibitor hydroquinone half-ethers and tocopherols are disclosed.
- the inventors have surprisingly discovered that by introducing a source of carbonate or hydrogen carbonate in the aqueous monomer mixture prior to entry into the reactor the aqueous monomer solution can be much more effectively deoxygenated prior to entry into the reactor compared to the methods known from the prior art using inert gas streams. Furthermore, since by using a carbonate or hydrogen carbonate source without any specific equipment or introduction of mechanical energy a dispersed gas phase is formed within the liquid phase whereby the gas phase comprises carbon dioxide and substantially all of the dissolved oxygen even a premature start of the polymerization reaction outside the reactor is sufficiently inhibited due to the presence of oxygen in the finally dispersed gas phase. Thus, blocking and fowling of transfer lines or offgas lines is minimized, even without further addition of any polymerization inhibitors.
- the residence time of the monomer mixture in any transfer lines after adding of the source of carbonate or hydrogen carbonate prior to entry into the reactor is less than 30s, usually less than 20s, but a residence time of even less than 10s is still sufficient to allow effective deoxygenation.
- the above defined goal has been achieved in an economic way without applying any complicated devices since the aqueous monomer mixture can be transferred to the reactor via a transfer line, as well known in the art, and the source of carbonate or hydrogen carbonate, preferably an aqueous solution of carbonate or hydrogen carbonate source, can be injected by usual ports into the transfer line.
- the source of carbonate or hydrogen carbonate preferably an aqueous solution of carbonate or hydrogen carbonate source
- the present invention involves the polymerization of a suitable monomer mixture in order to produce a superabsorbent polymer in a free radical polymerization process.
- the superabsorbent polymers prepared by the process of the present invention are water-swellable and lightly crosslinked polymers and can be selected from the known hydrophilic polymers which are capable of absorbing large quantities of fluids.
- Preferred water-absorbent polymers are water-absorbent polymers that contain carboxyl moieties. Preferably at least about 0.01 equivalent of carboxyl groups are present per 100 g of the water-absorbent polymer.
- carboxyl-containing water-absorbent polymers are partially neutralized products of starch-acrylic acid or polyvinyl alcohol graft copolymers, crosslinked products of hydrolysates of acrylamide copolymers, partially neutralized products of polyacrylic acids and crosslinked products of partially neutralized polyacrylic acids.
- the monomer mixture comprises at least one ethylenically unsaturated acid and at least one monomer bearing at least two ethylenically unsaturated groups that function as a covalent crosslinker.
- Suitable ⁇ , ⁇ -ethylenically unsaturated acids include, for example, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, itaconic acid and 2-acrylamido-2-methyl-1 -propane sulfonic acid. These acids can be used in the acidic form, but it is more preferred to use the ⁇ , ⁇ -ethylenically unsaturated acids in their at least partially neutralized form as alkali metal salts and ammonium salts.
- the preferred unsaturated acids include acrylic acid and methacrylic acid in their respective salt forms, such as alkali metal or ammonium salts.
- other water-soluble unsaturated monomers such as alkyl esters of the acid monomers including, for example, methylmethacrylate, methylacrylate, acrylamide or methacrylamide or (meth)acrylates of polyethyleneglycol methyl ether may be present in the monomer mixture.
- the monomers are employed in aqueous solution, preferably in amounts ranging from 10 wt% to 80 wt% based on the total weight of the aqueous monomer solution.
- the amount of monomer ranges from 15 wt% to 60 wt% based on the total weight of the aqueous monomer solution.
- certain grafting polymers such as, for example, polyvinyl alcohol, starch and water-soluble or -swellable cellulose ethers may be employed to prepare the products. Such grafting polymers when employed are used in amounts of up to about 10 wt% based on the ⁇ , ⁇ -ethylenically unsaturated monomer.
- the water-absorbent polymer is preferably lightly covalently crosslinked to render it water-insoluble and water-swellable.
- the desired crosslinked structure can be obtained by including into the monomer mixture a crosslinking agent possessing at least two polymerizable double bonds in the molecular unit.
- the crosslinking agent is employed in an amount effective to covalently crosslink the water-soluble polymer.
- the preferred amount of crosslinking agent is determined by the desired degree of absorption capacity and the desired strength to retain the absorbed fluid that is the desired absorption against pressure (AAP) respectively the absorption under load (AUL).
- the crosslinking agent advantageously is used in amounts ranging from 0.0005 to 5 parts by weight per 100 parts by weight of the ⁇ , ⁇ - ethylenically unsaturated monomer used. More preferably the amount ranges from 0.1 part by weight to 1 part by weight per 100 parts by weight of the ⁇ , ⁇ - ethylenically unsaturated monomer. Usually if an amount of higher than about 5 parts by weight of crosslinking agent per 100 parts of monomer is used the polymers will have a crosslinking density that is too high and will exhibit reduced absorption capacity and increased AUL.
- the polymer If the crosslinking agent is used in amounts of less than 0.0005 parts by weight per 100 parts of monomer the polymer usually has a crosslinking density that is too low and when contacted with the fluid to be absorbed becomes sticky and exhibits a lower initial absorption rate.
- the covalent crosslinking agent preferably is soluble in the aqueous solution of the ⁇ , ⁇ -ethylenically unsaturated monomer the crosslinking agent may be merely dispersed in such a solution.
- suitable dispersing agents include carboxymethyl cellulose suspending aids, methyl cellulose, hydroxypropyl cellulose and polyvinyl alcohol. Such dispersing agents are advantageously provided at a concentration between 0.0005 and 0.1 wt% based on the total weight of ⁇ , ⁇ -ethylenically unsaturated monomer.
- Exemplary covalent crosslinking agents include diallylamine; triallylamine; diacrylates and dimethacrylates of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, neopentyl glycol, trimethylolpropane and pentaerythritol; triacrylates and trimethacrylates of trimethylolpropane and pentaerythritol; tetra-acrylate and tetramethacrylate of pentaerythritol; allyl methacrylate; and tetraallyloxyethane; and acryl
- the polymerization may be carried out using acid monomers that are not neutralized or that have been fully or partially neutralized prior to the polymerization.
- Neutralization is conveniently achieved by contacting the aqueous monomer solution with an amount of base sufficient to neutralize between 10% and 95% of the acid groups present in the acid monomers.
- the amount of base will be sufficient to neutralize between 40% and 85%, and most preferably between 55% and 80% of the acid groups present in the acid monomers.
- Suitable compounds that are useful to neutralize the acid groups of the monomers include those bases that will sufficiently neutralize the acid groups without having a detrimental effect on the polymerization process.
- Examples of such compounds include alkali metal hydroxides, alkali metal carbonates and hydrogen carbonates.
- a conventional vinyl addition polymerization initiator may be used in the polymerization of the water-soluble monomers and the crosslinking agent.
- a free- radical polymerization initiator that is sufficiently soluble in the monomer solution to initiate polymerization is preferred.
- water-soluble persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate, and other alkali metal persulfates, hydrogen peroxide and water-soluble azo-compounds such as 2,2'-azobis-(2-amidinopropane)hydrochloride may be used.
- So-called redox initiator systems such as hydrogen peroxide or sodium persulfate which can be used as oxidizing component can be combined with reducing substances such as sulfites, amines or ascorbic acid.
- the amount of initiator used may range from 0.01 wt% to 1 wt%, preferably 0.01 wt% to 0.5 wt% based on the total weight of the ⁇ , ⁇ -ethylenically unsaturated monomer.
- fines of superabsorbent polymers into the preparation process.
- fines are considered those particles, which are too small for the desired application as defined by the product specification.
- This undesired product fraction is, therefore, removed from the granulated polymer.
- the fraction of fines can be determined by sieving using EDANA Standard Test Method WSP 220.2(5).
- Fines can also be generated by applying a fluidized bed for heating particulate superabsorbent polymers. By the hot air stream particles may be elutriated having a diameter of up to about 300 ⁇ m. Polymer particles having a particle size of less than 300 ⁇ m, or less than 200 ⁇ m are defined as fines in accordance with the present invention.
- the fines may be recycled to any stage of the process according to the present invention but, as will be discussed in more detail below, it is particularly preferred to recycle the fines into the monomer mixture.
- suitable additives may be added to the monomer mixture at a suitable point during the process, as will be discussed below.
- Other additives may be selected, for example, from alkali metal chlorate, polyethylene glycol, aqueous solution of pentasodium salt of diethylene triamine pentaacidic acid (Versenex 80), water insoluble organic or inorganic powder such as water insoluble metal oxides like silica or zinc oxide, surfactants, dispersing aids, agents to control odor like silver salts or other processing aids.
- the liquid aqueous monomer mixture is preferably an aqueous monomer solution that is continuously prepared in a circulation line with an integrated buffer vessel.
- a circulation line with an integrated buffer vessel.
- Several production lines can be served from this system for preparing the monomer solution. Upstream of the circulation line an inline mixing system with integrated heat exchanger for the dilution of the caustic (aqueous sodium hydroxide solution) from 50% to about 20% with deionized water, or preferably with process water, and for the addition of additives such as Versenex 80, is provided.
- the circulation of the monomer solution is forced by a pump. The pump sucks the monomer solution from the bottom side of the buffer vessel and conveys it via circulation lines and at least one integrated heat exchanger back to the top side of the vessel.
- the diluted caustic Between the discharge point of the vessel and the circulation pump there is injected into the circulation line in direction of the flow the diluted caustic first, followed by the injection of at least one part of the total required amount of acrylic acid.
- 70% of the total required amount of acrylic acid or less is injected at this point so that the monomer solution in the buffer vessel has a pH of at least 8 allowing the acrylic acid dimers and oligomers of the acrylic acid to be cracked into acrylic acid and ⁇ -hydroxy propionic acid.
- the entire degree of neutralization (DN) of the unsaturated acid, especially acrylic acid in the monomer solution prior to polymerization is in the range of 50% to 85%, more preferably between 65% and 75%. More than 70% or even all of acrylic acid needed for the desired degree of neutralization may be fed at this point of the process in case that the used acrylic acid has a low dimer concentration.
- the monomer solution in the circulation line between acrylic acid addition point and heat exchangers can reach temperatures of up to 8O 0 C.
- the heat exchangers control the temperature of the solution in the rest of the circulation line and in the buffer vessel in the range from 4°C to 40°C.
- the heat exchangers may be operated with either cooling water, by a glycol-water system or by other cooling media.
- the buffer vessel and the circulation lines consist of a suitable type of stainless steel.
- the surfaces on the product side are optionally post-passivated or provided with a suitable coating (Teflon, PTFE, cam-resist etc.).
- a suitable coating Teflon, PTFE, cam-resist etc.
- the vessel and the lines consist of a suitable plastic such as PE or PP.
- the amount of monomer solution for the continuously operated polymerization process is taken continuously from the circulation line of the monomer preparation system in flow direction after the last heat exchanger but before the injection of the caustic and is transferred to the reactor. At this point the monomer solution containing dissolved oxygen in general is saturated with dissolved oxygen.
- the transfer line can be of the same material and construction as the circulation line.
- the transferred monomer solution has preferably a temperature in the range of about 4°C to 35°C and its transfer rate to the reactor in one embodiment of the present invention equals a fraction in the range of 5% to 50% of the flow rate in the circulation line.
- the possibly still missing fraction of the ethylenically unsaturated acid, for example, acrylic acid in the monomer solution at this point is preferably about 30% of the total required amount.
- the remaining monomer, crosslinkers, at least some of the required initiators such as hydrogen peroxide, sodium persulfate and optionally a coinitiator, and optionally further required additives can be injected into the transfer line at the suitable position.
- the only important requirement is that prior to the addition of the source of carbonate or hydrogen carbonate to the aqueous monomer mixture the pH of the monomer solution should be adjusted by addition of the missing fraction of the unsaturated acid, for example, acrylic acid to obtain an acidic liquid aqueous monomer mixture.
- the oxidative component of the initiating system like hydrogen peroxide is added at an early point in the transfer line in flow direction and the reductive component of the initiating system, like ascorbic acid or salts thereof is added at the very end of the transfer line, i.e. just prior to the point where the monomer mixture enters the reactor.
- the reductive component may also be added directly to the reactor. But due to better homogenization in the transfer line it is preferred to add the reductive component at the very end of the transfer line just prior to entry into the reactor.
- the sequence of addition may be in the following order.
- the monomer solution has been withdrawn from the circulation line, as explained above, the remaining amount of, for example, acrylic acid in order to achieve the desired total degree of neutralization and to obtain an acidic liquid aqueous monomer mixture is added.
- the crosslinker is added, optionally followed by, for example, sodium chlorate, followed by the oxidative component of the redox initiation system , like hydrogen peroxide and/or sodium persulfate.
- the fines of superabsorbent polymer as defined above are added, followed by the introduction of the source of carbonate or hydrogen carbonate.
- the transfer line is equipped with at least one, preferably several inline mixers in order to obtain a homogenous distribution of the added components in the monomer solution.
- the inline mixers may be in the form of at least one disk having an eccentrically arranged boring of a suitable size for providing turbulent flow. Preferably several of those disks are inserted in series such that the holes are arranged in a staggered way so that a homogenous monomer solution is achieved.
- the portion of fines to be recycled to the process is 2 wt% to 20 wt%, preferably 5 wt% to 18 wt% based on the weight of the ethylenically unsaturated acid, for example, acrylic acid in the reaction mass.
- the advantage of recycling the fines into the monomer solution is that the particles get integrated and firmly bound in the polymer matrix obtained by polymerization of the monomer solution containing the dispersed fines. Particularly in process operations downstream, such as grinding, sieving and polymer post-treatment such recycled fines will no more separate from the polymer product.
- the disadvantage of this technology may be that the fines present during polymerization may reduce the final product quality either by grafting to the polymer or due to the oxygen that is adsorbed to the surface of the fines and thus will be carried into the monomer solution and are difficult to be removed. Due to the small particle size of the fines and thus resulting in high specific surface area the amount of air and thus oxygen adsorbed to the polymer fines and thus entrained into the monomer solution is considerable. That is one reason why fines previously were preferably not introduced into the monomer solution despite the above discussed advantages. For example, WO 03/022896 discloses to recycle the polymer fines into the first reactive zone and not to the monomer mixture.
- the problem of oxygen entrainment into the monomer solution by addition of the fines has been solved by the present invention.
- the source of carbonate or hydrogen carbonate is introduced into the aqueous monomer mixture after injection of the polymer fines in the transfer line in the direction of flow not only the oxygen dissolved in the monomer mixture but also the oxygen entrained into the monomer mixture by incorporation of the fines can be effectively removed from the monomer mixture.
- It is a surprising result of the present invention that even after addition of polymer fines in amounts within the above defined limits and thereafter introduction of a source of carbonate or hydrogen carbonate the oxygen concentration in the monomer mixture just prior to the entry point into the reactor at the end of the transfer line after phase separation is 0.3 ppm or lower. Consequently the present invention is particularly effective in a process where polymer fines are added prior to the introduction of a source of carbonate or hydrogen carbonate to the aqueous monomer mixture.
- any suitable material may be used. It is preferred to use an aqueous solution of an alkali metal carbonate or hydrogen carbonate, or mixtures thereof. Sufficient deoxygenation is achieved if 1 % to 15%, preferably 2% to 10%, and more preferred 2% to 7% of the total neutralization of the acidic functionality of the resultant superabsorbent polymer to achieve the respective degree of neutralization of the resultant superabsorbent polymer is performed by the source of carbonate or hydrogen carbonate.
- the source of carbonate or hydrogen carbonate is at least a part of a carbonate or hydrogen carbonate-containing aqueous scrubber solution that is obtained in the process of the present invention, as will be discussed below.
- the carbonate Upon contact with the acidic monomer mixture the carbonate neutralizes a further portion of the ethylenically unsaturated acid, for example, acrylic acid, thereby releasing carbon dioxide gas.
- a minor portion of this gas is dissolved in the solution but the major portion separates from the liquid phase by forming very homogenously distributed small gas bubbles.
- the monomer mixture prior to the incorporation of the source of carbonate or hydrogen carbonate contains and is preferably saturated with oxygen.
- More complete saturation can, for example, be achieved by continuously feeding air through a bottom valve into the monomer solution of the buffer vessel at an appropriate rate of preferably 0.5 m 3 /h to 15 m 3 /h. Due to the presence of oxygen in the monomer mixture any premature polymerization within the monomer mixture preparation section of the process of the present invention can be effectively avoided.
- reactors for the continuous process of the present invention any suitable reactor for a continuous solution and gel polymerization of superabsorbent polymers as known from the prior art can be used.
- reactors that are capable of mixing, kneading and forwarding the reaction mass through the reactor within a desirable time frame.
- continuous kneaders and extruders Particularly preferred are those reactors containing two or more screws or kneading shafts that function at least in part to convey the vessel content along the axis of the vessel.
- one of the shafts acts as a kneading shaft and the other acts as cleaning shaft.
- the rotation speed of the two shafts may be different although the speed can be the same for both shafts.
- these shafts rotate in opposite directions and the radius of the shafts is overlapping.
- the two shafts are at least substantially parallel to each other.
- Suitable reactors are available, for example, from List AG, CH-4422 Alsdorf, Switzerland, especially suitable is the Conti-Version of the Opposite-Rotating-Processor (ORP), the Discoterm Conti (DTP), the Co-Rotating Processor (CRP) and (AP) as well as the processor of the CRK type.
- Suitable kneader reactors are available from Buss AG, Hohenrainstrasse 10, 4133 Pratteln (Switzerland).
- Other suitable reactors are those described in DE-OS 34 32 690.
- apparatuses as described in DE-OS 35 44 770 disclosing belt reactors having an endless conveyer belt on which polymerization is continuously performed.
- the gas-liquid mixture wherein the gas phase is homogenously distributed in the aqueous monomer mixture is separated either immediately prior to entering the reactor or immediately after entering the reactor.
- the gas phase may be separated from the liquid phase by any device suitable for gas-liquid phase separation, like for example, a cyclone-type device. Any device or set-up applied for gas-liquid separation has to enable the gas bubbles to leave the monomer mixture prior gelation.
- the monomer mixture used according to the present invention preferably does not contain surfactants that might stabilize the bubbles of the dispersed gas phase phase separation occurs when the monomer mixture enters the reactor.
- the separated gas phase is then at least partially removed from the reactors, for example, via the vent system.
- a pressure difference between the transfer line in the reactor can be provided such that the pressure in the reactor is lower than the pressure in the monomer feed line.
- the pressure in the transfer line is kept above atmospheric pressure with the aid of a pressure valve and the pressure in the reactor is atmospheric or sub-atmospheric.
- the pressure difference is preferably in the range from 0.5 bar to 5 bar and the pressure in the reactor is from 500 mbar to 1 ,100 mbar absolute. More preferred is a pressure difference in the range of 1 to 3 bar and a pressure in the reactor of 600 - 850 mbar absolute.
- an inert gas feed stream may be introduced into the head space in the reactor in order to facilitate removal of the oxygen-containing gas phase from the polymerization reactor.
- an inert gas feed stream is not necessary according to the present invention and can be omitted without compromising control of the polymerization reaction and product quality.
- Suitable inert gases for the feed stream are those known from the prior art, for example nitrogen, carbon dioxide, or noble gases like argon, whereby nitrogen is particularly preferred.
- the pressure within the reactor may be sub-atmospheric by applying a light vacuum to the reactor which does not only facilitate the removal of the oxygen-containing gas phase but has additional advantages, as will discussed below.
- a reactor is used encompassing at least three zones, wherein the first zone is an initiation zone, the second zone is a gel phase zone and the third zone is a granulation zone, whereby the monomer mixture is fed to the initiation zone.
- the inlet connection of the transfer line is installed at the feed end of the reactor such that the solution is fed to zone one of the reactor, such that it is at the inside of the reactor centrically between the two shafts to be homogenously mixed with the reaction mass in this zone.
- the reactor may be continuously charged with monomer solution at the rate of 0.5 kg/h to 5 kg/h, preferably 1.2 kg/h to 3.5 kg/h per liter of total reactor volume.
- the monomer mixture as fed to the reactor has usually a temperature in the range of 4 0 C to 35°C. For economical reasons the temperature is preferably above 20 0 C. This saves energy for cooling down the solution and the temperature of the reaction mass during polymerization can be reliably controlled by other means.
- the following options can be used to control the total energy input into the system.
- the temperature of the monomer feed can be provided within the temperature range as given above, steam can be injected into the initiation zone of the reactor and finally there is the option of heating via jacket and shafts of the reactor. This might be required if the monomer feed cools the initiation zone in the reactor too much so that the rate of initiation and polymerization drops too much, resulting in a too long residence time in the reactor required for sufficient monomer conversion.
- the monomer concentration is usually not used to control the reaction temperature. For economical reasons it is desirable to raise the concentration to the highest possible level which is usually given by the limit of solubility. So, for temperature control there are all the other options left. Most preferably a combination of the options is applied by which the desired temperature in the various zones of the reactor is preferably addressed.
- the reaction mass in the first zone of the reactor has a temperature in the range of 50°C to 100 0 C, preferably 65°C to 90 0 C 1 in the second zone a temperature (peak temperature) in the range of 65°C to 110 0 C, preferably 80 0 C to 100°C and in the last zone a temperature below 100 0 C, preferably below 95°C.
- temperatures in the various zones can be reliably adjusted by the fact that jacket and shaft of the reactor are divided into several segments in which the temperature can be individually adjusted. This enables the temperature control of the initiation zone and of the last zone of the reactor.
- the peak temperature which occurs somewhere in the second zone is preferably reliably controlled by evaporation under the corresponding pressure for the desired temperature.
- the shafts of the reactor are preferably operated at a speed of about 50% of the operational limit.
- the shear forces generated by the kneading tools allow sufficient granulation of the hydro gel so that a free-flowing gel is obtained having a mass average gel particle size in the range of 3 mm to 5 mm containing a fraction of gel particles above 6 mm of no more than 30%.
- the reaction mass needs to stay in the reactor until sufficient conversion has occurred, the gel is sized to the desired degree and no further temperature control is required. At this point the conversion has reached a degree of at least 90%, more preferably 95% and most preferred more than 99%. This correlates to a residence time depending on the throughput in the range of 3 min to 40 min, more preferably from 4 min to 20 min. Throughputs in the range of 0.5 kg/h to 5 kg/h of monomer solution per liter of total reactor volume are possible.
- the gel is discharged from a last zone of the reactor which is located at the opposite end with respect to the feed or initiation zone of the reactor.
- the gel is wiped out of the reactor by the cleaning shaft over an adjustable weir through an opening in the housing at the side of the cleaning shaft.
- a buffer containment for polymer gel between the reactor and the next unit downstream of the process.
- the vessel also serves as a hold tank to allow further conversion of the polymer gel to a conversion of above 99%, even more preferred of above 99.5%. It furthermore provides an additional location where additives can be charged to the polymers and be mixed in.
- the design of that vessel is not critical as long as it provides tools for adequate agitation and for keeping up the desired temperature of the gel.
- the containment is insulated to keep the gel at the desired temperature, allows substantial plug flow and is designed such that the polymer gel can continuously and reliably be charged and discharged.
- the containment can be a vessel that is horizontally or vertically arranged, a single or multiple screw conveyor or a moving belt.
- the containment can serve multiple production line processes up- and downstream.
- Suitable drying means include fluidized bed dryers, rotary dryers, forced air ovens, through-circulation vent dryers and belt dryers. In some instances drying will occur in two or more stages, i.e. multistage drying.
- the polymer is further sized to form particles, preferably having a weight average diameter of less then 2 mm and more preferred less than 1 mm.
- the final polymer product has a weight average particle size of at least 300 ⁇ m.
- the superabsorbent polymer After drying and sizing usually the superabsorbent polymer is classified, for example, by sieving in order to remove particles having a too low particle size which is not acceptable for the intended commercial use of the superabsorbent polymers.
- the dried particles may be heat treated or surface treated in order to improve the product properties, as is known in the prior art.
- the dried particles may be heat treated in accordance with the procedures set forth in WO 93/05080 and/or US 5,629,377.
- Such heat treatment is preferably carried out at a temperature of at least 170°C, more preferably of at least 180 0 C, and most preferably of at least 190 0 C.
- Such heat treatment is preferably carried out at a temperature of less than 25O 0 C, more preferably less than 240 0 C.
- the method of heat treatment is not critical. For example, forced air ovens, fluidized bed heaters, paddle driers and heated screw conveyors can be successfully employed.
- the heated polymer may be remoisturized for ease in handling.
- a way to improve absorptive properties of the polymer particles may be to surface-crosslink the polymer particles.
- Procedures for surface- crosslinking are well known in the art and described in, for example, US 4,734,478 and US 4,466,983. These procedures may increase the modulus and/or the absorbency under load of the polymer particles. Surface modification may be also achieved by incorporation of additives like aluminum salts or silica.
- the total volume of condensates generated by the polymerization reaction depends on the process conditions. These conditions determine the final energy balance and hence the part evaporation has in the temperature control system.
- the total amount of energy in the system is a balance of the energy streams which either add or remove energy from the system. Adding energy streams are the polymerization and the feed streams (depending on their temperature), heat transfer from the jacket into the reactor, dissipation of mixing energy and optionally steam injection.
- the energy removing streams are the energy of the gel discharged according to the given heat capacity of it and depending on the gel discharge temperature, heat transfer from the reactor to the jacket and energy consumed by evaporation.
- the amount of water to be evaporated is in the range of about 8% to 18% based on the water present in the reaction mass. It can be removed from the reactor and separately be treated or it can be condensed and either be taken back to the gel in the reactor or to any of the downstream steps of the process until the gel is dried. It, alternatively, can be recycled to any of the suitable upstream steps of the process, preferably to the first zone of the reactor together with the reductive component of the redox initiator or to the unit for the preparation of the monomer solution.
- the condensate stream for diluting the caustic to be used for the scrubber.
- the condensate contains acrylic acid as the main component in a concentration in the range of 0.5 wt-% to 2 wt.-%.
- organic acids such as acidic acid and propionic acid
- Inhibitors such as MEHQ if applied and derivatives and degradation products of it
- metal ions i.e. Fe ions which may result from the contact of the acid with metallic surfaces of equipment or from other sources may be present, as will be discussed below.
- vent streams generated in the progress of the process of the present invention need to be treated prior to their release to the atmosphere in order to limit the emission of the plant to the required standards.
- vent streams are the inert gas stream which was used to deoxygenate the monomer solution, the vent stream from the reactor, from gel sizing and the major gas stream resulting from the gel drying operation.
- the vent streams from the storage tanks, in particular from the acrylic acid tanks, and optionally gas streams from the product post-treatment processes are also directed to the scrubber for purification.
- the scrubber comprises a vertical column packed with filling material, such as Raschig rings and diluted caustic is sprayed from the top onto the packing of the column and flows down through the packing material into the bottom area of the scrubber.
- filling material such as Raschig rings and diluted caustic is sprayed from the top onto the packing of the column and flows down through the packing material into the bottom area of the scrubber.
- the vent streams are fed to the bottom of the column and on its way to the top of the column the gas stream is finely divided by the packing and the impurities are taken up by the aqueous phase.
- the scrubber water that is when freshly prepared applied to the scrubber comprises up to about 5 wt-% of sodium hydroxide in order to be able to reliably remove all the traces of acrylic acid and other impurities from the vent streams.
- Some of the originally fed sodium hydroxide is, however, converted into carbonates or hydrogen carbonates resulting from the contact of the diluted caustic in the scrubber with the carbon dioxide in the vent stream. Therefore, the scrubber water as removed from the scrubber contains some residual caustic, from 4 wt.-% to 10 wt.-% carbonates or hydrogen carbonates, and in addition to the bases basically the same components as the condensate, but usually in higher concentrations.
- the total solids content of the scrubber solution is in the range of about 10 wt.-%.
- a portion thereof consists of the superabsorbent fines dust which is carried in by the vent stream from the gel dryers.
- the most crucial impurities are seen to be calcium and iron ions, acetic and formic acid, inhibitors and derivatives of it, and also carbonate and other impurities.
- a further concern of recycling scrubber water is its brown color which might discolor the final product if recycled to the process step.
- the scrubber water can be recycled at least in part to the monomer mixture as a source of carbonate or hydrogen carbonate according to the present invention.
- the scrubber water contains 4 wt.-% to 10 wt.-% of carbonate and/or hydrogen carbonate and is, therefore, well suited as a source for carbonate or hydrogen carbonate according to the present invention.
- the present invention provides for a continuous process for the preparation of superabsorbent polymers wherein all the process streams containing valuable materials can be effectively recycled to the process without jeopardizing process stability and product quality.
- the present invention relates to a continuous process for the production of a superabsorbent polymer comprising:
- the carbon dioxide containing offgas stream subjected to scrubbing comprises the gas stream removed from the reaction in step (d).
- a source of carbonate or hydrogen carbonate for deoxygenation of the monomer mixture allows to considerably reduce the amount of additional inert gas used for deoxygenation of the monomer mixture or as inert gas stream in the reactor. In fact, both can be even totally omitted.
- premature polymerization and the related problems like fowling and blocking of transfer lines, can be avoided while at the same time ensuring that the polymerization reaction is not adversely affected by inhibition or unwanted chain termination. This can be achieved without any additional complicated devices or the addition of further additives.
- AAP Absorption against Pressure (Absorption Under Pressure) EDANA, STANDARD TEST: WSP 242.2 (05) Gravimetric Determination of Absorption Under Pressure
- An electrochemical method is used for the determination of oxygen solved in the monomer solution.
- a membrane-covered electrochemical sensor having a gold cathode and a silver anode ( WTW Trioxmatic 203) Calibration cell WTW PE/OXI OxiCal 4-necked 250-ml glass vessel equipped with a magnetic stirring bar, a tight fitting for the sensor bar, a fitting for the nitrogen stream through the vessel, a fitting for the vent-gas stream and a fitting for charging the monomer solution.
- WTW Trioxmatic 203 Calibration cell
- a magnetic stirrer A hose pump PE-hoses of suitable size and length Procedure
- the calibration of the sensor is carried out in air saturated with water vapor using the Calibration cell WTW PE/OXI OxiCal. It was performed exactly as described in the user manual provided by WTW. To measure the oxygen concentration in the monomer solution the program was selected (PROG # 6), which is suitable for the monomer solution and which was developed in cooperation with the supplier of the equipment.
- the calibrated sensor is fixed to the glass reactor respectively to the glass vessel with a angle of about 45° relative to the surface of the monomer solution and the stirrer is switched on and set to a speed to guarantee the needed approach flow to the sensor but to prevent the gas from the head-space of the vessel to form gas bubbles in the solution.
- the oxygen concentration is measured and displayed in ppm (mg/l). The value is taken after it has stabilized, which may take some seconds.
- the buffering capability of the electrolyte solution is sufficient for short-term exposure; during long term exposure, however, carbon dioxide shifts the pH value into the acidic range and leads to increased values. For this reason, the sensor was entirely regenerated after each measurement according to the procedure given by WTW: The electrolyte solution of the sensor was exchanged, cathode and anode were cleaned and the membrane was exchanged for a new one.
- GFI Gel-Flow-lndex
- the sieves are stacked to form a sieve tower and place it in the plastic tray (see figure below).
- a gel sample taken from the source from which the sample needs to be analyzed is placed into the plastic bag, which is immediately put into the temperature- insulated box to be kept at the desired temperature until measured. From the sample in the plastic bag a portion of 200 g are carefully weighed into the plastic beaker and spread onto the top sieve of the sieve tower. Care must be taken not to touch or press the gel and not to allow any vibration to the sieves to not influence the natural, gravimetric flow behavior of the gel.
- the gel sample is left for 2 minutes to flow through the sieves and thereafter, the portions of gel on the sieves are determined by weighing.
- Wj weighed Wi * ⁇ / Wtot * 100
- w represents the weight of the gel on the sieve
- a t represents a sieve related weighting factor, where the factor is 0 for the 25-mm sieve, 0,2 for the 20 mm sieve, 0,4 for the 16-mm sieve, 0,6 for the 10-mm sieve, 0,8 for the 8-mm sieve and 1 ,0 for the gel weight in the tray and w tot represents the total gel weigh- in.
- Example 1 deoxygenation in a 250 ml glass reactor, reference example
- Monomer solution was prepared by mixing 86.67 g of 99.8% active acrylic, 60.55 g of 50% active NaOH, 77.7 g of water, 0.23 g of highly ethoxylated trimethylol propane triacrylate, having on average 15 EO-units in the molecule (HE-TMPTA) and 0.87 g of PEG 600.No fines were dispersed in it.
- the monomer solution was filled into a 250 ml glass reactor equipped with a magnetic stirring bar and a lid with three openings. One opening carried the membrane-covered electrochemical sensor which was inserted into the monomer solution for oxygen measurement. One opening was equipped with a gas one-way-valve and was used for gas release.
- Example 1 was repeated except that 86.67 g of 99.8% active acrylic and 68.79 g of 49% active NaOH were used and that, instead of the carbonate solution, 34.67 g of the scrubber water were added. Due to the presence of carbonate in the scrubber water its contact with the prepared monomer solution showed the same reaction with CO 2 -release as in the previous example. The oxygen concentration in the mixture dropped as shown in Table 2. Like in Example 1 , the addition of 0.05 g of a 35% active solution of H 2 O 2 , 1.3 g of a 10% active Na 2 S 2 O 8 and 0.34 g of a 1 % active ascorbic acid solution initiated the polymerization immediately and heated the reaction mass within 3 min to a peak temperature of 115 0 C.
- Reference examples 1 and 2 are related to batch processes and therefore are not examples according to the present invention but show the effectiveness of using a source of carbonate or hydrogen carbonate for deoxygenation of the monomer mixture and the usefulness of the scrubber water as carbonate source. In both examples oxygen concentration as low as those reported in US 4,656,232 using complicated puzzle arrangements is obtained.
- a monomer solution was continuously produced feeding to the preparation unit of the monomer solution 2050.7 kg/h of a 99.8 % active acrylic acid, 3322.8 kg/h of an 24% aqueous solution of sodium hydroxide to neutralize the acrylic acid to a degree of 70%, and 337.9 kg/h of water. Also continuously added were 3,8 kg/h of the 40.2 % active Versenex 80 (Trademark of The Dow Chemical Company;750 ppm b. o. AA), 14.8 kg/h of HE-TMPTA (7200 ppm b. o. AA) and 12.3 kg/h of PEG 600 (6000 ppm b. o. AA).
- This monomer solution having a temperature of 28 0 C was continuously transferred from the monomer preparation unit to the two screw reactor (List ORP 4000) at a feed rate of 5742,3 kg/hour.
- the rotation speed of the kneading shaft was set to 4 of the cleaning shaft to 16rpm.
- a 30 % active hydrogen peroxide solution 200 ppm b. o. AA
- 69.7 kg/h 1700 ppm active b. o. AA
- a 5% active aqueous sodium persulfate solution 245,7kg/h of superabsorbent fines (9% b. o.
- the evaporated water was condensed in the condenser above the reactor and refluxed onto the gel close to the discharge end in zone 3 of the reactor.
- the free flowing, granulated gel was continuously discharged from the reactor into the hold tank where it resided for about one hour at a temperature of 95-96 0 C, was minced through a die plate having 6-m wide slits, which were circularly arranged, and dried for about 20 minutes on a belt drier in an air stream having 190 0 C in the first zone and 210 0 C in the second zone of the drier, about 10 minutes each. After drying, the polymer was ground in a roll mill and sieved to obtain a particulate polymer having a particle size of between 150 and 850 m.
- the Scrubber ( Figure 2) was continuously operated.
- the scrubber which is made from stainless steel, has a total volume of 60 m 3 , of which 10 m 3 /h are filed with a propylene made packing.
- the scrubber was fed with about 260 m 3 /h vent stream from the reactor, consisting essentially of nitrogen containing the volatiles from the monomer solution, 3000m 3 /h of drying air resulting form the belt driers, which continuously dries the produced polymer gel, and 60 kg/h of water from the water ring pump of the vacuum system. From the bottom of the scrubber were continuously removed 410,1 kg/h of scrubber water to be charged to the reactor.
- the volume withdrawn was replaced by caustic and Dl-water in such rates that on a molar base the liquid in the scrubber maintained the basicity (NaOH and carbonate), which corresponds the bascity of a 5% caustic.
- the scrubber liquid in the scrubber was continuously circulated at a rate of 50 m 3 /h.
- the circulated stream was homogeneously distributed over the packing from where it trickled through the packing down to the bottoms, thereby generating an intimate mixing with the gas stream flowing upwards.
- Example 3 was repeated except that the scrubber water was continuously injected to the monomer solution in the transfer line and the injection of nitrogen into the transfer line was reduced to 8 kg/h. A sample of the monomer solution was taken at the feed point to the reactor and after gas phase separation the O 2 concentration in the monomer solution was measured to be 0.1 ppm.
- Example 4 was repeated except that the injection of nitrogen to the monomer solution in the transfer line and the additional sweep gas stream were completely omitted.
- a sample of the monomer solution was taken at the feed point to the reactor and after gas phase separation the O 2 concentration in the monomer solution was measured to be 0.3 ppm.
- the results demonstrate the importance of proper deoxygenation for which the scrubber water is a preferred aid. Additional nitrogen for deoxygenation can be reduced or even be completely omitted.
- Product quality in terms of AAP and extractables is improved and the gel flowability (after extrusion), the GFI, is increased. Due to reduced stickiness the gel can form more even layers on the belt drier resulting in more homogenous drying.
- Example 5 was repeated except that the additional nitrogen sweep stream over the head space of the reactor was set to be 100 m 3 /h. A sample of the monomer solution was taken at the feed point to the reactor and after gas phase separation the O 2 concentration in the monomer solution was measured to be 0.2 ppm.
- Example 7 Example 6 was repeated except that 40% of the condensate was separated after the condenser and fed into the scrubber to replace there the equal amount of process water.
- the HE-TMPTA concentration was reduced to 6700 ppm b. o. AA and the pressure in the reactor was also reduced to 960 mbar.
- Example 7 was repeated except that 100% of the condensate was separated after the condenser and fed into the scrubber to replace there the equal amount of process water.
- the polymer gel as extruded and fed to the drier has a solids content of 49.7%.
- Example 8 was repeated except that the sweep gas stream was stopped and the pressure in the reactor further reduced to 750 mbar. This controlled the peak temperature at about 85°C.
- Vacuum in the reactor is also helpful for improved deoxygenation of the monomer solution and accelerates the removal of oxygen in the head space of the reactor.
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EP09818792.5A EP2341950B1 (en) | 2008-10-07 | 2009-10-01 | A continuous process for the production of a superabsorbent polymer |
BRPI0920556-0A BRPI0920556A2 (en) | 2008-10-07 | 2009-10-01 | Continuous process for producing a superabsorbent polymer |
JP2011530396A JP5511827B2 (en) | 2008-10-07 | 2009-10-01 | Continuous process for the production of superabsorbent polymers |
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WO2015072536A1 (en) | 2013-11-14 | 2015-05-21 | 株式会社日本触媒 | Process for producing water-absorbing polyacrylic acid (salt) resin |
US20190276608A1 (en) * | 2016-05-31 | 2019-09-12 | Gerald Grünewald | Method for the production of superabsorbers |
EP3553092A4 (en) * | 2017-02-16 | 2020-01-22 | LG Chem, Ltd. | Method for producing super absorbent polymer |
WO2020038742A1 (en) * | 2018-08-20 | 2020-02-27 | Basf Se | Method for the production of superabsorbents |
US11560463B2 (en) | 2017-12-08 | 2023-01-24 | Lg Chem, Ltd. | Cross-linking agent compound and polymer prepared using the same |
US11578175B2 (en) | 2017-12-08 | 2023-02-14 | Lg Chem, Ltd. | Preparation method of super absorbent polymer |
WO2024132671A1 (en) | 2022-12-20 | 2024-06-27 | Basf Se | Method for producing superabsorbents |
WO2024132670A1 (en) | 2022-12-20 | 2024-06-27 | Basf Se | Method for producing superabsorbents |
US12030967B2 (en) | 2018-12-07 | 2024-07-09 | Lg Chem, Ltd. | Preparation method of super absorbent polymer |
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TWI500636B (en) * | 2008-10-07 | 2015-09-21 | Evonik Degussa Gmbh | A process for the production of a superabsorbent polymer |
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WO2015072536A1 (en) | 2013-11-14 | 2015-05-21 | 株式会社日本触媒 | Process for producing water-absorbing polyacrylic acid (salt) resin |
US9682362B2 (en) | 2013-11-14 | 2017-06-20 | Nippon Shokubai Co., Ltd. | Process for producing water-absorbing polyacrylic acid (salt) resin |
US20190276608A1 (en) * | 2016-05-31 | 2019-09-12 | Gerald Grünewald | Method for the production of superabsorbers |
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EP3553092A4 (en) * | 2017-02-16 | 2020-01-22 | LG Chem, Ltd. | Method for producing super absorbent polymer |
US10894245B2 (en) | 2017-02-16 | 2021-01-19 | Lg Chem, Ltd. | Method for preparing superabsorbent polymer |
US11560463B2 (en) | 2017-12-08 | 2023-01-24 | Lg Chem, Ltd. | Cross-linking agent compound and polymer prepared using the same |
US11578175B2 (en) | 2017-12-08 | 2023-02-14 | Lg Chem, Ltd. | Preparation method of super absorbent polymer |
WO2020038742A1 (en) * | 2018-08-20 | 2020-02-27 | Basf Se | Method for the production of superabsorbents |
US12030967B2 (en) | 2018-12-07 | 2024-07-09 | Lg Chem, Ltd. | Preparation method of super absorbent polymer |
WO2024132671A1 (en) | 2022-12-20 | 2024-06-27 | Basf Se | Method for producing superabsorbents |
WO2024132670A1 (en) | 2022-12-20 | 2024-06-27 | Basf Se | Method for producing superabsorbents |
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TW201030064A (en) | 2010-08-16 |
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