process for producing a water-absorbing polymer composition and process for producing a hydrogel pol

专利摘要:
PROCESS FOR PRODUCTION OF A POLYMER COMPOSITION, PROCESS FOR THE PRODUCTION OF A POLYMER, WATER ABSORPTION POLYMER, COMPOSITION, PROCESS FOR THE PRODUCTION OF A COMPOUND, USE OF THE POLYMER, FOAMS, MOLDS, FIBERS This invention is related to the method for production of water-absorbing polymer, including the following steps: (i) mixing (a1) 0.1-99.999% by weight, preferably 20 to 98.99% by weight and more preferably 30 to 98.95% by weight of polymerizable, ethylenically unsaturated monomers containing groups of acids, or their salts, or ethylenically unsaturated polymerizable monomers including protonated or quaternized nitrogen, or mixtures thereof, with particular preference being given to mixtures, including at least ethylenically unsaturated monomers containing acid groups, preferably acrylic acid; ((Alpha) 2) 0 to 70% by weight, preferably 1 to 60% by weight, and more preferably 1 to 40% by weight of polymerisable, ethylenically unsaturated copolymers with ((alpha) 1), ((Alpha) 3) 0.001 to 10% by weight, preferably from 0.01 to 7% by weight and more preferably from 0.05 to 5% by weight of one or more cross-linking agents, ((Alpha) 4 ) 0 to 30% by weight, preferably from 1 to 20% by weight and more preferably from 5 to 10% by weight of water-soluble polymers, and ((Alpha) 5) 0 to 20% by weight , preferably 0.01 to 7% by weight and more preferably 0.05 to 5% by (...).
公开号:BR112014009057B1
申请号:R112014009057-2
申请日:2012-11-12
公开日:2021-01-12
发明作者:Laurent Wattebled；Jörg Harren；Matthias Naumann；Franck Furno；Matthias Lobert；Rainer Teni
申请人:Evonik Operations Gmbh；
IPC主号:

专利说明:

[0001] [0001] The present invention relates to superabsorbent polymers with fast-absorbing properties and processes for producing them.
[0002] [0002] The current trend in fabric construction is to produce even thinner constructions with reduced cellulose fiber content and increased superabsorbent content. The advantage of thinner constructions is shown not only in improving wear comfort, but also in reducing packaging and storage costs. With the trend of more and more thin diaper constructions, the profile of the demands on superabsorbents has changed significantly. Of fundamental importance is now the ability of the hydrogel to conduct and distribute the liquid. Due to the increased load of the hygiene article (amount of superabsorbent per unit area), the swollen polymer must not form a barrier layer for the posterior liquid (gel block). If the product has good transport properties, optimal exploitation of the hygiene item in general can be ensured.
[0003] [0003] In addition to the permeability of superabsorbent materials (SAP) (reported in the form of what is called "Saline Conductivity Flow - SFC") and the absorption capacity under compression stress, the absorption rate of superabsorbent particles, in particular (reported in amount of liquid absorbed per gram of superabsorbent material per second) is also an essential criterion, which allows statements about whether an absorbent core that comprises this superabsorbent in a high concentration and has only a low fluff content is capable, in its first contact with liquids, to absorb them quickly (called "acquisition"). In the case of absorbent cores with a high content of superabsorbent material, this "acquisition" depends, among other factors, on the absorption rate of the superabsorbent material.
[0004] [0004] From the prior art, there are several known property rights that are assumed to allow an increase in the rate of absorption of superabsorbent particles. WO96 / 17884A1 discloses a water-absorbing resin for which a solid blowing agent with a particle diameter of 1 to 100 µm is used in the monomer solution. In principle, preference is given to organic azo compounds and here specifically to salts of acrylic azo compounds containing an amino group. Pure carbonates, ammonium nitride or mixtures can optionally be used.
[0005] [0005] Disadvantages here are the rapid conversion of azo compounds and the basic dispersion of small solid particles in the monomer solution. Larger particles cannot be dispersed well without separation of particles and monomer solution in the dispersion, before reaching the gelation point.
[0006] [0006] A disadvantage here, in the case of using superabsorbent materials known from the prior art, is that leakage problems occur, since SAP either absorbs the liquid very slowly and / or has inadequate liquid transport.
[0007] [0007] The current trend in particular in diaper construction is to produce even thinner absorbent cores with reduced cellulose fiber content and increased superabsorbent content. The advantage of thinner constructions is shown not only in improving wear comfort, but also in reducing packaging and storage costs. The newest generation of absorbent cores, which is described, for example, in WO-A-2008/155722, WO-A-2008/155711, WO-A-2008/155710, WO-A-2008/155702, WO- A - 2008/155701, WO-A-2008/155699, EP-A-1 225 857, WO-A-01/15647, WO-A-2011/120504, DE-A-10 2009 049 450, WO-A -2008/117109, WO-A97 / 11659, EP-A-0 826 349, WO-A-98/37846, WO-A-95/11653, WO-A95 / 11651, WO-A-95/11652, WO -A-95/11654, WO-A-2004/071363 or WOA-01/89439, is essentially cellulose-free (which is why the corresponding diapers are also referred to as "feather-free diapers"). The immobilization of superabsorbent particles, which in cellulose-containing absorbent cores is carried out by cellulose fibers, can be achieved in this new generation of absorbent cores such as, for example, the immobilization of superabsorbent particles on a substrate surface by means of thermoplastic fibers.
[0008] [0008] With the trend of increasingly thin diaper construction and the omission of temporary storage of liquid and the conduction function of cellulose fibers, the profile of requirements on superabsorbents has changed significantly. A crucially important factor is now the ability of the hydrogel to prevent leakage of urine directly during urination. This is achieved by establishing the superabsorbent / hydrogel to effectively absorb the liquid during swelling and distribute it in the gel layer, while simultaneously minimizing the amount of urine not stored in the diaper. Due to the good transport properties, advantageous superabsorbents also lead to the optimal exploitation of the total hygiene article.
[0009] [0009] US 5,154,713 describes water-absorbing polymers that are prepared by means of a carbonate blowing agent in the monomer solution. The carbonate particles are introduced here into the monomer solution before the actual polymerization, and the initiator is added 5 to 15 minutes after the dispersion of the carbonate blowing agent, as a result of which the homogeneous distribution of these carbonate particles is not ensured and a not negligible part of the carbonate can be discharged again.
[0010] [0010] EP0644207 describes superabsorbent polymers, which are also mixed with a carbonate from an organic blowing agent in the monomer solution. Disadvantages here are the use of amine compounds, as well as products for eliminating the remaining organic carbonates in the superabsorbent.
[0011] [0011] WO 2010/095427 describes water-absorbing polymers, in which a gas is dispersed in the monomer solution. This gas is nitrogen, argon, helium, carbon dioxide or the like, which is intended to ensure a more porous structure. The intention is to keep these microbubbles in the monomer solution by means of polyoxyethylene- (20) -sorbitan monostearate, until the polymerization sets are inside. A disadvantage is that surfactants can be washed out of the final product again and negatively affect performance.
[0012] [0012] A crucially important factor is now the ability of the hydrogel to prevent leakage of urine directly during urination. This is achieved by establishing the superabsorbent / hydrogel to effectively absorb the liquid during swelling and distribute it in the gel layer, while simultaneously minimizing the amount of urine not attached to the diaper. Due to the good transport properties, advantageous superabsorbents also lead to the optimal exploitation of the total hygiene article.
[0013] [0013] The term "remoam" is generally understood to mean the property of a superabsorbent material or a composite comprising a superabsorbent material to release liquid to an absorption layer under compression stress. The term "absorption plate" is understood, for example, as paper, filter paper, collagen, sponges, foams or the like.
[0014] [0014] EP1858998B1 discloses superabsorbent foams where the monomer solution gives rise to a foam only under a high pressure of 12 bar through the addition of carbon dioxide and surfactants.
[0015] [0015] However, the superabsorbent materials known to date from the prior art, are only of inadequate suitability for use in the new generation described above of cellulose-free diaper constructions.
[0016] [0016] In general, it is an object of the present invention to overcome the disadvantages arising from the prior art.
[0017] [0017] More particularly, it is an object of the present invention to provide a process for the production of a water-absorbing polymer, which has an improved ripple rate and a faster absorption of liquids, while maintaining the overall quality, and more particularly high permeability.
[0018] [0018] It is also another object to carry out the process in an economically simple way, with the intention of minimizing the use of organic additives, and also a mode of operation at ambient pressure.
[0019] [0019] It is a particular object of the present invention to provide a process by which water-absorbing polymers can be produced, and a high expansion rate can be ensured.
[0020] [0020] It is yet another object of the present invention, in addition, to provide a process by which it is possible to produce water-absorbing polymers that ensure the transport of active and fast liquid, for example, in thin diapers, such that the rapid absorption and good distribution, ie corresponding capillarity, are ensured.
[0021] [0021] It is another object of the invention, in particular, to specify a water-absorbing polymer, which comprises such water-absorbing composite polymers, and chemicals which comprise such water-absorbing polymers or composite materials, the water-absorbing polymers that have a greater absorption capacity for aqueous solutions.
[0022] [0022] These objects are achieved by the object of the category formation claims. Advantageous configurations and developments that can occur individually or in combination form the subject of the dependent claims in each case.
[0023] (α1) 0,1-99,999% em peso, de preferência 20 a 98,99% em peso e mais preferivelmente 30 a 98,95% em peso, de monômeros polimerizáveis, etilenicamente insaturados que contêm grupos de ácidos, ou seus sais, ou polimerizáveis, monômeros etilenicamente insaturados incluindo um nitrogênio protonado ou quaternizado, ou suas misturas, sendo dada preferência especial para misturas, incluindo, pelo menos, monômeros etilenicamente insaturados contendo grupos ácido, de preferência ácido acrílico, (α2) 0 a 70%, em peso, de preferência 1 a 60%, em peso, e mais preferivelmente 1 a 40%, em peso, de polimerizáveis, monômeros etilenicamente insaturados copolimerizáveis com (α1), (α3) de 0,001 a 10% em peso, de preferência de 0,01 a 7% em peso e mais preferencialmente de 0,05 a 5% em peso de um ou mais ligantes, (α4) 0 a 30%, em peso, de preferência de 1 a 20% em peso e mais preferencialmente de 5 a 10%, em peso, de polímeros solúveis em água, (α5) 0 a 20%, em peso, de preferência de 0,01 a 7% em peso e mais preferencialmente de 0,05 a 5% em peso de um ou mais auxiliares, em que a soma dos seus pesos (α1) a (α5) é 100%, em peso, (ii) polimerização de radical livre com reticulação para formar um insolúvel em água, polímero de hidrogel não tratado aquoso,(iii) secagem do polímero de hidrogel,(iv) moagem peneirando o polímero hidrogel com o tamanho,(v) pós-reticulação da superfície do solo e peneiramento do polímero hidrogel e(vi) secagem e acabamento do polímero de absorção de água,em quea solução aquosa de monômero, antes da adição do iniciador e do início da polimerização de radical livre, é misturada com 0,01 a 5% em peso, de preferência 0,02 a 2%, em peso, e mais preferivelmente 0,07 a 1% em peso de pelo menos um surfactante dentre o grupo dos agentes surfactantes não iônicos, iônicos ou anfotéricos e opcionalmente 0,01 a 5% em peso, de preferência 0,02 a 2%, em peso, e mais preferivelmente 0,07 a 1% em peso de um agente de expansão que tem um tamanho de partícula de 10 µm a 900 µm, com base no polímero de absorção de água.[0023] A contribution to the realization of the object indicated at the beginning is made by the process for the production of a water-absorbing polymer, comprising the stages of the process of (i) mixing (α1) 0.1-99.999% by weight, preferably 20 to 98.99% by weight and more preferably 30 to 98.95% by weight, of polymerisable, ethylenically unsaturated monomers containing groups of acids, or their salts, or polymerizable, ethylenically unsaturated monomers including protonated or quaternized nitrogen, or mixtures thereof, with particular preference being given to mixtures, including at least ethylenically unsaturated monomers containing acid groups, preferably acrylic acid, (α2) 0 to 70% by weight, preferably 1 to 60% by weight, and more preferably 1 to 40% by weight of polymerisable, ethylenically unsaturated monomers copolymerized with (α1), (α3) from 0.001 to 10% by weight, preferably from 0.01 to 7% by weight and more preferably from 0.05 to 5% by weight of one or more binders, (α4) 0 to 30% by weight, preferably 1 to 20% by weight and more preferably 5 to 10% by weight of water-soluble polymers, (α5) 0 to 20% by weight, preferably from 0.01 to 7% by weight and more preferably from 0.05 to 5% by weight of one or more auxiliaries, where the sum of their weights (α1) a (α5) is 100% by weight, (ii) free radical polymerization with crosslinking to form a water-insoluble, aqueous untreated hydrogel polymer, (iii) drying the hydrogel polymer, (iv) grinding by sieving the hydrogel polymer with the size, (v) post-crosslinking of the soil surface and sieving of the hydrogel polymer and (vi) drying and finishing the water-absorbing polymer, on what the aqueous monomer solution, before adding the initiator and starting the free radical polymerization, is mixed with 0.01 to 5% by weight, preferably 0.02 to 2% by weight, and more preferably 0.07 to 1% by weight of at least one surfactant among the group of nonionic, ionic or amphoteric surfactants and optionally 0.01 to 5% by weight, preferably 0.02 to 2% by weight, and more preferably 0, 07 to 1% by weight of a blowing agent that has a particle size of 10 µm to 900 µm, based on the water-absorbing polymer.
[0024] [0024] The term "water-absorbing polymer" is to be understood according to the invention to mean the superabsorbent.
[0025] (α1) 0,1-99,999% em peso, de preferência 20 a 98,99% em peso e mais preferivelmente 30 a 98,95% em peso de monômeros polimerizáveis, etilenicamente insaturados que contêm grupos ácidos, ou seus sais, ou polimerizáveis, monômeros etilenicamente insaturados incluindo um nitrogênio protonado ou quaternizado, ou suas misturas, sendo dada preferência especial para misturas, incluindo, pelo menos, monômeros etilenicamente insaturados contendo grupos ácido, de preferência ácido acrílico, (α2) 0 a 70%, em peso, de preferência 1 a 60%, em peso, e mais preferivelmente 1 a 40%, em peso, de polimerizável, monômeros etilenicamente insaturados copolimerizáveis com (α1), (α3) 0,001 a 10% em peso, de preferência de 0,01 a 7% em peso e mais preferencialmente de 0,05 a 5% em peso de um ou mais ligantes, (α4) 0 a 30%, em peso, de preferência de 1 a 20% em peso e mais preferencialmente 5 a 10%, em peso, de polímeros solúveis em água, (α5) 0 a 20%, em peso, de preferência de 0,01 a 7% em peso e mais preferencialmente de 0,05 a 5% em peso de um ou mais auxiliares, em que a soma dos pesos de (α1) a (α5) é 100%, em peso, (ii) polimerização de radical livre com reticulação para formar um insolúvel em água, polímero de hidrogel não tratado aquoso,(iii) secagem do polímero de hidrogel,(iv) moagem e peneiramento do polímero hidrogel com o tamanho,em quea solução aquosa de monômero, antes da adição do iniciador e do início da polimerização de radical livre, é misturada com 0,01 a 5% em peso, de preferência 0,02 a 2%, em peso, e mais preferivelmente 0,07 a 1% em peso de pelo menos um surfactante dentre o grupo dos agentes surfactantes não iônicos, iônicos ou anfotéricos e opcionalmente 0,01 a 5% em peso, de preferência 0,02 a 2%, em peso, e mais preferivelmente 0,07 a 1% em peso de um agente de expansão que tem um tamanho de partícula de 10 µm a 900 µm, com base no polímero hidrogel.[0025] In another embodiment, a hydrogel will be, understood by the stages of the process of (i) mixing (α1) 0.1-99.999% by weight, preferably 20 to 98.99% by weight and more preferably 30 to 98.95% by weight of polymerizable, ethylenically unsaturated monomers containing acidic groups, or their salts, or polymerizable , ethylenically unsaturated monomers including protonated or quaternized nitrogen, or mixtures thereof, with special preference being given to mixtures, including at least ethylenically unsaturated monomers containing acid groups, preferably acrylic acid, (α2) 0 to 70% by weight, preferably 1 to 60% by weight, and more preferably 1 to 40% by weight, of polymerisable, ethylenically unsaturated monomers copolymerized with (α1), (α3) 0.001 to 10% by weight, preferably from 0.01 to 7% by weight and more preferably from 0.05 to 5% by weight of one or more binders, (α4) 0 to 30% by weight, preferably 1 to 20% by weight and more preferably 5 to 10% by weight of water-soluble polymers, (α5) 0 to 20% by weight, preferably from 0.01 to 7% by weight and more preferably from 0.05 to 5% by weight of one or more auxiliaries, where the sum of the weights of (α1) a (α5) is 100% by weight, (ii) free radical polymerization with crosslinking to form a water-insoluble, aqueous untreated hydrogel polymer, (iii) drying the hydrogel polymer, (iv) grinding and sieving the hydrogel polymer to size, on what the aqueous monomer solution, before adding the initiator and starting the free radical polymerization, is mixed with 0.01 to 5% by weight, preferably 0.02 to 2% by weight, and more preferably 0.07 to 1% by weight of at least one surfactant among the group of nonionic, ionic or amphoteric surfactants and optionally 0.01 to 5% by weight, preferably 0.02 to 2% by weight, and more preferably 0, 07 to 1% by weight of a blowing agent that has a particle size of 10 µm to 900 µm, based on the hydrogel polymer.
[0026] [0026] This hydrogel polymer of the invention can be converted by means of thermally induced post-crosslinking of a water-absorbing polymer of the invention (superabsorbent).
[0027] [0027] It is preferred, according to the invention to ensure that the surfactants are polymerized in a polymer mesh. Advantageously, it greatly reduces the amount of extractable constituents of the surfactant and, accordingly, only minimally reduces the surface tension.
[0028] [0028] According to the invention, the addition of surfactants and blowing agents to the monomer solution after polymerization reaches a fine porous gel structure and provides superabsorbent powders with a greater surface area. Advantageously, the increase of the invention over the entire surface area allows for a faster absorption of the liquid compared to conventional SAPs. This is shown by what is called the FSR value. The water-absorbing polymers of the invention have an FSR in the range of 0.3 to 0.65, preferably 0.35 to 0.60. According to the invention, it is more preferable that the FSR value is greater than 0.40 g / g / s.
[0029] [0029] According to the invention, despite the use of surface agents, there is no reduction in the surface tension values of hydrogel or superabsorbent polymers.
[0030] [0030] According to the invention, the permeability, which is referred to as the SFC value (in the present invention, always based on 1.5 g), of the water-absorbing polymer composition, is in the range between 30 and 200, preferably 50 to 180 and more preferably in the range of 70 to 150.
[0031] [0031] According to the invention, the surface tension is in the range above 50 mN / m, preferably above 55 mN / m, more preferably above 60 mN / m and more preferably above 62 mN / m. According to the invention, the surface tension is not more than 68 mN / m.
[0032] [0032] According to the invention, the particle size distribution PSD of the polymer hydrogel is such that more than 60% of the particles are in the range of 300 µm to 600 µm and less than 5% of the particles are smaller than 150 µm.
[0033] [0033] In the case of a low surface tension, this generally leads to an increase in the rewetting values, for example, rewetting backing sheet, or leakage to the diapers in which such superabsorbents are used. Advantageously, this problem is prevented by the process according to the invention, and in the form of surfactants incorporable by polymerization. In addition, superabsorbent materials have a comparable performance with respect to retention (CRC) and back pressure absorption (AAP).
[0034] [0034] Adapted surfactants are added to the monomer solution for the production of the inventive superabsorbents. These specific surfactants contain functional groups that are polymerizable. Preferred chemical structures are: R1- (EO) n-block- (PO) m-R2 R1 or R2 = methyl, ethyl, n-propyl, iexpansãopil, n-butyl, isobutyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, -OH, acetyl or ally, en = 2 to 20 in = 2 a 20.
[0035] [0035] EO and PO are hydrophilic and hydrophobic blocks respectively to generate surfactant properties. Reactive allyl groups are preferred since, according to the invention, they are incorporated by polymerization later than acrylic groups and are more stable in hydrolysis.
[0036] [0036] It is more preferable when R1 or R2 is an allyl radical and the other radical is an acetyl group or OH radical.
[0037] [0037] In the context of the present invention, the term "EO" is understood to mean an ether which is formed by polyaddition of ethylene oxide and is referred to as polyether or polyethylene glycol. In the present application, the term "allyl (EO) n-" refers to a group with the formula CH2 = CH-CH2-O- (CH2-CH2-O) n -. In particular, it refers to compounds where n is an integer from 2 to 20.
[0038] [0038] Preference is given to compounds where n is 4 to 12 and more preferably n is 5 to 8.
[0039] [0039] In the context of the present invention, the term "PO" is, in principle, understood to mean propylene oxide according to the formula - (CH2-CH (CH3) -O) m. In this formula, m represents an integer from 2 to 20. Preference is given to compounds in which m is 3 to 12 and more preferably n is 4 to 7.
[0040] [0040] Preferably, for the distribution of the two different blocks, 2 <m <n <20, such that a hydrophilic-based structure is guaranteed and the surfactant has a defined water solubility.
[0041] [0041] Preference is given to surfactants with the following formula:
[0042] [0042] In the context of the present invention, individual PO units can be isotactic, syndiotactic or atactic sequences of the configuration of the molecule.
[0043] [0043] The blowing agents used can be all carbonates of the group of lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, or metal ions of greater valence, such as beryllium carbonate, carbonate calcium, magnesium carbonate, strontium carbonate or mixtures thereof. Other compounds also used can be granulate carbonates, which are also produced as mixtures of salts of a carbonate and / or percarbonate with another salt, which functions as an outer layer, for example a sulfate compound. According to the invention, the blowing agents have a particle size of 10 µm to 900 µm, preferably 50 µm to 500 µm and more preferably 100 µm to 450 µm.
[0044] [0044] According to the invention, surfactants are generally used simultaneously with the crosslinking agent. In one embodiment, the blowing agent is added after adding the surfactant. In other embodiments, the blowing agent can be delivered at the same time or before the surfactant.
[0045] [0045] By adding sodium carbonate or blowing agents, small bubbles are formed, these having a smaller diameter in the presence of surfactants.
[0046] [0046] According to the invention, surfactants stabilize the large surface area of the gas that appears in the solution by means of the blowing agent. The polymerization that proceeds in parallel corrects a fine porous structure (porous gel). Surfactants are "inactivated" during polymerization, which means that they can be incorporated into the polymer network or are incorporated, due to their reactive functionality.
[0047] [0047] The synergy observed between surfactants and blowing agents, advantageously, allows the use of small amounts of blowing agent, for example, carbonate. Typical disadvantages associated with carbonates include possible difficulties in mixing and adding the solution, and uncontrolled dispersion of the small bubbles formed, for example, significant coalescence or excessively large bubbles, or loss of other SAP properties.
[0048] [0048] Monoethylenically unsaturated (α1) monomers containing acidic groups may be partially or totally neutralized, preferably in part. The monoethylenically unsaturated monomers containing acid groups were neutralized, preferably to an extent of at least 10 mol%, more preferably to an extent of at least 25 to 50 mol% and even more preferably to an extent of 50 to 90 mol%. The neutralization of the monomers (α1) can precede or accompany the rest of the polymerization. In this case, partial neutralization is carried out to an extent of at least 10 mol%, more preferably to an extent of at least 25 to 50 mol% and even more preferably to an extent of 50 to 90 mol%. In addition, neutralization can be carried out with alkali metal hydroxides, alkaline earth metal hydroxides, ammonia, and carbonates and bicarbonates. In addition, any other base that forms a water-soluble salt with the acid is conceivable. Neutralization mixed with different bases is also conceivable. Preference is given to neutralization with ammonia or alkali metal hydroxides, more preferably with sodium hydroxide or ammonia.
[0049] [0049] In addition, groups of free acids in a polymer can be predominant, so that this polymer has a pH in the acid range. This acidic water-absorbing polymer can be at least partially neutralized by a polymer with free basic groups, preferably amine groups, which is basic in relation to the acid polymer. These polymers are referred to in the literature as "mixed bed ion-exchange absorbent polymers" (MBIEA polymers) and are disclosed in WO 99/34843, inter alia. WO 99/34843 disclosure is hereby incorporated by reference and is therefore considered to be part of the disclosure. In general, MBIEA polymers constitute a composition that includes first the basic polymers, capable of exchanging anions, and secondly a polymer that is acidic in comparison to the base polymer and is capable of cation exchange. The base polymer has basic groups and is typically obtained by polymerizing monomers that support basic groups or groups that can be converted to basic groups. These monomers are in particular those that have, secondary or tertiary primary amines or corresponding phosphines, or at least two of the above functional groups. This group of monomers includes especially ethyleneamine, allylamine, diallylamine, 4-aminobutene, alkyloxycyclines, vinylformamide, 5-aminopentene, carbodiimide, formaldacin, melamine and the like, and derivatives of secondary or tertiary amines thereof.
[0050] [0050] Preferred monoethylenically unsaturated monomers (α1) containing acid groups are acrylic acid, methacrylic acid, ethacrylic acid, a chloroacrylic acid, a cyanoacrylic acid, b-methylacrylic acid (crotonic acid), aphenylacrylic acid, b-acryloyloxypropionic acid, sorbic acid a-chlorosorbic acid, 2'-methylisocrotonic acid, cinnamic acid, p-chlorokinamic acid, b-stearyl acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, maleic acid, fumaric acid, and maleic and tricarboxyethylene anhydride , with particular preference being given to acrylic acid and methacrylic acid and, in addition to acrylic acid.
[0051] [0051] In addition to these monomers containing carboxylate groups, preferably monoethylenically unsaturated monomers (α1) containing acid groups additionally include ethylenically unsaturated sulfonic acid monomers or ethylenically unsaturated phosphonic acid monomers.
[0052] Preferred ethylenically unsaturated sulfonic acid monomers are allylsulfonic acid or aliphatic acids or aromatic or acrylic or acrylic or methacrylic sulfonic acids. Preferred aliphatic or aromatic vinylsulfonic acids are vinylsulfonic acid, 4-vinylbenzylsulfonic acid, viniltoluenesulfonic acid and styrenesulfonic acid. Preferred acryloyl- or methacryloylsulfonic acids are sulfoethyl, (meth) sulfopropyl acrylate, (meth) acrylate, 2-hydroxy-3-methacryloyloxypropylsulfonic acid, and (meth) acrylamidoalkylsulfonic acids such as 2-acrylamido-2-methylpropanesic acid.
[0053] [0053] Preferred ethylenically unsaturated phosphonic acid monomers are vinylphosphonic acid, allylphosphonic acid, vinylbenzylphosphonic acid, (meth) acrylamidoalkylphosphonic acids, acrylamidoalkylphosphonic acids, phosphonomethylated vinylamines and acid derivatives.
[0054] [0054] Preferred ethylenically unsaturated (α1) monomers containing a protonated nitrogen atom are preferably dialkylaminoalkyl (meth) acrylates in the protonated form, for example dimethylaminoethyl (meth) acrylate or dimethylaminoethyl hydrochloride, (methyl) acrylate and hydrosulfate acrylate, alkyl of (meth) acrylamides in protonated form, for example dimethylaminoethyl (meth) acrylamide hydrochloride, dimethylaminopropyl (meth) acrylamide hydrochloride, dimethylaminopropyl (meth) acrylamide or hydrosulfatodimethylaminoethyl (meth) acrylamide hydrosulfate.
[0055] [0055] Preferred ethylenically unsaturated (α1) monomers containing a quaternized nitrogen atom are dialkylammonioalkyl (meth) acrylates, in quaternized form, for example, trimethylammonium (meth) methosulfate or dimethylethylammonioethyl (meth) acrylate-ethosulfate, (and) acrylamidoalkylhydialkylamines in quaternized form, for example, (meth) acrylamidopropyltrimethylammonium, trimethylammonium chloride, (meth) acrylate or (meth) acrylamidopropyltrimethylammonium sulfate.
[0056] [0056] Monoethylenically unsaturated (α2) monomers copolymerizable with (α1) preferred are acrylamides and methacrylamides.
[0057] Preferred (Met) acrylamides are, in addition to acrylamide and methacrylamide, (meth) acrylamides or their substituted aminoalkyl- (meth) acrylamide derivatives, such as N-methylol (meth) acrylamide, N, N-dimethylamino ( met) acrylamide, dimethyl (meth) acrylamide or diethyl (meth) acrylamide. Possible vinylamides are, for example, N-vinylamides, Nvinylformamides, N-vinylacetamides, N-vinyl-N-methylacetamides, N-vinyl-N-methylformamides, vinylpyrrolidone. Among these monomers, in particular, preference is given to acrylamide.
[0058] [0058] Additionally preferred as monoethylenically unsaturated (α2) monomers copolymerizable with (α1) are water-dispersible monomers. Preferred water-dispersible monomers are acrylic esters and methacrylic esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl propyl (meth) acrylate or (meth) acrylate, and also vinyl, styrene and isobutylene acetate.
[0059] Preferred crosslinkers (α3) according to the invention are compounds that have at least two ethylenically unsaturated groups within a molecule (crosslinker class I), compounds that have at least two functional groups that can react with functional groups of monomers ( α1) or (α2) in a condensation reaction (= condensation crosslinking agents), in an addition reaction or a ring opening reaction (crosslinker class II), compounds that have at least one ethylenically unsaturated group and at least one functional group that can react with functional groups of monomers (α1) or (α2) in a condensation reaction, in an addition reaction or a ring opening reaction (crosslinker class III), or polyvalent metal cations (crosslinker class IV) . Cross-class I compounds achieve cross-linking of polymers through the polymerization of free radicals of the ethylenically unsaturated groups of the cross-linking molecule with mono-ethylenically unsaturated monomers (α1) or (α2), while class II compounds and the cation crosslinking agent of polyvalent metals of cross-linking class IV achieve cross-linking of polymers through a condensation reaction of the functional groups (class II) or cross-linking agent through the electrostatic interaction of the polyvalent metal cation (cross-linking class IV) with the functional groups of monomers (α1) or (α2). In the case of compounds of cross-linking class III, there is correspondingly cross-linking of the polymer either by polymerization of free radicals of the ethylenically unsaturated group or a condensation reaction between the functional group of the cross-linking agent and the functional groups of monomers (α1) or ( α2).
[0060] [0060] Preferred compounds of crosslinking agent class I are poly (meth) acrylic esters which are obtained, for example, by the reaction of a polyol, for example, ethylene glycol, propylene glycol, trimethylolpropane, 1,6-hexanediol, glycerol, pentaerythritol, polyethylene glycol or polypropylene glycol, an amino alcohol, a polyalkylene polyamine, for example, diethylene triamine or triethylene tetramine, or an alkoxylated polyol with acrylic acid or methacrylic acid. Preferred compounds of the class of cross-linking agent which are, in addition, polyvinyl compounds, poly (meth) ally compounds, (meth) acrylic esters, a monovinyl compound or (meth) acrylic esters, a mono (meth) allyl preferably composed of mono (meth) ally compounds of a polyol or an amino alcohol. In this context, reference is made to DE 195 43 366 and DE 195 43 368. The disclosures are hereby incorporated by reference and are therefore considered to be part of the invention.
[0061] [0061] Examples of compounds of the crosslinking agent class include alkenyl di (meth) acrylates, for example, ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butylene glycol di (met) acrylate, 1,3-butylene glycol di (met) acrylate, 1,6-hexanediol, di (met) acrylate, 1,10-decanediol di (met) acrylate, 1,12-dodecanediol di (met) acrylate, 1,18-octadecanediol di (meth) acrylate, cyclopentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, methylene di (meth) acrylate or pentaerythritol di (meth) acrylate, alkenyldi (meth) acrylamides, for example N -methyldi (meth) acrylamide, N, N'-3-methylbutylenebis (meth) acrylamide, N, N '- (1,2-dihydroxyethylene) bis (meth) acrylamide, N, N'- hexamethylenebis (meth) acrylacrylamide or N , N'-methylene-bis (meth) acrylamide, polyalkoxy di (meth) acrylates, for example diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di ( met) acrylate, tripropylene-gl bisphenol A (meth) acrylate or tetrapropylene glycol di bisphenol A (meth) acrylate ethoxylated di, (meth) acrylate, benzylidene di (meth) acrylate, 1,3-di (meth) esters acryloyloxy-2-propanol, hydroquinone di (meth) acrylate, trimethylolpropane di- (meth) acrylate which has been preferably alkoxylated, preferably ethoxylated, with 1 to 30 mol of alkylene oxide by a hydroxyl group, thioethylene glycol di (met) acrylate, thiopropylene glycol di (meth) acrylate, methyl thiopolethylene glycol di (meth) acrylate, thiopolypropylene glycol di (meth) acrylate, divinyl ethers, for example, 1,4-butanediol divinyl ether, divinyl esters, for example, adipate of divinyl, alkadiene, for example, butadiene, 1,6-hexadiene, divinylbenzene, di (meth) ally compounds, for example, di (meth) allyl or allyl di (meth) succinate, homo- and di-copolymers (meth) alildimethylammonium chloride and homo-e copolymers of (meth) allylaminomethyl (meth) acrylate chlorine ammonium chloride, vinyl (meth) acryloyl compounds, e.g. vinyl (meth) acrylate, (meth) allyl, (meth) acryloyl compounds, e.g. (meth) ally (meth) acrylate, (meth) allyl, (meth) ethoxylated acrylate with 1 to 30 mol of ethylene oxide per hydroxyl group, di (meth) allyl esters of polycarboxylic acids, for example, allyl di (meth) maleate, allyl di (meth) fumarate, di (meth) allyl or di (meth) allyl terephthalate succinate, compounds having 3 or more ethylenically unsaturated polymerizable groups, by free radicals, for example glyceryl tri (meth) acrylate, glycerol esters (meth) acrylate, which has been ethoxylated with preferably 1 to 30 mol of ethylene oxide per hydroxyl group, methyl tri (meth) acrylate, trimethylolpropane tri (meth) acrylate esters that have been preferably alkoxylated, preferably ethoxylated, with 1 to 30 mol of alkylene oxide per hydroxyl group, trimethacrylamide, (met) allylene di (meth) acrylate, methyl 3-allyloxy-1,2-propanediol di (meth) acrylate, tri (meth) allyl cyanurate, tri (meth) allyl isocyanurate, pentaerythritol esters of tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, (meth) acrylics of ethoxylated pentaerythritol with preferably 1 to 30 mol of ethylene oxide per hydroxyl group, tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate, trivinyl trimellitate, tri (meth) allylamine, di (meth) allylalkylamines, for example, di (meth) alimethylamine, tri (meth) allyl phosphate, tetra ( met) alylethylenediamine, poly (meth) allyl esters, tetra (meth) allyloxyethane or allylammonium tetra (meth) halides.
[0062] [0062] Preferred compounds of crosslinking class II are compounds that have at least two functional groups that can react in a condensation reaction (= condensation crosslinkers), to an addition reaction or a ring opening reaction with the groups functional monomers (α1) or (α2), preferably with the monomer acid groups (α1). These functional groups of the cross-linking class II compounds are preferably alcohol, amine, aldehyde, glycidyl, isocyanate, carbonate or epichlorine functions.
[0063] [0063] Examples of cross-linking class II compounds include polyols, for example ethylene glycol glycols, polyethylene, such as diethylene glycol, triethylene glycol and tetraethylene glycol, propylene glycol, polypropylene glycols, such as dipropylene glycol, tripropylene glycol or tetrapropylene glycol, 1 , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 1,6-hexanediol, 2,5-hexanediol, glycerol, polyglycerol, trimethylolpropane, polyoxypropylene, oxyethylene-oxypropylene block copolymers , fatty acid sorbitan esters, polyoxyethylene sorbitan fatty acid esters, pentaerythritol, sorbitol and polyvinyl alcohol, amino alcohols, for example, ethanolamine, diethanolamine, triethanolamine or propanolamine, polyamine compounds, for example ethylene diamine, triethylamine, diethylene triethylamine or pentaethylenehexamine, polyglycidyl ether compounds, such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether col, glycerol diglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, diglycidyl glycidyl ether, glycidyl ether, glycidyl glycyl ether, polyglycidyl glycol ether , diglycidyl adipate, 1,4-phenylenebis (2-oxazoline), glycidol, polyisocyanates, preferably diisocyanates, such as toluene, 2,4-diisocyanate and hexamethylene diisocyanate, polyaziridine compounds, such as tris 2,2-bishidroximetilbutanol [3 - (1-aziridinil) - propionato], 1,6-hexamethylenedietilenourea e diphenylmethanobis4, 4'-N, N'-diethylenourea, halogen peroxides, for example, epichloro-epibromhydrin and a d-α methylepichlorohydrin, alkylene carbonates, such as 1,3-dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolan-2-one (propylene carbonate), 4,5-dimethyl-1,3 -dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4- ethyl-1,3-dioxolan-2-one, 4-hydroxy-methyl-1,3-dioxolan-2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2- one, 4,6-dimethyl-1,3-dioxane-2-one, 1,3-dioxolan-2-one, poly-1,3-dioxolan-2-one, polyquaternary amines, such as dimethylamine condensation products and epichlorohydrin.
[0064] Preferred compounds of crosslinker class II are additionally polyoxazolines such as 1,2-ethylenebisoxazoline, crosslinking agents with silane groups, such as g-glycidoxypropyltrimethoxysilane and gaminopropyltrimethoxysilane, oxazolidinones, such as 2-oxazolidinone, bis- and poly-2 -oxazolidinones and diglycol silicates.
[0065] Preferred class III compounds include esters containing amino groups of (meth) acrylic-hydroxyl acid or, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, and also hydroxyl- or groups (meth) acrylamides containing amino or mono (meth) allyl compounds of diols.
[0066] [0066] Cross-linking class IV polyvalent metal cations are preferably derived from mono- or polyvalent cations, monovalent cations, especially from alkali metals such as potassium, sodium, lithium, with preference being given to lithium. Preferred divalent cations are derived from zinc, beryllium, alkaline earth metals, such as magnesium, calcium, strontium, with preference given to magnesium. In addition, higher valence cations usable according to the invention are the cations of aluminum, iron, chromium, manganese, titanium, zirconium and other transition metals, and also the double cation salts or mixtures of the mentioned salts. Preference is given to using aluminum and alum salts and the different hydrates thereof, for example, AlCl3 × 6H2O, NaAl (SO4) 2 x 12H2O, KAl (SO4) 2 × 12H2O2 or Al (SO4) 3 x 14-18 H2O. Particular preference is given to the use of Al2 (SO4) 3, and its hydrates, as cross-linking agents of cross-linking class IV.
[0067] [0067] The superabsorbent particles used in the process according to the invention are preferably crosslinked by crosslinkers of the following crosslinking classes, or by crosslinking agents of the following combinations of crosslinking classes: I, II, III, IV, I II, I III, I IV, I II III, I II IV, I III IV, II III IV, II IV, or III IV. The above combinations of crosslinking classes are each the preferred embodiment of a superabsorbent particle crosslinking agent used in the process according to the invention.
[0068] [0068] Other preferred embodiments of the superabsorbent particles used in the process according to the invention are polymers that are crosslinked by any of the crosslinking class I agents. Among these mentioned above, preference is given to agents water-soluble cross-linked. In this context, in particular, preference is given to N, N'-methylenebisacrylamide, polyethylene glycol di- (meth) acrylates, trialylmethylammonium chloride, tetraalylammonium chloride, and allyl nonaethylene glycol acrylate prepared with 9 mol of ethylene oxide per mol of acrylic acid .
[0069] [0069] As water-soluble polymers (α4), superabsorbent particles may comprise water-soluble polymers, such as polyvinyl alcohol, partially or fully hydrolyzed, polyvinylpyrrolidone, starch or starch derivatives, polyglycols or polyacrylic acid, preferably incorporated in the polymerized form. The molecular weight of these polymers is not critical, as long as they are soluble in water. Preferred water-soluble polymers are starch or starch derivatives or polyvinyl alcohol. Water-soluble polymers, preferably synthetic water-soluble polymers, such as polyvinyl alcohol, can also serve as a graft base for monomers to be polymerized.
[0070] [0070] The auxiliaries (α5) present in polymers are organic or inorganic particles, for example, odor binders, especially zeolites or cyclodextrins, skin substances, surfactants or anti-oxidants.
[0071] [0071] Preferred organic assistants include cyclodextrins or derivatives thereof and polysaccharides. Also preferred are cellulose and cellulose derivatives, such as CMC, cellulose ethers. Preferred cyclodextrins or cyclodextrin derivatives are those compounds disclosed in DE-A-198 25 486 on page 3 line 51 to page 4 line 61. The section of this published patent application is incorporated herein by reference and is considered to be part of description of the present invention. Particularly preferred cyclodextrins are non-derivatized α-, β-, γ- or δ-cyclodextrins.
[0072] [0072] The particulate inorganic auxiliaries used can be any materials that are typically used to modify the properties of water-absorbing polymers. Preferred inorganic auxiliaries include sulfates, such as Na2SO4, lactates, for example sodium lactate, silicates, especially structure silicates, such as zeolites, or silicates that have been obtained by drying aqueous silica solutions or colloidal silica solutions, for example commercially available products such as precipitated silicas and smoked silicas, for example Aerosils having a particle size in the range of 5 to 50 nm, preferably in the range of 8 to 20 nm, such as "Aerosil 200" from Evonik Industries AG , aluminates, titanium dioxides, zinc oxides, clay materials, and other mineral salts, familiar to those skilled in the art, and also inorganic carbonaceous materials.
[0073] [0073] Preferred silicates are all natural or synthetic silicates that are disclosed as silicates in Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie [Inorganic Chemistry], Walter de Gruyter-Verlag, edition 91a-100a of 1985, on pages 750-783. The section of this book mentioned above is hereby incorporated by reference and is considered to be part of the description of the present invention.
[0074] [0074] Particularly preferred silicates are zeolites. The zeolites used can be all synthetic or natural zeolites, known to those skilled in the art. The preferred natural zeolites are the zeolites of the natrolite group, the harmotone group, the mordenite group, the chabasite group, the faujasite group (sodalite group) or the analycite group. Examples of natural zeolites are analcime, leucite, polucite, wairakite, belbergite, bikitaite, boggsite, brewsterite, chabazite, wilhendersonite, cowlesite, dachiardite, edingtonite, epistilbite, erionite, faujasite, ferrierite, amygite, garronite, gironne , goosecreekite, harmotone, phillipsite, wellsite, clinoptilolite, heulandite, laumontite, levine, mazzite, merlinoite, montesomaite, mordenite, mesolite, natrolite, scolecite, ofretite, paranatrolite, paulingite, perlialite, barrerite, stilite, stilite, stilichite, stilichite . Preferred synthetic zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, or the ABSCENTS ® product.
[0075] [0075] The zeolites used can be zeolites that are called "intermediate" type, in which the SiO2 / AlO 2 ratio is less than 10; the SiO2 / AlO2 ratio of these zeolites is more preferably within a range of 2 to 10. In addition to these "intermediate" zeolites, it is also possible to use "higher" type zeolites, which include, for example, those known ZSM type "molecular sieve" zeolites, and βzeolite. These "upper" zeolites are preferably characterized by a SiO2 / AlO2 ratio of at least 35, more preferably by a SiO2 / AlO2 ratio in the range of 200 to 500.
[0076] [0076] The aluminates used are preferably natural spinel, especially common spinel, zinc spinel, iron spinel or chromium spinel.
[0077] [0077] Preferred titanium dioxide is pure titanium dioxide in the form of crystal, rutile, anatase and brookite, as well as titanium dioxides containing iron, for example, ilmenite, titanium dioxides containing calcium, such as titanite or perovskite .
[0078] [0078] Preferred clay materials are those disclosed as clay materials in Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter-Verlag, edition 91a-100a 1985, on pages 783-785. In particular, the section of the aforementioned book is hereby incorporated by reference and is considered to be part of the description of the present invention. Particularly preferred clay materials are kaolinite, illite, haloisite, montmorillonite and talc.
[0079] [0079] More preferred inorganics according to the invention are the metal salts of mono-, oligo- and polyphosphoric acids. Among these, preference is given especially to hydrates, in particular with preference given to mono- to decahydrates and trihydrates. Useful metals include metals, especially alkali metals and alkaline earth metals, with preference being given to alkaline earth metals. Among these, magnesium and calcium are preferred and Mg is particularly preferred. In the context of phosphates, phosphoric acids and their metal compounds, reference is made to Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter-Verlag, edition 91a-100a, 1985, on pages 651-669. The section of this book mentioned above is hereby incorporated by reference and is considered to be part of the description of the present invention.
[0080] [0080] Preferred carbonaceous but non-organic assistants are those pure carbons that are mentioned as graphites in Hollemann and Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter-Verlag, edition 91a-100a 1985, on pages 705-708. The section of this book mentioned above is hereby incorporated by reference and is considered to be part of the description of the present invention. Particularly preferred graphites are synthetic graphites, for example coke, pyrography, activated carbon or black carbon.
[0081] [0081] The water-absorbing polymers obtained in the process according to the invention are preferably obtained by first preparing a hydrogel polymer (PC) in the form of particles from the aforementioned monomers and cross-linking agents. This starting material for water-absorbing polymers is produced, for example, by mass polymerization, which is preferably carried out in kneading reactors, such as extruders, solution polymerization, spray polymerization, reverse emulsion polymerization or polymerization in reverse suspension. Preference is given to carrying out polymerization in solution in water as a solvent. Solution polymerization can be carried out continuously or discontinuously. The prior art reveals a wide range of possible variations with respect to the reaction conditions, such as temperature, type and quantity of the initiators, and reaction solution. Typical processes are described in the following patents: US 4,286,082, DE 27 06 135, US 4,076,663, DE 35 03 458, DE 40 20 780, DE 42 44 548, DE 43 23 001, DE 43 33 056, DE 44 18 818. Disclosures are incorporated herein by reference and are therefore considered to be part of the disclosure.
[0082] [0082] The initiators used to initiate polymerization can be all initiators that form free radicals, under the conditions of polymerization and are normally used in the production of superabsorbents. These include thermal initiators, redox initiators and photoinitiators, which are activated by means of high energy radiation. The polymerization initiators can be present dissolved or dispersed in a monomer solution of the invention. Preference is given to the use of water-soluble initiators.
[0083] [0083] Useful thermal initiators include all compounds that decompose to free radicals when heated and are known to those skilled in the art. Particular preference is given to thermal polymerization initiators having a half-life of less than 10 seconds, even more preferably less than 5 seconds at less than 180 ° C, even more preferably at least 140 ° C. Peroxides, hydroperoxides, hydrogen peroxide, persulfates and azo compounds, thermal polymerization initiators are particularly preferred. In some cases, it is advantageous to use mixtures of different thermal polymerization initiators. Among these mixtures, preference is given to those of hydrogen peroxide and sodium peroxodisulfate or potassium peroxodisulfate, which can be used in any conceivable proportion. Suitable organic peroxides are preferably acetylacetone peroxide, methyl ethyl ketone peroxide, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capryl peroxide, propyl peroxydicarbonate, 2-ethylhexyl peroxydicarbonate, t-butyl peroxydicarbonate , cumene hydroperoxide, t-amyl perpivalate, t-butyl perpivalate, t-butyl perneohexanoate, t-butyl isobutyrate, t-butyl-per-2-ethylhexanoate, t-butyl perisononanoate, t-butyl permaleate, t- butyl-perbenzoate, tbutyl-3,5,5-trimethyl and amyl perneodecanoate. Preferred thermal polymerization initiators are: azo compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, 2,2'-azobis (2-amidinopropane), azobisamidinopropane dihydrochloride, 2,2'-azobis dihydrochloride (N, N-dimethylene) isobutyramine - (carbamoylazo) isobutyronitrile and 4,4'-azobis (4-cyanovaleric acid). The mentioned compounds are used in usual amounts, preferably within a range of 0.01 to 5 mol%, preferably from 0.1 to 2 mol%, based on each case depending on the amount of monomers to be polymerized .
[0084] [0084] Redox initiators comprise, as the oxidic component, at least one of the above specified by compounds, and, as the reducing component, preferably ascorbic acid, glucose, sorbose, mannose, hydrogen ammonium, sulfate, thiosulfate, hyposulfite or sulfide, alkali metals, hydrogen sulfides, sulfate, thiosulfate, hyposulfite or sulfide, metal salts, such as iron (II) ions or silver ions, or sodium hydroxymethylsulfoxylate. The reducing component used in the redox initiator is preferably ascorbic acid or sodium pyrosulfite. Based on the amount of monomers used in the polymerization, 1 x 10-5 to 1 mol% of the redox initiator reduction component and 1 x 10-5 to 5 mol% of the oxidizing component of the redox initiator are used. Instead of the oxidation component of the redox initiator, or in addition to it, it is possible to use one or more azo compounds, preferably water-soluble.
[0085] [0085] If the polymerization is triggered by the action of high energy radiation, it is customary to use what is called photoinitiators, as the initiator. These can be, for example, what are called α-dividers, H-abstraction systems, or azides. Examples of such initiators are benzophenone derivatives, such as Michler's ketone, phenanthrene derivatives, fluorene derivatives, anthraquinone derivatives, thioxanthon and derivatives, coumarin derivatives, benzoyl ethers and their derivatives, azo compounds aforementioned free radicals, substituted hexaarylbisimidazols or acylphosphine oxides. Examples of azides are: 2- (N, N-dimethylamino) 4-azidocinamate, 2- (N, N-dimethylamino) ethyl 4-azidonafty-ketone, 2- (N, N-dimethylamino) ethyl 4-azidobenzoate , 5-azido-1-naphthyl 2 '- (N, Ndimethylamino) ethyl sulfone, N- (4-sulfonylazidophenyl) maleimide, N-acetyl-4-sulfonylazidoaniline, 4-sulfonylazidoaniline, 4-azidoaniline, 4-azidophenacyl bromide , p-azidobenzoic acid, 2,6-bis (p-azidobenzylidene) cyclohexanone and 2,6-bis (pazidobenzylidene) -4-methylcyclohexanone. If used, photoinitiators are typically used in amounts of 0.01 to 5% by weight, based on the monomers to be polymerized.
[0086] [0086] Preference is given, according to the invention, to the use of an initiator system consisting of hydrogen peroxide, sodium peroxodisulfate and ascorbic acid. In general, polymerization is initiated with the initiators within a temperature range of 0 ° C to 90 ° C.
[0087] [0087] The polymerization reaction can be triggered by an initiator or by a plurality of interacting initiators. In addition, polymerization can be carried out in such a way that one or more redox initiators are added first. Later, in polymerization, thermal initiators or photoinitiators are then applied, additionally, and the polymerization reaction in the case of photoinitiators is then initiated by the action of high energy radiation. The reverse sequence, that is, the initial opening of the reaction by means of high energy radiation and photoinitiators or thermal initiators and polymerization initiation, by means of one or more redox initiators later in the polymerization, is also conceivable.
[0088] [0088] In order to convert the hydrogel (PC) polymers thus obtained to a particulate form, which can first, after having been removed from the reaction mixture, be dried at a temperature within a range of 20 to 300 ° C, preferably within a range of 50 to 250 ° C and more preferably within a range of 100 to 200 ° C, up to a water content of less than 40% by weight, preferably less than 20% by weight, and even more preferably less than 10% by weight, based on each case in relation to the total weight of the hydrogel polymer (PC). Drying is preferably carried out in ovens or dryers known to those skilled in the art, for example, belt dryers, staged dryers, rotary tube ovens, fluidized bed dryers, tray dryers, paddle dryers and infrared dryers.
[0089] [0089] According to the present invention, fragmentation is preferably carried out by dry grinding, preferably by dry grinding in a hammer mill, a fixed disk mill, a ball mill or a roller mill. In another version of the present invention, the hydrogel polymer can also be crushed by combinations of two or more of the mills described above.
[0090] [0090] In a preferred embodiment of the processes according to the invention, the water-absorbing polymers obtained are particles having an inner region and a surface area bordering the inner region. The surface region has a different chemical composition than the inner region, or differs from the inner region of a physical property. Physical properties in which the internal region is different from the surface region are, for example, charge density, or degree of crosslinking.
[0091] [0091] These water-absorbing polymers having an inner region and a surface area bordering the inner region are preferably obtained by backcrossing reactive groups close to the surface of the particulate hydrogel (PC) particles. This backcross can be carried out thermally, chemically or photochemically.
[0092] [0092] Preferred backcrosses are compounds of crosslinking agent classes II and IV, mentioned in connection with crosslinking agents (α3).
[0093] [0093] Among these compounds, particularly preferred binders are diethylene glycol, triethylene glycol, polyethylene glycol, glycerol, polyglycerol, propylene glycol, diethanolamine, triethanolamine, polyoxypropylene, oxyethylene oxypropylene block copolymers, fatty acid sorbitan esters, esters polyoxyethylene sorbitol, trimethylolpropane, pentaerythritol, polyvinyl alcohol, sorbitol, 1,3-dioxolan-2-one (ethylene carbonate), 4-methyl1,3-dioxolan-2-one (propylene carbonate), 4,5-dimethyl -1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan -2-one, 1,3-dioxane-2-one, 4-methyl-1,3-dioxane-2-one, 4,6-dimethyl-1,3-dioxane-2-one, 1,3-dioxolan -2-one, poly-1,3-dioxolan-2-one.
[0094] [0094] Particular preference is given to the use of ethylene carbonate as a binder.
[0095] [0095] Preferred embodiments of the water-absorbing polymers are those which are crosslinkers of the following binding classes or by crosslinking agents of the following combinations of crosslinking classes: II, IV and II IV.
[0096] The crosslinker is preferably used in an amount within a range of 0.01-30% by weight, more preferably in an amount within a range of 0.1 to 20% by weight, and even more preferably in an amount within of a range of 0.3-5% by weight, based on each case in relation to the weight of the superabsorbent polymers in the crosslinker.
[0097] [0097] It is also preferred that the crosslinker is carried out by contacting a solvent which preferably comprises water, water-miscible organic solvents, for example, methanol or ethanol or mixtures of at least two of these, and the crosslinker with the outer region of the hydrogel polymer particles at a temperature within a range of 30 to 300 ° C, more preferably within a range of 100 to 200 ° C. The contact is preferably effected by spraying the mixture consisting of binder and solvent , on the hydrogel polymer particles and then mix the hydrogel polymer particles in contact with the mixture. The binder is present in the mixture, preferably in an amount in the range of 0.01 to 20% by weight, more preferably in an amount within the range of 0.1 to 10% by weight, based on the total weight of the mixture. It is further preferred that contact with the hydrogel polymer particles is made in an amount within a range of 0.01 to 50% by weight, more preferably in an amount within a range of 0.1 to 30% by weight, based in each case on the weight of the hydrogel polymer particles.
[0098] [0098] Useful condensation reactions preferably include the formation of ester, amide, imide or urethane bonds, with preference being given to the formation of ester bonds.
[0099] [0099] The hydrogel polymers of the invention and / or water-absorbing polymers can be further mixed with other additives and effect substances.
[0100] [0100] Preferred additives are additionally release agents, for example, inorganic or organic powder release agents. These release agents are preferably used in amounts within a range of 0 to 2% by weight, more preferably within a range of 0.1 to 1.5% by weight, based on the weight of the hydrogel polymer and / or water-absorbing polymer. Preferred release agents are: wood flour, cellulose fibers, powder bark, cellulose powder, fillers, minerals, such as perlite, synthetic fillers, such as nylon powder, rayon powder, diatomaceous earth, bentonite, kaolin, zeolites, talc, chalk, ash, coal dust, magnesium silicates, fertilizers or mixtures of the substances. Finely divided smoked silica, as sold under the trade name Aerosil by Evonik Degussa, is preferred.
[0101] [0101] In another preferred embodiment of the process according to the invention, the hydrogel polymer particles and / or the water-absorbing polymer particles are brought into contact with an effect substance, for example, a sugar sugar, a polyphenol compound, for example, hydrolyzable tannins or a compound containing silicon, oxygen, or a mixture of at least two effect substances based thereon. The effect substance can be added in solid form (powder) or in the form dissolved with a solvent, the effect substance being added not before the process of step iii). In the context of the present invention, an effect substance is understood to mean a substance that serves to inhibit odors.
[0102] [0102] According to the invention, this is understood to mean poly-sugars, so the person skilled in the art understands from the group of known starches and their derivatives, celluloses and their derivatives, cyclodextrins. Cyclodextrins are preferably understood to mean α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin or mixtures of these cyclodextrins.
[0103] [0103] The preferred compounds containing silicon-oxygen are zeolites. The zeolites used can be all synthetic or natural zeolites, known to those skilled in the art. The preferred natural zeolites are the zeolites of the natrolite group, the harmotome group, the mordenite group, the chabazite group, the faujasite group (sodalite group) or the analycite group. Examples of natural zeolites are analcime, leucite, polucite, wairakite, belbergite, bikitaite, boggsite, brewsterite, chabazite, wilhendersonite, cowlesite, dachiardite, edingtonite, epistilbite, erionite, faujasite, ferrierite, amygite, garronite, gironne , goosecreekite, harmotome, philipsite, wellsite, clinoptilolite, heulandite, laumontite, levine, mazita, merlinoite, montesomaite, mordenite, mesolite, natrolite, scolecite, ofretite, paranatrolite, paulingite, perlialite, barrerite, stilichite, stilichite, steller . Preferred synthetic zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, or ABSCENTS ® products.
[0104] [0104] The cations present in the zeolites used in the process according to the invention are the alkali metal cations, preferably such as Li +, Na +, K +, Rb +, Cs + or Pe + and / or metal cations alkaline earths such as Mg 2 +, Ca 2 +, Sr 2 + or Ba 2 +.
[0105] [0105] The zeolites used can be zeolites that are called "intermediate" type, where the SiO2 / AlO2 ratio is less than 10, the SiO2 / AlO2 ratio of these zeolites is more preferably within a range of 2 to 10. In addition to these "intermediate" zeolites, it is also possible to use "higher" type zeolites, which include, for example, the known ZSM type "molecular sieve" zeolites and beta-zeolites. These "upper" zeolites are preferably characterized by a SiO2 / AlO2 ratio of at least 35, more preferably by a SiO2 / AlO2 ratio in the range of 200 to 500.
[0106] [0106] Zeolites are preferably used in the form of particles with an average particle size within the range of 1 to 500 µm, more preferably within the range of 2- 200 µm and even more preferably within the range from 5 to 100 µm.
[0107] [0107] The effect substances are used in the processes according to the invention, preferably in an amount ranging from 0.1 to 50% by weight, more preferably within the range of 1 to 40% by weight, and furthermore more preferably in an amount within a range of 5 to 30% by weight, based on each case with respect to the weight of the hydrogel polymer particles and / or water-absorbing polymer particles.
[0108] [0108] Preferred microbe inhibiting substances are, in principle, all substances active against Gram-positive bacteria, for example, 4-hydroxybenzoic acid, and salts and esters thereof, N- (4-chlorophenyl) -N '- (3, 4-dichlorophenyl) urea, 2,4,4'-trichloro-2'-hydroxydiphenyl ether (Triclosan), 4-chloro-3,5-dimethylphenol, 2,2'-methylenebis (6-bromo-4-chlorophenol), 3-methyl-4- (1-methyl-ethyl) phenol, 2-benzyl-4-chlorophenol, 3- (4-chlorophenoxy) -1,2-propanediol, 3-iodine -2-propynyl butylcarbamate, chlorhexidine, 3, 4,4'- trichlorocarbonylide (TTC), antibacterial perfumes, thymol, thyme oil, eugenol, clove oil, menthol, mint oil, famesol, phenoxyethanol, glyceryl monocaprate, glyceryl monocaprylate, glyceryl monolaurate (GML), diglyceril monocaprate (DMC), N-alkylsalicylamides, for example, Nnoctylsalicylamide or Nn-decylsalicylamide.
[0109] [0109] Suitable enzyme inhibitors are, for example, esterase inhibitors. These are preferably trialkyl citrates, such as trimethyl citrate, tripropyl citrate, tripyl citrate, tributyl citrate and especially triethyl citrate (CAT Hydagen TM, Cognis GmbH, Dusseldorf, Germany). The substances inhibit the activity of the enzyme and, as a result, reduce the formation of odor. Other substances useful as esterase inhibitors are sterol or phosphate sulphates, for example, lanosterol or phosphate, cholesterol or phosphate sulphate, campesterol sulphate or phosphate, stigmasterol sulphate or phosphate and sitosterol or phosphate sulphate, carboxylic acids and esters, for example, glutaric acid, monoethyl glutarate, diethyl glutarate, adipic acid, monoethyl adipate, diethyl adipate, malonic acid and diethyl malonate, hydroxy carboxylic acids and their esters, for example, citric acid, malic acid, tartaric acid or diethyl tartrate, and zinc glycinate.
[0110] [0110] Suitable odor absorbers are substances that can absorb and substantially retain odor-forming substances. They reduce the partial pressure of the individual components and thus also reduce the speed of their propagation. It is important that the perfumes must remain intact. Odor absorbers have no effect against bacteria. They contain, for example, as the main constituent, a zinc salt complex of ricinoleic acid, or substantially neutral odor-specific fragrances known to the person skilled in the art as "fixatives", for example, labdanum or stirax extracts or in particular derivatives of abietic acid. The function of odor maskers is filled by odors or perfume oils, which, in addition to their function as odor maskers, give their particular fragrance note to deodorants. Examples of perfume oils include mixtures of natural and synthetic odors. Natural odors are extracts of flowers, stems and leaves, fruits, fruit peels, roots, woods, herbs and grasses, needles and branches, as well as resins and balms. In addition, useful are raw materials of animal origin, for example, civet and castoreum. Typical synthetic odorant compounds are products such as ester, ether, aldehyde, ketone, alcohol and hydrocarbon. Odorant compounds of the ester type are, for example, benzyl acetate, p-tert-butylcyclohexyl acetate, linally acetate, phenylethyl acetate, linally benzoate, benzyl formate, allyl cyclohexylpropionate, stiralyl propionate and benzyl salicylate. Ethers include, for example, benzyl ethyl ether; aldehydes include, for example, linear alkanols having from 8 to 18 carbon atoms, citral, citronelal, citroneliloxyacetaldehyde, cyclamen, hydroxycitronelal, lilial and bourgeonal aldehyde; ketones include, for example, ionones and cedryl methyl ketone; alcohols include anethole, citronelol, eugenol, isoeugenol, geraniol, linalool, phenylethyl alcohol and terpineol; hydrocarbons mainly include terpenes and balms. Preference is given, however, to the use of mixtures of different odorants, which together produce a pleasant fragrance note. Suitable perfume oils are also essential oils of relatively low volatility, which are generally used as aroma components, for example sage oil, chamomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lemon flower oil, Juniperberry oil, vetiver oil, frankincense oil, galbanum oil, labdanum oil and lavender oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, liral, citronelol, phenylethyl alcohol, alpha-hexylcinamaldehyde, geraniol, benzylacetone, cyclamen aldehyde, linalool, Boisambrene Forte, ambroxan, indole, hedione, Sandelice, lemon oil, oil mandarin, orange oil, allyl amyl glycolate, cyclovertal, lavender oil, sage oil, beta-damask, bourbon, geranium oil, Vertofix Coeur cycle salicylate, Iso-E-Super, Fixolide NP, Evernyl, range iraldein, phenylacetic acid, geranyl acetate, ethyl benzyl, rosa oxide, Romilat, Irotyl and Floramat, alone or in mixtures.
[0111] [0111] Antiperspirants reduce the formation of sweat by influencing the activity of the sweat glands and tissues, and thus prevent underarm wetting and body odor. Suitable astringent antiperspirant active ingredients are in particular aluminum, zirconium or zinc salts. Such anti-hydrotically suitable active ingredients are, for example, aluminum chloride, aluminum hydrochloride, aluminum dichlorohydrate, aluminum sesquichlorohydrate and their complexes, for example, with 1,2-propylene glycol, aluminum hydroxyalanthinate, aluminum chloride tartrate , zirconium and aluminum trihydrochloride, aluminum and zirconium tetrachlorohydrate, aluminum and zirconium pentachlorohydrate and their complexes, for example, with amino acids, such as glycine.
[0112] [0112] Apparatus suitable for mixing or spraying is any device that allows homogeneous distribution of a solution, powder, suspension or dispersion in or with hydrogel polymer (PC) particles or water-absorbing polymers. Examples are Lodige mixers (manufactured by Gebrüder Lödige Maschinenbau GmbH), Gericke multi-flow mixers (manufactured by Gericke GmbH), Drais mixers (manufactured by Drais GmbH Spezialmaschinenfabrik Mannheim), Hosokawa mixers (Hosokawa Mokron CO.), Ruberg mixers (manufactured by Ruberg (. Gebr. Ruberg GmbH & Co. KG Nieheim), Hüttlin coaters (manufactured by ICM Hüttlin Steinen GmbH), fluidized bed dryers or spray granulators AMMAG (manufactured by AMMAG Gunskirchen, Austria) or Heinen (manufactured by A. Heinen AG Anlagenbau Varel ), Patterson-Kelly mixers, NARA paddle mixers, screw mixers, pan mixers, fluid bed dryers or Schugi mixers. To contact a fluidized bed, it is possible to employ all fluidized bed processes which are known to those skilled in the art and appear to be suitable. For example, it is possible to use a fluid bed coater.
[0113] [0113] Another contribution to the realization of the objects described above is made by a composite including the polymers of the invention that absorb water or the hydrogel polymer or water absorption polymers or hydrogel polymers that can be obtained by the process according to the invention, and a substrate. It is preferred that the water-absorbing polymers of the invention or hydrogel polymers and the substrate are fixedly connected to each other. Preferred substrates are polymer films, for example, polyethylene, polypropylene or polyamide, metals, nonwovens, down, fabrics, fabrics made of natural or synthetic fibers, or foams. It is further preferred according to the invention that the compound comprises at least one region comprising the water-absorbing polymers or hydrogel polymers, in an amount ranging from about 15 to 100% by weight, preferably about 30 to 100% by weight, more preferably from about 50 to 99.99% by weight, even more preferably from about 60 to 99.99% by weight and even more preferably from about 70 to 99% by weight, with based on each case in relation to the total weight of the region of the compound in question, this region preferably having a size of at least 0.01 cm 3, preferably at least 0.1 cm 3 and more preferably at least 0, 5 cm 3.
[0114] [0114] Another contribution to the realization of at least one of the objects established at the beginning is made by a process for the production of a compound, in which the water-absorbing polymers or superabsorbents can be obtained by the process according to the invention and a substrate and, optionally, an additive which are contacted with each other. The substrates used are preferably the substrates that have already been mentioned above, in connection with the inventive compound.
[0115] [0115] The contribution to the realization of at least one of the objects indicated at the beginning is also made by a compound obtained by the process described above, this compound, preferably having the same properties as the inventive compound described above.
[0116] [0116] Another contribution to the realization of at least one of the objects established at the beginning is made by chemicals, including the water-absorbing polymers of the invention or polymers of hydrogel or a compound of the invention. Preferred chemicals are especially foams, moldings, fibers, sheets, films, cables, sealing materials, liquid-absorbing hygiene items, mainly diapers and hygienic pads, vehicles for plant growth or fungi growth regulators or active ingredients plant protection products, additives for building materials, packaging materials or soil additives.
[0117] [0117] The use of the water-absorbing polymers of the invention or the composition of the invention in chemicals, preferably in relation to the chemicals mentioned above, especially in hygiene items, such as diapers or hygienic pads, and the use of the particles of water-absorbing polymers, such as fungal growth plant transport agents or growth regulators or plant protection active ingredients make a contribution to the realization of at least one of the objects stated at the beginning. In case it is used as a plant growth carrier or fungal growth regulator or phytopharmaceutical active ingredient, it is preferred that the plant growth agent or fungal growth regulator or phytopharmaceutical active ingredient can be released over a period controlled by the carrier. Testing methods
[0118] [0118] Unless otherwise specified in the following numbers, the measurements performed here are in accordance with ERT methods. "ERT" means Recommended Test EDANA and "EDANA" for European Disposable and Nonwoven Association. All test methods are, in principle, unless otherwise stated, conducted at an ambient temperature of 23 + 2 ° C and a relative humidity of 50 + 10%. Particle size distribution (PSD)
[0119] [0119] The particle size distribution of the water-absorbing polymer particles is determined in a manner analogous to the recommended EDANA test method No. WSP 220.3-10 "Particle Size Distribution". Centrifuge Holding Capacity (CRC)
[0120] [0120] The retention capacity of the centrifuge was determined by EDANA (European Disposable and Nonwoven Association) recommended test method WSP 241.3-10 "Centrifuge Retention Capacity". Determination of the Free Swelling Rate (FSR)
[0121] [0121] The absorption rate was determined by measuring what is called the Free Swelling Rate (FSR), using the test method described in EP-A-0 443 627 on page 12. Absorption against a pressure of 0.7 psi (AAP)
[0122] [0122] Absorption under pressure was determined as PAA (Absorption Under Pressure) with WSP 242.3-10 in the total particle fraction. In this way, 0.90 g of the test substance (sieved out between 150 and 850 µm) was weighed into a 60.0 mm internal diameter test cylinder with a sieve base (400 meshes) (concentration: 0.032 g / cm 2) and homogeneously distributed. A cylindrical weight (50 g / cm 2 = 0.7 psi) with an outside diameter of 59.2 mm was placed on the test substance. The filter plates were placed on a plastic plate, and were covered with filter paper. The plastic dish was filled with a 0.9% NaCl solution, until the liquid level ended with the top edge of the filter plate. Subsequently, the prepared test units are placed on the filter plates. After an expansion time of 60 minutes, the test units are removed and the weight is removed. The amount of liquid absorbed is determined gravimetrically and converted to 1 gram of substance. Determination of permeability (saline flow conductivity - SFC)
[0123] [0123] Permeability is determined by measuring the "Flow of Saline Conductivity-SFC" by the test method described in WO-A-95/26209. The starting weight of the super absorbent material is 1.5 g instead of 0.9 g. Determination of "fixed height absorption" (FHA) (0.3 psi, 20 cm)
[0124] [0124] The determination is made by measuring what is called "fixed height absorption" (FHA), by the test method described in patent EP 149 34 53 A1 on page 9 [0078] on page 10, paragraph [0087]. Determination of surface tension (ST)
[0125] [0125] The determination is made by measuring according to the test method described in patent EP 1 493 453 A1, according to page 12 paragraphs [0105] to [0111]. A Kruss K11 tensiometer with a Wilhelmy plate was used. Determination of extractable polyether fractions
[0126] [0126] The determination of extractable polyether fractions is based on the HPTLC method (H-III 14a dated 05/30.95) Gemeinschaftsarbeiten of DGF 152. Mitteilung [German Society of Fat Science, Collaborative Studies, 152nd Communication]. The samples were ground, extracted with hot methanol, in a Soxhlet extractor (1 hour), concentrated and then determined by thin layer chromatography on silica gel of 60 TLC plates of dimensions 20 x 20 cm. The samples are applied in a standardized manner. The eluent used was a mixture of chloroform / methanol / water (88/11/1 volume percent). The derivation was performed with Dragendorff's reagent. A Camag TLC CD60 scanner with a measuring wavelength of 520 nm was used. The assessment was carried out through the peak areas, which were expressed as a proportion in relation to the peak areas of the standards. Determination of BET surface area
[0127] [0127] The BET surface area of the superabsorbents was determined using a Kr Tristar 3020 instrument from Micromeritics (with krypton gas instead of nitrogen), similar to ISO 9277. The initial weight was 4.6 g and was evacuated, at room temperature and a vacuum of 0.02 mbar overnight and weighed again. Evacuation was carried out using the door analysis, the evacuation being carried out over a period of 6 minutes, when 10 mm Hg were obtained. The dead volume was also determined. The analysis temperature was 77.1 K. p0 was defined as 2.32 mm Hg (using krypton gas). The equilibrium time was measured at least 10 times (5 sec, with a variation rate of less than 0.01%). Examples
[0128] [0128] The following examples serve to further illustrate the invention, but are not restricted to them.
[0129]
[0130] [0130] The following examples of the invention show the synergistic effect on the FSR value by the simultaneous use of polymerizable surfactants and carbonate. In this context, a defined particle size distribution (PSD) was used (150 µm to 710 µm). The standard mixture used is a composition of four particle fractions before the crosslinking surface, which has the following distribution: 15% by weight of a particle size from 150 µm to 300 µm, 50% by weight, 300 µm to 500 µm , 30% by weight from 500 µm to 600 µm and 5% by weight from 600 µm to 710 µm. The PSD is established for hydrogel polymers.
[0131] [0131] EP1 701.786 B1, in paragraphs [0115-0117], defines the average mass of the particle diameter D50. According to the invention, preference is given to a range between 300 and 600 µm. Particular preference is given to a range of 350-550 µm, and very particular preference in a range between 400 and 500 µm.
[0132] [0132] A blowing agent is preferred, where more than 35% by weight of the particles have a particle size of 100-300 µm.
[0133] [0133] The term "SX", as used in the description, means the thermal crosslinking surface of the precursor (PC). The precursor corresponds to the hydrogel polymer obtained after the first drying step, with the distribution of the aforementioned particles.
[0134] [0134] In principle, the percentages of surfactant are based on acrylic acid (unless otherwise stated, 320 g) and those for the carbonate in the mixture (1,000 g). Example 1
[0135] [0135] Surfactant No. 1, "allyl-10EO-b-10PO-acetyl", from Table 1, was used as the additive. The amounts of surfactants used and carbonate varied.
[0136] [0136] Use without polymerizable surfactant and sodium carbonate: Example 1A (reference)
[0137] [0137] 0.775 g of polyethylene glycol-300 diacrylate (PEG300DA) (0.2% based on the acid / acrylic ester content, which corresponds to 83%) and 1.639 g of polyethylene glycol-440 acrylate monoalyl ether (PEGMAE-A) (0.4% based on the content of acrylic acid / ester, corresponding to 78%) as a crosslinking agent were dissolved in 975,201 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total monomer concentration of 39.82%. The monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes to remove dissolved oxygen. At a temperature of 4 ° C, polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely ground, ground and adjusted to the particle distribution described above. Example 1B (2nd reference)
[0138] [0138] 0.697 g of polyethylene glycol-300 diacrylate (0.18% based on acid / acrylic ester content = 83%) and 1.475 g of polyethylene glycol-440 methyl acrylate monoalyl ether (0.36% based on the acid / acrylic ester content, which corresponds to 78%) as a crosslinker were dissolved in 975.443 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total monomer concentration of 39.81%. The monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes, in order to remove dissolved oxygen. At a temperature of 4 ° C, polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely ground, ground and adjusted to the particle distribution described above.
[0139] [0139] Use without polymerizable surfactant and with 0.2% light sodium carbonate: Example 1C
[0140] [0140] 0.697 g of polyethylene glycol-300 diacrylate (0.18% based on acid / acrylic ester content = 83%) and 1.475 g of polyethylene glycol-440 methyl acrylate monoalyl ether (0.36% based on the acid / acrylic ester content, which corresponds to 78%) as a crosslinker were dissolved in 973.443 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total monomer concentration of 39.89%. The monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes, in order to remove dissolved oxygen. At a temperature of 4 ° C, 2 g of finely calcined sodium carbonate (Solvay) were added and polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely ground, ground and adjusted to the particle distribution described above.
[0141] [0141] Use of 0.3% of polymerizable surfactant: Example 1D
[0142] [0142] 0.775 g of polyethylene glycol-300 diacrylate (0.2% based on acid / acrylic ester content = 83%) and 1.639 g of polyethylene glycol-440 acrylate monoalyl ether (0.4% based in the content of acrylic acid / ester, which corresponds to 78%) as a crosslinker were dissolved in 965.601 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total concentration monomer content of 40.22%. Subsequently, 9.6 g of a 10% aqueous solution of No. 1 co-monomer "allyl-10EO- b-10PO-acetyl" were added to this solution and the monomer solution was purged with nitrogen in a polymerization vessel of plastic for 30 minutes to remove dissolved oxygen. At a temperature of 4 ° C, polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely ground, ground and adjusted to the particle distribution described above.
[0143] [0143] Use of 0.3% of polymerizable surfactant and 0.2% of light sodium carbonate: Example 1E
[0144] [0144] 0.697 g of polyethylene glycol-300 diacrylate (0.18% based on acid / acrylic ester content = 83%) and 1.475 g of polyethylene glycol-440 methyl acrylate monoalyl ether (0.36% based on the acid / acrylic ester content, which corresponds to 78%) as a crosslinker were dissolved in 963.843 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total monomer concentration of 40.29%. Subsequently, 9.6 g of a 10% aqueous solution of No. 1 co-monomer "allyl-10EOb-10PO-acetyl" were added to this solution and the monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes to remove dissolved oxygen. At a temperature of 4 ° C, 2 g of finely calcined sodium carbonate (Solvay) were added and polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of distilled water. 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely ground, ground and adjusted to the particle distribution described above.
[0145] [0145] The surface crosslinker of the precursors thus obtained ("PC") was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum sulfate in a proportion of 1/3 / 0.4 / 0.3 % based on 100 g of the precursor and subsequent heating to 170 ° C for a period of 90 min in a drying oven.
[0146] [0146] The results for Examples 1A-1E are summarized in Table 2:
[0147] [0147] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-10PO-b-10EOacetyl (PE7087, Evonik Industries). The amounts of surfactant and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum sulfate lactate / aluminum in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of precursor and subsequent heating at 170 ° C for a period of 90 min in a drying oven. The results for Examples 2D and 2E were summarized in Table 3:
[0148] [0148] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-10EO-b-10POacetyl (PE7086, Evonik Industries). The amounts of surfactant and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum sulfate lactate / aluminum in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of precursor and subsequent heating at 170 ° C for a period of 90 min in a drying oven.
[0149] [0149] The results for Examples 3D and 3E are summarized in Table 4:
[0150] [0150] The experimental configuration corresponded to that of Example 1, except that the additive used was Pluriol ® A111 R (BASF). The amounts of surfactants and carbonates used varied.
[0151] [0151] Use of 0.3% of polymerizable surfactant and 0.2% of light sodium carbonate: Example 4D
[0152] [0152] 0.775 g of polyethylene glycol-300 diacrylate (0.2% based on the acid / acrylic ester content, which corresponds to 83%) and 1.639 g of polyethylene glycol-440 acrylate monoalyl ether (0, 4% based on the acid / acrylic ester content, which corresponds to 78%) as a crosslinking agent were dissolved in 963.601 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (based on acrylic acid) and a total monomer concentration of 40.30%. Subsequently, 9.6 g of a 10% aqueous solution of comonomer No. 4 Pluriol ® A111 R (BASF) was added to this solution and the monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes to remove dissolved oxygen. At a temperature of 4 ° C, 2 g of finely calcined sodium carbonate (Solvay) were added and polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely crushed, ground and sieved to size.
[0153] [0153] The surface crosslinker of the precursors thus obtained (PC) was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum sulfate in a proportion of 1/3 / 0.4 / 0.3% based in 100 g of the precursor and subsequent heating to 170 ° C for a period of 90 min in a drying oven.
[0154] [0154] The results for Examples 4A-4E are summarized in Table 5:
[0155] [0155] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-6EO-b-6PO-acetyl (PE7514, Evonik Industries). The amounts of surfactants used and carbonate varied.
[0156] [0156] Use of 0.3% of polymerizable surfactant and 0% of light sodium carbonate: Example 5D
[0157] [0157] 0.697 g of polyethylene glycol-300 diacrylate (0.18% based on the acid / acrylic ester content, which corresponds to 83%) and 1.475 g of polyethylene glycol-440 methyl acrylate monoalyl ether ( 0.36% based on the acid / acrylic ester content, which corresponds to 78%) as a crosslinking agent were dissolved in 965.843 g of an aqueous solution of sodium acrylate with a neutralization level of 70 mol% (with based on acrylic acid) and a total monomer concentration of 40.21%. Subsequently, 9.6 g of a 10% aqueous solution of comonomer No. 5 allyl-6EO-b-6PO-acetyl were added to this solution and the monomer solution was purged with nitrogen in a plastic polymerization vessel for 30 minutes to remove dissolved oxygen.
[0158] [0158] At a temperature of 4 ° C, polymerization was initiated by the successive addition of 0.3 g of sodium peroxodisulfate in 10 g of distilled water, 0.07 g of 35% hydrogen peroxide solution in 10 g of water distilled water and 0.015 g of ascorbic acid in 2 g of distilled water. Once the final temperature (approx. 100 ° C) was reached, the gel was ground with a meat grinder and dried at 150 ° C in a forced air drying cabinet for 2 hours. The dry precursor was coarsely crushed, ground and sieved to size.
[0159] [0159] The surface crosslinker binder of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of precursor and subsequent heating to 170 ° C over a period of 90 min in a drying oven.
[0160] [0160] The results for Examples 5C-5E are summarized in Table 6:
[0161] [0161] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-6EO-b-6POhydroxyl (PE7316 / 02, Evonik Industries). The amounts of surfactants and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of the precursor and subsequent heating at 170 ° C for a period of 90 min in a drying oven.
[0162] [0162] The results for Examples 6C-6E are summarized in Table 7:
[0163] [0163] The experimental configuration corresponded to that of Example 1, except that the additive used was Pluriol ® A111 R (BASF). The amounts of surfactants and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of the precursor and subsequent heating to 170 ° C over a 90 min period in a drying oven.
[0164] [0164] The results for Examples 7C-7F are summarized in Table 8:
[0165] [0165] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-10PO-b-20EOhydroxyl (PE7065, Evonik Industries). The amounts of surfactants and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum sulfate in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of superabsorbent and subsequent heating to 170 ° C for a period of 90 min in a drying oven.
[0166] [0166] The results for Examples 8D-8E are summarized in Table 9:
[0167] [0167] The experimental configuration corresponded to that of Example 1, except that the surfactant used was allyl-10PO-b-20EOacetyl (PE7081, Evonik Industries). The amounts of surfactants and carbonate used varied. The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum sulfate in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of the precursor and subsequent heating to 170 ° C for a period of 90 min in a drying oven.
[0168] [0168] The results for Examples 9D-9E are summarized in Table 10:
[0169] [0169] The experimental configuration corresponded to that of Example 1, except that the surfactant used was sodium laurylethersulfate (Hansa-Grupo AG, Duisburg). NaLES is a surfactant that cannot be incorporated by polymerization. The amounts of surfactants and carbonate used varied.
[0170] [0170] The surface crosslinker of the precursors thus obtained was made by coating with a solution consisting of ethylene carbonate / water / aluminum lactate / aluminum sulfate in a proportion of 1/3 / 0.4 / 0.3% based on 100 g of the precursor and subsequent heating to 170 ° C over a period of 90 min in a drying oven.
[0171] [0171] The results for Examples 10D-10E are summarized in Table 11:
[0172] [0172] In the case of the surfactant not incorporable by polymerization, a significant deterioration of the FHA value was found.
[0173] [0173] The ST values of the water-absorbing polymers according to the examples of the invention described above are more than 50 mN / m, preferably more than 55 mN / m, more preferably more than 60 mN / m and even more preferably more than 62 mN / m. The ST value must not exceed a value of 68 nM / m. Advantageously, this minimizes the rewetting value (e.g., rewetting backing sheet) in diapers and maintains the capillarity of the superabsorbent material in the absorbent diaper core, which thus corresponds to high FHA values. The use of EO and PO blocks in surfactant co-monomers avoids a significant reduction in ST values.
[0174] [0174] Advantageously, the simultaneous use of surfactant and carbonate comonomers leads to a synergistic increase in the values of FSR and FHA. According to the invention, the aforementioned effect is found particularly in the case of water-absorbing polymers with an ST value greater than 60. The water-absorbing polymers of the invention, in addition, exhibit good parameter properties in terms of refers to the CRC, SFC and AAP values.
[0175] [0175] According to the table below, it was demonstrated that, according to the invention, copolymerizable surfactants ("surfactant monomers", SM) were incorporated into the hydrogel polymer network. Extractables are reported in the last column of the table. The amount of extractable polyether fractions based on the total amount of copolymerizable surfactants (SM) used for% polymerization was examined here. According to the invention, less than 10% of extractable surfactants / surfactant monomers was found. This showed that the surfactant has been incorporated into the superabsorbent polymer matrix.
[0176] [0176] Based on the measurements of the BET surface area, it was surprisingly possible to show that the hydrogel polymers of the invention have an 18% increase in the BET surface area among the reference hydrogel polymers without surfactants and sodium carbonate.
[0177] [0177] Results of BET measurements:

权利要求:
Claims (17)
[0001]
Process for the production of a water-absorbing polymer composition, characterized by understanding the stages of the process of (i) mixing (α1) 0.1-99.999% by weight of polymerizable, ethylenically unsaturated monomers, containing groups of acids, or their salts, or polymerizable, ethylenically unsaturated monomers, including protonated or quaternized nitrogen, or mixtures thereof, with special preference being given for mixtures, including at least ethylenically unsaturated monomers containing acid groups, (α2) 0 to 70% by weight of polymerizable, ethylenically unsaturated monomers, copolymerizable with (α1), (α3) 0,001 to 10% by weight of one or more cross-linking agents, (α4) 0 to 30% by weight of water-soluble polymers, and (α5) 0 to 20%, by weight, of one or more auxiliaries, where the sum of the weights from (α1) to (α5) is 100%, by weight, to form an aqueous monomer solution, (ii) add an initiator to promote cross-linked free radical polymerization to form an untreated, water-insoluble aqueous hydrogel polymer, (iii) drying the hydrogel polymer, (iv) grind and sieve the hydrogel polymer to size, (v) post-cross-link the soil surface and sieve the hydrogel polymer and (vi) drying and finishing the water-absorbing polymer, on what the aqueous monomer solution, before adding the initiator and starting the free radical polymerization, is mixed with 0.01 to 5% by weight of at least one surfactant, based on the monomer containing an acid group, from the group of non-surfactants ionic, ionic or amphoteric which are copolymerizable with the monomers specified in (α1) and 0.01 to 5% by weight of a blowing agent having a particle size from 10 µm to 900 µm, based on the composition of the absorption polymer of water; the Free Swelling Rate (FSR) is in the range of 0.3 to 0.65 g / g / s and the surface tension (ST) is above 50 mN / m.
[0002]
Process for the production of a hydrogel polymer, characterized by understanding the steps of the process of (i) mixing (α1) 0.1-99.999% by weight of polymerizable, ethylenically unsaturated monomers, containing groups of acids, or their salts, or polymerizable, ethylenically unsaturated monomers including protonated or quaternized nitrogen, or mixtures thereof, with special preference being given for mixtures, including at least ethylenically unsaturated monomers containing acid groups, (α2) 0 to 70% by weight of polymerizable, ethylenically unsaturated monomers copolymerized with (α1), (α3) 0,001 to 10% by weight of one or more cross-linking agents, (α4) 0 to 30% by weight of water-soluble polymers, (α5) 0 to 20% by weight of one or more auxiliaries, where the sum of the weights from (α1) to (α5) is 100% by weight, (ii) polymerize via free radical with crosslinking to form an untreated aqueous hydrogel polymer, insoluble in water, (iii) drying the hydrogel polymer, (iv) grind and sieve the hydrogel polymer to size, on what the aqueous monomer solution, before adding the initiator and starting the free radical polymerization, is mixed with 0.01 to 5% by weight of at least one surfactant from the group of nonionic, ionic or amphoteric surfactants and tt0, 01 to 5% by weight of a blowing agent that has a particle size of 10 µm to 900 µm, based on the hydrogel polymer.
[0003]
Process according to claim 1, characterized in that the aqueous monomer solution has at least one surfactant from the group of nonionic, ionic or amphoteric surfactants, and 0.01 to 5% by weight of blowing agent with a Particle sizes from 10 µm to 900 µm are added, based on the water-absorbing polymer.
[0004]
Process, according to claim 1, characterized by the fact that the surfactant is selected from the group of nonionic surfactants.
[0005]
Process according to claim 1, characterized in that the surfactant is selected from the group of R1- (EO) n-block- (PO) m-R2 in which R1 or R2 represents a methyl, ethyl, n- propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, -OH, acetyl or allyl radical en = 2 to 20 and = 2 to 20.
[0006]
Process, according to claim 5, characterized by the fact that the surfactant is selected from the group of R1- (EO) n-block- (PO) m-R2, where n is 4 to 12 and m is 3 to 12.
[0007]
Process, according to claim 5, characterized by the fact that the surfactant is selected from the group of R1- (EO) n-block- (PO) m-R2 where n is 5 to 8 and m is 4 to 7.
[0008]
Process, according to claim 5, characterized by the fact that, for n and m in the formula R1- (EO) n-block- (PO) m-R 2, 2 ≤m ≤n ≤20.
[0009]
Process according to claim 5, characterized in that the radicals R1 or R2 are allyl or acetyl and R1 or R2 are a methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, npentyl, 2-methylbutyl group, 2,2-dimethylpropyl, -OH, acetyl or allyl radical.
[0010]
Process according to claim 5, characterized in that R1 or R2 is an allyl radical and the other radical is an acetyl group or the -OH radical.
[0011]
Process according to claim 1, characterized in that the surfactant and the blowing agent are added together to the monomer solution.
[0012]
Process according to claim 1, characterized in that the blowing agents consist of a powder of inorganic particles.
[0013]
Process according to claim 1, characterized in that the blowing agents consist of sodium carbonate particles.
[0014]
Process according to claim 1, characterized in that the blowing agent has a particle size from 10 µm to 900 µm.
[0015]
Process according to claim 1, characterized in that more than 35%, by weight, of the blowing agents have a particle size of 100-300 µm.
[0016]
Process, according to claim 1, characterized by the fact that the permeability, such as the Saline Conductivity Flow, SFC (1.5 g), is in the range of 30 to 200 units.
[0017]
Process according to claim 5, characterized by the fact that R1 or R2 are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, 2-methylbutyl, 2,2-dimethylpropyl, -OH , acetyl or allyl radical.

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法律状态:
2019-10-01| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-06-30| B25D| Requested change of name of applicant approved|Owner name: EVONIK OPERATIONS GMBH (DE) |

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2020-08-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-12| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/11/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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DE102011086516A|DE102011086516A1|2011-11-17|2011-11-17|Superabsorbent polymers with fast absorption properties and process for its preparation|

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DE102011086516.0|2011-11-17|

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PCT/EP2012/072352|WO2013072268A1|2011-11-17|2012-11-12|Super-absorbing polymers with rapid absorption properties and method for producing the same|

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