DE10204937A1 - Process for post-crosslinking of a water absorbing polymer surface with a cyclic urea useful in foams, fibers, films, cables, especially sealing materials and liquid absorbing hygiene articles - Google Patents
Process for post-crosslinking of a water absorbing polymer surface with a cyclic urea useful in foams, fibers, films, cables, especially sealing materials and liquid absorbing hygiene articlesInfo
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- DE10204937A1 DE10204937A1 DE2002104937 DE10204937A DE10204937A1 DE 10204937 A1 DE10204937 A1 DE 10204937A1 DE 2002104937 DE2002104937 DE 2002104937 DE 10204937 A DE10204937 A DE 10204937A DE 10204937 A1 DE10204937 A1 DE 10204937A1
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- water
- post
- postcrosslinker
- crosslinking
- polymer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/14—Water soluble or water swellable polymers, e.g. aqueous gels
Abstract
Description
Die im folgenden beschriebene Erfindung liegt auf dem Gebiet der wasserabsorbierenden organischen Polymeren und betrifft ein Verfahren zur Nachvernetzung im Bereich der Oberfläche solcher Polymeren, die auf diese Weise erhältlichen Polymeren und deren Verwendung. The invention described below lies in the field of water-absorbing organic polymers and relates to a method for post-crosslinking in the area of the surface of such polymers, which can be obtained in this way Polymers and their use.
Zahlreiche organische, im wesentlichen wasserunlösliche Polymere, die aus hydrophilen Monomeren aufgebaut sind, besitzen die Eigenschaft, unter Quellung und Ausbildung von Hydrogelen Wasser und wässrige Flüssigkeiten aufzunehmen und die absorbierten Flüssigkeiten festzuhalten. Zu derartigen Polymeren zählen quellbare Naturprodukte, wie beispielsweise Guarderivate, modifizierte Naturprodukte, wie vernetzte Cellulose- oder Stärkeether, beispielsweise vernetzte Carboxymethylcellulose, insbesondere aber vollsynthetische Produkte, wie beispielsweise teilvernetztes Polyalkylenoxid, sowie insbesondere die durch radikalische Polymerisation von hydrophilen Monomeren erhältlichen Homopolymerisate, Copolymerisate und Propfpolymerisate auf geeignete Pfropfgrundlagen. Besondere Bedeutung kommt hier den carboxylgruppenhaltigen Polymeren zu. Polymere, die in der Lage sind, besonders große Mengen an wässrigen Flüssigkeiten unter Gelbildung aufzunehmen, werden auch als superabsorbierende Polymere (SAP) oder kurz als Superabsorber bezeichnet. Die Herstellung und Verwendung derartiger zur Hydrogelbildung befähigter Polymerer ist in zahlreichen Patentanmeldungen, beispielsweise EP 316792, EP 400283, EP 343427, EP 205674 und DE 44 18 818, beschrieben worden. Numerous organic, essentially water-insoluble polymers that are derived from hydrophilic monomers have the property of swelling and formation of hydrogels to absorb water and aqueous liquids and to hold the absorbed liquids. Such polymers include swellable natural products, such as guar derivatives, modified Natural products, such as crosslinked cellulose or starch ethers, for example crosslinked Carboxymethyl cellulose, but especially fully synthetic products such as for example, partially cross-linked polyalkylene oxide, and especially those by radical Polymerization of homopolymers obtainable from hydrophilic monomers, Copolymers and graft polymers on suitable graft bases. The polymers containing carboxyl groups are of particular importance here. polymers which are able to take particularly large amounts of aqueous liquids Absorbing gel formation are also called superabsorbent polymers (SAP) or referred to briefly as a super absorber. The manufacture and use There are numerous such polymers capable of hydrogel formation Patent applications, for example EP 316792, EP 400283, EP 343427, EP 205674 and DE 44 18 818, have been described.
Zur Verbesserung der Eigenschaften dieser wasserabsorbierenden Polymeren, insbesondere zur Verbesserung des Wasseraufnahmevermögens unter Druck, hat es sich als zweckmäßig herausgestellt, die Polymerpartikel einer nachträglichen Oberflächenvernetzung zu unterwerfen. Auch für diese zusätzliche Vernetzung im Bereich der Oberfläche der Polymeren sind zahlreiche Verfahren in der Literatur beschrieben worden. Es sei hier nur auf die deutschen Offenlegungsschriften 19807502 und 19807504 und die dort zitierte Literatur zu diesem Thema verwiesen. To improve the properties of these water-absorbing polymers, especially to improve the water absorption capacity under pressure it turned out to be expedient, the polymer particles a subsequent Subject to surface crosslinking. Also for this additional networking in the The surface area of the polymers are numerous methods in the literature have been described. It is only here on the German published documents 19807502 and 19807504 and the literature cited there on this subject directed.
Keines der bisher für die Nachvernetzung im Bereich der Oberfläche der wasserabsorbierenden Polymeren vorgeschlagenen Nachvernetzerreagenzien ist aber ohne Nachteile. So sind die hochreaktiven Nachvernetzer aus den Gruppen der Epoxide, der Epichlorhydrine, der Isocyanate und der Diglykolsilikate zwar zu einer schnellen Vernetzung in der Lage. Da die Reaktion aber unmittelbar nach dem Aufbringen auf das Polymer eintritt, ergeben sich Schwierigkeiten bei der gleichmäßigen Verteilung des Nachvernetzers auf der Oberfläche. Darüber hinaus sind die meisten Nachvernetzer aus diesen chemischen Gruppen nicht oder nur schlecht wasserlöslich, so dass zum Auftrag auf die Polymeroberfläche organische Lösungsmittel verwendet werden müssen. Demgegenüber erlauben Nachvernetzer aus den Gruppen der Polyole, Polyester und Polyamine wegen ihrer geringen Reaktivität eine gleichmäßige Verteilung auf der Oberfläche der Polymeren, erfordern aber für die eigentliche Vernetzungsreaktion hohe Temperaturen, die in vielen Fällen zu unerwünschten Verfärbungen oder Zersetzungen der Polymeren oder aber zu unerwünschten stärkeren Vernetzungen im Inneren der Polymerpartikel führen. Aufgrund der geschilderten Nachteile wird weiterhin nach neuen, besser geeigneten Reagenzien für die Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren, insbesondere von Superabsorbern, gesucht. None of the previously used for post-crosslinking in the area of the post-cross-linking reagents proposed for water-absorbing polymers without disadvantages. The highly reactive postcrosslinkers from the groups of Epoxies, the epichlorohydrins, the isocyanates and the diglycol silicates admittedly too able to network quickly. Since the reaction immediately after the application occurs on the polymer, difficulties arise in the even distribution of the post-crosslinker on the surface. Furthermore most post-crosslinkers from these chemical groups are not or only poorly water-soluble, so that organic to apply to the polymer surface Solvents must be used. In contrast, post-crosslinkers allow from the groups of polyols, polyesters and polyamines because of their low Reactivity an even distribution on the surface of the polymers, but require high temperatures for the actual crosslinking reaction, which in in many cases to undesirable discoloration or decomposition of the polymers or but to undesired stronger cross-links inside the polymer particles to lead. Because of the disadvantages described, new ones will continue to be better suitable reagents for postcrosslinking in the area of water-absorbing polymers, especially superabsorbents, sought.
Auch der vorliegenden Erfindung lag die Aufgabe zugrunde, Alternativen für die bisher bekannten Verfahren zur Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren zu finden und insbesondere die Nachteile der Verfahren des Standes der Technik nach Möglichkeit zu vermeiden sowie diese Verfahren oder die daraus resultierenden Produkte zu verbessern. The present invention was also based on the object of alternatives for previously known methods for post-crosslinking in the area of to find water-absorbing polymers and in particular the disadvantages of Avoid prior art methods as much as possible, as well as these Process or improve the resulting products.
Diese und weitere Aufgaben werden gelöst durch ein Verfahren zur
Nachvernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren, bei dem
ein solches Polymer mit der Lösung eines Nachvernetzers in Kontakt gebracht
wird und die Vernetzungsreaktion bei erhöhter Temperatur, vorzugsweise bei
einer Temperatur in einem Bereich von 50 bis 300°C, besonders bevorzugt in einem
Bereich von 100 bis 250°C, ganz besonders bevorzugt in einem Bereich von 150
bis 210°C und darüber hinaus bevorzugt in einem Bereich von 180 bis 200°C
ausgeführt wird, wobei als Nachvernetzer ein cyclischer Harnstoff mit der Formel I
verwendet wird, in der x die Werte 2 oder 3 annehmen kann und R1 und R2 jeweils
unabhängig voneinander ein H oder ein C1- bis C4-Alkylrest darstellen.
Vorzugsweise sind in Formel I sowohl R1 als auch R2 Wasserstoffatome. Weiterhin ist
bevorzugt, dass x in Formel I den Wert 2 hat.
These and other objects are achieved by a method for postcrosslinking in the area of the surface of water-absorbing polymers, in which such a polymer is brought into contact with the solution of a postcrosslinker and the crosslinking reaction at an elevated temperature, preferably at a temperature in a range from 50 to 300 ° C, particularly preferably in a range from 100 to 250 ° C, very particularly preferably in a range from 150 to 210 ° C and furthermore preferably in a range from 180 to 200 ° C, with a cyclic urea as postcrosslinker with the formula I.
is used, in which x can assume the values 2 or 3 and R 1 and R 2 each independently represent an H or a C 1 - to C 4 -alkyl radical. In formula I, both R 1 and R 2 are preferably hydrogen atoms. It is further preferred that x in formula I has the value 2.
Die erfindungsgemäß verwendeten Nachvernetzer sind im allgemeinen gut wasserlösliche Verbindungen, so dass sie vorzugsweise ohne Verwendung organischer Lösungsmittel in die Vernetzungsreaktion eingebracht werden können. Trotz ihrer Reaktivität gegenüber den Polymeren sind sie in wässriger Lösung stabil. Da die eigentliche Vernetzungsreaktion erst beim Erwärmen eintritt, ist eine gleichmäßige Verteilung des Nachvernetzers auf der Oberfläche der Polymerpartikel ohne besondere Aufwendungen zu erreichen. Die Reaktivität in der Vernetzungsreaktion lässt sich durch Zusatz von sauren Verbindungen noch steigern, so dass die Vernetzungsreaktion unter Bedingungen durchgeführt werden kann, die nicht zur Schädigung des Polymeren führt. Zur Verfahrenserleichterung tragen weiterhin der niedrige Dampfdruck und die toxikologische Unbedenklichkeit der erfindungsgemäß eingesetzten Vernetzungsreagenzien bei. The postcrosslinkers used according to the invention are generally good water soluble compounds, so they are preferably without use organic solvents can be introduced into the crosslinking reaction. Despite their reactivity to the polymers, they are in aqueous solution stable. Since the actual crosslinking reaction only occurs when heated an even distribution of the postcrosslinker on the surface of the To achieve polymer particles without special expenses. The reactivity in the Crosslinking reaction can still be done by adding acidic compounds increase so that the crosslinking reaction can be carried out under conditions can, which does not damage the polymer. To facilitate the procedure continue to bear the low vapor pressure and toxicological Harmlessness of the crosslinking reagents used according to the invention.
Die aus dem erfindungsgemäßen Verfahren resultierenden Produkte zeichnen sich unter anderem durch ungewöhnlich hohe Wasserabsorption und Gelfestigkeit aus. Vor allem die Wasserabsorption unter Druck erreicht besonders hohe Werte. Dieser Effekt tritt auch dann auf, wenn die erfindungsgemäß als Nachvernetzer verwendeten cyclischen Harnstoffe zusätzlich zu anderen herkömmlichen Nachvernetzern für die Nachvernetzung eingesetzt werden. Aufgrund dieser besonderen Eigenschaften sind die durch das erfindungsgemäße Verfahren erhältlichen Produkte ein eigener Gegenstand der Erfindung. The products resulting from the process according to the invention stand out among other things by unusually high water absorption and gel strength. Above all, the water absorption under pressure reaches particularly high values. This effect also occurs when the postcrosslinker according to the invention cyclic ureas used in addition to other conventional ones Postcrosslinkers can be used for postcrosslinking. Because of this special Properties are those obtainable by the process according to the invention Products a separate subject of the invention.
Ein weiterer Gegenstand der Erfindung ist die Verwendung der im erfindungsgemäßen Verfahren erhältlichen, im Bereich der Oberfläche vernetzten, wasserabsorbierenden Polymeren in Schäumen, Formkörpern, Fasern, Folien, Filmen, Kabeln, insbesondere in Dichtungsmaterialien, flüssigkeitsaufnehmenden Hygieneartikeln, Verpackungsmaterialien, Nonwoven-Textilien sowie als Bodenzusätze, Baustoffe und als Trägermaterial für Agrarchemikalien. Besonders bevorzugt ist die Verwendung in Hygieneprodukten, wie Windeln, Tampons und Damenbinden, und die Verwendung als Trägermaterial für Agrarchemikalien. Another object of the invention is the use of the Processes according to the invention which are crosslinked in the area of the surface, water-absorbing polymers in foams, moldings, fibers, foils, films, Cables, especially in sealing materials, absorbent Hygiene articles, packaging materials, non-woven textiles and as floor additives, Building materials and as a carrier material for agricultural chemicals. Is particularly preferred use in hygiene products such as diapers, tampons and Sanitary napkins, and the use as a carrier material for agricultural chemicals.
Bei den wasserabsorbierenden Polymeren, die im erfindungsgemäßen Verfahren
im Bereich der Oberfläche vernetzt werden, handelt es sich in erster Linie um
Carboxylgruppen enthaltende synthetische Homo- und Copolymerisate aus
zumindest überwiegend hydrophilen Monomeren, um Pfropf(co)polymere von
einem oder mehreren hydrophilen Monomeren auf eine geeignete Pfropfgrundlage,
um vernetze Cellulose- oder Stärkeether oder in wässrigen Flüssigkeiten quellbare
Naturprodukte, wie beispielsweise Guarderivate. Wichtigstes gemeinsames
Kennzeichen ist ein hohes Absorptionsvermögen für Wasser und wässrige
Flüssigkeiten. Vorzugsweise besitzen die für das erfindungsgemäße Verfahren vorgesehenen
Polymeren wenigstens eine der folgenden Eigenschaften (ERT = EDANA
Recommended Test):
- A) maximale Aufnahme von 0,9 Gew.-% er NaCl-Lösung liegt nach ERT 440.1-99 in einem Bereich von mindestens 10 bis 1000 g/g, bevorzugt von 15 bis 500 und besonders bevorzugt von 20 bis 300 g/g;
- B) der mit 0,9 Gew.-% er wässriger NaCl-Lösung extrahierbare Anteil beträgt nach ERT 470.1-99 weniger als 30 Gew.-%, bevorzugt weniger als 20 Gew.-% und besonders bevorzugt weniger als 10 Gew.-%, jeweils bezogen auf das Polymer;
- C) die Schüttdichte liegt nach ERT 460.1-99 im Bereich von 300 bis 1000 g/l, bevorzugt von 310 bis 800 g/l und besonders bevorzugt von 320 bis 700 g/l;
- D) der pH-Wert von 1 g des Polymeren in 1 l Wasser liegt gemäß ERT 400.1- 99 im Bereich von 4 bis 10, bevorzugt von 5 bis 9 und besonders bevorzugt von 5,5 bis 7,5;
- E) die Centrifugation Retention Capacity (CRC) gemäß ERT 441.1-99 liegt im Bereich von 10 bis 100 g/g, bevorzugt von 15 bis 80 und besonders bevorzugt von 20 bis 60 g/g.
- A) maximum absorption of 0.9% by weight of NaCl solution according to ERT 440.1-99 is in a range from at least 10 to 1000 g / g, preferably from 15 to 500 and particularly preferably from 20 to 300 g / g;
- B) the proportion extractable with 0.9% by weight of aqueous NaCl solution is, according to ERT 470.1-99, less than 30% by weight, preferably less than 20% by weight and particularly preferably less than 10% by weight , each based on the polymer;
- C) the bulk density according to ERT 460.1-99 is in the range from 300 to 1000 g / l, preferably from 310 to 800 g / l and particularly preferably from 320 to 700 g / l;
- D) the pH of 1 g of the polymer in 1 l of water is in the range from 4 to 10, preferably from 5 to 9 and particularly preferably from 5.5 to 7.5 according to ERT 400.1-99;
- E) the centrifugation retention capacity (CRC) according to ERT 441.1-99 is in the range from 10 to 100 g / g, preferably from 15 to 80 and particularly preferably from 20 to 60 g / g.
Die sich aus den vorstehenden Eigenschaften ergebenden Eigenschaftskombinationen von zwei oder mehr dieser Eigenschaften stellen jeweils bevorzugte Ausführungsformen des für das erfindungsgemäße Verfahren vorgesehene Polymer dar. Weiterhin als erfindungsgemässe Ausführungsformen besonders bevorzugt sind Verfahren, in denen das absorbierende Polymer die nachfolgend als Buchstaben oder Buchstabenkombinationen dargestellten Eigenschaften oder Eigenschaftskombinationen zeigt: A, B, C, D, E, AB, ABC, ABCD, ABCDE, BC, BCD, BCDE, CD, CDE, DE. The resulting from the above properties Property combinations of two or more of these properties each are preferred Embodiments of the polymer provided for the inventive method. Furthermore, are particularly preferred as embodiments according to the invention Procedures in which the absorbent polymer is referred to below as letters properties or combinations of letters Property combinations shows: A, B, C, D, E, AB, ABC, ABCD, ABCDE, BC, BCD, BCDE, CD, CDE, DE.
Die für das erfindungsgemäße Verfahren besonders bevorzugten Homo- und Copolymerisate von hydrophilen Monomeren werden vorzugsweise durch radikalische Polymerisation hergestellt. Sie basieren vorzugsweise auf polymerisationsfähigen ethylenisch ungesättigten Carbonsäuren, aber auch polymerisationsfähigen ungesättigten Sulfonsäuren und Phosphonsäuren. Weitere in derartigen wasserabsorbierenden Polymeren häufig verwendete hydrophile Monomere sind Amide, Hydroxyalkylester und aminogruppen- oder ammoniumgruppenhaltige Ester und Amide dieser Säuren, insbesondere der Carbonsäuren. Weitere geeignete Monomere sind N-Vinyl- und N-Allylverbindungen sowie Vinyl- und Allylether. The particularly preferred homo- and Copolymers of hydrophilic monomers are preferably by radical polymerization. They are preferably based on polymerizable ethylenically unsaturated carboxylic acids, but also polymerizable unsaturated sulfonic acids and phosphonic acids. More in such water-absorbing polymers commonly used hydrophilic monomers are amides, Hydroxyalkyl esters and esters containing amino groups or ammonium groups and Amides of these acids, especially the carboxylic acids. More suitable Monomers are N-vinyl and N-allyl compounds as well as vinyl and allyl ethers.
Beispiele geeigneter monoethylenisch ungesättigter carboxylgruppenhaltiger Monomerer sind Acrylsäure, Methacrylsäure, Ethacrylsäure, α-Chloracrylsäure, α-Cyanoacrylsäure, Crotonsäure, α-Phenylacrylsäure, β-Acryloxypropionsäure, Sorbinsäure, α-Chlorsorbinsäure, 2'-Methylisocrotonsäure, Zimtsäure, p- Chlorzimtsäure, Itaconsäure, Citraconsäure, Mesaconsäure, Glutaconsäure, Aconitsäure, Maleinsäure, Fumarsäure, Tricarboxyethylen und Maleinsäureanhydrid. Von diesen werden Methacrylsäure und insbesondere Acrylsäure bevorzugt. Examples of suitable monoethylenically unsaturated carboxyl-containing Monomers are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, α-cyanoacrylic acid, crotonic acid, α-phenylacrylic acid, β-acryloxypropionic acid, Sorbic acid, α-chlorosorbic acid, 2'-methylisocrotonic acid, cinnamic acid, p- Chlorocinnamic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, Aconitic acid, maleic acid, fumaric acid, tricarboxyethylene and maleic anhydride. Of these, methacrylic acid and especially acrylic acid are preferred.
Zu den ethylenisch ungesättigten Sulfonsäuremonomeren zählen aliphatische und aromatische Vinylsulfonsäuren, beispielsweise Vinylsulfonsäure, Allylsulfonsäure, 4-Vinybenzylsulfonsäure, Vinyltoluolsulfonsäure und Styrolsulfonsäure, sowie Sulfoethylacrylat, Sulfoethylmethacrylat, Sulfopropylacrylat, Sulfopropylmethacrylat, 2-Hydroxy-3-methacryloxypropylsulfonsäure und 2-Acrylamido-2- methylpropansulfonsäure. Beispiele ethylenisch ungesättigter Phosphonsäuremonomerer sind Vinylphosphonsäure, Allylphosphonsäure, Vinylbenzylphosphonsäure, (Meth)Acrylamidoalkylphosphonsäuren, (Meth)Acryloylamidoalkyldiphosphonsäuren und phosphonomethylierte Vinylamine. The ethylenically unsaturated sulfonic acid monomers include aliphatic and aromatic vinylsulfonic acids, for example vinylsulfonic acid, allylsulfonic acid, 4-vinylbenzyl sulfonic acid, vinyl toluenesulfonic acid and styrene sulfonic acid, and Sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, Sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropylsulfonic acid and 2-acrylamido-2- methylpropanesulfonic. Examples of ethylenically unsaturated Phosphonic acid monomers are vinylphosphonic acid, allylphosphonic acid, Vinylbenzylphosphonic acid, (meth) acrylamidoalkylphosphonic acids, (Meth) acryloylamidoalkyldiphosphonic acids and phosphonomethylated vinylamines.
Beispiele für weitere geeignete hydrophile Monomere sind 2- Hydroxyethylacrylat, N,N-Dimethylaminoethylacrylat, Acrylamid, Dimethylacrylamid, Diethylacrylamid, N-Methylolacrylamid, N,N- Dimethylaminoethylacrylamid, Acrylamidopropyltrimethylammoniumchlorid und die analogen Ester bzw. Amide der Methacrylsäure. Weitere Beispiele sind N- Vinylformamid, N-Vinylacetamid, N-Vinyl-N-methylacetamid, N-Vinyl-N- methylformamid und N-Vinylpyrrolidon. Von diesen genannten Monomeren werden Methacrylamid und insbesondere Acrylamid bevorzugt eingesetzt. Examples of other suitable hydrophilic monomers are 2- Hydroxyethyl acrylate, N, N-dimethylaminoethyl acrylate, acrylamide, Dimethylacrylamide, diethylacrylamide, N-methylolacrylamide, N, N- Dimethylaminoethyl acrylamide, acrylamidopropyl trimethyl ammonium chloride and the analogous esters or amides of methacrylic acid. Other examples are N- Vinylformamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl-N- methylformamide and N-vinyl pyrrolidone. Of these monomers mentioned methacrylamide and especially acrylamide are preferably used.
Vorzugsweise bestehen die erfindungsgemäß eingesetzten Polymeren überwiegend aus Säuregruppen, insbesondere Carbonsäuregruppen enthaltenden Monomeren. Insbesondere liegt der Anteil dieser Monomeren bei über 60 Gew.-%, ganz besonders bevorzugt bei mehr als 90 Gew.-%. The polymers used according to the invention preferably consist predominantly from acid groups, in particular those containing carboxylic acid groups Monomers. In particular, the proportion of these monomers is over 60% by weight particularly preferred at more than 90 wt .-%.
In geringen Mengen von üblicherweise nicht mehr als 20 Gew.-% können neben hydrophilen Monomeren auch solche Monomeren eingesetzt werden, deren Homopolymerisate nicht wasserlöslich sind, beispielsweise Methyl(meth)acrylat, Ethyl(meth)acrylat, Butyl(meth)acrylat, Vinylacetat, Styrol und Isobutylen. Vorzugsweise liegt die Menge dieser Monomeren nicht über 15 Gew.-%, insbesondere nicht über 5 Gew.-%, jeweils bezogen auf die Gesamtmenge der zur Herstellung der Polymeren eingesetzten Monomeren. Die Untergrenze kann 0,01 Gew.-%, vorzugsweise 0,1 Gew.-% und insbesondere 0,5 Gew.-% betragen. Monomere, die wie Acrylnitril oder Vinylacetat nach der Polymerisation gegebenenfalls zu hydrophilen Bestandteilen hydrolysiert werden, können aber auch mit wesentlich höheren Anteilen eingesetzt werden. In small amounts of usually not more than 20% by weight, besides hydrophilic monomers, such monomers are also used, the Homopolymers are not water-soluble, for example methyl (meth) acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, styrene and isobutylene. The amount of these monomers is preferably not more than 15% by weight, in particular not more than 5% by weight, based in each case on the total amount of the Production of the monomers used in polymers. The lower limit can be 0.01% by weight, preferably 0.1% by weight and in particular 0.5% by weight. monomers those such as acrylonitrile or vinyl acetate after the polymerization, if necessary Hydrophilic components are hydrolyzed, but can also be essential higher proportions are used.
Die selben hydrophilen Monomeren, wie sie zur Herstellung von wasserabsorbierenden Homo- und Copolymerisaten verwendet werden, können auch zur Herstellung von Pfropfpolymeren eingesetzt werden. Geeignete Pfropfgrundlagen für wasserabsorbierende Pfropfpolymere können natürlichen oder synthetischen Ursprungs sein. Beispiele sind Stärke, Cellulose oder Cellulosederivate sowie andere Polysaccharide und Oligosaccharide, Polyalkylenoxide, insbesondere Polyethylenoxide und Polypropylenoxide sowie Ethylenoxid-Propylenoxid- Copolymerisate und auch hydrophile Polyester. The same hydrophilic monomers as used to make water-absorbing homopolymers and copolymers can also be used Production of graft polymers can be used. Suitable graft bases for Water-absorbing graft polymers can be natural or synthetic Be of origin. Examples are starch, cellulose or cellulose derivatives and others Polysaccharides and oligosaccharides, polyalkylene oxides, in particular Polyethylene oxides and polypropylene oxides as well as ethylene oxide propylene oxide Copolymers and also hydrophilic polyesters.
Die wasserabsorbierenden Polymeren, die in das erfindungsgemäße Verfahren eingesetzt werden, sind vorzugsweise vernetzt. Üblicherweise wird die Vernetzung durch Einpolymerisieren mehrfunktioneller Monomerer in geringer Menge erreicht. Geeignete Vernetzer für die durch radikalische Polymerisation erhältlichen Polymeren sind insbesondere Methylenbisacrylamid, Methylenbismethacrylamid, Ester ungesättigter Carbonsäuren von Polyolen, beispielsweise Polyethylenglykoldiacrylat, Polyethylenglykoldimethacrylatund Trimethylolpropantriacrylat sowie Allylverbindungen, wie Allyl(meth)acrylat, Triallylcyanurat, Maleinsäurediallylester, Triallylamin und Allylether, beispielsweise Pentaerythrittri- und -tetraallylether, Polyethylenglykoldiallylether, Glycerindi- und -triallylether und Polyallylether von Sorbit. The water-absorbing polymers used in the process according to the invention are preferably networked. Usually the Crosslinking by polymerizing multifunctional monomers in small quantities reached. Suitable crosslinkers for radical polymerization available polymers are in particular methylenebisacrylamide, Methylene bis methacrylamide, esters of unsaturated carboxylic acids of polyols, for example Polyethylene glycol diacrylate, polyethylene glycol dimethacrylate and Trimethylolpropane triacrylate and allyl compounds such as allyl (meth) acrylate, triallyl cyanurate, Maleic acid diallyl ester, triallylamine and allyl ether, for example pentaerythritol tri- and -tetraallyl ether, polyethylene glycol diallyl ether, glycerol di and triallyl ether and Polyallyl ether from sorbitol.
Der Vernetzungsgrad wird durch die Menge an zugesetzten Vernetzern bestimmt. Üblicherweise liegt die Menge an Vernetzern zwischen etwa 0,001 und etwa 10 mol-%, vorzugsweise zwischen etwa 0,1 und etwa 5 mol-%, bezogen auf die Gesamtmenge der Monomeren. The degree of crosslinking is determined by the amount of crosslinking agents added. The amount of crosslinking agents is usually between about 0.001 and about 10 mol%, preferably between about 0.1 and about 5 mol%, based on the Total amount of monomers.
Die wasserabsorbierenden Polymeren können nach verschiedenen an sich bekannten Polymerisationsverfahren hergestellt werden. Bevorzugt ist die radikalische Polymerisation in homogener Phase, insbesondere in wässriger Lösung als sogenannte Gelpolymerisation. Weitere Möglichkeiten sind die Fällungspolymerisation aus organischen Lösungsmitteln, wie zum Beispiel aus Alkoholen, oder die Suspensions-, Emulsions- oder Mikroemulsionspolymerisation. In Sonderfällen sind anstelle der radikalischen Polymerisation auch über einen ionischen Mechanismus ablaufende Polymerisationen brauchbar. The water-absorbing polymers can have various per se known polymerization processes are prepared. The radical one is preferred Polymerization in homogeneous phase, especially in aqueous solution as so-called gel polymerization. Other options are Precipitation polymerization from organic solvents, such as from alcohols, or the Suspension, emulsion or microemulsion polymerization. In special cases are instead of radical polymerization via an ionic Mechanistic polymerizations are useful.
Eine andere Möglichkeit zur Herstellung vernetzter Ausgangspolymerer für das erfindungsgemäße Verfahren besteht darin, zunächst unvernetzte, insbesondere lineare Polymere, vorzugsweise auf radikalischem Wege aus den vorgenannten monoethylenisch ungesättigten Monomeren herzustellen und diese dann mit vernetzend wirkenden Reagenzien umzusetzen. Diese Variante wird vorzugsweise dann eingesetzt, wenn die wasserabsorbierenden Polymeren zunächst in formgebenden Verfahren, beispielsweise zu Fasern, Folien oder anderen Flächengebilden, wie Geweben, Gewirken, Gespinsten oder Vliesen verarbeitet und in dieser Form vernetzt werden sollen. Another way of producing crosslinked starting polymers for the The method according to the invention consists in first of all uncrosslinked, in particular linear polymers, preferably by radical means from the aforementioned to produce monoethylenically unsaturated monomers and then using them to implement cross-linking reagents. This variant is preferred used when the water-absorbing polymers first in shaping processes, for example fibers, foils or others Flat structures, such as woven, knitted, spun or nonwovens processed and in this Form should be networked.
Als Vernetzer kommen in diesem Fall vor allem mehrfunktionelle Verbindungen in Betracht, die über Additions- oder Kondensationsreaktionen mit den funktionellen Gruppen, insbesondere den Carboxylgruppen der Polymerketten reagieren und die Ketten auf diese Weise verbinden können. Auch komplexbildende Reagenzien können geeignet sein. Zu nennen sind hier beispielsweise Polyglycidylether, wie Ethylenglykoldiglycidylether, Polyaziridine, Polyamine, wie Ethylendiamin und Diethylentriamin, Polyisocyanate, wie 2,4-Toloylendiisocyanat und Hexamethylendiisocyanat, Polyamidoamine, Haloepoxyverbindungen, Polyoxazoline, wie beispielsweise 1,2-Ethylenbisoxazolin, Oxazolidinone, Silangruppen enthaltende Vernetzer, Diglykolsilikate sowie Salze mehrwertiger Metalle, wie beispielsweise Aluminium-, Zink- oder Calciumsalze. Bevorzugt werden an dieser Stelle Vernetzer eingesetzt, die sich zunächst ohne Reaktion mit den Polymeren mischen lassen und erst während oder nach der Formgebung, beispielsweise durch Erhitzen, die eigentliche Vernetzungsreaktion eingehen. Beispiele derartiger Vernetzer sind Polyalkohole wie Diethylenglykol, Triethylenglykol, Polyethylenglykol, Glycerin, Polyglycerin, Propylenglykol, Dipropylenglykol, Polypropylenglykol, Ethylenoxid-Propylenoxid- Mischpolymere, Sorbitanfettsäureester, ethoxylierte Sorbitanfettsäureester, Trimethylolpropan, Pentaerythrit, Polyvinylalkohol und Sorbit, sowie Aminoalkohole, wie Mono-, Di- und Triethanolamin. Zu den besonders geeigneten Vernetzern zählen auch die cyclischen Carbonate, beispielsweise 1,3- Dioxolan-2-on (Ethylencarbonat), 4-Methyl-1,3-dioxolan-2-on, 4-Ethyl-1,3- dioxolan-2-on, 4,5-Dimethyl-1,3-dioxolan-2-on, 4,4-Dimethyl-1,3-dioxolan-2-on, 4-Hydroxymethyl-1,3-dioxolan-2-on, 1,3-Dioxan-2-on, 4-Methyl-1,3-dioxan-2- on, 4,6-Dimethyl-1,3-dioxan-2-on, 1,3-Dioxepan-2-on und Poly-1,3-dioxolan-2- on. In this case, multi-functional connections are used as crosslinkers considered, the addition or condensation reactions with the functional groups, especially the carboxyl groups of the polymer chains react and connect the chains in this way. Even complex-forming Reagents can be suitable. These include, for example Polyglycidyl ethers, such as ethylene glycol diglycidyl ether, polyaziridines, polyamines, such as Ethylene diamine and diethylene triamine, polyisocyanates such as 2,4-toloylene diisocyanate and Hexamethylene diisocyanate, polyamidoamines, haloepoxy compounds, Polyoxazolines, such as, for example, 1,2-ethylene bisoxazoline, oxazolidinones, Crosslinkers containing silane groups, diglycol silicates and salts of polyvalent ones Metals, such as aluminum, zinc or calcium salts. Prefers crosslinkers are used at this point, which are initially without reaction with let the polymer mix and only during or after shaping, for example by heating, the actual crosslinking reaction. Examples of such crosslinkers are polyalcohols such as diethylene glycol, Triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, Dipropylene glycol, polypropylene glycol, ethylene oxide propylene oxide Copolymers, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, Trimethylolpropane, pentaerythritol, polyvinyl alcohol and sorbitol, as well Amino alcohols, such as mono-, di- and triethanolamine. To the particularly suitable crosslinkers also include the cyclic carbonates, for example 1,3- Dioxolan-2-one (ethylene carbonate), 4-methyl-1,3-dioxolan-2-one, 4-ethyl-1,3- dioxolan-2-one, 4,5-dimethyl-1,3-dioxolan-2-one, 4,4-dimethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3-dioxan-2-one, 4-methyl-1,3-dioxan-2- on, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxepan-2-one and poly-1,3-dioxolan-2- on.
In den wasserabsorbierenden Polymeren, wie sie in das erfindungsgemäße Verfahren eingesetzt werden, sollen die enthaltenen Säuregruppen, vorzugsweise anteilig, beispielsweise zu 25 bis 100 mol-% und insbesondere zu 50 bis 85 mol-%, in neutralisierter Form vorliegen. Dies kann dadurch erreicht werden, dass in die Polymerisationsreaktion ein entsprechender Teil der säuregruppenhaltigen Monomeren in neutralisierter Form eingesetzt wird, aber auch dadurch, dass die zunächst in saurer Form hergestellten Polymeren vor oder nach ihrer Vernetzung nachträglich neutralisiert werden. Bevorzugte Salze sind die Alkalisalze, insbesondere die Natriumsalze, aber auch die Ammoniumsalze. Zur nachträglichen Neutralisation der sauren Polymeren werden daher vorzugsweise Alkalimetallhydroxide und -carbonate, insbesondere Natriumhydroxid, Natriumcarbonat und Natriumhydrogencarbonat eingesetzt. Die Polymeren in Gelform werden üblicherweise mit wässrigen Lösungen der Alkalien oder aber auch mit pulverförmigen Alkalien in Geräten neutralisiert, die für eine Zerkleinerung des Gels und eine intensive Mischung mit dem Neutralisationsmittel geeignet sind. In the water-absorbing polymers, as in the invention Processes are used, the acid groups contained, preferably pro rata, for example 25 to 100 mol% and in particular 50 to 85 mol%, are in neutralized form. This can be achieved by using the Polymerization reaction a corresponding part of the acid group Monomers are used in neutralized form, but also in that the polymers initially produced in acidic form before or after their crosslinking subsequently neutralized. Preferred salts are the alkali salts, especially the sodium salts, but also the ammonium salts. For subsequent Neutralization of the acidic polymers are therefore preferred Alkali metal hydroxides and carbonates, especially sodium hydroxide, sodium carbonate and Sodium bicarbonate used. The polymers are in gel form usually with aqueous solutions of the alkalis or also with powdered alkalis neutralized in devices that are used for crushing the gel and intensive mixing with the neutralizing agent are suitable.
Besonders bevorzugte wasserabsorbierende Polymere für das erfindungsgemäße Verfahren sind Polymere auf Basis von Acrylsäure mit vorzugsweise mehr als 90 Gew.-% Acrylsäure, die vorzugsweise 0,01 bis 5 Gew.-% Vernetzer enthalten. In diesen Polymeren liegen vorzugsweise etwa 40 bis etwa 90 mol-%, insbesondere etwa 50 bis etwa 80 mol-% der Acrylsäureeinheiten in Form des Natriumsalzes vor. Particularly preferred water-absorbing polymers for the invention Processes are polymers based on acrylic acid with preferably more than 90% by weight Acrylic acid, which preferably contain 0.01 to 5 wt .-% crosslinker. In these polymers are preferably about 40 to about 90 mol%, in particular about 50 to about 80 mol% of the acrylic acid units in the form of the sodium salt in front.
Die bei der Herstellung im allgemeinen in Form eines Gels anfallenden wasserabsorbierenden Polymeren werden vor der Vernetzung im Bereich der Oberfläche üblicherweise getrocknet, vorzugsweise bis auf einen Restfeuchtegehalt von weniger als 10 Gew.-%, insbesondere unter 5 Gew.-%. Hierfür eignen sich beispielsweise Bandtrockner oder Walzentrockner. Anschließend können die wasserabsorbierenden Polymeren beispielsweise auf Walzenstühlen, in Stiftmühlen oder in Schwingmühlen auf das gewünschte Maß zerkleinert und die anfallenden Partikel, wenn gewünscht, in Größenfraktionen, beispielsweise durch entsprechende Siebvorgänge, aufgeteilt werden. Für das erfindungsgemäße Verfahren werden die wasserabsorbierenden Polymeren vorzugsweise mit Partikelgrößen im Bereich zwischen etwa 45 und etwa 1000 µm, insbesondere zwischen etwa 45 und etwa 850 µm und ganz besonders bevorzugt zwischen etwa 200 und etwa 850 µm eingesetzt. Those which are generally produced in the form of a gel Water-absorbing polymers are used in the surface area before crosslinking usually dried, preferably to a residual moisture content of less than 10% by weight, in particular less than 5% by weight. Are suitable for this for example belt dryer or drum dryer. Then you can water-absorbing polymers, for example on roller mills, in pin mills or crushed to the desired size in vibrating mills and the resulting Particles, if desired, in size fractions, for example by appropriate ones Sieving operations can be divided. For the method according to the invention, the water-absorbing polymers preferably with particle sizes in the range between approximately 45 and approximately 1000 μm, in particular between approximately 45 and approximately 850 µm and very particularly preferably between about 200 and about 850 µm used.
Werden die wasserabsorbierenden Polymeren in Faserform in das erfindungsgemäße Verfahren eingesetzt, so werden hier Faserstärken zwischen etwa 0,5 und etwa 5, insbesondere zwischen etwa 1 und etwa 3 dtex, bevorzugt. Dies gilt auch, wenn sie als Fasern in Geweben, Gewirken, Gespinsten oder Vliesen eingearbeitet sind Auch faserförmige oder folienförmige wasserabsorbierende Polymere werden in das erfindungsgemäße Verfahren üblicherweise in trockener Form eingesetzt. Are the water-absorbent polymers in fiber form in the Method used according to the invention, fiber thicknesses between about 0.5 and about 5, especially between about 1 and about 3 dtex, preferred. This is also valid, if they are incorporated as fibers in fabrics, knitted fabrics, spun fabrics or nonwovens Are also fibrous or film-shaped water-absorbent polymers usually used in dry form in the process according to the invention.
Bei dem im erfindungsgemäßen Verfahren als Nachvernetzer für die
wasserabsorbierenden Polymeren eingesetzten cyclischen Harnstoffe der Formel I
handelt es sich um Ethylenharnstoff (x = 2; R1, R2 = H), der mit systematischem
Namen auch als Imidazolidin-2-on bezeichnet wird, um Propylenharnstoff (x = 3;
R1, R2 = H), der auch als Tetrahydropyrimidin-2-on bezeichnet wird und um deren
N-substituierte Derivate. R1 und R2 können unabhängig voneinander Wasserstoff
oder ein C1- bis C4-Alkylrest, vorzugsweise ein Methylrest oder ein Ethylrest,
bedeuten. Die unsubstituierten Verbindungen (R1 = R2 = H) werden bevorzugt
eingesetzt. Von diesen wird wiederum Ethylenharnstoffbesonders bevorzugt.
In the cyclic ureas of the formula I used as postcrosslinker for the water-absorbing polymers in the process according to the invention
is ethylene urea (x = 2; R 1 , R 2 = H), which is also referred to systematically as imidazolidin-2-one, propylene urea (x = 3; R 1 , R 2 = H), which is also referred to as tetrahydropyrimidin-2-one and its N-substituted derivatives. R 1 and R 2 can independently of one another denote hydrogen or a C 1 - to C 4 -alkyl radical, preferably a methyl radical or an ethyl radical. The unsubstituted compounds (R 1 = R 2 = H) are preferably used. Of these, ethylene urea is particularly preferred.
Im erfindungsgemäßen Verfahren können als Nachvernetzer Einzelverbindungen aus der genannten Verbindungsklasse, aber auch mehrere Nachvernetzer dieses Typs gleichzeitig eingesetzt werden. Dia Menge an Nachvernetzer, die eingesetzt wird, richtet sich im wesentlichen nach den Eigenschaften, die die auf diese Weise modifizierten Polymeren nach der Behandlung aufweisen sollen. Vorzugsweise werden daher zwischen etwa 0,1 und etwa 3 Gew.-%, insbesondere zwischen etwa 0,25 und etwa 1,5 Gew.-% an derartigen cyclischen Harnstoffen, bezogen auf das wasserabsorbierende Polymer zur Vernetzung verwendet. Zu einer gleichmäßigen Verteilung des Nachvernetzers auf den Polymerpartikeln wird der Nachvernetzer in Form einer Lösung mit dem Polymeren in Kontakt gebracht. Als Lösungsmittel eignen sich insbesondere Wasser und niedere Alkohole mit 1 bis 4 C-Atomen sowie Gemische diese Flüssigkeiten, wobei vorzugsweise allein Wasser als Lösungsmittel für den Nachvernetzer verwendet wird. Bedingt durch die gute Löslichkeit der erfindungsgemäß verwendeten Nachvernetzer können hochkonzentrierte Lösungen hergestellt werden, so dass mit geringen Lösungsmittelmengen gearbeitet werden kann und dadurch die Trocknung nach der Vernetzungsreaktion erleichtert wird. Die Menge an aufgebrachter Nachvernetzerlösung liegt vorzugsweise zwischen etwa 1 und etwa 20 Gew.-%, insbesondere zwischen etwa 2,5 und etwa 15 Gew.-%, bezogen auf das eingesetzte wasserabsorbierende Polymer. Der Auftrag der Nachvernetzerlösung auf das Polymere erfolgt vorzugsweise in Mischapparaturen, in denen die Polymerpartikel unter Umwälzung mit der Nachvernetzerlösung gleichmäßig besprüht werden können. Geeignete Mischanlagen sind beispielsweise Lödigemischer, BEPEX®-Mischer, NAUTA®-Mischer und Schugi-Mischer. Individual compounds can be used as postcrosslinkers in the process according to the invention from the named connection class, but also several post-crosslinkers of this Type can be used simultaneously. The amount of postcrosslinker used is essentially determined by the properties that this way should have modified polymers after the treatment. Preferably are therefore between about 0.1 and about 3% by weight, in particular between about 0.25 and about 1.5 wt .-% of such cyclic ureas, based on the water-absorbent polymer used for crosslinking. To an even one Distribution of the postcrosslinker on the polymer particles becomes the postcrosslinker brought into contact with the polymer in the form of a solution. As a solvent water and lower alcohols with 1 to 4 carbon atoms are particularly suitable and mixtures of these liquids, preferably water alone as Solvent for the postcrosslinker is used. Due to the good Solubility of the postcrosslinker used according to the invention can Highly concentrated solutions are made, so that with small amounts of solvent can be worked and thereby drying after the crosslinking reaction is facilitated. The amount of postcrosslinker solution applied is preferably between about 1 and about 20% by weight, in particular between about 2.5 and about 15% by weight, based on the water-absorbing polymer used. The The postcrosslinker solution is preferably applied to the polymer in Mixing apparatus in which the polymer particles are circulated with the Post-crosslinker solution can be sprayed evenly. Suitable mixing plants are for example Lödige mixers, BEPEX® mixers, NAUTA® mixers and Schugi mixer.
Nachdem die Nachvernetzerlösung mit den Polymerpartikeln in Kontakt gebracht worden ist, werden die Partikel auf höhere Temperaturen erwärmt, bei denen die Vernetzungsreaktion ablaufen kann. Vorzugsweise werden Reaktionstemperaturen zwischen etwa 50 und etwa 300°C gewählt, wobei höhere Temperaturen zu einer schnelleren und weitergehenden Vernetzung führen. Besonders bevorzugt werden Reaktionstemperaturen zwischen etwa 100 und etwa 250°C gewählt, besonders bevorzugt zwischen 150 und 200°C. Die Reaktionszeiten bei diesen Temperaturen liegen vorzugsweise zwischen etwa 10 und etwa 90 min. insbesondere zwischen etwa 20 und etwa 60 min. abhängig von der jeweiligen Reaktionstemperatur und der gegebenenfalls unterschiedlichen Reaktivität der einzelnen Nachvernetzer. Bei Verwendung von Ethylenharnstoff werden als Reaktionsbedingungen etwa 30 min bei etwa 190°C besonders bevorzugt. Die Reaktion kann in geeigneten Wärmegeräten, beispielsweise in Umluftheizern oder aber in heizbaren Mischgeräten durchgeführt werden. After the postcrosslinker solution is brought into contact with the polymer particles the particles are heated to higher temperatures at which the Crosslinking reaction can take place. Preferably be Reaction temperatures between about 50 and about 300 ° C selected, with higher temperatures lead to faster and more extensive networking. Particularly preferred reaction temperatures between about 100 and about 250 ° C. are selected, particularly preferably between 150 and 200 ° C. The response times for these Temperatures are preferably between about 10 and about 90 minutes. in particular between about 20 and about 60 minutes. depending on the particular Reaction temperature and the possibly different reactivity of the individual Postcrosslinker. When using ethylene urea are considered Reaction conditions at about 190 ° C. for about 30 minutes are particularly preferred. The reaction can occur in suitable heating devices, for example in convection heaters or in heatable ones Mixers are carried out.
Sofern nötig kann das Polymer nach der Vernetzungsreaktion getrocknet werden, um das mit der Nachvernetzerlösung eingetragene Lösungsmittel und das Reaktionswasser zu entfernen. Die Trocknung kann in einem nachgeschalteten Trockner, zum Beispiel einem Hordentrockner, einem Drehrohrofen oder einem Wirbelschichttrockner vorgenommen werden, doch ist es in vielen Fällen ohne weiteres möglich, die Reaktion bei erhöhter Temperatur und das Trocknen in einem Schritt und in einem Gerät durchzuführen. In besonders vorteilhafter Weise können sowohl das Einmischen der Nachvernetzerlösung als auch die Reaktion und das nachfolgende Trocknen in ein und derselben Anlage, beispielsweise in einem beheizbaren Mischer, vorzugsweise in einer Wirbelschichtanlage durchgeführt werden. If necessary, the polymer can be dried after the crosslinking reaction, to the solvent entered with the postcrosslinker solution and the To remove water of reaction. Drying can be carried out in a downstream dryer, for example a tray dryer, a rotary kiln or one Fluid bed dryers are made, but in many cases it is straightforward possible, the reaction at elevated temperature and drying in one step and perform in one device. Can in a particularly advantageous manner both the mixing of the postcrosslinker solution and the reaction and that subsequent drying in one and the same system, for example in one heatable mixer, preferably carried out in a fluidized bed system become.
Polymere in Faserform oder Folienform können beispielsweise in geeigneten Durchlaufapparaturen mit der Nachvernetzerlösung besprüht, erhitzt und ggf. getrocknet werden. In analoger Weise kann die erfindungsgemäße Vernetzung im Bereich der Oberfläche gegebenenfalls auch an anderen Flächengebilden, die die wasserabsorbierenden Polymeren enthalten, durchgeführt werden. Polymers in fiber form or film form can, for example, in suitable Continuous equipment sprayed with the postcrosslinker solution, heated and, if necessary be dried. The crosslinking according to the invention can be carried out in an analogous manner Area of the surface, if necessary, also on other flat structures that form the contain water-absorbing polymers.
Die Vernetzungsreaktion zwischen den wasserabsorbierenden Polymeren und den cyclischen Harnstoffen kann durch saure Verbindungen katalysiert werden, so dass sie in Gegenwart derartiger Katalysatoren bei niedrigeren Temperaturen oder in kürzeren Zeiten durchgeführt werden kann. Als Katalysatoren eigenen sich in erster Linie anorganische und organische Säuren und deren Anhydride oder Lewis-Säuren. Beispiele für saure Verbindungen, die sich als Katalysatoren besonders eignen, sind HCl, H2SO4 oder H3PO4 als anorganische Säuren oder Ameisen-, Essig- oder Propionsäure als organische Säuren. Beispiele für Lewis-Säuren sind AlCl3 und Al2(SO4)3. The crosslinking reaction between the water-absorbing polymers and the cyclic ureas can be catalyzed by acidic compounds, so that it can be carried out in the presence of such catalysts at lower temperatures or in shorter times. Inorganic and organic acids and their anhydrides or Lewis acids are primarily suitable as catalysts. Examples of acidic compounds which are particularly suitable as catalysts are HCl, H 2 SO 4 or H 3 PO 4 as inorganic acids or formic, acetic or propionic acid as organic acids. Examples of Lewis acids are AlCl 3 and Al 2 (SO 4 ) 3 .
Vorzugsweise werden nicht mehr als etwa 5 Gew.-% an saurer Verbindung als Katalysator, bezogen auf das Polymere während der Vernetzungsreaktion zugesetzt. Insbesondere liegt die Katalysatormenge zwischen etwa 0,1 und etwa 4 Gew.-%. Die Zugabe kann in der Nachvernetzerlösung, aber auch getrennt von dieser, vorzugsweise in Form einer eignen Lösung, erfolgen. Preferably no more than about 5% by weight of acidic compound is used Catalyst based on the polymer during the crosslinking reaction added. In particular, the amount of catalyst is between about 0.1 and about 4% by weight. The addition can be in the postcrosslinker solution, but also separately from this, preferably in the form of a suitable solution.
Die besonders vorteilhaften Eigenschaften der aus dem erfindungsgemäßen Verfahren resultierenden, im Bereich der Oberfläche vernetzten, wasserabsorbierenden Polymeren sind auch dann zu beobachten, wenn nur sehr geringe Nachvernetzermengen eingesetzt werden oder die erfindungsgemäß verwendeten Nachvernetzer zusammen mit anderen Nachvernetzern, vorzugsweise zusammen mit anderen Nachvernetzern, wie sie für die Vernetzung im Bereich der Oberfläche von wasserabsorbierenden Polymeren bekannt sind, verwendet werden. Dabei kommt es nicht darauf an, dass die erfindungsgemäß verwendeten Nachvernetzer gleichzeitig mit den anderen Nachvernetzern zu Reaktion gebracht werden, sondern es ist auch möglich, die erfindungsgemäß verwendeten cyclischen Harnstoffe vor oder insbesondere nach einer Vernetzung im Bereich der Oberfläche der wasserabsorbierenden Polymeren mit den anderen Nachvernetzern mit dem Polymer zur Reaktion zu bringen. Werden die cyclischen Harnstoffe im erfindungsgemäßen Verfahren zusätzlich zu einem oder mehreren anderen Nachvernetzern angewandt, so liegt das Gewichtsverhältnis von cyclischem Harnstoff zur Gesamtmenge der anderen Nachvernetzer vorzugsweise zwischen etwa 0,1 und etwa 10, insbesondere zwischen etwa 0,2 und etwa 4. Die Gesamtmenge an angewandtem Nachvernetzer einschließlich cyclischem Harnstoff hängt wesentlich von der Reaktivität des oder der anderen Nachvernetzer ab und kann daher ohne weiteres auch bis zu etwa 10 Gew.-% und mehr, bezogen auf das wasserabsorbierende Polymer betragen. Vorzugsweise liegt die Gesamtmenge an Nachvernetzer aber zwischen etwa 0,1 und etwa 2 Gew.-%, insbesondere zwischen etwa 0,2 und etwa 1 Gew.-%. The particularly advantageous properties of the from the invention Resulting process, cross-linked in the area of the surface, Water-absorbing polymers can also be observed even if only very few Postcrosslinker amounts are used or those used according to the invention Postcrosslinker together with other postcrosslinkers, preferably together with other post-crosslinkers, such as those used for crosslinking in the area of the surface of water-absorbent polymers are used. there it does not matter that the postcrosslinker used according to the invention are reacted simultaneously with the other postcrosslinkers, but it is also possible to use the cyclic ureas used according to the invention before or especially after crosslinking in the area of the surface of the water-absorbent polymers with the other post-crosslinkers with the polymer to react. Are the cyclic ureas in The inventive method in addition to one or more other post-crosslinkers applied, the weight ratio of cyclic urea to Total amount of the other postcrosslinkers preferably between about 0.1 and about 10, especially between about 0.2 and about 4. The total amount of applied Postcrosslinker including cyclic urea depends largely on the Reactivity of the or the other postcrosslinker and can therefore easily also up to about 10 wt .-% and more, based on the water-absorbing Polymer. However, the total amount of postcrosslinker is preferably between about 0.1 and about 2% by weight, in particular between about 0.2 and about 1% by weight.
Als andere Nachvernetzer, die im erfindungsgemäßen Verfahren neben den cyclischen Harnstoffen eingesetzt werden können, kommen prinzipiell alle für diesen Zweck geeigneten Verbindungen in Betracht. Insbesondere sind hier die aus der Literatur für diesen Zweck bekannten Nachvernetzer geeignet, sofern man die mit diesen Nachvernetzern gegebenenfalls verbundenen Nachteile in Kauf nimmt. Zu nennen sind hier beispielsweise Polyole wie beispielsweise Ethylenglykol, Polethylenglykole wie Diethylenglykol, Triethylenglykol und Tetraethylenglykol, Propylenglykol, Polypropylenglykole wie Dipropylenglykol, Tripropylenglykol oder Tetrapropylenglykol, 1,3-Butandiol, 1,4-Butandiol, 1,5-Pentandiol, 2,4- Pentandiol, 1,6-Hexandiol, 2,5-Hexandiol, Glycerin, Polyglycerin, Trimethylolpropan, Polyoxypropylen, Oxyethylen-Oxypropylen-Blockcopolymere, Sorbitanfettsäureester, Polyoxyethylensorbitanfettsäureester, Pentaerythrit, Polyvinylalkohol und Sorbitol, Aminoalkohole wie beispielsweise Ethanolamin, Diethanolamin, Triethanolamin oder Propanolamin, Polyaminverbindungen wie beispielsweise Ethylendiamin, Diethylentriaamin, Triethylentetraamin, Tetraethylenpentaamin oder Pentaethylenhexaamin, Polyglycidylether-Verbindungen wie Ethylenglykoldiglycidylether, Polyethylenglykoldiglycidylether, Glycerindiglycidylether, Glycerinpolyglycidylether, Pentareritritpolyglycidylether, Propylenglykoldiglycidylether Polypropylenglykoldiglycidylether, Neopentylglykoldiglycidylether, Hexandiolglycidylether, Trimethylolpropanpolyglycidylether, Sorbitolpolyglycidylether, Phtahlsäurediglycidylester, Adipinsäurediglycidylether, 1,4- Phenylen-bis(2-oxazolin), Glycidol, Polyisocyanate, vorzugsweise Diisocyanate wie 2,4-Toluoldiisocyanat und Hexamethylendiisocyanat, Polyaziridin- Verbindungen wie 2,2-Bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionat], 1,6-Hexamethylendiethylenharnstoff und Diphenylmethan-bis-4,4'-N,N'- diethylenharnstoff, Halogenepoxide wie beispielsweise Epichlor- und Epibromhydrin und α-Methylepichlorhydrin, Alkylencarbonate, insbesondere cyclische Carbonate, wie 1,3-Dioxolan-2-on (Ethylencarbonat), 4-Methyl-1,3-dioxolan-2-on (Propylencarbonat), 4,5-Dimethyl-1,3-dioxolan-2-on, 4,4-Dimethyl-1,3-dioxolan- 2-on, 4-Ethyl-1,3-dioxolan-2-on, 4-Hydroxymethyl-1,3-dioxolan-2-on, 1,3- Dioxan-2-on, 4-Methyl-1,3-dioxan-2-on, 4,6-Dimethyl-1,3-dioxan-2-on, 1,3- Dioxolan-2-on, Poly-1,3-dioxolan-2-on, polyquartäre Amine wie Kondensationsprodukte von Dimethylaminen und Epichlorhydrin, Polyoxazoline wie 1,2- Ethylenbisoxazolin, Nachvernetzer mit Silangruppen wie γ- Glycidoxypropyltrimethoxysilan und γ-Aminopropyltrimethoxysilan, Oxazolidinone wie 2-Oxazolidinon, Bis- und Poly-2-oxazolidinone und Diglykolsilikate. Als andere Nachvernetzer sind des Weiteren polyvalente Metallkationen geeignet. Diese leiten sich vorzugsweise von mehrwertigen Kationen ab. Bevorzugte zweiwertige Kationen leiten sich von Zink, Beryllium, Erdalkalimetallen, wie Magnesium, Calcium, Strontium ab, wobei Calcium bevorzugt wird. Weiter erfindungsgemäß einsetzbare höherwertige Kationen sind Kationen von Aluminium, Eisen, Chrom, Mangan, Titan, Zirkonium und andere Übergangsmetalle sowie Doppelsalze solcher Kationen oder Mischungen der genannten Salze. Bevorzugt werden Aluminiumsalze und Alaune und deren unterschiedliche Hydrate wie z. B. AlCl3 × 6 H2O, NaAl(SO4)2 × 12 H2O, KAl(SO4)2 × 12 H2O oder Al2(SO4)3 × 14-18 H2O eingesetzt. In principle, all compounds suitable for this purpose are suitable as other postcrosslinkers which can be used in the process according to the invention in addition to the cyclic ureas. In particular, the postcrosslinkers known for this purpose from the literature are suitable here, provided the disadvantages associated with these postcrosslinkers are accepted. Examples include polyols such as ethylene glycol, polyethylene glycols 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, glycerin, polyglycerol, trimethylolpropane, polyoxypropylene, oxyethylene-oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, pentaerythritol, polyvinyl alcohol and sorbitol, amino alcohols such as, for example, ethanolamine, diethanolamine, ethanolamine, diethanolamine such as, for example, ethylene diamine, diethylene triaamine, triethylene tetraamine, tetraethylene pentaamine or pentaethylene hexaamine, polyglycidyl ether compounds such as ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol diglycidyl ether, glycerol polyglycidyl ether, pentareritritol polyglycidyl ether, glycidyl ether polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol glycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, phthalic acid diglycidyl ester, adipic acid diglycidyl ether, 2, 4-phenylene diol, di (2-phenylene) diol such as 1,4-phenylene-diolate, such as 1,4-phenylene-bis-diol, -Bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,6-hexamethylene-diethyleneurea and diphenylmethane-bis-4,4'-N, N'-diethyleneurea, haloepoxides such as epichloro- and epibromohydrin and α-methylepichlorohydrin, alkylene carbonates , in particular cyclic 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- on, 4,4-dimethyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2-one, 1,3- Dioxan-2-one, 4-methyl-1,3-dioxan-2-one, 4,6-dimethyl-1,3-dioxan-2-one, 1,3-dioxolan-2-one, pol y-1,3-dioxolan-2-one, polyquaternary amines such as condensation products of epichlorohydrin and dimethyl amines, such as 1,2-ethylenebisoxazoline polyoxazolines, post-crosslinking with silane groups such as γ- glycidoxypropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, oxazolidinones such as 2-oxazolidinone, bis- and Poly-2-oxazolidinones and diglycol silicates. Polyvalent metal cations are also suitable as other postcrosslinkers. These are preferably derived from polyvalent cations. Preferred divalent cations are derived from zinc, beryllium, alkaline earth metals, such as magnesium, calcium, strontium, calcium being preferred. Other higher-value cations which can be used according to the invention are cations of aluminum, iron, chromium, manganese, titanium, zirconium and other transition metals, and also double salts of such cations or mixtures of the salts mentioned. Aluminum salts and alums and their different hydrates such as, for. B. AlCl 3 × 6 H 2 O, NaAl (SO 4 ) 2 × 12 H 2 O, KAl (SO 4 ) 2 × 12 H 2 O or Al 2 (SO 4 ) 3 × 14-18 H 2 O are used.
Die Erfindung betrifft weiterhin die durch das erfindungsgemäße Verfahren erhältlichen Polymere. The invention further relates to those by the method according to the invention available polymers.
Die durch das erfindungsgemäße Verfahren erhältlichen Polymeren beinhalten
einen Innenbereich, einen den Innenbereich umgebenden Aussenbereich sowie
einen den Aussenbereich umgebenden Oberflächenbereich, wobei der
Außenbereich stärker als der Innenbereich vernetzt ist. Die erfindungsgemäßen Polymeren
zeichnen sich in ihren Gebrauchseigenschaften als flüssigkeitsabsorbierende
Mittel durch ein sehr positives Eigenschaftsprofil aus, das wesentlich durch die
erfindungsgemäße Nachvernetzung bestimmt wird. Insbesondere weisen die
erfindungsgemäßen Polymere wenigstens eine der folgenden Eigenschaften auf:
- 1. (β1) CRC nach ERT 441.1-99 vom mindestens 14, bevorzugt von mindestens 16 und besonders bevorzugt von mindestens 18 g/g, darüber hinaus bevorzugt mindestens 20 g/g,
- 2. (β2) ein AAP nach ERT 442.1-99 bei einer Belastung von 0,3 psi von mindestens 15, bevorzugt mindestens 20 g/g,
- 3. (β3) ein AAP nach ERT 442.1-99 bei einer Belastung von 0,7 psi von mindestens 10, bevorzugt mindestens 15 g/g,
- 1. (β1) CRC according to ERT 441.1-99 of at least 14, preferably at least 16 and particularly preferably at least 18 g / g, furthermore preferably at least 20 g / g,
- 2. (β2) an AAP according to ERT 442.1-99 at a load of 0.3 psi of at least 15, preferably at least 20 g / g,
- 3. (β3) an AAP according to ERT 442.1-99 at a load of 0.7 psi of at least 10, preferably at least 15 g / g,
Die sich aus den vorstehenden Eigenschaften ergebenden Eigenschaftskombinationen von zwei oder mehr dieser Eigenschaften stellen jeweils bevorzugte Ausführungsformen des erfindungsgemässen Verfahrens dar. Weiterhin als erfindungsgemässe Ausführungsformen besonders bevorzugt sind Verfahren, in denen das wasserabsorbierende Polymer die nachfolgend als Buchstaben oder Buchstabenkombinationen dargestellten Eigenschaften oder Eigenschaftskombinationen zeigt: β1, β2, β3, β1β2, β2β3, β1β3, β1β2β3. The resulting from the above properties Property combinations of two or more of these properties each are preferred Embodiments of the method according to the invention. Furthermore as Embodiments according to the invention are particularly preferred in which the water-absorbent polymer which is referred to below as letters or Character combinations shown properties or combinations of properties shows: β1, β2, β3, β1β2, β2β3, β1β3, β1β2β3.
Gemäß einer erfindungsgemäßen Ausführungsform des erfindungsgemäßen Verfahrens sowie der erfindungsgemäßen Polymere ist es bevorzugt, dass die nur mit einer Untergrenze angegebenen Werte von erfindungsgemäßen Merkmalen eine Obergrenze besitzen, die das 20-fache, vorzugsweise das 10-fache und besonders bevorzugt das 5-fache des am meisten bevorzugten Wertes der Untergrenze besitzen. According to an embodiment of the invention Process and the inventive polymers, it is preferred that the only with values of features according to the invention given a lower limit Have an upper limit that is 20 times, preferably 10 times and especially preferably 5 times the most preferred value of the lower limit have.
In 477,8 g Wasser, die sich in einem Becherglas befanden, wurden zunächst 140 g Acrylsäure, dann eine Mischung von 140 g Acrylsäure mit 0,29 g Polyethylenglykol-300-diacrylat und 0,55 g Allyloxypolyethylenglykolacrylsäureester gelöst. Die Lösung wurde auf 10°C gekühlt. Danach wurden unter Kühlen insgesamt 217,5 g 50%ige Natronlauge so langsam zugesetzt, dass die Temperatur nicht 30°C überstieg. Anschließend wurde die Lösung bei 20°C mit Stickstoff gespült und dabei weiter abgekühlt. Nach Erreichung der Starttemperatur von 4°C wurden die Initiatorlösungen (0,1 g 2,2'-Azobis-2-amidinopropan-dihydrochlorid in 10 g Wasser; 0,3 g Natriumperoxydisulfat in 3 g Wasser; 0,07 g 30%ige Wasserstoffperoxidlösung in 0,7 g Wasser; 1 g Na2CO3 in 6,7 g Wasser und 0,015 g Ascorbinsäure in 2 g Wasser) zugesetzt. Nachdem die Endtemperatur 102°C erreicht war, wurde das entstandene Gel mit einem Fleischwolf zerkleinert und bei 150°C 90 min lang im Umlufttrockenschrank getrocknet. Das getrocknete Polymerisat wurde grob zerstoßen und in einer Retsch Labormühle gemahlen, und daraus dann eine Fraktion mit einer Partikelgröße von 150 bis 850 µm ausgesiebt. First, 140 g of acrylic acid, then a mixture of 140 g of acrylic acid with 0.29 g of polyethylene glycol 300 diacrylate and 0.55 g of allyloxypolyethylene glycol acrylic acid ester were dissolved in 477.8 g of water in a beaker. The solution was cooled to 10 ° C. A total of 217.5 g of 50% sodium hydroxide solution were then added so slowly that the temperature did not exceed 30 ° C. The solution was then flushed with nitrogen at 20 ° C. and further cooled. After the start temperature of 4 ° C. had been reached, the initiator solutions (0.1 g of 2,2'-azobis-2-amidinopropane dihydrochloride in 10 g of water; 0.3 g of sodium peroxydisulfate in 3 g of water; 0.07 g of 30% strength Hydrogen peroxide solution in 0.7 g water; 1 g Na 2 CO 3 in 6.7 g water and 0.015 g ascorbic acid in 2 g water) added. After the final temperature had reached 102 ° C., the gel formed was comminuted with a meat grinder and dried at 150 ° C. for 90 minutes in a forced-air drying cabinet. The dried polymer was roughly crushed and ground in a Retsch laboratory mill, and a fraction with a particle size of 150 to 850 μm was then sieved from it.
In einem Becherglas wurden 476,6 g Wasser vorgelegt und mit 140 g Acrylsäure vermischt. Zu dieser Lösung wurde außerdem ein Gemisch aus 0,85 g Polyethylenglykol-300-diacrylat, 1,25 g Allyloxypolyethylenglykolacrylsäureester und 140 g Acrylsäure hinzugefügt. Die Lösung wurde dann auf 10°C gekühlt. Danach wurden unter Kühlen insgesamt 217,5 g 50%ige Natronlauge so langsam zugesetzt, dass die Temperatur nicht 30°C überstieg. Anschließend wurde die Lösung bei 20°C mit Stickstoff gespült und dabei weiter abgekühlt. Nach Erreichung der Starttemperatur von 4°C wurden die Initiatorlösungen (0,1 g 2,2'-Azobis-2- amidinopropan-dihydrochlorid in 10 g Wasser; 0,3 g Natriumperoxydisulfat in 3 g Wasser; 0,07 g 30%ige Wasserstoffperoxidlösung in 0,7 g Wasser; 1 g Na2CO3 in 6,7 g Wasser und 0,015 g Ascorbinsäure in 2 g Wasser) zugesetzt. Nachdem die Endtemperatur 102°C erreicht war, wurde das entstandene Gel mit einem Fleischwolf zerkleinert und bei 150°C 90 min lang im Umlufttrockenschrank getrocknet. Das getrocknete Polymerisat wurde grob zerstoßen und in einer Retsch Labormühle gemahlen, und daraus dann eine Fraktion mit einer Partikelgröße von 150 bis 850 µm ausgesiebt. 476.6 g of water were placed in a beaker and mixed with 140 g of acrylic acid. A mixture of 0.85 g of polyethylene glycol 300 diacrylate, 1.25 g of allyloxypolyethylene glycol acrylic acid ester and 140 g of acrylic acid was also added to this solution. The solution was then cooled to 10 ° C. A total of 217.5 g of 50% sodium hydroxide solution were then added so slowly that the temperature did not exceed 30 ° C. The solution was then flushed with nitrogen at 20 ° C. and further cooled. After the start temperature of 4 ° C. had been reached, the initiator solutions (0.1 g of 2,2'-azobis-2-amidinopropane dihydrochloride in 10 g of water; 0.3 g of sodium peroxydisulfate in 3 g of water; 0.07 g of 30% strength Hydrogen peroxide solution in 0.7 g water; 1 g Na 2 CO 3 in 6.7 g water and 0.015 g ascorbic acid in 2 g water) added. After the final temperature had reached 102 ° C., the gel formed was comminuted with a meat grinder and dried at 150 ° C. for 90 minutes in a forced-air drying cabinet. The dried polymer was roughly crushed and ground in a Retsch laboratory mill, and a fraction with a particle size of 150 to 850 μm was then sieved from it.
In einem Becherglas wurden 474,5 g Wasser vorgelegt und mit 140 g Acrylsäure vermischt. Zu dieser Lösung wurde weiterhin eine Mischung aus 1,68 g Polyethylenglykol-300-diacrylat und 2,52 g Allyloxypolyethylenglykolacrylsäureester und 140 g Acrylsäure hinzugegeben. Die Lösung wurde auf 10°C gekühlt. Danach wurden unter Kühlen insgesamt 217,5 g 50%ige Natronlauge so langsam zugesetzt, dass die Temperatur nicht 30°C überstieg. Anschließend wurde die Lösung bei 20°C mit Stickstoff gespült und dabei weiter abgekühlt. Nach Erreichung der Starttemperatur von 4°C wurden die Initiatorlösungen (0,1 g 2,2'-Azobis-2- amidinopropan-dihydrochlorid in 10 g Wasser; 0,3 g Natriumperoxydisulfat in 3 g Wasser; 0,07 g 30%ige Wasserstoffperoxidlösung in 0,7 g Wasser; 1 g Na2CO3 in 6,7 g Wasser und 0,015 g Ascorbinsäure in 2 g Wasser) zugesetzt. Nachdem die Endtemperatur 102°C erreicht war, wurde das entstandene Gel mit einem Fleischwolf zerkleinert und bei 150°C 90 min lang im Umlufttrockenschrank getrocknet. Das getrocknete Polymerisat wurde grob zerstoßen und in einer Retsch Labormühle gemahlen, und daraus dann eine Fraktion mit einer Partikelgröße von 150 bis 850 µm ausgesiebt. 474.5 g of water were placed in a beaker and mixed with 140 g of acrylic acid. A mixture of 1.68 g of polyethylene glycol 300 diacrylate and 2.52 g of allyloxypolyethylene glycol acrylic acid ester and 140 g of acrylic acid was further added to this solution. The solution was cooled to 10 ° C. A total of 217.5 g of 50% sodium hydroxide solution were then added so slowly that the temperature did not exceed 30 ° C. The solution was then flushed with nitrogen at 20 ° C. and further cooled. After the start temperature of 4 ° C. had been reached, the initiator solutions (0.1 g of 2,2'-azobis-2-amidinopropane dihydrochloride in 10 g of water; 0.3 g of sodium peroxydisulfate in 3 g of water; 0.07 g of 30% strength Hydrogen peroxide solution in 0.7 g water; 1 g Na 2 CO 3 in 6.7 g water and 0.015 g ascorbic acid in 2 g water) added. After the final temperature had reached 102 ° C., the gel formed was comminuted with a meat grinder and dried at 150 ° C. for 90 minutes in a forced-air drying cabinet. The dried polymer was roughly crushed and ground in a Retsch laboratory mill, and a fraction with a particle size of 150 to 850 μm was then sieved from it.
Von einer Lösung von 10,00 g Ethylenharnstoff in 23,08 g Wasser wurden jeweils
2,15 g auf 50 g der Polymeren 1, 2 beziehungsweise 3 mittels eines
Haushaltsmixers gleichmäßig aufgetragen. Die derart oberflächlich behandelten Pulver wurden
für 30 min auf 190°C erhitzt und auf diese Weise nachvernetzt. Anschließend
wurden die Absorptionseigenschaften im Vergleich zu den unbehandelten
Polymeren bestimmt:
2.15 g of a solution of 10.00 g of ethylene urea in 23.08 g of water were applied uniformly to 50 g of polymers 1, 2 and 3 by means of a household mixer. The powders treated in this way on the surface were heated to 190 ° C. for 30 minutes and subsequently crosslinked. The absorption properties compared to the untreated polymers were then determined:
Je 50 g der Polymeren 2 und 3 wurden mit 2 g einer Lösung, bestehend aus 0,5 g
Ethylencarbonat und 1,5 g Wasser mittels eines Haushaltsmixers in Kontakt
gebracht und für 30 min bei 190°C nachvernetzt. Die nachvernetzten Polymere
wiesen folgende Absorptionskenndaten auf:
50 g each of the polymers 2 and 3 were brought into contact with 2 g of a solution consisting of 0.5 g of ethylene carbonate and 1.5 g of water by means of a household mixer and post-crosslinked at 190 ° C. for 30 minutes. The post-crosslinked polymers had the following absorption characteristics:
Die Beispiele dokumentieren, dass mit den erfindungsgemäßen Nachvernetzungsmitteln pulverförmige Absorberharze mit ausgezeichnetem Absorptionsvermögen gegen einen äußeren Druck zugänglich sind. The examples document that with the inventive Post-crosslinking agent powdery absorption resins with excellent Absorbance against an external pressure are accessible.
Claims (12)
in der x die Werte 2 oder 3 annehmen kann und R1 und R2 jeweils unabhängig voneinander H oder einen C1- bis C4-Alkylrest darstellen. 1. A method for postcrosslinking in the area of the surface of water-absorbing polymers, in which such a polymer is brought into contact with the solution of a postcrosslinker and the crosslinking reaction is carried out at a temperature in a range from 50 to 300 ° C., characterized in that as Postcrosslinker a cyclic urea of formula I is used
in which x can assume the values 2 or 3 and R 1 and R 2 each independently represent H or a C 1 - to C 4 -alkyl radical.
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2006015729A2 (en) * | 2004-08-04 | 2006-02-16 | Basf Aktiengesellschaft | Method for the secondary crosslinking of water-absorbing polymers with cyclic carbamates and/or cyclic ureas |
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