DE10017133A1 - Use of polysuccinimide or polyaspartic acid polymers as set retardants for gypsum compositions - Google Patents
Use of polysuccinimide or polyaspartic acid polymers as set retardants for gypsum compositionsInfo
- Publication number
- DE10017133A1 DE10017133A1 DE2000117133 DE10017133A DE10017133A1 DE 10017133 A1 DE10017133 A1 DE 10017133A1 DE 2000117133 DE2000117133 DE 2000117133 DE 10017133 A DE10017133 A DE 10017133A DE 10017133 A1 DE10017133 A1 DE 10017133A1
- Authority
- DE
- Germany
- Prior art keywords
- polymer
- gypsum
- polysuccinimide
- setting
- gypsum compositions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010440 gypsum Substances 0.000 title claims abstract description 24
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims abstract description 23
- 229920000805 Polyaspartic acid Polymers 0.000 title claims description 5
- 108010064470 polyaspartate Proteins 0.000 title claims description 5
- 239000000203 mixture Substances 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000000979 retarding effect Effects 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000003340 retarding agent Substances 0.000 claims 1
- 125000002730 succinyl group Chemical group C(CCC(=O)*)(=O)* 0.000 claims 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 abstract 2
- CKLJMWTZIZZHCS-REOHCLBHSA-N aspartic acid group Chemical group N[C@@H](CC(=O)O)C(=O)O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 abstract 1
- 229960002317 succinimide Drugs 0.000 abstract 1
- 239000011505 plaster Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 8
- 239000011975 tartaric acid Substances 0.000 description 8
- 235000002906 tartaric acid Nutrition 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 1
- PQHYOGIRXOKOEJ-UHFFFAOYSA-N 2-(1,2-dicarboxyethylamino)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)NC(C(O)=O)CC(O)=O PQHYOGIRXOKOEJ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000011507 gypsum plaster Substances 0.000 description 1
- 229940080260 iminodisuccinate Drugs 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
Stuck- und Putzgipse haben eine kurze Abbindezeit. Diese Eigenschaft der relativ kurzen Abbindezeit von Stuck- und Putzgips zwang den Verarbeiter schon früh, Additive zu finden, um an Ort und Stelle größere Mischungen hintereinander, ohne an kurze Taktzeiten gebunden zu sein, verarbeiten zu können.Stucco and plastering plasters have a short setting time. This property of the relatively short The setting time of stucco and plaster of plaster forced the processor to find additives early on, in order to mix larger ones in a row without being tied to short cycle times to be able to process.
Die zur Verzögerung geeigneten Substanzen wurden schon in den dreißiger und vierziger Jahren in der Literatur beschrieben und von verschiedenen Autoren (Kruis und Späth, Benz, Harvey und Neville (vergl. Kunze, R. A.; Thayer, A. G.; Gypsum and Plaster; Cem. Res. Prog. (1986), S. 267-283) erwähnt. Der Verarbeitungszeitraum eines Gipses erstreckt sich zwischen Versteifungsbeginn (VB) und Versteifungsende (VE). Der Abbindeverlauf kann mit Hilfe der frei werdenden Hydratationswärme bestimmt werden (obgleich indirekt und nicht exakt; siehe in Hans-Bertram Fischer, Martin Werner: Hydratationsverhalten von Gipsmischungen, Stuck, Putz, Trockenbau, 9/94 S. 16-22), sowie nach der Vicat-Methode, DIN 1168, Teil 2 oder mit Hilfe von Ultraschallmessungen, in Con. Chem.-Journal, 4. Jahrgang, 3/96.The substances suitable for delay were already in the thirties and forties Years in the literature and by various authors (Kruis and Späth, Benz, Harvey and Neville (see Kunze, R.A .; Thayer, A.G .; Gypsum and Plaster; Cem. Res. Prog. (1986), pp. 267-283). The processing period of a plaster extends between the start of stiffening (VB) and the end of stiffening (VE). The course of setting can be done with The heat of hydration released can be determined (although indirectly and not exactly; see in Hans-Bertram Fischer, Martin Werner: Hydration behavior of Gypsum mixes, stucco, plaster, drywall, 9/94 p. 16-22), and according to the Vicat method, DIN 1168, part 2 or with the help of ultrasonic measurements, in Con. Chem.-Journal, 4. Vintage, 3/96.
Geeignete Abbindeverzögerer schieben also den Versteifungsbeginn hinaus und/bzw. erhöhen die Zeitdifferenz zwischen VE und VB. Derartige Verzögerer sind beispielsweise Kolloidbildner (Celluloseether, Casein, Dextrin) oder amphoter wirkende anorganische Verbindungen (Zink- und Bleioxid) und vor allem Komplexbildner für Calcium bzw. solche, die mit Calcium schwerlösliche Verbindungen bilden, z. B. Phosphate, Phosphonate, Silikofluoride, Borsäure, Borate, Weinsäure, Gluconsäure, Heptonsäure, Citronensäure, Gallussäure, Saccharose, Glucose, Fructose, Äpfelsäure. Der Reproduzierbarkeit wegen, vor allem aber aus Preisgründen, haben in der Praxis fast nur Fruchtsäuren als Verzögerer Verwendung gefunden. Als Abbindeverzögerer für Gips wird zur Zeit hauptsächlich Weinsäure eingesetzt.Suitable retarders delay the start of stiffening and / or. increase the time difference between VE and VB. Such retarders are, for example Colloid formers (cellulose ether, casein, dextrin) or amphoteric inorganic ones Compounds (zinc and lead oxide) and especially complexing agents for calcium or those which form poorly soluble compounds with calcium, e.g. B. phosphates, phosphonates, Silicofluoride, boric acid, borates, tartaric acid, gluconic acid, heptonic acid, citric acid, Gallic acid, sucrose, glucose, fructose, malic acid. For reproducibility, before but mostly for price reasons, in practice almost only have fruit acids as retarders Found use. The main retardant for gypsum is currently Tartaric acid used.
Die mit Weinsäure verarbeiteten Gipse zeigen typischerweise einen flachen Abbindeverlauf und eine große Differenz zwischen VE-VB, was den Bedürfnissen des Anwenders sehr entgegenkommt. Nachteilig ist allerdings die gegenüber polymeren Elektrolyten geringe Verzögerungswirkung hinsichtlich VB. Ein naheliegender Weinsäureersatzstoff - die Zitronensäure - ergibt bei der maschinengerechten Applikation häufig Abbindestörungen und daraus resultierende Reklamationen.The gypsum processed with tartaric acid typically shows a flat setting course and a big difference between VE-VB, which is very user needs accommodates. The disadvantage, however, is the low level compared to polymeric electrolytes Delay effect with regard to VB. An obvious tartaric acid substitute - the Citric acid - often results in binding problems and machine application resulting complaints.
Aus Zement, Kalk und Gips International, Nr. 9/1999, ist es bekannt, die dimere Verbindung,
Imidodisuccinat, bzw. das Natriumsalz Na-IDS gemäß der folgenden Formel
From cement, lime and gypsum international, No. 9/1999, it is known the dimeric compound, imidodisuccinate, or the sodium salt Na-IDS according to the following formula
als Verzögerer für Maschinenputzgipse einzusetzen. Diese Verbindung hat sehr gute Eigenschaften in Bezug auf die Abbindung des Gipses. Der Nachteil bei der Verwendung dieser Verbindung besteht jedoch darin, daß sie zwar sehr gut die Abbindung verzögert, jedoch ein sehr kurzes Verarbeitungsintervall zeigt: Als Verarbeitungsintervall wird die Zeit genannt zwischen Abbindeanfang und Abbindeende. Nur durch Zusatz des bekannten Verzögerers der Weinsäure in Mengen von 0.03 bis 0.04 Gew.-% zur Iminodisuccinat kann dieses Intervall ausgeweitet werden.use as a retarder for machine plastering plasters. This connection has very good ones Properties related to the setting of the plaster. The disadvantage of using it However, this connection is that while it delays the setting very well, however, a very short processing interval shows that time becomes the processing interval named between the beginning and end of the setting. Only by adding the known Retarders of tartaric acid in amounts of 0.03 to 0.04% by weight to iminodisuccinate can this interval can be extended.
Es stellte sich also die Aufgabe, Abbindeverzögerer für Gips- und Gipszubereitungen zu finden, die die Vorteile von Polymeren, nämlich starke Verzögerung von VB, mit denen der Weinsäure, nämlich großes Intervall zwischen VE-VB verbindet und preiswert zugleich sind.The task was therefore to delay the setting of gypsum and gypsum preparations find the advantages of polymers, namely strong retardation of VB with which the Tartaric acid, namely large interval between VE-VB connects and are inexpensive at the same time.
Diese Aufgabe wird durch die Verwendung des in Hauptanspruch genannten Polymeren gelöst und durch die Merkmale der Unteransprüche gefördert. This object is achieved through the use of the polymer mentioned in the main claim solved and promoted by the features of the subclaims.
Die erfindungsgemäßen Polymeren, im folgenden als Polysuccinimid bezeichnet, weisen
folgende wiederkehrende Formeleinheiten auf:
The polymers according to the invention, hereinafter referred to as polysuccinimide, have the following recurring formula units:
in denen R für OH, OLi, ONa, OK und OCa steht.in which R stands for OH, OLi, ONa, OK and OCa.
Je nach Herstellbedingungen und pH-Wert bei der Anwendung überwiegen die ringgeschlossenen oder offenen Einheiten, wobei die im Handel erhältlichen Polyasparaginsäuresalze und das Polysuccinimid aus wirtschaftlichen Gründen bevorzugt sind. Die Verbindungen stellen auf Grund der Herstellungsmethoden Gemische mit unterschiedlichem Gehalt an den verschiedenen Untereinheiten und unterschiedlichen Polymerisationsgrad dar. Durchschnittliche Molekulargewichte liegen zwischen 500 bis über 10.000, bevorzugt 1000 bis 5000.Depending on the manufacturing conditions and pH value during use, the predominate ring-closed or open units, with the commercially available Polyaspartic acid salts and the polysuccinimide are preferred for economic reasons are. The compounds make up mixtures on the basis of the production methods different content of different subunits and different Degree of polymerization. Average molecular weights are between 500 to over 10,000, preferably 1,000 to 5,000.
Die Polymeren wurden der Gipssuspension in einer Menge von 0,01 bis 0,5 Gew.-%, vorzugsweise 0,05 bis 0,2 Gew.-% bezogen auf den Gipsanteil zugefügt, wobei die Menge je nach verwendeter Gipstype (Putzgipse, Estrichgipse, beta-Halbhydrat) und gewünschter Abbindeverzögerung variiert wird. Der Beginn des Versteifens (VB) kann dadurch um bis zu 2 Stunden verschoben werden und die Zeitspanne zwischen Beginn und Ende der Versteifung (VE-VB) auf 20 bis 50 Minuten erhöht werden.The polymers were added to the gypsum suspension in an amount of 0.01 to 0.5% by weight, preferably 0.05 to 0.2 wt .-% based on the gypsum content added, the amount depending depending on the type of plaster used (plaster of Paris, screed plaster, beta hemihydrate) and the desired one Setting delay is varied. The start of stiffening (VB) can be up to 2 hours and the time between the start and end of the stiffening (VE-VB) can be increased to 20 to 50 minutes.
Diese Polymere weisen sehr gute Verzögerungseigenschaften bei den in der Industrie eingesetzten Gipsen- und Gipszubereitungen auf. Polyasparaginsäure bzw. Polysuccinimid sind aus preiswerten Rohstoffen z. B. aus Maleinsäureanhydrid und Ammoniak leicht zugänglich, so z. B. in DE-OS 43 00 020, DE-OS 43 05 368, EP 0 640 641 A1 und DE 197 40 787 A1.These polymers have very good retardation properties in the industry used plaster and plaster preparations. Polyaspartic acid or polysuccinimide are made of inexpensive raw materials such. B. from maleic anhydride and ammonia easily accessible, e.g. B. in DE-OS 43 00 020, DE-OS 43 05 368, EP 0 640 641 A1 and DE 197 40 787 A1.
Polyasparaginsäure bzw. Polysuccinimid wurden bisher als Ausgangsprodukte für Arzneimittel (EP 0 640 641 B1), vor allem aber als Dispergiermittel für Zement, keramische Massen oder Pigmente (DE 198 43 455 A1, DE 197 40 787 A1 und DE 43 00 020 A1) oder als kessselsteinverhindernde Zusammensetzung eingesetzt.Polyaspartic acid or polysuccinimide have so far been the starting products for Medicaments (EP 0 640 641 B1), but especially as a dispersant for cement, ceramic Compositions or pigments (DE 198 43 455 A1, DE 197 40 787 A1 and DE 43 00 020 A1) or used as a scale preventing composition.
Die Verwendung des Polysuccinimids als Abbindeverzögerer für Gips oder Gipszubereitungen ist neu und überraschend.The use of the polysuccinimide as a setting retarder for gypsum or Gypsum preparations are new and surprising.
Für die Messung der Abbindezeit existieren im wesentlichen zwei anerkannte Methoden.There are essentially two recognized methods for measuring the setting time.
- a) Messung nach der Penetrationsmethode, oder Vicat-Methode, enthalten und beschrieben in der DIN 1168, Teil 2, 1975, Baugipse, Anforderungen, Prüfung und Überwachung.a) Measurement according to the penetration method, or Vicat method, included and described in DIN 1168, Part 2, 1975, construction plaster, requirements, testing and monitoring.
- b) Nach der Ultraschallmethode.b) According to the ultrasound method.
Diese Methode beruht auf der Tatsache, daß die Schallgeschwindigkeit in der zu untersuchenden Mischung während des gesamten Hydratationsverlaufes stetig zunimmt. Die Messung ist zerstörungsfrei und kann auch in langen Meßzeiträumen beliebig häufig vorgenommen werden. Gleichzeitig kann auch die Festigkeitsentwicklung beurteilt werden. Es gibt dazu ein entsprechendes Prüfgerät, das mit einer Schallfrequenz von ca. 45 kHz arbeitet, was auch die Messung von inhomogenem Material erlaubt. Die Methode ist in Con. Chem Journal, 2/1996 von J. Balau genau beschrieben. Die Methode findet bereits Anwendung bei der Messung des Abbindeverhaltens von Zementmischungen, in Con. Chem. Journal, 4, 3/1996, von T. Staffel und G. Brix.This method is based on the fact that the speed of sound in the investigating mixture increases steadily during the entire course of hydration. The Measurement is non-destructive and can occur as often as required, even in long measurement periods be made. At the same time, the development of strength can also be assessed. There is a corresponding test device for this, which has a sound frequency of approx. 45 kHz works, which also allows the measurement of inhomogeneous material. The method is in Con. Chem Journal, 2/1996 by J. Balau described in detail. The method already takes place Application in measuring the setting behavior of cement mixtures, in Con. Chem. Journal, 4, 3/1996, by T. Staffel and G. Brix.
In der vorliegenden Erfindung wurde zur Messung des Abbindeverhaltens der Gipse die Ultraschallmethode angewandt.In the present invention, to measure the setting behavior of the gypsum Ultrasound method applied.
Die nachfolgenden Beispiele beschreiben die Vorteile der Erfindung näher.The following examples describe the advantages of the invention in more detail.
Polysuccinimide sind in der Wirksamkeit als Abbindeverzögerer in Gipsmassen besser oder gleich wie Weinsäure. Polysuccinimides are better or less effective in retarding setting in plaster materials same as tartaric acid.
Die Verzögerungswirkung wurde getestet im Vergleich mit Weinsäure und Zitronensäure an Maschinenputz-Gips mit Leitungswasser, bei Fließestrich (Basis: Rauchgasentschwefelungsgips), sowie β-Halbhydrat mit Zusatz von 1% Kalk.The retarding effect has been tested in comparison with tartaric acid and citric acid Machine plaster gypsum with tap water, with flowing screed (basis: Flue gas desulfurization gypsum), as well as beta hemihydrate with the addition of 1% lime.
Die Tabelle 1 enthält die erzielten Messwerte. Zur Beurteilung der verbesserten Wirkung des erfindungsgemäßen Produktes dient die letzte Spalte "Zeitspanne", die die Differenz zwischen Versteifungsbeginn und Versteifungsende angibt. Je größer diese Zeitspanne ist, um so besser ist die verzögernde Wirkung des entsprechenden Produktes.Table 1 contains the measured values achieved. To assess the improved effect of the The product according to the invention serves the last column "time span", which is the difference between Stiffening start and end of stiffening indicates. The longer this period of time, the better is the retarding effect of the corresponding product.
Claims (10)
in denen R für OH, OLi, ONa, OK, OCa steht.1. A process for retarding the setting of gypsum and gypsum preparations, characterized in that an amount of 0.01 to 1 wt .-%, based on the weight of the gypsum, is added to at least one polymer with recurring succinyl units, the polymer repeating units one of the following structures:
in which R stands for OH, OLi, ONa, OK, OCa.
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| DE2000117133 DE10017133B4 (en) | 2000-04-06 | 2000-04-06 | Use of prepolymers for setting retardation of gypsum or gypsum preparations |
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| DE2000117133 DE10017133B4 (en) | 2000-04-06 | 2000-04-06 | Use of prepolymers for setting retardation of gypsum or gypsum preparations |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1193229A3 (en) * | 2000-09-29 | 2002-08-21 | Halliburton Energy Services, Inc. | Method of cementing in subterranean zone |
| WO2002098817A1 (en) * | 2001-06-02 | 2002-12-12 | Henkel Kommanditgesellschaft Auf Aktien | Plaster retarder |
| WO2004094777A1 (en) * | 2003-04-22 | 2004-11-04 | Halliburton Energy Services, Inc | Biodegradable cement retarder compositions and methods of cementing in a subterranean formation |
| WO2006021332A2 (en) | 2004-08-24 | 2006-03-02 | Bk Giulini Gmbh | Method for retarding plaster setting and plaster preparation |
| CN115448631A (en) * | 2022-10-31 | 2022-12-09 | 济宁无内新材料技术研发中心(有限合伙) | An amino acid gypsum retarder with strong alkali resistance |
| CN115490452A (en) * | 2022-10-31 | 2022-12-20 | 济宁无内新材料技术研发中心(有限合伙) | Preparation method of modified protein gypsum retarder |
| CN115677257A (en) * | 2022-10-31 | 2023-02-03 | 济宁无内新材料技术研发中心(有限合伙) | Green efficient gypsum retarder |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016463A1 (en) * | 1991-03-19 | 1992-10-01 | Donlar Corporation | Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor |
| JPH08169741A (en) * | 1994-12-16 | 1996-07-02 | Mitsui Toatsu Chem Inc | Admixture for sustained release cement |
| DE19740787A1 (en) * | 1997-09-17 | 1999-03-18 | Bayer Ag | Process for improving the plasticity of ceramic materials and reversing this effect |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19914367A1 (en) * | 1998-04-17 | 1999-10-21 | Henkel Kgaa | Hydraulic binder compositions based on inorganic hydraulic binder and assistant |
-
2000
- 2000-04-06 DE DE2000117133 patent/DE10017133B4/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992016463A1 (en) * | 1991-03-19 | 1992-10-01 | Donlar Corporation | Polyaspartic acid as a calcium sulfate and a barium sulfate inhibitor |
| JPH08169741A (en) * | 1994-12-16 | 1996-07-02 | Mitsui Toatsu Chem Inc | Admixture for sustained release cement |
| DE19740787A1 (en) * | 1997-09-17 | 1999-03-18 | Bayer Ag | Process for improving the plasticity of ceramic materials and reversing this effect |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1193229A3 (en) * | 2000-09-29 | 2002-08-21 | Halliburton Energy Services, Inc. | Method of cementing in subterranean zone |
| WO2002098817A1 (en) * | 2001-06-02 | 2002-12-12 | Henkel Kommanditgesellschaft Auf Aktien | Plaster retarder |
| WO2004094777A1 (en) * | 2003-04-22 | 2004-11-04 | Halliburton Energy Services, Inc | Biodegradable cement retarder compositions and methods of cementing in a subterranean formation |
| US7166160B2 (en) | 2003-04-22 | 2007-01-23 | Halliburton Energy Services, Inc. | Biodegradable cement retarder compositions and methods of cementing in a subterranean formation |
| WO2006021332A2 (en) | 2004-08-24 | 2006-03-02 | Bk Giulini Gmbh | Method for retarding plaster setting and plaster preparation |
| RU2383507C2 (en) * | 2004-08-24 | 2010-03-10 | Бк Джиулини Гмбх | Method for moderation of gypsum setting and preparations with gypsum |
| CN115448631A (en) * | 2022-10-31 | 2022-12-09 | 济宁无内新材料技术研发中心(有限合伙) | An amino acid gypsum retarder with strong alkali resistance |
| CN115490452A (en) * | 2022-10-31 | 2022-12-20 | 济宁无内新材料技术研发中心(有限合伙) | Preparation method of modified protein gypsum retarder |
| CN115677257A (en) * | 2022-10-31 | 2023-02-03 | 济宁无内新材料技术研发中心(有限合伙) | Green efficient gypsum retarder |
| CN115448631B (en) * | 2022-10-31 | 2023-10-20 | 济宁无内新材料技术研发中心(有限合伙) | Amino acid gypsum retarder with strong alkali resistance |
| CN115677257B (en) * | 2022-10-31 | 2024-01-19 | 济宁无内新材料技术研发中心(有限合伙) | Green efficient gypsum retarder |
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|---|---|
| DE10017133B4 (en) | 2005-09-29 |
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