EP1189990A1 - Utilization of emulsifiers - Google Patents

Utilization of emulsifiers

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Publication number
EP1189990A1
EP1189990A1 EP00936898A EP00936898A EP1189990A1 EP 1189990 A1 EP1189990 A1 EP 1189990A1 EP 00936898 A EP00936898 A EP 00936898A EP 00936898 A EP00936898 A EP 00936898A EP 1189990 A1 EP1189990 A1 EP 1189990A1
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EP
European Patent Office
Prior art keywords
aminophenyl
fatty acid
polymers
use according
quaternized
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Granted
Application number
EP00936898A
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German (de)
French (fr)
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EP1189990B1 (en
Inventor
Joaquin Bigorra Llosas
Maria Escoda
Rafael Pi Subirana
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BASF Personal Care and Nutrition GmbH
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Cognis Deutschland GmbH and Co KG
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Publication of EP1189990A1 publication Critical patent/EP1189990A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • C10L1/328—Oil emulsions containing water or any other hydrophilic phase

Definitions

  • the invention is in the field of bitumen emulsions and relates to new emulsifiers for the production of bitumen emulsions and the use of cation polymers as additives for the production of such preparations.
  • Bitumen is a dark-colored, semi-solid to hard, meltable, high-molecular hydrocarbon mixture obtained during the gentle processing of petroleum. Usually it is a colloidal system, especially brine, in an oily matrix (Maltene) dark, resin or carbon-like particles with molar Contain masses in the range of about 300 to 3000, which are referred to as asphaltenes.
  • Aqueous bitumen emulsions are mainly used in road construction. Diamines, for example N-stearylpropylene diamine, or fatty acid amidoamines, such as, for example, tallow fatty acid amidopropylamine, have proven to be suitable as emulsifiers for this purpose.
  • bitumen emulsions When producing bitumen emulsions, there are basically two different types of processes: If the bitumen is to be processed directly on site, it is important that the open time, ie the time until setting, is as short as possible. In practice, this means that the bitumen emulsion should break as quickly as possible when it comes into contact with the fillers; in this context one also speaks of a high breaking speed. In the second case, the bitumen emulsion is produced in the factory, so that, conversely, one is interested in a large open time so that the bitumen does not set during transport. The lowest possible breaking speed is desired here.
  • a simple test procedure has been established to characterize the breaking speed of a bitumen emulsion: 100 g of a bitumen emulsion are added under strong shear until fillers are added until the emulsion breaks, ie the water separates out. The fracture index is then calculated from the weight ratio of added filler to emulsion multiplied by a factor of 100. The higher the proportion of filler, the "slower" the emulsion, ie the lower the breakage speed. So far, the only possibility is the breakage speed to control a bitumen emulsion roughly by the nature of the emulsifier and its amount, therefore the object of the present invention was to provide emulsifiers which can be used to adjust the breaking rate as required. Description of the invention
  • the invention relates to the use of emulsifiers containing
  • Fatty acid amidoamines are known fatty substances which can be obtained by the relevant processes in organic chemistry. Fatty acids are preferably condensed together with polyvalent amines and the water of reaction is continuously removed from equilibrium. As a rule, the fatty acid amidoamines follow the formula (I)
  • R 1 CO represents a linear or branched, saturated or unsaturated acyl radical
  • R 2 and R 3 independently of one another represent hydrogen or an alkyl radical having 1 to 3 carbon atoms and n represents numbers from 1 to 10.
  • Typical examples are fatty acid, the fatty acid component is nol Listere of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, Li, linolenic acid, eleostearic acid, arachidonic acid, gadoleic , Behenic acid and erucic acid and their technical mixtures.
  • ethylenediamine N-methylethylenediamine, N, N-dimethylethylenediamine, propylenediamine, N-methylpropylenediamine, NN-dimethylpropylenediamine, butylenediamine, N-methyl-butylenediamine, N, N, dimethylbutylenediamine, pentylenediamine, pentylenediamine N, N, dimethylpen-tylenediamine, He- xylenediamine, N-methylhexylenediamine, N, N, dimethylhexylenediamine, heptylenediamine, N-methylheptylenediamine, N, N, dimethylheptylenediamine, octylenediamine, N-methyloctylenediamine, NNDimethyloctylenediamine, nonylenediamine, dimethylnonylenediamine, N-methyl
  • Fatty acid amidoamines of the formula (I) are preferably used, in which R 1 CO represents the acyl radical of coconut fatty acid, tallow fatty acid and partially hydrogenated tallow fatty acid and / or R 2 and R 3 is methyl and n is 3.
  • Suitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole polymers such as e.g. Luviquat® (BASF), condensation products of polyglycols and
  • Amines such as, for example, lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (sand) diethylenetriamine (sand) Acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), cholinates, polyaminopolyamides, as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene len, such as, for example, dibromobutane with bisdialkylamines, such as, for example,
  • the emulsifiers are used in amounts of 0.15 to 1% by weight, based on the bitumen emulsions.
  • the aqueous emulsifier solution and the bitumen from separate tanks are preferably placed in a mixing apparatus in which the homogenization takes place under strong shear.
  • a mixing apparatus for example, an Ultra-Turrax or a colloid mill are suitable for this purpose.
  • the emulsifiers are usually heated to 50 to 70 ° C., while the bitumen has temperatures above 120 and preferably from 140 to 150 ° C. for reasons of processability and pumpability.
  • the resulting emulsion generally has a mixing temperature in the range of 60 to 90 ° C.
  • bitumen emulsions allow the breaking rate to be controlled, ie the setting of a defined breaking index, and leads to an improvement in the stability of the emulsions.
  • Another object of the invention therefore relates to the use of cation polymers as auxiliaries for the preparation of bitumen emulsions in which they - preferably together with fatty acid amidoamines - in amounts of 0.05 to 0.5 and in particular 0.1 to 0.2 wt. -% - based on the emulsions - may be included.
  • Example H 540 g (2 mol) of tallow fatty acid and 1 g of hypophosphoric acid were placed in a 1 liter three-necked flask equipped with a stirrer, reflux condenser and distillation head at 70 ° C. The temperature was raised to 140 ° C. and 218 g (2.1 mol) of dimethylaminopropylamine (DAPA) were then added in portions over the course of 2 hours. The mixture was then kept at 200 ° C. for 3 hours and the water of condensation was continuously separated until the reaction product had an acid number below 5 mg KOH / g. The temperature was then reduced to 160 ° C. and unreacted DAPA was distilled off in vacuo.
  • DAPA dimethylaminopropylamine
  • A acrylamide-diallylammonium chloride copolymer
  • B acrylamide-acrylcholinate copolymer

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Polyamides (AREA)
  • Cosmetics (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to the utilization of emulsifiers containing: (a) fatty acid amidoamines and (b) cationic polymers for the production of aqueous bitumen emulsions.

Description

Verwendung von EmulgatorenUse of emulsifiers
Gebiet der ErfindungField of the Invention
Die Erfindung befindet sich auf dem Gebiet der Bitumenemulsionen und betrifft neue Emulgatoren zur Herstellung von Bitumenemulsionen sowie die Verwendung von Kationpolymeren als Zusatzstoffe zur Herstellung derartiger Zubereitungen.The invention is in the field of bitumen emulsions and relates to new emulsifiers for the production of bitumen emulsions and the use of cation polymers as additives for the production of such preparations.
Stand der TechnikState of the art
Bitumen stellt ein bei der schonenden Aufarbeitung von Erdöl gewonnenes dunkelfarbiges, halbfestes bis springhartes, schmelzbares, hochmolekulares Kohlenwasserstoffgemisch dar. Üblicherweise handelt es sich um kolloide Systeme, speziell Sole, die in einer öligen Grundmasse (Maltene) dunkle, harz- oder kohlenartige Teilchen mit molaren Massen im Bereich etwa 300 bis 3000 enthalten, welche als Asphaltene bezeichnet werden. Wäßrige Bitumenemulsionen werden überwiegend im Straßenbau eingesetzt. Als Emulgatoren haben sich für diesen Zweck Diamine, beispielsweise N-Stearylpropylen-diamin, oder Fett- säureamidoamine, wie z.B. Talgfettsäureamidopropylamin als geeignet erwiesen. Bei der Herstellung von Bitumenemulsionen lassen sich grundsätzlich zwei unterschiedliche Verfahrensformen unterscheiden: Soll der Bitumen vor Ort direkt verarbeitet werden, ist man daran interessiert, daß die offene Zeit, d.h. die Zeit bis zum Abbinden möglichst kurz ist. In der Praxis bedeutet dies, daß die Bitumenemulsion beim Kontakt mit den Füllstoffen möglichst rasch brechen soll; man spricht in diesem Zusammenhang auch von einer hohen Bruchgeschwindigkeit. Im zweiten Fall erfolgt die Herstellung der Bitumenemulsion im Werk, so daß man umgekehrt gerade an einer großen offenen Zeit interessiert ist, damit der Bitumen nicht während des Transportes abbindet. Hier wird also eine möglichst niedrige Bruchgeschwindigkeit gewünscht. Zur Charakterisierung der Bruchgeschwindigkeit einer Bitumenemulsion hat sich ein einfaches Testverfahren etabliert: Hierzu werden 100 g einer Bitumen-emulsion unter starker Scherung solange Füllstoffe zugesetzt, bis es zum Bruch der Emulsion, d.h. zur Abscheidung des Wassers kommt. Der Bruchindex berechnet sich dann aus dem Gewichtsverhältnis von zugesetztem Füllstoff zu Emulsion multipliziert mit dem Faktor 100. Je höher der Füllstoffanteil ist, um so „langsamer" ist die Emulsion, d.h. um so niedriger ist die Bruchgeschwindigkeit. Bislang besteht die einzige Möglichkeit, die Bruchgeschwindigkeit einer Bitumenemulsion grob durch die Art des Emulgators und dessen Menge zu steuern. Demzufolge hat die Aufgabe der vorliegenden Erfindung darin bestanden, Emulgatoren zur Verfügung zu stellen, mit deren Hilfe man die Bruchgeschwindigkeit nach Bedarf einstellen kann. Beschreibung der ErfindungBitumen is a dark-colored, semi-solid to hard, meltable, high-molecular hydrocarbon mixture obtained during the gentle processing of petroleum. Usually it is a colloidal system, especially brine, in an oily matrix (Maltene) dark, resin or carbon-like particles with molar Contain masses in the range of about 300 to 3000, which are referred to as asphaltenes. Aqueous bitumen emulsions are mainly used in road construction. Diamines, for example N-stearylpropylene diamine, or fatty acid amidoamines, such as, for example, tallow fatty acid amidopropylamine, have proven to be suitable as emulsifiers for this purpose. When producing bitumen emulsions, there are basically two different types of processes: If the bitumen is to be processed directly on site, it is important that the open time, ie the time until setting, is as short as possible. In practice, this means that the bitumen emulsion should break as quickly as possible when it comes into contact with the fillers; in this context one also speaks of a high breaking speed. In the second case, the bitumen emulsion is produced in the factory, so that, conversely, one is interested in a large open time so that the bitumen does not set during transport. The lowest possible breaking speed is desired here. A simple test procedure has been established to characterize the breaking speed of a bitumen emulsion: 100 g of a bitumen emulsion are added under strong shear until fillers are added until the emulsion breaks, ie the water separates out. The fracture index is then calculated from the weight ratio of added filler to emulsion multiplied by a factor of 100. The higher the proportion of filler, the "slower" the emulsion, ie the lower the breakage speed. So far, the only possibility is the breakage speed to control a bitumen emulsion roughly by the nature of the emulsifier and its amount, therefore the object of the present invention was to provide emulsifiers which can be used to adjust the breaking rate as required. Description of the invention
Gegenstand der Erfindung ist die Verwendung von Emulgatoren, enthaltendThe invention relates to the use of emulsifiers containing
(a) Fettsäureamidoamine und(a) fatty acid amidoamines and
(b) Kationpolymere(b) cationic polymers
zur Herstellung von wäßrigen Bitumenemulsionen.for the production of aqueous bitumen emulsions.
Überraschenderweise wurde gefunden, daß der Zusatz von Kationpolymeren zu bekannten Emulgatoren vom Typ der Fettsäureamidoamine die Bruchgeschwindigkeit deutlich verzögert, so daß über die Menge der zugesetzten Polymere die Geschwindigkeit nach Belieben gesteuert werden kann. Durch den Zusatz der Kationpolymere ist es beispielsweise möglich, bei gleichem Gehalt an Amidoamin-Emulgator die Bruchgeschwindigkeit von schnell nach extrem langsam zu verändern, d.h. den Bruchindex signifikant zu erhöhen. Die Erfindung schließt dabei die Erkenntnis ein, daß die resultierenden Bitumenemulsionen bei gleichem Feststoffgehalt eine höhere Stabilität aufweisen, d.h. eine geringe Tendenz zur Sedimentation zeigen.Surprisingly, it has been found that the addition of cation polymers to known emulsifiers of the fatty acid amidoamine type significantly delays the breaking rate, so that the rate can be controlled as desired via the amount of the added polymers. By adding the cation polymers, it is possible, for example, to change the breaking rate from fast to extremely slow with the same content of amidoamine emulsifier, i.e. to significantly increase the fracture index. The invention includes the finding that the resulting bitumen emulsions have a higher stability with the same solids content, i.e. show a slight tendency to sedimentation.
Fettsäureamidoaminefatty acid
Fettsäureamidoamine stellen bekannte Fettstoffe dar, die nach den einschlägigen Verfahren der organischen Chemie erhalten werden können. Vorzugsweise werden dabei Fettsäuren zusammen mit mehrwertigen Aminen kondensiert und das Reaktionswasser kontinuierlich aus dem Gleichgewicht entfernt. In der Regel folgen die Fettsäureamidoamine der Formel (I),Fatty acid amidoamines are known fatty substances which can be obtained by the relevant processes in organic chemistry. Fatty acids are preferably condensed together with polyvalent amines and the water of reaction is continuously removed from equilibrium. As a rule, the fatty acid amidoamines follow the formula (I)
R1CO-NH.(CH2)nNR2R3 (I)R 1 CO-NH. (CH 2 ) nNR2R3 (I)
in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest, R2 und R3 unabhängig voneinander für Wasserstoff oder einen Alkylrest mit 1 bis 3 Kohlenstoffatomen und n für Zahlen von 1 bis 10 steht. Typische Beispiele sind Fettsäureamidoamine, deren Fettsäurekomponente sich von Capronsäure, Caprylsäure, 2-Ethylhexansäure, Caprinsäure, Laurinsäure, Isotridecansäure, Myristinsäure, Palmitinsäure, Palmoleinsäure, Stearinsäure, Isostearinsäure, Ölsäure, Elaidinsäure, Petroselinsäure, Li- nolsäure, Linolensäure, Elaeostearinsäure, Arachinsäure, Gadoleinsäure, Behensäure und Erucasäure sowie deren technische Mischungen ableiten. Für die Kondensation mit den Fettsäuren kommen beispielsweise Ethylendiamin, N-Methylethylendiamin, N,N-Dimethylethylendiamin, Propylendiamin, N- Methylpropylendiamin, N.N-Dimethylpropylendiamin, Butylendiamin, N-Methyl-butylendiamin, N,N,Dimethylbutylendiamin, Pentylendiamin, N-Metyhlpentylendiamin, N,N,Dimethylpen-tylendiamin, He- xylendiamin, N-Methylhexylendiamin, N,N,Dimethylhexylendiamin, Heptylendiamin, N- Methylheptylendiamin, N,N,Dimethylheptylendiamin, Octylendiamin, N-Methyloctylendiamin, N.N.Dime- thyloctylendiamin, Nonylendiamin, N-Methylnonylendiamin, N,N,Dimethylnonylendiamin, Decylen-diamin, N-Methyldecylendiamin, N,N,Dimethyldecylendiamin sowie deren Gemische. Vorzugsweise setzt man Fettsäureamidoamine der Formel (I) ein, in der R1CO für den Acylrest der Kokosfettsäure, der Taigfettsäure sowie der teilgehärteten Taigfettsäure und/oder R2 und R3 für Methyl und n für 3 steht.in which R 1 CO represents a linear or branched, saturated or unsaturated acyl radical, R 2 and R 3 independently of one another represent hydrogen or an alkyl radical having 1 to 3 carbon atoms and n represents numbers from 1 to 10. Typical examples are fatty acid, the fatty acid component is nolsäure of caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, Li, linolenic acid, eleostearic acid, arachidonic acid, gadoleic , Behenic acid and erucic acid and their technical mixtures. For the condensation with the fatty acids there are, for example, ethylenediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, propylenediamine, N-methylpropylenediamine, NN-dimethylpropylenediamine, butylenediamine, N-methyl-butylenediamine, N, N, dimethylbutylenediamine, pentylenediamine, pentylenediamine N, N, dimethylpen-tylenediamine, He- xylenediamine, N-methylhexylenediamine, N, N, dimethylhexylenediamine, heptylenediamine, N-methylheptylenediamine, N, N, dimethylheptylenediamine, octylenediamine, N-methyloctylenediamine, NNDimethyloctylenediamine, nonylenediamine, dimethylnonylenediamine, N-methylaminodiamine N-methyldecylenediamine, N, N, dimethyldecylenediamine and mixtures thereof. Fatty acid amidoamines of the formula (I) are preferably used, in which R 1 CO represents the acyl radical of coconut fatty acid, tallow fatty acid and partially hydrogenated tallow fatty acid and / or R 2 and R 3 is methyl and n is 3.
KationpolvmereKationpolvmere
Geeignete Kationpolymere sind beispielsweise kationische Cellulosederivate, wie z.B. eine quaternierte Hydroxyethylcellulose, die unter der Bezeichnung Polymer JR 400® von Amerchol erhältlich ist, kationische Stärke, Copolymere von Diallylammoniumsalzen und Acrylamiden, quaternierte Vinylpyrroli- don/Vinylimidazol-Polymere, wie z.B. Luviquat® (BASF), Kondensationsprodukte von Polyglycolen undSuitable cationic polymers are, for example, cationic cellulose derivatives, e.g. a quaternized hydroxyethyl cellulose available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone / vinyl imidazole polymers such as e.g. Luviquat® (BASF), condensation products of polyglycols and
Aminen, quaternierte Kollagenpolypeptide, wie beispielsweise Lauryldimonium hydroxy propyl hydro- lyzed collagen (Lamequat®L/Grünau), quaternierte Weizenpolypeptide, Polyethylenimin, kationische Siliconpolymere, wie z.B. Amidomethicone, Copolymere der Adipinsäure und Dimethylaminohydroxypro- pyldiethylentriamin (Cartaretine®/Sandoz), Copolymere der Acrylsäure mit Dimethyldiallylammo-nium- chlorid (Merquat® 550/Chemviron), Cholinaten, Polyaminopolyamide, wie z.B. beschrieben in der FR 2252840 A sowie deren vernetzte wasserlöslichen Polymere, kationische Chitinderivate wie beispielsweise quaterniert.es Chitosan, gegebenenfalls mikrokristallin verteilt, Kondensationsprodukte aus Dihalogenalky- len, wie z.B. Dibrombutan mit Bisdialkylaminen, wie z.B. Bis-Dimethylamino-1 ,3-propan, kationischer Guar- Gum, wie z.B. Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 der Firma Celanese, quaternierte Ammoniumsalz-Polymere, wie z.B. Mirapol® A-15, Mirapol® AD-1 , Mirapol® AZ-1 der Firma Miranol. Ferner können auch Polymere auf Basis von Adipinsäure und Diethylentriamin eingesetzt werden, welche mit Dimethylsulfat oder Methylchlorid quatemiert und unter der Bezeichnung Fibrabon® im Handel erhältlich sind. Vorzugsweise setzt man Kationpolymere ein, die als Monomer oder Co-Monomer Acrylsäure und/oder Methacrylsäure oder deren Amide enthalten. Im Sinne der Erfindung ist es möglich, die Fettsäureamidoamine und die Kationpolymere - jeweils bezogen auf den Feststoffgehalt - im Gewichtsverhältnis 99,9 : 0,1 bis 50 : 50 einzusetzen. Die Einsatzmenge der Kationpolymere richtet sich danach, welche Bruchgeschwindigkeit eingestellt werden soll. Dabei gilt es zu beachten, daß die Geschwindigkeit mit der Menge der Kationpolymere in erster Näherung abnimmt. Eine deutliche Beeinflussung der Bruchgeschwindigkeit beobachtet man bei einem Einsatzverhältnis von 95 : 5, während oberhalb eines Verhältnisses 80 : 20 der Effekt abzuklingen beginnt. Der Einsatzbereich 95 : 5 bis 80 : 20 und insbesondere 90 : 10 bis 85 : 15 ist daher besonders bevorzugt. Gewerbliche AnwendbarkeitAmines, quaternized collagen polypeptides, such as, for example, lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat®L / Grünau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, such as, for example, amidomethicones, copolymers of adipic acid and dimethylaminohydroxypropyldiethylenetriamine (sand) diethylenetriamine (sand) Acrylic acid with dimethyldiallylammonium chloride (Merquat® 550 / Chemviron), cholinates, polyaminopolyamides, as described, for example, in FR 2252840 A and their crosslinked water-soluble polymers, cationic chitin derivatives such as, for example, quaternized chitosan, optionally microcrystalline, condensation products from dihaloalkylene len, such as, for example, dibromobutane with bisdialkylamines, such as, for example, bis-dimethylamino-1, 3-propane, cationic guar gum, such as, for example, Jaguar® CBS, Jaguar® C-17, Jaguar® C-16 from Celanese, quaternized ammonium salt polymers , such as Mirapol® A-15, Mirapol® AD-1, Mirapol® AZ-1 from Miranol. It is also possible to use polymers based on adipic acid and diethylenetriamine, which are quaternized with dimethyl sulfate or methyl chloride and are commercially available under the name Fibrabon®. Cation polymers are preferably used which contain acrylic acid and / or methacrylic acid or their amides as monomer or co-monomer. In the sense of the invention it is possible to use the fatty acid amidoamines and the cation polymers - in each case based on the solids content - in a weight ratio of 99.9: 0.1 to 50:50. The amount of cation polymers used depends on the breaking rate to be set. It should be noted that the speed decreases with the amount of cation polymers in a first approximation. A marked influence on the breaking speed is observed at an operating ratio of 95: 5, while above a ratio of 80:20 the effect begins to subside. The application range 95: 5 to 80: 20 and in particular 90: 10 to 85: 15 is therefore particularly preferred. Industrial applicability
In der Regel werden die Emulgatoren in Mengen von 0,15 bis 1 Gew.-% - bezogen auf die Bitumenemulsionen - eingesetzt. Zur Herstellung der Emulsionen legt man vorzugsweise die wäßrige Emulgatorlö- sung und den Bitumen aus separaten Tanks in eine Mischapparatur vor, in der die Homogenisierung unter starker Scherung erfolgt. Für diesen Zweck eignen sich beispielsweise ein Ultra-Turrax oder eine Kolloidmühle. Die Emulgatoren werden üblicherweise auf 50 bis 70 °C temperiert, während der Bitumen aus Gründen der Verarbeitbar- und Pumpbarkkeit Temperaturen oberhalb von 120 und vorzugsweise von 140 bis 150 °C aufweist. Die resultierende Emulsion weist in der Regel eine Mischtemperatur im Bereich von 60 bis 90 °C auf.As a rule, the emulsifiers are used in amounts of 0.15 to 1% by weight, based on the bitumen emulsions. To prepare the emulsions, the aqueous emulsifier solution and the bitumen from separate tanks are preferably placed in a mixing apparatus in which the homogenization takes place under strong shear. For example, an Ultra-Turrax or a colloid mill are suitable for this purpose. The emulsifiers are usually heated to 50 to 70 ° C., while the bitumen has temperatures above 120 and preferably from 140 to 150 ° C. for reasons of processability and pumpability. The resulting emulsion generally has a mixing temperature in the range of 60 to 90 ° C.
Der Zusatz von Kationpolymeren zu Bitumenemulsionen erlaubt die Kontrolle der Bruchgeschwindigkeit, d.h. die Einstellung eines definierten Bruchindizes, und führt zu einer Verbesserung der Stabilität der Emulsionen. Ein weiterer Gegenstand der Erfindung betrifft daher die Verwendung von Kationpolymeren als Hilfsmittel zur Herstellung von Bitumenemulsionen, in denen sie - vorzugsweise zusammen mit Fett- säureamidoaminen - in Mengen von 0,05 bis 0,5 und insbesondere 0,1 bis 0,2 Gew.-% - bezogen auf die Emulsionen - enthalten sein können. The addition of cation polymers to bitumen emulsions allows the breaking rate to be controlled, ie the setting of a defined breaking index, and leads to an improvement in the stability of the emulsions. Another object of the invention therefore relates to the use of cation polymers as auxiliaries for the preparation of bitumen emulsions in which they - preferably together with fatty acid amidoamines - in amounts of 0.05 to 0.5 and in particular 0.1 to 0.2 wt. -% - based on the emulsions - may be included.
BeispieleExamples
Beispiel H1. In einem 1-l-Dreihalskolben mit Rührer, Rückflußkühler und Destillationsaufsatz wurden bei 70 °C 540 g (2 Mol) Taigfettsäure und 1 g Hypophosphorsäure vorgelegt. Die Temperatur wurde bis auf 140 CC gesteigert und dann innerhalb von 2 h portionsweise 218 g (2,1 Mol) Dimethylaminopropyl-amin (DAPA) zugegeben. Anschließend wurde die Mischung 3 h bei 200 CC gehalten und das Kondensationswasser kontinuierlich abgetrennt, bis das Reaktionsprodukt eine Säurezahl unter 5 mg KOH/g aufwies. Danach wurde die Temperatur auf 160 °C zurückgenommen und nicht umgesetztes DAPA im Vakuum abdestilliert.Example H1. 540 g (2 mol) of tallow fatty acid and 1 g of hypophosphoric acid were placed in a 1 liter three-necked flask equipped with a stirrer, reflux condenser and distillation head at 70 ° C. The temperature was raised to 140 ° C. and 218 g (2.1 mol) of dimethylaminopropylamine (DAPA) were then added in portions over the course of 2 hours. The mixture was then kept at 200 ° C. for 3 hours and the water of condensation was continuously separated until the reaction product had an acid number below 5 mg KOH / g. The temperature was then reduced to 160 ° C. and unreacted DAPA was distilled off in vacuo.
Beispiel 2. Zur Herstellung der wäßrigen Emulgatorphase wurden die gewünschten Mengen des Amido- amins und des Kationpolymers (A = Acrylamid-Diallylammoniumchlorid-Copolymer; B = Acrylamid- Acrylcholinat-Copolymer) bei etwa 45 °C in einer Wasserphase dispergiert, die durch Zugabe von Salzsäure auf einen pH-Wert von 1 ,5 eingestellt wurde. Die Herstellung der Bitumenemulsionen erfolgte dann in einer Pilotanlage der Firma Atomix. Hierzu wurden die wäßrigen Emulgatoren (56 °C) und der Bitumen (140 °C) in zwei verschiedenen Tanken vorgelegt und unter starker Scherung (9.000 Upm) mit Hilfe einer Kolloidmühle kontinuierlich vermischt (Temperatur der Mischung : 75 °C). Die Ergebnisse sind in Tabelle 1 zusammengefaßt. Bei der Bruchgeschwindigkeit wurde zwischen „s" (= schnell) und „I" (= langsam) unterschieden. In der Zeile „Füllstoffmenge" ist die Menge Füllstoff angegeben, die der Emulsion bis zum Bruch zugesetzt werden konnte. Der Trockenrückstand der Emulsionen wurde nach einer Behandlung von 2 h bei 105 °C und 1 h bei 163 °C bestimmt. Die Beispiele 1 bis 8 sind erfindungsgemäß, Beispiel V1 dient zum Vergleich.Example 2. To prepare the aqueous emulsifier phase, the desired amounts of the amido amine and the cation polymer (A = acrylamide-diallylammonium chloride copolymer; B = acrylamide-acrylcholinate copolymer) were dispersed at about 45 ° C. in a water phase, which by adding Hydrochloric acid was adjusted to a pH of 1.5. The bitumen emulsions were then produced in a pilot plant from the Atomix company. For this purpose, the aqueous emulsifiers (56 ° C) and the bitumen (140 ° C) were placed in two different tanks and continuously mixed with strong shear (9,000 rpm) using a colloid mill (temperature of the mixture: 75 ° C). The results are summarized in Table 1. A distinction was made between "s" (= fast) and "I" (= slow) at the breaking speed. The line “amount of filler” indicates the amount of filler that could be added to the emulsion until it broke. The dry residue of the emulsions was determined after a treatment of 2 h at 105 ° C. and 1 h at 163 ° C. Examples 1 to 8 are according to the invention, Example V1 is used for comparison.
Tabelle 1Table 1
Bitumenemulsionen (Mengenangaben als Gew.-%)Bitumen emulsions (quantities as% by weight)

Claims

Patentansprüche claims
1. Verwendung von Emulgatoren, enthaltend1. Use of emulsifiers containing
(a) Fettsäureamidoamine und(a) fatty acid amidoamines and
(b) Kationpolymere(b) cationic polymers
zur Herstellung von wäßrigen Bitumenemulsionen.for the production of aqueous bitumen emulsions.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, daß man Fettsäureamidoamine einsetzt, die der Formel (I) folgen,2. Use according to claim 1, characterized in that fatty acid amidoamines are used which follow the formula (I),
R1CO-NH-(CH2)nNR2R3 (|)R 1 CO-NH- (CH 2 ) n NR2R3 (|)
in der R1CO für einen linearen oder verzweigten, gesättigten oder ungesättigten Acylrest, R2 und R3 unabhängig voneinander für Wasserstoff oder einen Alkylrest mit 1 bis 3 Kohlenstoffatomen und n für Zahlen von 1 bis 10 steht.in which R 1 CO represents a linear or branched, saturated or unsaturated acyl radical, R 2 and R 3 independently of one another represent hydrogen or an alkyl radical having 1 to 3 carbon atoms and n represents numbers from 1 to 10.
3. Verwendung nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß man Fettsäureamidoamine der Formel (I) einsetzt, in der R1CO für den Acylrest der Kokosfettsäure, der Taigfettsäure sowie der teilgehärteten Taigfettsäure steht.3. Use according to claims 1 and / or 2, characterized in that fatty acid amidoamines of the formula (I) are used in which R 1 CO represents the acyl radical of coconut fatty acid, tallow fatty acid and partially hardened tallow fatty acid.
4. Verwendung nach mindestens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man Fettsäureamidoamine der Formel (I) einsetzt, in der R2 und R3 für Methyl und n für 3 steht.4. Use according to at least one of claims 1 to 3, characterized in that fatty acid amidoamines of the formula (I) are used in which R 2 and R 3 are methyl and n is 3.
5. Verwendung nach mindestens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß man Kationpolymere einsetzt, die ausgewählt sind aus der Gruppe, die gebildet wird von quaternierten Hy- droxyethylcellulosen, kationischen Stärken, Copolymeren von Diallylammoniumsalzen und Acrylami- den, quaternierten Vinylpyrrolidon/Vinylimidazol-Polymeren, Kondensationsprodukten von Poly- glycolen und Aminen, quaternierten Kollagenpolypeptiden, quaternierten Weizenpolypeptiden, Po- lyethyleniminen, kationischen Siliconpolymeren , Copolymeren der Adipinsäure und Dimethyla- minohydroxypropyldiethylentriamin, Copolymeren der Acrylsäure mit Dimethyldiallylammoniumchlorid, Cholinaten, Polyaminopolyamiden sowie deren vernetzten wasserlöslichen Polymeren, kationischen Chitinderivaten, Kondensationsprodukten aus Dihalogenalkylen mit Bisdialkylaminen, kationischem Guar-Gum, quaternierten Ammoniumsalz-Polymeren, quaternierte Polyamide auf Basis von Adipinsäure und Diethylentriamin sowie deren Gemischen. 5. Use according to at least one of claims 1 to 4, characterized in that cation polymers are used which are selected from the group formed by quaternized hydroxyethyl celluloses, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / Vinylimidazole polymers, condensation products of polyglycols and amines, quaternized collagen polypeptides, quaternized wheat polypeptides, polyethylenimines, cationic silicone polymers, copolymers of adipic acid and dimethylaaminohydroxypropyldiethylenetriamine, copolymers of acrylic acid with dimethyldiallylamidonidene, polyethylenephenol aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyl aminophenyls , Condensation products from dihaloalkylene with bisdialkylamines, cationic guar gum, quaternized ammonium salt polymers, quaternized polyamides based on adipic acid and diethylenetriamine and their mixtures chen.
6. Verwendung nach mindestens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man Kationpolymere einsetzt, die als Monomer oder Co-Monomer (Meth-)Acrylsäure oder deren Amide enthalten.6. Use according to at least one of claims 1 to 5, characterized in that cation polymers are used which contain (meth) acrylic acid or its amides as a monomer or co-monomer.
7. Verwendung nach mindestens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß man die Fettsäureamidoamine und die Kationpolymere - jeweils bezogen auf den Feststoffgehalt - im Gewichtsverhältnis 99,9 : 0,1 bis 50 : 50 einsetzt.7. Use according to at least one of claims 1 to 6, characterized in that the fatty acid amidoamines and the cation polymers - each based on the solids content - in a weight ratio of 99.9: 0.1 to 50:50.
8. Verwendung nach mindestens einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß man die Fettsäureamidoamine und die Kationpolymere - jeweils bezogen auf den Feststoffgehalt - im Gewichtsverhältnis 95 : 5 bis 80 : 20 einsetzt.8. Use according to at least one of claims 1 to 7, characterized in that the fatty acid amidoamines and the cation polymers - each based on the solids content - in a weight ratio of 95: 5 to 80:20.
9. Verwendung nach mindestens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß man die Emulgatoren in Mengen von 0,15 bis 1 Gew.-% - bezogen auf die Bitumenemulsionen - einsetzt.9. Use according to at least one of claims 1 to 8, characterized in that the emulsifiers are used in amounts of 0.15 to 1% by weight, based on the bitumen emulsions.
10. Verwendung von Kationpolymeren als Hilfsstoffe zur Herstellung von Bitumenemulsionen. 10. Use of cation polymers as auxiliaries for the production of bitumen emulsions.
EP00936898A 1999-06-29 2000-06-20 Utilization of emulsifiers Expired - Lifetime EP1189990B1 (en)

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DE10224847B4 (en) * 2002-06-05 2006-04-13 Clariant Gmbh Reaction products of mixtures of long-chain fatty acids and aliphatic diamines and their use
EP1783173B1 (en) 2005-11-03 2010-08-25 Cognis IP Management GmbH PIT emulsions
EP2083050A1 (en) 2008-01-22 2009-07-29 Cognis IP Management GmbH Compositions for road contruction
BR112017011254A2 (en) 2014-12-05 2018-04-03 Akzo Nobel Chemicals Int Bv water bitumen emulsion composition, water bitumen emulsion, surface paving application method, and additive composition suitable for use with a mixture of bitumen material and aggregates
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US4464286A (en) * 1982-04-26 1984-08-07 Westvaco Corporation Cationic bituminous emulsions
DD291330A5 (en) * 1990-01-03 1991-06-27 "Otto Grotewohl" Boehlen,De PROCESS FOR BREAKING TIME REGULATION OF NONIONOGENIC AND CATIONACTIVE BITUMENE EMULSIONS
US5019610A (en) * 1990-10-18 1991-05-28 Sherex Chemical Company, Inc. Process for the production of polymer-modified asphalts and asphalts emulsions
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ES2193084T3 (en) 2003-11-01

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