EP1189990B1 - Utilization of emulsifiers - Google Patents

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

Field of the Invention

The invention is in the field of bitumen emulsions and relates to new emulsifiers for Production of bitumen emulsions and the use of cation polymers as additives for Production of such preparations.

State of the art

Bitumen is a dark-colored, semi-solid bis obtained from the gentle processing of petroleum hard, meltable, high molecular weight hydrocarbon mixture. Usually it is are colloidal systems, especially brine, which are dark, resinous or in an oily matrix (Maltene) contain carbon-like particles with molar masses in the range of about 300 to 3000, which as asphaltenes be designated. Aqueous bitumen emulsions are mainly used in road construction. As For this purpose, emulsifiers have been diamines, for example N-stearylpropylene diamine, or fatty acid amidoamines, such as. Tallow fatty acid amidopropylamine proved to be suitable. In the manufacture of Bitumen emulsions can basically be divided into two different types of processes: target the bitumen are processed directly on site, one is interested in the fact that the open time, i.e. the time until setting is as short as possible. In practice, this means that the bitumen emulsion on contact break with the fillers as quickly as possible; in this context one speaks of one high breaking speed. In the second case, the bitumen emulsion is produced in the factory, so that conversely, one is currently interested in a large open time so that the bitumen does not Transportes sets. The lowest possible breaking speed is desired here. For characterization The breaking speed of a bitumen emulsion has established a simple test procedure: For this purpose, 100 g of a bitumen emulsion are added under strong shear as long as fillers are until the emulsion breaks, i.e. to separate the water. The fractional index is calculated then from the weight ratio of added filler to emulsion multiplied by a factor of 100. The higher the filler content, the "slower" the emulsion, i.e. the lower the breaking speed. So far, the only way is the breaking speed of a bitumen emulsion roughly controlled by the type of emulsifier and its amount. Accordingly, the task of the present Invention consisted in providing emulsifiers, by means of which the breaking speed can adjust as needed.

A similar task is presented by FR-A-2 525 618, in which the use of an amidoamine as a solution Di- or tricarboxylic acid is proposed as an emulsifier.

Description of the invention

(a) Fettsäureamidoamine, die der Formel (I) folgen, R¹CO-NH-(CH₂)_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
und

(b) Kationpolymere die ausgewählt sind aus der Gruppe, die gebildet wird von quaternierten Hydroxyethylcellulosen, kationischen Stärken, Copolymeren von Diallylammoniumsalzen und Acrylamiden, quatemierten Vinylpyrrolidon/Vinylimidazol-Polymeren, Kondensationsprodukten von Polyglycolen und Aminen, quaternierten Kollagenpolypeptiden, quaternierten Weizenpolypeptiden, Polyethyleniminen, kationischen Siliconpolymeren , Copolymeren der Adipinsäure und Dimethylaminohydroxypropyldiethylentriamin, 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

zur Herstellung von wäßrigen Bitumenemulsionen mit der Maßgabe daß die Fettsäureamidoamine und die Kationpolymere - jeweils bezogen auf den Feststoffgehalt - im Gewichtsverhältnis 95: 5 bis 80 : 20 eingesetzt werden.The invention relates to the use of emulsifiers containing

(a) fatty acid amidoamines which follow the formula (I) , R ¹ CO-NH- (CH ₂ ) _n NR ² R ³ (I) 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
and

(b) Cationpolymers selected from the group consisting of quaternized hydroxyethyl celluloses, cationic starches, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, condensation products of polyglycols and amines, quaternized collagen polypropylene polymers, quaternized polyphenolated polymers, quaternized polyphenidated polymers, quaternized polyesters, quaternized polymers , copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine, copolymers of acrylic acid with dimethyldiallylammonium chloride, Cholinaten, polyaminopolyamides as well as their crosslinked water-soluble polymers, cationic chitin derivatives, condensation products of dihaloalkyls with bis-dialkylamines, cationic guar gum, quaternized ammonium salt polymers, quaternized polyamides based on adipic acid and diethylenetriamine and their mixtures

for the production of aqueous bitumen emulsions with the proviso that the fatty acid amidoamines and the cation polymers - in each case based on the solids content - are used in a weight ratio of 95: 5 to 80:20.

Surprisingly, it was found that the addition of cation polymers to known emulsifiers of the type of fatty acid amidoamines significantly slowed down the breaking rate, so that over the amount of the added polymers the speed can be controlled at will. By the addition of the cationic polymers it is possible, for example, for the same amount of amidoamine emulsifier To change the breaking speed from fast to extremely slow, i.e. the fracture index significantly increase. The invention includes the knowledge that the resulting bitumen emulsions the same solids content have a higher stability, i.e. a slight tendency to sedimentation demonstrate.

fatty acid

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. Typical examples are fatty acid, the fatty acid component from caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, lsotridecansäure, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic and erucic acid and their technical mixtures. For the condensation with the fatty acids, for example, ethylenediamine, N-methylethylenediamine, N, N-dimethylethylenediamine, propylenediamine, N-methylpropylenediamine, N, N-dimethylpropylenediamine, butylenediamine, N-methyl-butylenediamine, N, N, dimethylbutylenediamine, nentylenediamine Methylpentylenediamine, N, N, Dimethylpen-tylenediamine, Hexylenediamine, N-Methylhexylenediamine, N, N, Dimethylhexylenediamine, Heptylenediamine, N-Methylheptylenediamine, N, N, Dimethylheptylenediamine, Octylenediamine, N-Methyloctylenediamine, Naminodiamine, Naminodiamine Methylnonylenediamine, N, N, dimethylnonylenediamine, decylenediamine, N-methyldecylenediamine, N, N, dimethyldecylenediamine and mixtures thereof. It is preferred to use fatty acid amidoamines of the formula (I) in which R ¹ CO is the acyl radical of coconut fatty acid, tallow fatty acid and the partially hydrogenated tallow fatty acid and / or R ² and R ^{3 is} methyl and n is 3.

cationic polymers

Suitable cation polymers are, for example, cationic cellulose derivatives, such as, for example, a quaternized hydroxyethyl cellulose, which is available under the name Polymer JR 400® from Amerchol, cationic starch, copolymers of diallylammonium salts and acrylamides, quaternized vinylpyrrolidone / vinylimidazole polymers, such as, for example, Luviquat® (BASF). condensation products of polyglycols and amines, quaternized collagen polypeptides, for example lauryldimonium hydroxy propyl hydrolyzed collagen (Lamequat®L / Grunau), quaternized wheat polypeptides, polyethyleneimine, cationic silicone polymers, for example, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyl (Cartaretine® / Sandoz), copolymers of 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 chito san, optionally microcrystalline, condensation products of dihaloalkylene, such as dibromobutane with bisdialkylamines, such as bis-dimethylamino-1,3-propane, cationic guar gum, such as 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 the 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 90:10 to 85:15 is preferred.

Industrial applicability

As a rule, the emulsifiers are used in amounts of 0.15 to 1% by weight, based on the bitumen emulsions - used. To prepare the emulsions, the aqueous emulsifier solution is preferably placed and the bitumen from separate tanks in a mixing apparatus in which the homogenization is carried out strong shear occurs. For example, an Ultra-Turrax or a colloid mill are suitable for this purpose. The emulsifiers are usually tempered to 50 to 70 ° C, while the bitumen out For reasons of processability and pumpability, temperatures above 120 and preferably 140 up to 150 ° C. The resulting emulsion usually has a mixing temperature in the range of 60 to 90 ° C.

The addition of cation polymers to bitumen emulsions allows the breaking rate to be controlled, i.e. the setting of a defined fractional 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 an aid to the production 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.

Examples

Example H1 . 540 g (2 mol) of tallow fatty acid and 1 g of hypophosphoric acid were placed in a 1 l three-necked flask equipped with a stirrer, reflux condenser and distillation head at 70 ° C. The temperature was raised to 140 ° C. and then 218 g (2.1 mol) of dimethylaminopropylamine (DAPA) were 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.

Example 2. To prepare the aqueous emulsifier phase, the desired amounts of the amidoamine and the cation polymer (A = acrylamide-diallylammonlumchloride copolymer; B = acrylamide-acrylcholinate copolymer) were dispersed at about 45 ° C. in a water phase, which was obtained by adding hydrochloric acid a pH of 1.5 was set. 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 under strong shear (9,000 rpm) using a colloid mill (temperature of the mixture: 75 ° C). The results are summarized in Table 1. The breakage speed was differentiated between "s" (= fast) and "I" (= slow). 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 treatment for 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.

Claims (5)

1. The use of emulsifiers containing

   (a) fatty acid amidoamines corresponding to formula (I): R¹CO-NH-(CH₂)_nNR²R³   (I) in which R¹CO is a linear or branched, saturated or unsaturated acyl group, R² and R³ independently of one another represent hydrogen or an alkyl group containing 1 to 3 carbon atoms and n is a number of 1 to 10, and

   (b) cationic polymers selected from the group consisting of quaternized hydroxyethyl celluloses, cationic starches, copolymers of diallyl ammonium salts and acrylamides, quaternized vinyl pyrrolidone/vinyl imidazole polymers, condensation products of polyglycols and amines, quaternized collagen polypeptides, quaternized wheat polypeptides, polyethyleneimines, cationic silicone polymers, copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine, copolymers of acrylic acid with dimethyl diallyl ammonium chloride, cholinates, polyaminopolyamides and crosslinked water-soluble polymers thereof, cationic chitin derivatives, condensation products of dihaloalkyls with bis-dialkylamines, cationic guar gum, quaternized ammonium salt polymers, quaternized polyamides based on adipic acid and diethylene triamine and mixtures thereof,

   for the production of aqueous bitumen emulsions, with the proviso that the fatty acid amidoamines and the cationic polymers are used in a ratio by weight of 95:5 to 80:20, based on their solids contents.
2. The use claimed in claim 1, characterized in that fatty acid amidoamines corresponding to formula (I), in which R¹CO is the acyl group of coconut fatty acid, tallow fatty acid and partly hydrogenated fatty acid, are used.
3. The use claimed in at least one of claims 1 to 2, characterized in that fatty acid amidoamines corresponding to formula (I), in which R² and R³ are methyl and n = 3, are used.
4. The use claimed in at least one of claims 1 to 3, characterized in that cationic polymers containing (meth)acrylic acid or amides thereof as monomer or comonomer are used.
5. The use claimed in at least one of claims 1 to 4, characterized in that the emulsifiers are used in quantities of 0.15 to 1% by weight, based on the bitumen emulsions.