WO2001000734A1

WO2001000734A1 - Utilization of emulsifiers

Info

Publication number: WO2001000734A1
Application number: PCT/EP2000/005668
Authority: WO
Inventors: Joaquin Bigorra Llosas; Maria Escoda; Rafael Pi Subirana
Original assignee: Cognis Deutschland Gmbh
Priority date: 1999-06-29
Filing date: 2000-06-20
Publication date: 2001-01-04
Also published as: DE19929962C2; EP1189990A1; AU5222100A; DE50001337D1; ES2193084T3; ATE233298T1; EP1189990B1; DE19929962A1

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

Use of emulsifiers

Field of the Invention

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.

State of the art

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. 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

(a) fatty acid amidoamines and

(b) cationic polymers

for the production of aqueous bitumen emulsions.

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.

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. As a rule, the fatty acid amidoamines follow the formula (I)

R ¹ CO-NH. (CH ₂ ) nNR2R3 (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. 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.

Kationpolvmere

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, 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

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.

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.

Examples

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.

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.

Table 1

Bitumen emulsions (quantities as% by weight)

Claims

claims

1. Use of emulsifiers containing

(a) fatty acid amidoamines and

(b) cationic polymers

for the production of aqueous bitumen emulsions.

2. Use according to claim 1, characterized in that fatty acid amidoamines are used which follow the formula (I),

R ¹ CO-NH- (CH ₂ ) _n NR2R3 (|)

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. 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. 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. 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. 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. 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. 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. 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. Use of cation polymers as auxiliaries for the production of bitumen emulsions.