EP1189990B1 - Utilisation d'emulsifiants - Google Patents

Utilisation d'emulsifiants Download PDF

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Publication number
EP1189990B1
EP1189990B1 EP00936898A EP00936898A EP1189990B1 EP 1189990 B1 EP1189990 B1 EP 1189990B1 EP 00936898 A EP00936898 A EP 00936898A EP 00936898 A EP00936898 A EP 00936898A EP 1189990 B1 EP1189990 B1 EP 1189990B1
Authority
EP
European Patent Office
Prior art keywords
fatty acid
polymers
quaternized
cationic
acid
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.)
Expired - Lifetime
Application number
EP00936898A
Other languages
German (de)
English (en)
Other versions
EP1189990A1 (fr
Inventor
Joaquin Bigorra Llosas
Maria Escoda
Rafael Pi Subirana
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Personal Care and Nutrition GmbH
Original Assignee
Cognis Deutschland GmbH and Co KG
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Filing date
Publication date
Application filed by Cognis Deutschland GmbH and Co KG filed Critical Cognis Deutschland GmbH and Co KG
Publication of EP1189990A1 publication Critical patent/EP1189990A1/fr
Application granted granted Critical
Publication of EP1189990B1 publication Critical patent/EP1189990B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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 Production of bitumen emulsions and the use of cation polymers as additives for Production of such preparations.
  • 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.
  • emulsifiers have been diamines, for example N-stearylpropylene diamine, or fatty acid amidoamines, such as. Tallow fatty acid amidopropylamine proved to be suitable.
  • Bitumen emulsions 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.
  • 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.
  • 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, lsotridecanklare, 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.
  • 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, dimethyln
  • 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.
  • 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).
  • 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-dimethylamin
  • 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.
  • 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.
  • the emulsifiers are used in amounts of 0.15 to 1% by weight, based on the bitumen emulsions - used.
  • 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.
  • a mixing apparatus in which the homogenization is carried out strong shear occurs.
  • 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.
  • bitumen emulsions allow 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.
  • 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.
  • DAPA dimethylaminopropylamine
  • A acrylamide-diallylammonlumchloride copolymer
  • B acrylamide-acrylcholinate copolymer
  • 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 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.

Landscapes

  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Polyamides (AREA)
  • Cosmetics (AREA)

Claims (5)

  1. Utilisation d'agents émulsionnants contenant :
    (a) des d'amidoamines d'acide gras qui répondent à la formule (I) R1 CO-NH-(CH2)n NR2R3 dans laquelle R1CO représente un reste acyle linéaire ou ramifié, saturé ou non saturé, R2 et R3 indépendamment l'un de l'autre représentent de l'hydrogène ou un reste alkyle ayant de 1 à 3 atomes de carbone et n représente des nombres allant de 1 à 10,
    et
    (b) des polymères cationiques choisis dans le groupe formé d'hydroxyéthylcelluloses quaternisées, des amidons cationiques , des copolymères de sels de dialkyl ammonium et d'acrylamides, des polymères de vinylpyrolidone/ vinylimidazole quaternisés, des produits de condensation de polyglycols et d'aminés, des polypeptides de collagène quaternisés, des polypeptides de blé quaternisés, des polyéthylèneimines, des polymères de silicone cationiques, des copolymères d'acide adipique et de diméthylaminohydroxy propyldiéthylènetriamine, des copolymères d'acide acrylique avec le chlorure de diméthyldiallylammonium, des cholinates des polyaminopolyamides, ainsi que de leurs polymères solubles dans l'eau réticulés, des dérivés de chitine cationique, des produits de condensation à base de dihalogénoalkylène avec des bisdialkylamines, de la gomme guar cationique, des polymères de sels d'ammonium quaternisés, des polyamides quaternisés à base d'acide adipique et de diéthylène-triamine, ainsi que de leurs mélanges,
    en vue de la préparation d'émulsions de bitumes aqueuses, avec la restriction que les amidoamines d'acide gras et les polymères de cation à chaque fois rapporté à la teneur en matière solide sont mis en oeuvre dans un rapport en poids de 95 :5 à 80 : 20.
  2. Utilisation d'agents émulsionnants selon la revendication 1,
    caractérisée en ce qu'
    on met en oeuvre des amidoamines d'acide gras de formule (I) dans laquelle R1CO représente le reste acyle des acides gras de coco, des acides gras de suif ainsi que des acides gras de suif partiellement durcis.
  3. Utilisation d'agents émulsionnants selon au moins une des revendications 1 à 2,
    caractérisée en ce qu'
    on met en oeuvre des amidoamines d'acide gras de formule (I) dans laquelle R2 et R3 représentent un méthyle et n représente 3.
  4. Utilisation d'agents émulsionnants selon au moins une des revendications 1 à 3,
    caractérisée en ce qu'
    on met en oeuvre des polymères de cation qui renferment comme monomère ou comme co-monomère de l'acide (méth)acrylique ou leurs amides.
  5. utilisation d'agents émulsionnants selon au moins une des revendications 1 à 4
    caractérisée en ce qu'
    on met en oeuvre les agents émulsionnants en quantités allant de 0,15 à 1 % en poids, rapporté à l'émulsion de bitume.
EP00936898A 1999-06-29 2000-06-20 Utilisation d'emulsifiants Expired - Lifetime EP1189990B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19929962 1999-06-29
DE19929962A DE19929962C2 (de) 1999-06-29 1999-06-29 Verwendung von Emulgatoren
PCT/EP2000/005668 WO2001000734A1 (fr) 1999-06-29 2000-06-20 Utilisation d'emulsifiants

Publications (2)

Publication Number Publication Date
EP1189990A1 EP1189990A1 (fr) 2002-03-27
EP1189990B1 true EP1189990B1 (fr) 2003-02-26

Family

ID=7913055

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00936898A Expired - Lifetime EP1189990B1 (fr) 1999-06-29 2000-06-20 Utilisation d'emulsifiants

Country Status (6)

Country Link
EP (1) EP1189990B1 (fr)
AT (1) ATE233298T1 (fr)
AU (1) AU5222100A (fr)
DE (2) DE19929962C2 (fr)
ES (1) ES2193084T3 (fr)
WO (1) WO2001000734A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2083050A1 (fr) 2008-01-22 2009-07-29 Cognis IP Management GmbH Compositions pour construction de route
US7922802B2 (en) 2005-11-03 2011-04-12 Cognis Ip Management Gmbh PIT emulsions

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10224847B4 (de) * 2002-06-05 2006-04-13 Clariant Gmbh Umsetzungsprodukte aus Mischungen langkettiger Fettsäuren und aliphatischen Diaminen und deren Verwendung
CA2968760C (fr) 2014-12-05 2021-06-22 Akzo Nobel Chemicals International B.V. Stabilisants polymeres pour emulsions bitumineuses
GB201707556D0 (en) 2017-05-11 2017-06-28 Quadrise Int Ltd Oil-in water emulsions
FR3148031A1 (fr) 2023-04-24 2024-10-25 Arkema France Agents stabilisants pour compositions bitumineuses

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1769804C3 (de) * 1967-07-19 1975-09-11 Kao Soap Co., Ltd., Tokio Asphalt-in-Wasser-Emulsion
US4464286A (en) * 1982-04-26 1984-08-07 Westvaco Corporation Cationic bituminous emulsions
DD291330A5 (de) * 1990-01-03 1991-06-27 "Otto Grotewohl" Boehlen,De Verfahren zur brechzeitregulierung nichtionogener und kationaktiver bitumenemulsionen
US5019610A (en) * 1990-10-18 1991-05-28 Sherex Chemical Company, Inc. Process for the production of polymer-modified asphalts and asphalts emulsions
US5242492A (en) * 1991-05-13 1993-09-07 Asphalt Technology & Consulting, Inc. Microsurfacing system
US5362314A (en) * 1992-06-15 1994-11-08 Exxon Chemical Patents, Inc. Additive modified bituminous emulsions
US5328505A (en) * 1992-10-16 1994-07-12 Westvaco Corporation Cationic aqueous bituminous aggregate slurries for hot climates

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7922802B2 (en) 2005-11-03 2011-04-12 Cognis Ip Management Gmbh PIT emulsions
EP2083050A1 (fr) 2008-01-22 2009-07-29 Cognis IP Management GmbH Compositions pour construction de route

Also Published As

Publication number Publication date
DE50001337D1 (de) 2003-04-03
EP1189990A1 (fr) 2002-03-27
AU5222100A (en) 2001-01-31
WO2001000734A1 (fr) 2001-01-04
ES2193084T3 (es) 2003-11-01
ATE233298T1 (de) 2003-03-15
DE19929962A1 (de) 2001-01-11
DE19929962C2 (de) 2002-11-14

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