WO1997001528A1 - Procede de production de concentres de betaine aqueux de faible viscosite - Google Patents

Procede de production de concentres de betaine aqueux de faible viscosite Download PDF

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Publication number
WO1997001528A1
WO1997001528A1 PCT/EP1996/002657 EP9602657W WO9701528A1 WO 1997001528 A1 WO1997001528 A1 WO 1997001528A1 EP 9602657 W EP9602657 W EP 9602657W WO 9701528 A1 WO9701528 A1 WO 9701528A1
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WO
WIPO (PCT)
Prior art keywords
carbon atoms
viscosity
acids
weight
acid
Prior art date
Application number
PCT/EP1996/002657
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German (de)
English (en)
Inventor
Günter Uphues
Peter Neumann
Bernd Fabry
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1997001528A1 publication Critical patent/WO1997001528A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/18—Quaternary ammonium compounds

Definitions

  • the invention relates to processes for the production of low-viscosity, storage-stable aqueous betaine concentrates using condensation products of polybasic carboxylic acids with polyamines and the use of these condensates for the production of the concentrates.
  • Betaines or amphoteric surfactants are extremely skin-friendly and have excellent cleaning properties. They are therefore particularly suitable for assembling a large number of surface-active products.
  • their preparation is based on tertiary amines, which are reacted with sodium chloroacetate to form alkyl betaines.
  • the reaction of fatty acid aminoamides or imidazolines with sodium chloroacetate leads to the formation of amphoteric surfactants of the glycinate type; If acrylic acid esters are used as alkylating agents, aminopropionates form. Connections of the type mentioned are described in a large number of overview articles, of which only Parf. Cosm. Aroma. 70, 67 (1986), HAPPI, 70, (Nov. 1986) and Soap Cosm. Chem. Spec. 46, (Apr. 1990).
  • a particular concern in the production of betaines or amphoteric surfactants is to provide products that are as pure as possible and thus dermatologically and toxicologically safe. For example, traces of free are undesirable Amines, chloroacetic acid and especially dichloroacetic acid in the surfactants. Preservatives which are intended to protect betaines or amphoteric surfactants from microbial attack are also often not desired, so that there is a further need for products which are stabilized against germ attack even without the addition of auxiliaries.
  • a third object of the invention was to provide the lightest possible, storage-stable products with a high solids content, preferably in the range from 40 to 60 and a betaine content in the range from 40 to 55% by weight.
  • DE-Al 39 39 264 proposes to reduce the chloroacetic acid content in amphoteric surfactants by subsequently treating the aqueous solutions with ammonia, amino acids or oligopeptides.
  • DE-OS 29 26 479 Th. Goldschmidt
  • a method is known in which the quaternization is carried out in the pH range from 7.5 to 10.5 and thus the residual content of free alkylating agent is minimized.
  • the teaching of DE-A 20 63 424 points in the same direction and describes the pH regulation for the alkylation of imidazolines.
  • DE-C 37 26 322 Th.
  • Goldschmidt describes a process for the after-treatment of betaines, in which mineral acids are added to the substances in amounts such that the pH of the solution is 1 to 4.5. However, these processes have no influence on the content of dichloroacetic acid.
  • DE-Al 42 05 880 Th. Goldschmidt
  • DE-Cl 42 07 386 Th.
  • Goldschmidt contains betaine concentrates with solids contents above 40% by weight, which contain 1 to 3% by weight of free fatty acid and 0 to 4% by weight of glycerol of free amidoamine of less than 1% by weight and having a pH in the range from 5 to 8.
  • the invention relates to a process for the preparation of low-viscosity, aqueous betaine concentrates, in which one first amidates polyvalent carboxylic acids having 2 to 12 carbon atoms with polyamines and then betaines the resulting amides in a manner known per se with halocarboxylic acids or their alkali metal salts.
  • condensation products of polyvalent carboxylic acids with polyamines reduce the viscosity of conventional betaine concentrates and stabilize them - especially in the presence of selected polyols - before gelling.
  • the condensates are preferably betainized together with the tertiary amines or amidoamines.
  • inventive idea also includes the possibility of either reacting mixtures of conventional fatty acids and dicarboxylic acids with polyamines and then betainizing them, or betaines based on the condensates of polyvalent carboxylic acids and polyamines as conventional betaines before, during or after the betainization Add viscosity regulators.
  • Polyvalent carboxylic acids to be used in accordance with the invention have 2 to 12 carbon atoms and 2 to 4 carboxyl groups; one or more hydroxyl groups can also be present in the molecule. They preferably contain 1 to 5 carbon atoms per carboxyl group. Typical examples are succinic acid, glutaric acid, azelaic acid, tartaric acid, malic acid, tartronic acid, citric acid, aconitic acid or sugar acids. The use of adipic acid is particularly preferred. In addition to the acids, their esters with lower alcohols having 1 to 4 carbon atoms can also be used.
  • R 1 and R 2 independently of one another are alkyl groups with 1 to 4 carbon atoms, X for linear or branched alkylene groups with 2 to 4 carbon atoms and n for 0 or numbers from 1 to 5.
  • Typical examples of these are dimethylaminoethylene diamine and especially dimethylaminopropylamine.
  • co-betainization takes place, in which mixtures of condensates of polyvalent carboxylic acids and polyamines are reacted together with “conventional” starting materials for betaines, namely tertiary fatty amines or fatty acid amidoamines with halocarboxylic acids or their salts.
  • Suitable fatty amines follow the formula (JH),
  • R 3 represents an optionally hydroxy-substituted alkyl and / or alkenyl radical having 8 to 22 carbon atoms and R 4 and R 5 independently of one another an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms.
  • Typical examples are dimethyl octylamine, dimethyldecylamine, dimethyldodecylamine, dimethylcetylamine and dimethylstearylamine.
  • Suitable fatty acid amidoamines follow the formula (IH),
  • R 6 CO-N- (CH 2 ) m NR 9 (ÜI) in which R 6 CO for a saturated and / or unsaturated acyl radical having 6 to 22 carbon atoms, R 7 for hydrogen or an alkyl radical with 1 to 4 carbon atoms, R 8 and R 9 independently of one another for an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and m stands for numbers from 2 to 4.
  • Typical examples are condensation products of technical coconut fatty acid with dimethylaminopropylamine.
  • the amides of the dicarboxylic acids and the fatty amines or the fatty acid amdoamines are usually used in a weight ratio of 1:99 to 30:70, preferably 5:95 to 25:75.
  • Halogen carboxylic acids are generally understood to mean chloro- or bromocarboxylic acids with 2 to 4 carbon atoms, preferably chloroacetic or chloropropionic acid.
  • their alkali metal salts preferably the sodium salts, can also be used.
  • the tertiary nitrogen compounds for example a mixture of a coconut fatty acid amidoamine and an adipic acid amidoamine, and sodium chloroacetate
  • the betaine concentrates according to the invention have a solids content of at least 40, preferably from 40 to 60 and in particular from 50 to 58% by weight, based on the concentrates.
  • the active substance content ie the betaine content
  • the proportion of inorganic salts for example sodium chloride, can make up 5 to 10% by weight.
  • the content of free fatty acid aminoamide and soap is usually less than 1.5 and in particular less than 0.8 wt.
  • 0.1 to 3% by weight of a polyol, preferably glycerin, sorbitol or butyl glucoside, can be added.
  • the invention therefore also relates to an analogous process for the preparation of aqueous low-viscosity betaine concentrates, in which mixtures of a) fatty acids of the formula (TV),
  • R 10 CO stands for a saturated and / or unsaturated acyl radical with 6 to 22 carbon atoms
  • Suitable carboxylic acids of the formula (IV) are preferably those having 8 to 18 carbon atoms, for example technical coconut fatty acid.
  • Another object of the invention therefore relates to an analogous process for the production of aqueous low-viscosity betaine concentrates, in which betaines before, during or after the betainization, betaines based on reaction products of polyvalent carboxylic acids with 2 to 12 carbon atoms and polyamines as viscosity regulators in amounts of 1 to 30% by weight, based on the betaine - adds.
  • aqueous betaines according to the invention are also highly concentrated, liquid, stable in storage and have a minimized proportion of undesirable secondary constituents. They are suitable for the production of surface-active agents, in particular cleaning products and hair treatment and care agents, in which they can be present in amounts of 1 to 30, preferably 2 to 10% by weight, based on the agent.
  • Another object of the invention therefore relates to the use of reaction products of polyvalent carboxylic acids with 2 to 12 carbon atoms and polyamines, optionally after alkylation with halocarboxylic acids or their alkali salts as viscosity regulators for the preparation of aqueous low-viscosity betaine concentrates with a betaine content in the range of 40 up to 55% by weight.
  • adipic acid bis-amidoamine Preparation of an adipic acid bis-amidoamine. 510 g (5.0 mol) of dimethylaminopropylamine (DMAP) were placed in a simple stirring / distillation apparatus and 0.8 g of 50% by weight hypophosphorous acid was added. Thereafter, 292 g (2.0 mol) of adipic acid were added over a period of 1 hour while maintaining a temperature range of 80 to 100 ° C. The mixture which was clear at the end of the addition was then stirred at a reaction temperature of 140 to 145 ° C. until the distillate formation had ended. To complete the reaction, the temperature was raised to 200 ° C. At this point in time, the acid number determined for the reaction control was 23.
  • DMAP dimethylaminopropylamine
  • the acid number was reduced to 5.4 by adding a further 30 g (0.3 mol) of DMAP. To remove unreacted amine, stirring was continued for a further hour at a reduced pressure of 15 to 20 mbar. The solid present after cooling was ground to a powder that was easily dissolved in water.
  • the reaction was terminated after a total of 3 hours after the amount of free amino function had dropped below the detection limit of 0.05 mmol / l 00 g was.
  • the amount of base required for pH control was 13.1 g.
  • a pH of 7.0 was adjusted by adding a small amount of hydrochloric acid.
  • Betaines ad 100% by weight b) To destroy mono- and dichloroacetic acid, 365.8 g of the product obtained according to 3a) were treated with 25.2 g of aqueous 37% by weight sodium hydroxide solution - corresponding to a pH of 12.5 in 10% .-% product solution - added and heated for 1 hour at 120 ° C in a pressure-resistant apparatus. After cooling, a pH of 6.8 was set by adding 31.8 g of a 24% by weight hydrochloric acid. The medium-viscosity liquid remained stable and unchanged after standing for several weeks at room temperature.
  • Betaines ad 100% by weight
  • Betaines ad 100% by weight

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de production de concentrés de bétaïne aqueux, selon lequel on amidifie des acides carboxyliques ayant plusieurs valences et comportant entre 2 et 12 atomes de carbone, avec des polyamides et ensuite, on procède à la bétaïnisation des amides résultants, de manière connue, avec des hydracides halogénés ou avec leurs sels alcalins. Cela permet d'obtenir des concentrés stables au stockage et de faible viscosité, avec une teneur en bétaïne comprise entre 40 et 55 % en poids.
PCT/EP1996/002657 1995-06-28 1996-06-19 Procede de production de concentres de betaine aqueux de faible viscosite WO1997001528A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19523477.4 1995-06-28
DE19523477A DE19523477C2 (de) 1995-06-28 1995-06-28 Verfahren zur Herstellung wäßriger, niedrigviskoser Betainkonzentrate

Publications (1)

Publication Number Publication Date
WO1997001528A1 true WO1997001528A1 (fr) 1997-01-16

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WO (1) WO1997001528A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2142266A1 (es) * 1997-02-21 2000-04-01 Kao Corp Procedimiento para la produccion de tensoactivos que contienen un grupo amido.
JP2001247893A (ja) * 2000-03-07 2001-09-14 Kao Corp 増泡剤及び洗浄剤組成物
EP2036882A1 (fr) * 2007-08-23 2009-03-18 Evonik Goldschmidt GmbH Connexions zwitterioniques et leur utilisation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004055549A1 (de) 2004-11-17 2006-05-18 Goldschmidt Gmbh Verfahren zur Herstellung hochkonzentrierter fließfähiger wässriger Lösungen von Betainen

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4227391C1 (de) * 1992-08-19 1993-09-30 Goldschmidt Ag Th Wäßrige Zubereitungen, die Betaine auf Basis polymerer Fettsäuren enthalten
EP0656346A1 (fr) * 1993-12-02 1995-06-07 Witco Surfactants GmbH Procédé pour la préparation des solutions des betaines qui sont fluxables et très concentrés

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2700768B1 (fr) * 1993-01-25 1995-02-24 Rhone Poulenc Chimie Procédé de préparation d'un monoamide alpha-amino omega-ester et procédé de fabrication d'un polyamide.

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4227391C1 (de) * 1992-08-19 1993-09-30 Goldschmidt Ag Th Wäßrige Zubereitungen, die Betaine auf Basis polymerer Fettsäuren enthalten
EP0656346A1 (fr) * 1993-12-02 1995-06-07 Witco Surfactants GmbH Procédé pour la préparation des solutions des betaines qui sont fluxables et très concentrés

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 107, no. 22, 30 November 1987, Columbus, Ohio, US; abstract no. 200975m, YAMAMURA: "Synthesis and properties of alpha,omega-bisamidobetaine-type amphoteric surfactants from long chaim dibasic acids" XP002017347 *
CHEMICAL ABSTRACTS, vol. 112, no. 4, 22 January 1990, Columbus, Ohio, US; abstract no. 22799a, KROB: "Surface-active, low-foaming amino betaines for use in laundry dertergents" XP000154364 *
YAKUGAKU, vol. 36, no. 8, 1987, pages 565 - 570 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2142266A1 (es) * 1997-02-21 2000-04-01 Kao Corp Procedimiento para la produccion de tensoactivos que contienen un grupo amido.
JP2001247893A (ja) * 2000-03-07 2001-09-14 Kao Corp 増泡剤及び洗浄剤組成物
JP4619478B2 (ja) * 2000-03-07 2011-01-26 花王株式会社 増泡剤及び洗浄剤組成物
EP2036882A1 (fr) * 2007-08-23 2009-03-18 Evonik Goldschmidt GmbH Connexions zwitterioniques et leur utilisation
US8138372B2 (en) 2007-08-23 2012-03-20 Evonik Goldschmidt Gmbh Zwitterionic compounds and use thereof

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Publication number Publication date
DE19523477C2 (de) 1997-10-02
DE19523477A1 (de) 1997-01-02

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