EP0900259A1 - Solutions aqueuses fortement concentrees de composes quaternaires d'ester - Google Patents

Solutions aqueuses fortement concentrees de composes quaternaires d'ester

Info

Publication number
EP0900259A1
EP0900259A1 EP97921691A EP97921691A EP0900259A1 EP 0900259 A1 EP0900259 A1 EP 0900259A1 EP 97921691 A EP97921691 A EP 97921691A EP 97921691 A EP97921691 A EP 97921691A EP 0900259 A1 EP0900259 A1 EP 0900259A1
Authority
EP
European Patent Office
Prior art keywords
methyl
formula
rco
weight
radical
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.)
Withdrawn
Application number
EP97921691A
Other languages
German (de)
English (en)
Inventor
Oliver Eyrisch
Günther Hertel
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant GmbH filed Critical Clariant GmbH
Publication of EP0900259A1 publication Critical patent/EP0900259A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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

Definitions

  • the invention relates to highly concentrated aqueous solutions of quaternary carboxylic acid alkanolamine ester salts, a process for the preparation of these solutions and their use.
  • Quaternary carboxylic acid alkanolamine ester salts also referred to as ester quats
  • ester quats are highly effective and versatile cationic surfactants.
  • these surfactants are suitable as detergent softeners, basic cosmetic products, active ingredients relating to soil release and redeposition, antistatic agents, finishing agents, biocides and phase transfer catalysts. Because these esterquats due to their biological
  • Degradability are also ecologically advantageous, they have recently replaced the classic fatty alkyl quats such as distearyldimethylammonium chloride.
  • DE-A-37 10 064 describes quaternary ester amines which are obtained by esterification of alkanolamines with glycerides and quaternization (alkylation) of the esterification product with an alkyl halide or alkyl sulfate as concentrated solutions in isopropanol (see Examples 1 to 5).
  • these solutions have the disadvantage that the esterquat compound is not present as such, but instead contains a more or less large amount of glyceride or partial glyceride, and that, in the case of very high concentrations, the fluidity at room temperature leaves something to be desired.
  • CS-B-246 133 and CS-B-264 073 describe the preparation of pastes of ethanolamine ester sulfates in the presence of water. It is claimed that in contrast to the prior art, that is tetraalkylammonium compounds, no dispersions or gels occur.
  • Aqueous compositions of esterquat compounds have now been found which, even with a very high active ingredient content (at room temperature or, if appropriate, higher temperatures), are not paste-like, but rather liquid and free-flowing.
  • the aqueous solutions according to the invention are characterized by a content of at least 70% by weight, based on the solution, of at least one ester quat compound of the formula (1) below
  • RCO is an aliphatic acyl radical with 6 to
  • R ' is a hydrogen atom or a Cj to C 2 2 ⁇ A l k y 1 - rest -'
  • R 1 is a methyl or ethyl radical
  • R 2 is a C j to C 8 alkyl radical
  • R 3 is a C 3 to C 8 alkyl radical
  • X ⁇ is a halide, methyl or ethyl carbonate, methyl or ethyl phosphate or a methyl or ethyl sulfate.
  • Preferred esterquats corresponding to formula (1) are those where RCO is an aliphatic acyl radical having 8 to 18 carbon atoms, R 'is H or CH 3, H, R preferably 1 CH 3, R 2 is a C j to C 4 -alkyl radical and R 3 a Is C 3 or C 4 alkyl and X ⁇ stands for halide or methyl sulfate (methosulfate), preferably for halide.
  • ester quats of the formula (1) have been found to be those in which RCO is an aliphatic acyl radical having 8 to 18 carbon atoms, R 'H and X ⁇ Cl " or CH3OSO 3 -, preferably Cl ⁇ , and R 1 , R 2 and R 3 represents the following alkyl radicals: R 1 methyl, R 2 methyl, R 3 propyl (Esterquat la), R 1 methyl, R 2 methyl, R 3 butyl (Esterquat lb), R 1 methyl, R 2 propyl, R 3 Propyl (Esterquat lc) and R 1 methyl, R 2 butyl, R 3 butyl (Esterquat ld).
  • RCO is an aliphatic acyl radical having 8 to 18 carbon atoms
  • R 1 , R 2 and R 3 represents the following alkyl radicals: R 1 methyl, R
  • the alkyl radicals mentioned for R ', R 1 , R 2 and R 3 can be straight or branched, with preference being given to this.
  • the aliphatic acyl radical is preferably a fatty acyl radical with the stated number of Carbon atoms. It can be saturated or unsaturated (preferably mono- to tri-unsaturated). Examples include the acyl residues of caprylic, capric, lauric, palmitic, stearic and oleic acids, as well as cocosacyl, tallow acyl, preferably hardened tallow acyl, and the like.
  • the fatty acid radical is often a mixture of two or more acyl groups, for example, C 12 and C 14 acyl (C 12/14), C 16 and C 18 acyl (C 16/18) C 12 or C 18 acyl bi ⁇ (C 12 _ 18 ).
  • Preferred solutions according to the invention essentially consist of a) 70 to 98% by weight, preferably 80 to 95% by weight, of at least one compound of the formula (1) and b) water in an amount of 100% by weight,
  • Further preferred solutions according to the invention essentially consist of a) 81 to 98% by weight, preferably 85 to 95% by weight, of at least one compound of the formula (1), where RCO, R 1 , R 1 , R 2 and R 3 have the meanings mentioned and X ⁇ is a methyl or ethyl sulfate, and b) water in the amount to 100 wt .-%, weight percent based on the solution.
  • esterquat solutions according to the invention are prepared by quaternization (alkylation) of carboxylic acid alkanolamine ester compounds of the formula (2) below
  • R- wherein RCO, R ', R 2 - and R 3 have the meanings given, with a quaternizing agent corresponding to the anion X ⁇ in formula (1), preferably with methyl chloride or dimethyl sulfate, in bulk or in the presence of water.
  • the esterification is carried out in a first step and then the esterification product obtained is quaternized.
  • a preferred process according to the invention is therefore characterized in that a) an alkanolamine compound of the formula (3) below
  • RCO has the meaning given, is esterified in bulk to give the carboxylic acid alkanolamine compound and b) the esterification product obtained in step a) is quaternized as described above.
  • Alkanolamines of formula (3) or alkanolamine esters of formula (2) result from the meanings given for formula (1) for R ', R 2 , R 3 and RCO.
  • the conversion of alkanolamine compound and carboxylic acid to the ester compound is carried out in bulk, that is to say in the absence of organic or other solvents.
  • the temperature of the esterification reaction is 100 to 250 ° C, preferably 130 to 200 ° C.
  • the reaction components alkanolamine of the formula (3) and carboxylic acid of the formula (4) are used in a molar ratio of 0.8 to 1.2 mol of carboxylic acid, preferably 1 to 1.05 mol of carboxylic acid, per mol of alkanolamine.
  • Esterification catalysts can be used to accelerate the esterification reaction. Acidic catalysts are preferred, namely hydrohalic acids such as hydrochloric acid; Phosphoric acids such as hypophosphorous acid or orthophosphoric acid; Sulfuric acid and sulfonic acids such as methanesulfonic acid, paratoluenesulfonic acid or dodecylbenzenesulfonic acid. Phosphoric acids and sulfonic acids are preferred.
  • the amount of acidic catalyst is generally 0.05 to 0.5% by weight, based on the weight of the alkanolamine used. Depending on
  • reaction temperature and type of reaction components the reaction will take place without pressure or under the onset of pressure. It is preferred to maintain an inert gas atmosphere, for example nitrogen atmosphere, during the reaction. It is also preferred to remove the water of reaction from the reaction mixture, for example with the aid of an inert gas stream and / or vacuum.
  • the esterification reaction is expediently carried out by gas chromatographic analysis or determination of the acid number. The reaction time is generally in the range of 5 to 15 hours.
  • the esterification product obtained, which is optionally washed with water, is liquid to waxy at room temperature and consists essentially of the desired carboxylic acid alkanolamine ester compound of the formula (2).
  • the quaternization reaction of the process according to the invention is preferably carried out on the esteramine product obtained with the esterification reaction described above. Esteramine products of the formula (2) obtained or commercially available in other ways can also be used.
  • the quaternization can be carried out without solvent or in the presence of water as the solvent, a temperature of 40 to 150 ° C., preferably 50 to 100 ° C., being advantageous.
  • the water is used in such an amount that after the
  • the alkyl halide as the alkylating agent is used in an amount such that a pressure of at most 10 bar is present, preferably from 2 to 8 bar.
  • the other (liquid) alkylating agents such as dimethyl sulfate are used in an amount of 0.8 to 1 mol, preferably 1 mol, per mol of ester amine. It is appropriate that
  • the reaction time is generally 5 to 15 hours.
  • the method according to the invention can be carried out both in batch operation and continuously.
  • the continuous procedure is preferably carried out in at least two, preferably two to three, cascade-shaped Ruhr tanks. It is advantageous to continuously add esteramine and alkylating agent to the first kettle after conversion of esteramine and alkylating agent of about 10 to 30 mol%, based on esteramine, and to adjust the residence time of the product mass in the Ruhr kettles so that the Product from the last kettle has the desired degree of quaternization.
  • the highly concentrated compositions according to the invention are not paste-like, gel-like or dispersion-like; rather, they often represent liquid products which are liquid, low-viscosity and therefore readily flowable (pourable), even at room temperature.
  • esterquat solutions according to the invention with a very high active ingredient content are advantageously suitable wherever cationic surfactants are desired, for example in all the fields of application mentioned at the beginning.
  • Their use according to the invention is preferably in the preparation of detergents and cosmetics.
  • the highly concentrated aqueous esterquat mixtures are also advantageously suitable for the preparation of solid formulations by using them in the usual way
  • Active substance content of 70% by weight, 80% by weight and 90% by weight is prepared by stirring the (melted) esterquat compound according to the invention into the corresponding amount of water at 70 ° C.
  • the three highly concentrated mixtures are at 25 "C and
  • Aqueous solutions of N, N-dibutyl-N-methyl- [1-oxododecyl (tetradecyl) oxyethyl] ammonium chloride with an active substance content of 80% by weight, 90% by weight and 95% by weight are prepared by stirring the ester quat compound according to the invention in the corresponding amount of water at 70 ° C.
  • the three highly concentrated mixtures are visually checked at 25 ° C and 70 "C with regard to their appearance and physical state.
  • An aqueous solution of N, N-diisopropyl-N-methyl- [1-oxododecyl (tetradecyl) oxyethyl] ammonium methosulfate with an active substance content of 90% by weight is prepared by stirring the esterquat compound according to the invention into the corresponding amount of water at 70 ° C. The highly concentrated mixture is visually checked at 70 ° C. with regard to its appearance and physical state.
  • the mixture has a clear appearance and is easy to pour.
  • ester quat compound N N-dipropyl-N-methyl- [1-oxododecyl (tetradecyl) oxyethyl] - ammonium methosulfate used and treated as in Example 4.
  • the mixture has a clear appearance and is easy to pour.
  • Aqueous solutions of N, N-dipropyl-N-methyl- [l-oxododecyl (tetradecyl) oxyethyl] ammonium chloride with an active substance content of 80% by weight and 90% by weight are prepared by stirring the esterquat compound according to the invention into the corresponding amount of water at 70 'C.
  • the two highly concentrated mixtures are visually checked at 25 ° C and 70 ° C with regard to their appearance and physical state.
  • the 90% by weight mixture has a clear appearance at 25 ° C. and 70 ° C. and is easy to pour;
  • Aqueous solutions of N-butyl-N, N-dimethyl- [l-oxododecyl (tetradecyl) oxyethyl] ammonium methosulfate with an active substance content of 80% by weight and 90% by weight are prepared by stirring in the inventive
  • Aqueous solutions of N-butyl-N, N-dimethyl- [l-oxododecyl (tetradecyl) oxyethyl] ammonium chloride with an active substance content of 70% by weight and 80% by weight are prepared by stirring the esterquat compound according to the invention into the corresponding amount of water at 70 "C.
  • the 70% by weight solution is clear and easy to pour at 70 ° C and the 80% by weight solution at 25 and 70 ° C.
  • esterquat compound N N-diethyl-N-methyl- [l-oxododecyl (tetradecyl) oxyethyl] ammonium chloride is used and treated as in Comparative Example 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

Ces solutions de composés quaternaires d'ester contiennent au moins 70 % en poids, par rapport à la solution, d'au moins un composé quaternaire d'ester de formule (I), dans laquelle RCO représente un radical acyle aliphatique avec 6 à 22 atomes de carbone; R' représente H ou un radical alkyle C1-C22; R1 représente un radical méthyle ou éthyle; R2 représente un radical alkyle C¿1?-C8; R?3¿ représente un radical alkyle C¿1?-C8 et X?-¿ représente un halogénure, un carbonate d'alkyle, phosphate d'alkyle ou sulfate d'alkyle, alkyle pouvant représenter méthyle ou éthyle. Ces composés sont produits par quaternisation d'alcanolamine-esters d'acide carboxylique appropriés avec de préférence du chlorure de méthyle ou de sulfate de diméthyle. Les solutions aqueuses décrites s'utilisent de façon avantageuse pour la préparation de détergents et de produits cosmétiques.
EP97921691A 1996-04-25 1997-04-22 Solutions aqueuses fortement concentrees de composes quaternaires d'ester Withdrawn EP0900259A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19616482 1996-04-25
DE19616482A DE19616482A1 (de) 1996-04-25 1996-04-25 Hochkonzentrierte wäßrige Esterquat-Lösungen
PCT/EP1997/002026 WO1997041195A1 (fr) 1996-04-25 1997-04-22 Solutions aqueuses fortement concentrees de composes quaternaires d'ester

Publications (1)

Publication Number Publication Date
EP0900259A1 true EP0900259A1 (fr) 1999-03-10

Family

ID=7792389

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97921691A Withdrawn EP0900259A1 (fr) 1996-04-25 1997-04-22 Solutions aqueuses fortement concentrees de composes quaternaires d'ester

Country Status (7)

Country Link
US (1) US5811385A (fr)
EP (1) EP0900259A1 (fr)
JP (1) JP2000510171A (fr)
AU (1) AU2767197A (fr)
BR (1) BR9709168A (fr)
DE (1) DE19616482A1 (fr)
WO (1) WO1997041195A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1584674B1 (fr) * 2004-03-29 2007-08-15 Clariant Produkte (Deutschland) GmbH Composés d'esters quaternaires concentrés facilement dispersible
US7148256B1 (en) 2004-07-21 2006-12-12 Surfatech Corporation Dimer poly-quaternary ester compounds
US7193111B1 (en) 2004-08-02 2007-03-20 Surfa Tech Corporation Dimer poly-quaternary compounds
US7169313B2 (en) * 2005-05-13 2007-01-30 Endicott Interconnect Technologies, Inc. Plating method for circuitized substrates
US7750044B2 (en) * 2008-04-01 2010-07-06 Surfatech Corporation Dimer poly-quaternary ester compounds
JP5281388B2 (ja) * 2008-12-25 2013-09-04 花王株式会社 液体洗浄剤組成物
DE102010038887A1 (de) * 2010-08-04 2012-02-09 Wacker Chemie Ag β-Ketocarbonylquatverbindungen und Verfahren zu deren Herstellung
US8703981B2 (en) 2012-08-03 2014-04-22 Xerox Corporation Lignosulfonate compounds for solid ink applications
US8741041B2 (en) 2012-08-03 2014-06-03 Xerox Corporation Phase change ink compositions containing lignosulfonate compounds
WO2020011876A1 (fr) 2018-07-11 2020-01-16 Clariant International Ltd Préparation et utilisation d'esterquats de haute qualité à partir d'acides gras de son de riz
WO2022148673A1 (fr) 2021-01-11 2022-07-14 Clariant International Ltd Esterquats hydrogénés à partir d'acides gras de son de riz et leur préparation

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1172652A (fr) * 1979-07-02 1984-08-14 James M. Richmond Agent assouplisseur de tissus, et methode connexe
EP0295739A3 (fr) * 1987-06-09 1990-01-17 The Procter & Gamble Company Méthode pour préparer des compositions biodégradables pour le traitement du linge
US4789491A (en) * 1987-08-07 1988-12-06 The Procter & Gamble Company Method for preparing biodegradable fabric softening compositions
US5066414A (en) * 1989-03-06 1991-11-19 The Procter & Gamble Co. Stable biodegradable fabric softening compositions containing linear alkoxylated alcohols
US5116520A (en) * 1989-09-06 1992-05-26 The Procter & Gamble Co. Fabric softening and anti-static compositions containing a quaternized di-substituted imidazoline ester fabric softening compound with a nonionic fabric softening compound
NZ235490A (en) * 1989-10-16 1993-08-26 Colgate Palmolive Co Fabric-softening compositions
US5427696A (en) * 1992-04-09 1995-06-27 The Procter & Gamble Company Biodegradable chemical softening composition useful in fibrous cellulosic materials
US5447644A (en) * 1994-05-12 1995-09-05 International Flavors & Fragrances Inc. Method of controlling viscosity of fabric softeners
DE19607824A1 (de) * 1996-03-01 1997-09-04 Hoechst Ag Niedrigschmelzende Esterquats

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9741195A1 *

Also Published As

Publication number Publication date
JP2000510171A (ja) 2000-08-08
WO1997041195A1 (fr) 1997-11-06
DE19616482A1 (de) 1997-10-30
BR9709168A (pt) 2000-05-09
US5811385A (en) 1998-09-22
AU2767197A (en) 1997-11-19

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