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WO1993010897A1 - Procede de fabrication de phosphates alcalino-terreux hydrophobes - Google Patents

Procede de fabrication de phosphates alcalino-terreux hydrophobes Download PDF

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Publication number
WO1993010897A1
WO1993010897A1 PCT/EP1992/002632 EP9202632W WO9310897A1 WO 1993010897 A1 WO1993010897 A1 WO 1993010897A1 EP 9202632 W EP9202632 W EP 9202632W WO 9310897 A1 WO9310897 A1 WO 9310897A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkaline earth
earth metal
metal phosphates
fatty acids
acid
Prior art date
Application number
PCT/EP1992/002632
Other languages
German (de)
English (en)
Inventor
Wolfgang Breuer
Ansgar Behler
Hans-Christian Raths
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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 Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP92923729A priority Critical patent/EP0618841A1/fr
Publication of WO1993010897A1 publication Critical patent/WO1993010897A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
    • B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/04—Formation or introduction of functional groups containing oxygen of ether, acetal or ketal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/02—Preparation of ethers from oxiranes
    • C07C41/03—Preparation of ethers from oxiranes by reaction of oxirane rings with hydroxy groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/48—Ring-opening reactions

Definitions

  • the invention relates to hydrophobized alkaline earth metal phosphates obtainable by reacting alkaline earth metal phosphates with fatty acids, a process for their preparation and their use as catalysts for the alkoxylation of compounds with active oxygen atoms and fatty acid esters.
  • German Patent Application DE 38 43 713 AI and US Pat. No. 4,962,237 describe processes for the alkoxylation of compounds with active hydrogen atoms which are carried out in the presence of hydrotalcites.
  • the hydrotalcites must first be converted into a calcined ("activated") form suitable for catalytic purposes by heating at temperatures from 400 to 600 ° C. for several hours.
  • the narrowing of the homolog distribution of the nonionic surfactants obtainable by this process can be regarded as satisfactory, the preparation of the catalyst, particularly with regard to the calcination, is associated with a high expenditure of energy and time and is therefore disadvantageous.
  • calcined compounds are susceptible to traces of water and the carbon dioxide in the air (back-reaction of the calcination), so that their area of application and their storage stability are limited as a result of the loss of activity.
  • sparingly soluble alkaline earth metal phosphates are also suitable as heterogeneous catalysts for the alkoxylation.
  • the narrowing of the homogeneous distribution achieved with them is not sufficient for a number of fields of application.
  • the object of the invention was therefore to develop new heterogeneous alkoxylation catalysts which are free from the disadvantages described.
  • the invention relates to a process for the preparation of hydrophobized alkaline earth metal phosphates, which is characterized in that alkaline earth metal phosphates are reacted with fatty acids.
  • Alkaline earth metal phosphates are to be understood as the calcium, magnesium, strontium or barium salts of orthophosphoric acid or phosphorous acid.
  • Typical examples are calcium phosphate, calcium hydrogen phosphate, magnesium phosphate, magnesium hydrogen phosphate, strontium phosphate, strontium hydrogen phosphate, barium phosphate, barium hydrogen phosphate and the mixed salts of the phosphates mentioned with the corresponding alkaline earth metal hydroxides (“basic phosphates”).
  • basic phosphates the alkaline earth metal phosphates can be used alone or in a mixture, it being immaterial whether mixtures of different alkaline earth metal phosphates are hydrophobicized together or whether a mixture of different hydrophobicized alkaline earth metal phosphates is used.
  • Suitable fatty acids are carboxylic acids of the formula (I)
  • R ⁇ CO for a linear or branched, aliphatic, optionally hydroxy-substituted acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and
  • X represents hydrogen or an alkali metal
  • Typical examples are caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, elaidic acid, petroselinic acid, ricinoleic acid, 12-hydroxystearic acid, linoleic acid, linolenic acid, arachic acid, and galenic acid, behenic acid, behenic acid .
  • Fatty acids with 12 to 18 carbon atoms in particular lauric acid and stearic acid and their sodium or potassium salts, are preferred.
  • fatty acids such as those used in the pressure splitting of natural fats and oils, for example coconut oil, palm oil, palm kernel oil, cottonseed oil, peanut oil, soybean oil, rape oil, sunflower oil, linseed oil, coriander oil, castor oil , Beef tallow or fish oil.
  • Technical C12 / I8 "ke- relationship as Ci2 / 14 ⁇ fat are preferred äuregemische based on coconut oil.
  • the alkaline earth metal phosphates and the fatty acids can be used in a molar ratio of 10: 1 to 1: 5, preferably 5: 1 to 1: 2.
  • the production can take place according to different methods:
  • the alkaline earth metal phosphates and the fatty acids are reacted in the absence of water in a homogenizer, for example a kneader or an extruder, and then at a temperature over a period of 0.5 to 5, preferably 1 to 2, hours heated from 150 to 200 ° C.
  • a homogenizer for example a kneader or an extruder
  • the alkaline earth metal phosphates and the fatty acids are initially introduced in aqueous suspension and reacted at a temperature of 50 to 100 ° C. with stirring over a period of 1 to 10, preferably 2 to 5 hours.
  • the reaction products are then filtered off and dried to constant weight.
  • hydrophobized alkaline earth metal phosphates are prepared in accordance with the embodiments of process B) or C) according to the invention, it is necessary to maintain the products to constant weight, ie. H. to dewater to a residual water content of less than 1% by weight, based on the resulting solid. In a preferred embodiment, it is recommended to spread the filtered solid on tray trays and to dry it at temperatures from 100 to 200 ° C., if appropriate under reduced pressure.
  • the invention further relates to hydrophobized alkaline earth metal phosphates which are obtained by using alkaline earth metal phosphates which are selected from the group formed by calcium, magnesium, strontium and barium salts of orthophosphoric acid and phosphorous acid Implement fatty acids of formula (I), RiCO-OX (I)
  • R ⁇ -CO for a linear or branched, aliphatic, optionally hydroxy-substituted acyl radical having 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds and
  • X represents hydrogen or an alkali metal
  • Another object of the invention relates to the use of hydrophobized alkaline earth metal phosphates as catalysts for the alkoxylation of compounds having active hydrogen atoms and fatty acid esters.
  • hydrophobicized alkaline earth phosphates prepared according to the invention allows the alkoxylation of compounds with active hydrogen atoms and of fatty acid esters in short reaction times and high yields.
  • the reaction products have an advantageous narrowed homolog distribution, the distribution curve coming close to the ideal Poisson distribution.
  • the reaction products are also characterized by low levels of unreacted starting materials and dioxane.
  • the hydrophobized alkaline earth phosphates prepared according to the invention can easily be incorporated into the reaction mixture. Since they do not dissolve in the mixture, their separation, for example by filtration, is straightforward. However, they can also remain in the reaction mixture if their Presence does not impair the further use of the products.
  • Examples of compounds with active hydrogens which can be alkoxylated in the presence of the hydrophobized alkaline earth metal phosphates obtainable by the process according to the invention are fatty acids, hydroxyfatty acids, fatty acid amides, fatty alcohols, alkylphenols, polyglycols, fatty amines, fatty acid alkanolamides and vicinal hydroxy- or alkoxy- substituted alkanes.
  • the alkoxylation is a known industrial process which is carried out at temperatures from 120 to 220, preferably 150 to 190 ° C. and pressures of 1 to 6 bar.
  • the hydrophobized alkaline earth metal phosphates can be used in amounts of 0.1 to 10, preferably 0.5 to 5% by weight, based on the end product of the alkoxylation.
  • Example 2 Analogously to Example 1, an aqueous solution of 110 g (0.49 mol) of sodium laurate in 600 ml of water was added to 70 g (0.51 mol) of calcium hydrogenphosphate and the mixture was heated to about 85 ° C. for 3 hours with stirrers. The suspension was then filtered, the residue washed with water and dried.
  • Decanol / dodecanol-7E0 Analogously to Examples 8 to 11, a mixture of 170 g (1.1 mol) decanol (Lorol ( R ) C10, Henkel KGaA, Düsseldorf, FRG) and 55 g (0.3 mol) dodecanol (Lorol ( R ) C12, Fa. Henkel KGaA, Düsseldorf, FRG) with 6.3 of the catalyst from Example 1. The reaction mixture was then reacted with 413 g (9.4 mol) of ethylene oxide.

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

Abstract

Des phosphates alcalino-terreux hydrophobes sont fabriqués en faisant réagir des phosphates alcalino-terreux avec des acides gras. Les produits obtenus conviennent comme catalyseurs d'alcoxylation pour la fabrication d'agents tensioactifs non ioniques à distribution limitée en homologues.
PCT/EP1992/002632 1991-11-25 1992-11-16 Procede de fabrication de phosphates alcalino-terreux hydrophobes WO1993010897A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP92923729A EP0618841A1 (fr) 1991-11-25 1992-11-16 Procede de fabrication de phosphates alcalino-terreux hydrophobes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19914138631 DE4138631A1 (de) 1991-11-25 1991-11-25 Hydrophobierte erdalkaliphosphate
DEP4138631.0 1991-11-25

Publications (1)

Publication Number Publication Date
WO1993010897A1 true WO1993010897A1 (fr) 1993-06-10

Family

ID=6445481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/002632 WO1993010897A1 (fr) 1991-11-25 1992-11-16 Procede de fabrication de phosphates alcalino-terreux hydrophobes

Country Status (3)

Country Link
EP (1) EP0618841A1 (fr)
DE (1) DE4138631A1 (fr)
WO (1) WO1993010897A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085167A1 (fr) * 1981-12-24 1983-08-10 Conoco Phillips Company Alcoxylation avec des sels de calcium et de magnésium
WO1991012220A1 (fr) * 1990-02-07 1991-08-22 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de composes tensioactifs non ioniques
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0085167A1 (fr) * 1981-12-24 1983-08-10 Conoco Phillips Company Alcoxylation avec des sels de calcium et de magnésium
WO1991012220A1 (fr) * 1990-02-07 1991-08-22 Henkel Kommanditgesellschaft Auf Aktien Procede de fabrication de composes tensioactifs non ioniques
DE4010606A1 (de) * 1990-04-02 1991-10-10 Henkel Kgaa Verwendung von hydrophobierten hydrotalciten als katalysatoren fuer die ethoxylierung bzw. propoxylierung

Also Published As

Publication number Publication date
EP0618841A1 (fr) 1994-10-12
DE4138631A1 (de) 1993-05-27

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