WO1991012344A2 - Salts of sulphonated phosphoric acid esters for use as leather-oiling agents - Google Patents
Salts of sulphonated phosphoric acid esters for use as leather-oiling agents Download PDFInfo
- Publication number
- WO1991012344A2 WO1991012344A2 PCT/EP1991/000206 EP9100206W WO9112344A2 WO 1991012344 A2 WO1991012344 A2 WO 1991012344A2 EP 9100206 W EP9100206 W EP 9100206W WO 9112344 A2 WO9112344 A2 WO 9112344A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphoric acid
- acid esters
- different
- alkyl
- indices
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
- C14C9/02—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes using fatty or oily materials, e.g. fat liquoring
Definitions
- the invention relates to greasing agents for leather, a process for the production of leathers with favorable water behavior and the use of sulfonated phosphoric acid ester salts for the production of leathers with favorable water behavior.
- the hydrophobizing effect of the phosphoric acid alkyl esters is due to their poor emulsifiability and their low level Resistance to emulsions.
- alkyl phosphates and / or alkyl polyoxyalkylene phosphates with 12 to 14 carbon atoms in the alkyl radicals are often used in practice, which are easier to emulsify in the alkyl radicals than the corresponding phosphoric acid esters with 16 and more carbon atoms.
- none of these measures to improve the emulsifiability and the emulsion resistance lead to satisfactory performance properties of the leather. Due to the insufficient emulsion resistance, the leather is only insufficiently greased and the result is a hard grip.
- Combinations of the phosphoric acid esters with other fatliquoring agents for example sulfonated paraffins, sulfonated fats and / or sulfonated oils, result in an improved grip, but lead to a reduction in the water repellency effect.
- the object on which the invention is based was therefore the development of fatliquoring agents for leather which give leather a favorable water behavior combined with good usage properties, such as grip, grain resistance and / or fullness. Furthermore, the fatliquors to be developed should have good emulsifying power and high emulsion resistance.
- the invention accordingly relates to fatliquoring agents for leather containing alkali, amine and / or ammonium salts of sulfonated phosphoric acid esters, obtainable by reacting phosphoric acid esters of the general formula I.
- radicals R - * - an alkyl or alkenyl group with 8 to 22 C atoms and R ** - and R3 are identical or different and each represent H or an alkyl or alkenyl group with 8 to 22 C atoms, which Indices m, n and p are identical or different and each represent a number between 2 and 4 and the indices x, y and z are identical or different and each represent a number between 0 and 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali hydroxides, ammonium hydroxide and / or amines.
- a further subject of the invention is a process for the production of leathers with favorable water behavior, which is characterized in that leather is obtained by reaction after tanning, retanning or dyeing with alkali, A in and / or ammonium salts of sulfonated phosphoric acid esters of phosphoric esters of the general formula I
- the invention furthermore relates to the use of alkali metal, amine and / or ammonium salts of sulfonated phosphoric acid esters, obtainable by reacting phosphoric acid esters of the general formula I.
- radicals R are an alkyl or alkenyl group with 8 to 22 C atoms and R 2 and R3 are identical or different and each represent H or an alkyl or alkenyl group with 8 to 22 C atoms
- the indices, n and p are identical or different and each represent a number between 2 and 4
- the indices x, y and z are identical or different and each represent a number from 0 to 30, with sulfonating agents and subsequent hydrolysis of the products obtained with alkali metal hydroxides, ammonium hydroxide and / or
- leathers with favorable water behavior are understood to mean leathers in which the water passage through the leather cross section is significantly delayed under dynamic conditions and which absorb only small amounts of water in a certain time unit (penetrometer test according to DIN 53338).
- the fatliquoring agents according to the invention preferably contain alkali salts of sulfonated phosphoric acid esters and particularly preferably alkali salts of sulfonated phosphoric acid esters, which are accessible by reaction of those phosphoric acid esters of the general formula I in which the radicals R are an alkyl or alkenyl group with 12 to 18 C atoms and R 2 and R - are the same or different and each represent H or an alkyl or alkenyl group with 12 to 18 C atoms, the indices m, n and p stand for the number 2 and the indices x, y and z are the same or different and each represent a number between 0 and 10.
- the sulfonation of the phosphoric acid esters of the general formula I are carried out analogously to the processes described in DE-OS 3802815 and DE-0S 38 12 718, preferably at temperatures between 20 and 120 ° C., particularly preferably at temperatures between 30 and 100 ° C., for example performed with sulfuric acid, oleum, chlorosulfonic acid or S ⁇ 3 ⁇ containing gas mixtures.
- Gas mixtures of SO3 and air or inert gases, for example nitrogen, in which the S03 content is between 1 and 10% by volume are particularly preferred as sulfonating agents.
- the molar ratio of the double bond equivalents contained in the starting material to be used SO3 is preferably between 20 and 0.5, particularly preferably between 10 and 0.6.
- the sulfonations are carried out continuously or batchwise in customary reactors suitable and customary for the sulfation of fatty alcohols or the sulfonation of fatty acid esters, alkylbenzenes or olefins, for example of the Fallfil type, (Kirk-Othmer: "Encyclopedia of Chemical Technology” 22 , 28 ff (1983)).
- reaction mixture After sulfonation has ended, it may be expedient to subject the reaction mixture to an aging process.
- the reaction mixture is left to stand or stirred for more than 0 to 240 minutes, particularly preferably within 1 to 30 minutes, preferably at 10 to 120 ° C., particularly preferably at 60 to 100 ° C.
- the mixture is then hydrolyzed with an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines or with anhydrous amines by adding the reaction mixture to the aqueous solution or the anhydrous amines or the aqueous solution or the anhydrous amines to the reaction mixture.
- the optionally aged sulfonation product is preferably added to an aqueous solution of alkali metal hydroxides, ammonium hydroxide and / or amines, 1 to 1.5 moles of hydroxides and / or amines being used per mole of sulfur trioxide added.
- Sodium hydroxide, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine and / or pyridine are preferably used for neutralization. It is particularly preferred to hydrolyze with aqueous solutions of sodium and / or potassium hydroxide.
- the concentration of the hydroxides and / or amines in the aqueous solutions is preferably chosen so that the end product forms a still free-flowing or pumpable aqueous solution.
- Alkali, amine and / or ammonium salts of sulfonated phosphoric acid esters are in the form of dark to light yellow solutions. If desired, these solutions can be bleached with hydrogen peroxide solution or alkali hypochlorite solution (chlorine solution) in a manner known per se at 40 to 55 ° C.
- the phosphoric esters of the general formula I required for the preparation of sulfonated phosphoric acid ester salts are obtainable by processes known from the literature. Their preparation is based on alkyl and / or alkenyl alcohols having 8 to 22 carbon atoms, for example octyl, decyl, lauryl, myristyl, cetyl, palmitoleyl, stearyl, oleyl and / or behenyl alcohol . Alkyl and / or alkenyl alcohols having 12 to 18 carbon atoms are preferably used.
- the alkoxylations of saturated and / or unsaturated alcohols with ethylene oxide, propylene oxide and / or butylene oxide, preferably with ethylene oxide, are carried out using known industrial processes ("Chemical Technology", Volume 7, pages 131 to 132, Carl-Hanser-Verlag, Kunststoff, Germany). Vienna (1986)).
- the average degree of alkoxylation x, y or z of the mixtures of homologous alkoxylates obtained corresponds to the molar amount of the alkylene oxides attached and is preferably between 0 and 10.
- the phosphating of optionally alkoxylated alkyl and / or alkenyl alcohols is carried out in a manner known per se ("Chemische Technologie", Volume 7, page 123 ff, Carl-Hanser-Verlag, Kunststoff-Vienna (1986)), in which the alcohols contain phosphorus pentoxide or Polyphosphoric acid are implemented. In these processes, mixtures of phosphoric acid mono-, di- and triesters are formed. With the use of water entraining agents, such ester mixtures can also be obtained directly using orthophosphoric acid.
- reaction conditions above 160 ° C this does not involve conventional esterification, but primarily the formation of di- and polyphosphoric acid, which react in a known manner with alcohols and / or alcohol polyoxyalkylene ethers.
- the optionally alkoxylated alcohols can be reacted with phosphorus oxychloride to produce high-purity phosphoric acid mono-, di- and triesters.
- Sulfonated phosphoric acid ester salts can be used alone or in combination with other fatliquoring agents, for example mineral oils, paraffins and / or silicones, preferably in emulsified form, with polyvalent metal ions soap-forming emulsifiers, such as fatty acid sarcosides, partial esters of polybasic carboxylic acids, such as monoacetic acid esters and sulfonic acid esters, and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters and alkenyl esters / or oils are used.
- other fatliquoring agents for example mineral oils, paraffins and / or silicones, preferably in emulsified form, with polyvalent metal ions soap-forming emulsifiers, such as fatty acid sarcosides, partial esters of polybasic carboxylic
- the weight ratio of sulfonated phosphoric ester salts to other fatliquoring agents is preferably between 0.1 and 9.
- the fatliquoring agents according to the invention are obtained in amounts of preferably 1 to 20% by weight, particularly preferably 2 to 14% by weight on the fold weight of the leather - used.
- the process according to the invention for the production of leathers with favorable water behavior is carried out in such a way that the sulfonated phosphoric acid ester salts, if appropriate in combination with other fatliquoring agents following the tanning or retanning and optionally dyeing and after removal of excess tanning agents by washing, can be used as a licker.
- the temperatures during the greasing are typically between 30 and 50 ° C.
- the pH of the liquor liquor is adjusted to 3.5 to 4.1, preferably to 3.8 to 4.0, using acids, preferably formic acid, acetic acid and / or sulfuric acid.
- the liquor based on the weight of the seam, is 2 to 6% by weight of chromium and / or aluminum tanning agents added in order to fix the salts of the sulfonated phosphoric acid esters by forming the appropriate chromium and / or aluminum soaps. Then work continues in a manner known per se.
- the sulfonated phosphoric acid ester salts to be used according to the invention have good emulsifying power and high emulsion resistance.
- All types of leather for example cowhide, pig leather or sheep leather, can be treated with the fatliquoring agents according to the invention.
- the leathers treated with the fatliquoring agents according to the invention have better leather properties, in particular a better grip and better grain strength, and, owing to a delayed water penetration and a lower water absorption, a significantly improved impregnation effect.
- reaction mixture was stirred into a dilute solution of 56 g (1 mol) of potassium hydroxide in 700 ml of water and heated at 95 ° C. for one hour on a steam bath. After cooling to 20 ° C., the pH of the reaction mixture was adjusted to 7.5 by adding HCl solution.
- Example 2 Analogously to Example 1, 1.5 mol of ethyl alcohol-0.5 mol of ethylene oxide were reacted with 0.5 MoV phosphorus pentoxide.
- the phosphoric acid ester obtained had an average molecular weight of 478 and 1.3 double bond equivalents per mole of phosphate.
- the sulfonation of 240 g (0.5 mol) of oleyl-0.5 mol of ethylene oxide phosphate was carried out analogously to Example 1.
- the sulfonated product obtained had the following characteristics
- Unsulfated fractions (DGF-G-III-6b): 5% by weight potassium sulfate: 2% by weight potassium phosphate: 1% by weight water (according to Fischer): 72% by weight average molecular weight: 635
- Example 2 Analogously to Example 1, 1.5 mol of ethyl alcohol-2 mol of ethylene oxide were reacted with 0.5 mol of phosphorus pentoxide.
- the phosphoric acid ester obtained had an average molecular weight of 570 and 1.3 double bond equivalents per mole of phosphate.
- the greasing was carried out with one of the following greasing agents:
- the following table contains the tests carried out on the leathers treated with the various greasing agents specified above and the test results.
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP91903401A EP0515426B1 (en) | 1990-02-13 | 1991-02-04 | Method of preparing salts of sulphonated phosphoric acid esters and their use as leather-oiling agents |
BR919106036A BR9106036A (en) | 1990-02-13 | 1991-02-04 | SULPHONATED PHOSPHORIC ACID ESTER SALTS AS LEATHER GREASE ANGLES |
DE59102749T DE59102749D1 (en) | 1990-02-13 | 1991-02-04 | Process for the preparation of salts of sulfonated phosphoric acid esters and their use as leather fatliquors. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP4004293.6 | 1990-02-13 | ||
DE4004293A DE4004293A1 (en) | 1990-02-13 | 1990-02-13 | Dubbing agent for leather |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1991012344A2 true WO1991012344A2 (en) | 1991-08-22 |
WO1991012344A3 WO1991012344A3 (en) | 1991-10-03 |
Family
ID=6399982
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1991/000206 WO1991012344A2 (en) | 1990-02-13 | 1991-02-04 | Salts of sulphonated phosphoric acid esters for use as leather-oiling agents |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0515426B1 (en) |
JP (1) | JPH05504161A (en) |
AT (1) | ATE110792T1 (en) |
BR (1) | BR9106036A (en) |
DE (2) | DE4004293A1 (en) |
ES (1) | ES2060363T3 (en) |
WO (1) | WO1991012344A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996010651A1 (en) * | 1994-10-04 | 1996-04-11 | Henkel Kommanditgesellschaft Auf Aktien | Greasing agent for leather and pelts |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3504308A1 (en) * | 1984-02-22 | 1985-08-22 | Sandoz-Patent-GmbH, 7850 Lörrach | Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather |
GB2198452A (en) * | 1986-12-04 | 1988-06-15 | Sandoz Ltd | Fatting compositions |
EP0338191A2 (en) * | 1988-04-16 | 1989-10-25 | Henkel Kommanditgesellschaft auf Aktien | Surface active sulfo derivatives of saturated (partial) phosphoric acid alkyl esters |
-
1990
- 1990-02-13 DE DE4004293A patent/DE4004293A1/en not_active Withdrawn
-
1991
- 1991-02-04 AT AT91903401T patent/ATE110792T1/en active
- 1991-02-04 EP EP91903401A patent/EP0515426B1/en not_active Expired - Lifetime
- 1991-02-04 WO PCT/EP1991/000206 patent/WO1991012344A2/en active IP Right Grant
- 1991-02-04 JP JP3503702A patent/JPH05504161A/en active Pending
- 1991-02-04 ES ES91903401T patent/ES2060363T3/en not_active Expired - Lifetime
- 1991-02-04 BR BR919106036A patent/BR9106036A/en not_active Application Discontinuation
- 1991-02-04 DE DE59102749T patent/DE59102749D1/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3504308A1 (en) * | 1984-02-22 | 1985-08-22 | Sandoz-Patent-GmbH, 7850 Lörrach | Process for the simultaneous fat-liquoring and water-repellent finishing of tanned leather |
GB2198452A (en) * | 1986-12-04 | 1988-06-15 | Sandoz Ltd | Fatting compositions |
EP0338191A2 (en) * | 1988-04-16 | 1989-10-25 | Henkel Kommanditgesellschaft auf Aktien | Surface active sulfo derivatives of saturated (partial) phosphoric acid alkyl esters |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996010651A1 (en) * | 1994-10-04 | 1996-04-11 | Henkel Kommanditgesellschaft Auf Aktien | Greasing agent for leather and pelts |
Also Published As
Publication number | Publication date |
---|---|
JPH05504161A (en) | 1993-07-01 |
BR9106036A (en) | 1993-02-02 |
ATE110792T1 (en) | 1994-09-15 |
DE59102749D1 (en) | 1994-10-06 |
EP0515426A1 (en) | 1992-12-02 |
WO1991012344A3 (en) | 1991-10-03 |
ES2060363T3 (en) | 1994-11-16 |
DE4004293A1 (en) | 1991-08-14 |
EP0515426B1 (en) | 1994-08-31 |
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