DE4239390A1 - Sulphated poly:hydroxy cpds. prepn. - by ring opening long chain epoxide(s) with alkyl or alkenyl oligo:glycoside(s) then sulphating and neutralising - Google Patents

Abstract

Prepn. of sulphated polyhydroxy cpds. comprises ring-opening long-chain epoxide cpds. with alkyl or alkenyl oligoglycosides of formula R'-O-(G)p (I) and then sulphating and neutralising the obtd. polyhydroxy cpds. by known methods. R' is 1-22C aliphatic hydrocarbon contg. 0-1 double bonds; G is 5-6C sugar residue; and p is 1-10. USE/ADVANTAGE - (A) are useful for the prepn. of washing, rinsing and cleaning agents, and hair and body care prods.. (A) are readily bio-degradable and show improved skin cosmetic compatibility, whilst retaining good foaming, wetting and cleaning properties.

Description

Field of the invention

The invention relates to new sulfated polyhydroxy compound tions, a process for their preparation in which long-chain epoxy compounds with alkyl and / or alkenyl oligoglycosides subjected to ring opening and the resul subsequently sulfated polyhydroxy compounds as well as the use of these products for the production of surfactants.

State of the art

Surfactants, such as hand harness Flushing or hair shampoos usually stand out characterized by a high foam, wetting and cleaning power and are usually prepared using anionic surfactants formulated. In the wake of a growing consumer consciousness his is in the production of such funds, which in direct contact with the human skin or mucosa an increased need for ingredients, in addition to excellent detergent properties and full of biodegradability especially by a  particularly high dermatological compatibility should.

From the state of the art are already a variety of anionic surfactants, which are considered to be particularly "mild" can be net. In the review article by B. Fabry in Soap-Oils-Fats-Waxes, 117, 3 (1991) are included here For example fatty alcohol ether sulfates, sulfosuccinates, Ise thionates, taurides, sarcosinates and ether carboxylic acid salts Nannt.

Also anionic derivatives of sugar surfactants, such as sulfated alkyl oligoglycosides [DE 40 06 841, Henkel], sulfated sorbitan esters [DE 39 41 061, Henkel] or sulfa Hydroxycarboxylic acid esters [WO 91/11504, Henkel] are known as extremely skin-friendly from the prior art be known.

From the context outlined it is clear that the Ten sidindustrie a constant need for anionic top Has surface-active substances that are characterized by a high Foam, wetting and cleaning ability to distinguish the Range of commercial products to complement and flexible to respond to the changing demands of the market can. In particular, there is a need for ecological or toxicologically harmless anionic surfactants.

The object of the invention was therefore to new anioni surfactants with good foaming, wetting and cleaning properties as well as a high ecological and skin-cosmetic To develop compatibility.  

Description of the invention

The invention relates to new sulfated polyhydroxy connections obtained by

• a) long-chain epoxy compounds with alkyl and / or Alke nyloligoglykosiden of the formula (I) ter a ring opening, R ¹ -O- [G] _p (I) in the
  R ^{1 is} an aliphatic hydrocarbon radical having 1 to 22 carbon atoms and 0 or 1 double bond,
  G for a sugar residue with 5 or 6 carbon atoms and
  p for numbers from 1 to 10
  stands, and
• b) the resulting polyhydroxy compounds in per se sulfated and neutralized known manner.

Another object of the invention relates to a method for the preparation of sulfated polyhydroxy compounds one man

• a) long-chain epoxy compounds with alkyl and / or alkenyl oligoglycosides of the formula (I) subjected to a Ringöff opening, R ¹ -O- [G] _p (I) in the
  R ^{1 is} an aliphatic hydrocarbon radical having 1 to 22 carbon atoms and 0 or 1 double bond,
  G for a sugar residue with 5 or 6 carbon atoms and
  p for numbers from 1 to 10
  stands, and
• b) the resulting polyhydroxy compounds in per se sulfated and neutralized known manner.

feedstocks

Under long-chain epoxy compounds substances are to be understood hen that have at least one oxirane group in the molecule These are known compounds that are after the relevant method of preparative organic Che are accessible. A common procedure for her For example, it is unsaturated Starting materials in situ with performic or peracetic acid to epoxidize. As typical starting materials for the manufacturer development of the polyhydroxy compounds of the invention come in consideration:

• a) epoxides of olefins of the formula (II), R ² -CH = CH-R ³ (II) in the
  R ^{2 is} an alkyl radical having 6 to 16 carbon atoms and
  R ^{3 is} H or an alkyl radical having 6 to 16 carbon atoms.
  Typical examples thereof are octene-1, nonene-1, decene-1, undecene-1, dodecene-1, hexadecene-1, octadecene-1, octene-2, octene-3, decene-2, decene-3, decene -4, dodecene-2, dodecene-4, hexadecene-8, octadecene-9 and their technical mixtures. Preferably, olefin epoxides are used having 8 to 14 carbon atoms.
• b) epoxides of unsaturated fatty acid lower alkyl esters of the formula (III), R ⁴ CO-OR ⁵ (III) in the
  R ⁴ CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 1, 2 or 3 double bonds and
  R ^{5 is} an alkyl radical having 1 to 4 carbon atoms.
  Typical examples are the epoxidized methyl, ethyl, propyl and butyl esters of palmoleic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, gadoleic acid and erucic acid. Preference is given to using epoxidized oleic acid methyl ester.
• c) epoxides of unsaturated fatty acid glycerol esters of the formula (IV), in the
  R ⁶ CO, R ⁷ CO and R ⁸ CO independently represent alipha tables acyl groups having 6 to 22 carbon atoms and 1, 2 or 3 double bonds.

Typical examples are the epoxides of unsaturated tri glycerides of natural origin, such as epoxidized peanut oil, cottonseed oil, olive oil, rapeseed oil, Sunflower oil, linseed oil and especially soybean oil. The un Saturated triglycerides can also share ge saturated fatty acids and mono- and diglycerides ent if their proportion does not exceed 25 Wt .-% makes up.  

The epoxide compounds used can in addition to the epoxide groups also contain double bonds. For a series Of applications, it may even be advantageous if the Epoxidation not 100, but for example 25 to 75% is.

Alkyl and / or alkenyl oligoglycosides are also be knew substances that are classified according to the relevant methods of preparative organic chemistry can be obtained. On Process for their preparation is, for example, the acid catalyzed acetalization of glucose with fatty alcohol represent. Representing the extensive literature be to the European patent application EP-A1-0 301 298 ver grasslands.

Preference is given to alkyl and / or alkenyl oligoglycosides which from aldoses or ketoses, and because of their slight effects derive particularly from the glucose availability. The before ferred Alkyloligoglykoside are thus the Alkyloligogluco side.

The index number p in the general formula (I) gives the oli degree of degummation (DP degree), d. H. the distribution of mono and Oligoglycosides and stands for a number between 1 and 10. While p in a given compound is always integer must be here and above all the values p = 1 to 6 assume can, is the value p for a particular alkyl and / or Al kenyloligoglycoside an analytically determined arithmetic Size, which usually represents a fractional number. Prefers are alkyl oligoglycosides having a moderate oligomerization degree of p from 1.1 to 3.0; particularly preferred are those  Alkyl and / or alkenyl oligoglycosides, their oligomerization degree is less than 1.7 and in particular between 1.2 and 1.4 lies.

The radical R ¹ can be derived from saturated and / or unsaturated primary alcohols having 1 to 22, preferably 8 to 10 or 12 to 18 carbon atoms. Typical examples are methanol, butanol, capric alcohol, 2-ethylhexanol, capryl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, lanolyl alcohol, linolenyl alcohol, arachyl alcohol, gadoleyl alcohol, Behenyl alcohol and erucyl alcohol and technical sections that can hold these alcohols in different amounts ent. Preference is given to alkyl and / or Alkenyloligo glycosides of the formula (I) is used, in which R ^{1 is} alkyl radicals having 8 to 18 carbon atoms, G is a glucose residue and p is a number from 1 to 3.

ring opening

The ring opening is preferably in the presence of acid kata lysatoren, such as sulfuric acid, sulfosuccinic acid acid or p-toluenesulfonic acid, wherein the Concentration 0.1 to 5, preferably 0.5 to 3 wt .-% - be attracted to the epoxy compound - can amount.

To avoid unnecessary boiler occupancy times, it has proved to be advantageous, the reaction at temperatures of  50 to 220, preferably 70 to 170 ° C, optionally under to carry out increased pressure.

It is recommended to use the catalyst after finishing the ring neutralize opening reaction. If desired, this can Crude product are then purified by distillation.

sulfation

The sulfation of the polyhydroxy compounds may be in the for Fatty acid lower alkyl esters known manner [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin- Heidelberg, 1987, p. 61], whereby reactors which are after working the falling film principle, are preferred. As Sulfiermit tel come chlorosulfonic acid and especially gaseous Sulfur trioxide into consideration. The latter is usually with an inert gas, preferably air or nitrogen diluted and in the form of a gas mixture containing the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5 vol .-% contains, used.

The molar use ratio of polyhydroxy compounds to Sulfurizing agent may be 1: 0.95 to 1: 3 and preferably 1: 1.1 to 1: 2.5. Usually, the sulfation carried out at temperatures of 40 to 98 ° C. In terms of on the viscosity of the starting materials on the one hand and the color quality of the resulting sulfation products of others On the other hand, it has proved to be optimal, the reaction in egg temperature range from 70 to 90 ° C.  

The acid sulfonation products obtained in the sulfation are stirred into aqueous bases, neutralized and adjusted to a pH of 6.5 to 8.5. Suitable bases for the neutralization are alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C _2-4 -alkanolamines, for example mono -, di- and triethanolamine and primary, secondary or tertiary C _1-4 alkyl amines and Gluca mine into consideration. The neutralization bases are preferably used in the form of 5 to 55% strength by weight aqueous solutions, 5 to 25% strength by weight aqueous sodium hydroxide solutions being preferred.

The sulfation products can after neutralization in an known manner by the addition of hydrogen peroxide or Bleached sodium hypochlorite solution. In doing so, based on the solids content in the solution of the sulphate tion products, 0.2 to 2 wt .-% hydrogen peroxide, calculated as 100% substance, or equivalent amounts of sodium hypo chlorite used. The pH of the solutions may be below Ver use of suitable buffering agents, e.g. B. with sodium phosphate or citric acid are kept constant. To stabilize tion against bacterial attack is also recommended a Kon Serving, z. With formaldehyde solution, p-hydroxybenzoate, Sorbic acid or other known preservatives.  

Industrial Applicability

The sulfated polyhydroxy compounds of the invention have surface-active properties. That's how they promote For example, the wetting of solid surfaces, form a rich, creamy foam and do not emulsify otherwise mutually miscible liquid phases. They are also under anaerobic conditions are well biodegradable and have one high skin-cosmetic compatibility.

Another object of the invention therefore relates to their Use for the production of washing, rinsing and cleaning as well as hair and body care products in which in amounts of 1 to 70, preferably 10 to 30 wt .-% - based on the funds - may be included.

The following examples are intended to form the subject of the invention explain it in more detail without restricting it to it.

Examples example 1

a) Ring opening. In a 1 liter three-necked flask, 519 g (1.5 mol) of a Lauryloligoglucosids with a through average degree of polymerization (DP degree) of 1.4 initially charged, heated to 90 to 100 ° C and in 1038 g (4.5 mol) dissolved alpha-tetradecenepoxide. The reaction Mi was 25 g of a 30 wt .-% solution of Sodium methylate in methanol - equivalent to 0.75% by weight based on the epoxide - added and the methanol in Distilled off water jet vacuum. After that, the Reak tion mixture over a period of 5 h to 160 ° C he heated, with the residual epoxide oxygen content down to 0.2 wt .-% plummeted. After cooling, the poly was obtained hydroxy compound in virtually quantitative yield as a white solid (hydroxyl number 239, molecular weight 939).

b) sulfation. In a 1 liter sulfonation reactor with jacket 160 g (0.17 mol) of the polyhydroxy compound were cooled from Example 1a) and at 90 ° C with 34 g (0.42 mol) of gaseous sulfur trioxide reacted. The Sulfur trioxide was by heating from a entspre amount of 65% oleum is expelled to one Concentration of 3 vol .-% diluted and within 15 min introduced into the starting material. After the sulfa tion was the acidic reaction mixture in aqueous 50th % by weight sodium hydroxide solution and stirred neutral lisiert.

Characteristics of the product anionic surfactant 15.3% by weight Unsulfonated fractions 6.6% by weight sodium sulphate 2.2% by weight water 75.9% by weight

Example 2

a) Ring opening. Example 1a) was repeated using 197 g (0.55 mol) of technical C _12/16 cocoalkyl oligoglucoside (DP = 1.4) and 368 g (1.65 mol) of alpha-tetradecene epoxide. After a reaction time of 3 hours, the polyhydroxy compound was obtained in virtually quantitative yield from a white solid (hydroxyl number 241, molecular weight 931).

b) sulfation. Analogously to Example 1b) 140 g (0.15 mol) the polyhydroxy compound from Example 2a) with 14.5 g Sulfated (0.18 mol) sulfur trioxide and then neutralized.

Characteristics of the product anionic surfactant 12.1% by weight Unsulfonated fractions 8.2% by weight sodium sulphate 0.8% by weight water 78.9% by weight

The anionic surfactant content (WAS) as well as the unsulfonated portions (US) according to the DGF standard methods, Stuttgart 1950-1984, H-III-10 and G-II-6b determined.

Claims (14)

1. Sulfated polyhydroxy compounds, obtainable by reacting

• a) long-chain epoxy compounds with alkyl and / or alkenyl oligoglycosides of the formula (I) subjected to a Ringöff opening, R ¹ -O- [G] _p (I) in the
  R ^{1 is} an aliphatic hydrocarbon radical having 1 to 22 carbon atoms and 0 or 1 double bond,
  G for a sugar residue with 5 or 6 carbon atoms and
  p for numbers from 1 to 10
  stands, and
• b) sulfating and neutralizing the resulting polyhydroxy compounds in a conventional manner.

2. A process for the preparation of sulfated polyhydroxy compounds, in which

• a) long-chain epoxy compounds with alkyl and / or alkenyl oligoglycosides of the formula (I) subjected to a ring opening, R ¹ -O- [G] _p (I) in the
  R ^{1 is} an aliphatic hydrocarbon radical having 1 to 22 carbon atoms and 0 or 1 double bond,
  G for a sugar residue with 5 or 6 carbon atoms and
  p for numbers from 1 to 10
  stands, and
• b) sulfating and neutralizing the resulting polyhydroxy compounds in a conventional manner.

3. The method according to claim 2, characterized in that one uses as long-chain epoxy compounds epoxides of olives of the formula (II), R ² -CH = CH-R ³ (II) in the
R ^{2 is} an alkyl radical having 6 to 16 carbon atoms and
R ^{3 is} H or an alkyl radical having 6 to 16 carbon atoms. 4. The method according to claim 2, characterized in that one uses as long-chain epoxy compounds epoxides of unge saturated fatty acid lower alkyl esters of the formula (III), R ⁴ CO-OR ⁵ (III) in the
R ⁴ CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 1, 2 or 3 double bonds and
R ^{5 is} an alkyl radical having 1 to 4 carbon atoms. 5. The method according to claim 2, characterized in that one sets as long-chain epoxy compounds epoxides of unge saturated fatty acid glycerol esters of the formula (IV), in the
R ⁶ CO, R ⁷ CO and R ⁸ CO independently represent alipha tables acyl groups having 6 to 22 carbon atoms and 1, 2 or 3 double bonds. 6. The method according to claim 2, characterized in that alkyloligoglycosides of the formula (I) is used, in which R ^{1 is} alkyl radicals having 8 to 18 carbon atoms, G is a glucose residue and p is a number from 1 to 3. 7. The method according to claim 2, characterized in that the ring opening in the presence of acidic catalysts performs. 8. The method according to claim 2, characterized in that the ring opening at temperatures of 50 to 220 ° C, optionally carried out under elevated pressure. 9. The method according to claim 2, characterized in that the sulfation with chlorosulfonic acid or gasför miges sulfur trioxide as the sulfonating agent. 10. The method according to claim 2, characterized in that the sulfation in a continuous reactor performing on the falling film principle. 11. The method according to claim 1, characterized in that the polyhydroxy compounds and the sulfonating agents in molar ratio of 1: 0.95 to 1: 3 used. 12. The method according to claim 1, characterized in that the sulfation at temperatures of 40 to 98 ° C. performs. 13. The method according to claim 1, characterized in that the neutralization with 5 to 55 wt .-% aqueous bases of the alkali metal hydroxides, alkaline earth metal talloxides and hydroxides, ammonia, mono-, di- and tri-C _2-4 Alkanolamines and primary, secondary and tertiary C _1-4 alkylamines performs. 14. Use of sulfated polyhydroxy compounds according to Claim 1 for the production of washing, rinsing and cleaning and hair and body care products.