DE2629849A1 - PROCESS FOR THE PRODUCTION OF ALKYLATED AND SULFATED, IF NECESSARY ALCOXYLATED DIALCANOLAMINES - Google Patents

Description

Patent attorneys

Ing.Hans-Jürgen Müller
υ rcrfnat Thomas Berend

D8 Munich 80 Lucile-Grahn-StraBeSö MP 201

ALBRIGHT & WILSON LIMITED, Oldbury , Warley, West Midlands (England)

Process for the production of alkylated and sulfated, optionally alkoxylated dialkanolamines.

The invention relates to improved surfactants useful in shampoo formulations. In particular, the invention relates to a process for the preparation of alkylated and sulfated, optionally alkoxylated dialkanolamines.

It has already been proposed that certain amphoteric, nitrogen-containing ether sulfates, such as fatty acid amide ether sulfates of the formula RCONH (C ₂ H ^ O) _n SO ^ X and amine ether sulfates of the formula RNH (C ₂ H ^ O) _η 30 ^ Χ, in which formulas R denotes an alkyl group, η has the value 2 to 20 and X is an alkali metal or ammonium ion, to be incorporated into shampoo formulations. The alkylamine ether sulfates were prepared by reacting an amine of the formula RNH ₂ with ethylene oxide and then sulfating the amine ether obtained. In this production method, an amine ether sulfate of the formula mentioned is predominantly used

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formed, where Rz. B. is a tertiary alkyl group. However, when R represents a primary alkyl group, it is believed that the second hydrogen atom of the amine RNHp is more labile, so that the product contains a significant amount of at least one of the following amine bis (polyalkyleneoxy) sulfates

"\ (C ₂ H ₄ 0) _m S0 ₄ X

may contain.

In practice it is found that primary alkylamine ether sulfates which are prepared by the methods mentioned have skin-irritating properties to a certain extent. It is believed that this skin irritation is at least in part due to the small amount of the primary alkylamine RNHp and / or the alkylamine mono (polyalkyleneoxy) sulfate RNH (C ₂ H ₂ O) _n SO ^ X in the product. It is believed that the amine free hydrogen of these compounds is capable of causing skin irritation.

A new product has now been found which, although almost identical to the amine ether sulfates, with regard to its desirable surface properties, surprisingly, is very mild to the skin, though it is compared with the known products.

The invention provides alkylated dialkanolamine sulfates and alkylated dialkanolamine ether sulfates which have these properties.

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The term "alkylation" is used as a designation in the following the reaction of a secondary amine with a compound of the formula RX, where R is an alkyl group or an interrupted alkyl group which has one or more ether bonds and / or a benzene ring and X is the residue of a strong acid HX, to form a tertiary amine containing the R group.

The new alkylated dialkanolamine sulfates according to the invention are prepared by alkylating a dialkanolamine, preferably diethanolamine, e.g. B. through implementation with an alkyl halide, e.g. B. an alkyl chloride or preferably an alkyl sulfate or an alkyl sulfuric acid and subsequent sulfation of the hydroxyalkyl side chain. However, the alkylated dialkanolamine is preferred (preferably alkylated diethanolamine) alkoxylated, e.g. B. by reaction with ethylene oxide before sulfation, to provide the alkylated dialkanolamine ether sulfates. According to an alternative procedure the latter products are also obtained by alkylating a bis (polyoxyalkyl) amine and sulfating it obtained alkylated dialkanolamine ethers.

The alkyl group is preferably an n-alkyl group having 8 to 23, preferably 10 to 16 carbon atoms. Branched chain including tertiary alkyl groups and aralkyl groups can also be used. Alkyl groups interrupted by one or more ether bonds are also useful in the process, e.g. B. Groups of the formula R (OR ¹ J _n »in which R is an alkyl group having 8 to 22 and preferably 10 to 16 carbon atoms, R ^{1 is} an alkylene group, preferably

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Represents a diethylene group and η is a number from 1 to 10, e.g. B. 1 to 5 represents. The alkylation of the dialkanolamine or dialkanolamine ethers can be carried out by any of the known methods suitable for the alkylation of amines, e.g. B. by reaction of the dialkanolamine, e.g. B. diethenolamine, with the corresponding halide, e.g. B. an alkyl chloride or bromide. Preferably, however, an alkylsulfuric acid such as is formed when a fatty alcohol or an ethoxylated fatty alcohol is reacted with a sulfating agent such as a chlorosulfonic acid is neutralized with an excess of the dialkanolamine ether. Other sulfating agents such as sulfamic acid or, preferably, sulfur trioxide can be used to prepare the alkyl sulfuric acid. Usually the mixture is heated in an inert atmosphere (e.g., under Sticlsboff) for a sufficient time to fully react. Usually the mixture is at a temperature above 100 ⁰ C up to 300 ⁰ C, z. B. at 200 to 250 ⁰ C, preferably about 220 ⁰ C for 2 to 10 hours, for. B. heated for 5 hours. A stoichiometric excess (e.g. a 3 to 10 molar excess) of the alkanolamine is preferably used, after which the mixture is separated into two phases and the excess phase is separated off for the recovery of alkanolamine. The product must be cleaned, e.g. B. by washing with hot water to remove residual dialkanolamine or dialkanolamine ether. The alkylated dialkanolamine or alkylated dialkanolamine ethers is preferably dried, e.g. B. by heating under vacuum.

The alkoxylation of the alkylated dialkanolamine (or alkylated dialkanolamine ethers) can be carried out according to any of the

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known methods for the alkoxylation of alcohols, all of which are well known, can be carried out. Preferably the alkylated dialkanolamine is reacted with propylene oxide or preferably with ethylene oxide. The alkoxylated In a typical embodiment, product can have an average of up to 20 ethyleneoxy units in total contained per molecule, e.g. B. 1 to 6, preferably 2 to 4 such units.

In a typical procedure, the alkylated dialkanolamine is charged to a reactor and contacted with excess alkylene oxide in the presence of a basic catalyst (e.g., an alkali metal hydroxide or alkoxide such as sodium methoxide). Preferably the alkylene oxide is added at a rate sufficiently slow to maintain a maximum reaction pressure of 3.5 kg / cm through the entire reaction. The mixture can e.g. B. to temperatures of 100 to 200 ⁰ C, preferably about 120 ⁰ C for up to 5 hours and then any excess alkylene oxide present can be stripped off, z. B. by heating under vacuum.

The sulfation of the alkylated dialkanolamine or its ether can easily be carried out by any known method be carried out for sulfating alcohols, z. B. by means of chlorosulfonic acid, concentrated sulfuric acid, sulfamic acid or preferably sulfur trioxide.

The products are preferably produced as sodium, potassium, lithium, ammonium or amine salts according to an known methods. For example, the ammonium salt can be prepared by using sulfamic acid in the sulfation step can be obtained in the corresponding

609883 H.

Alkali metal salt by boiling with the appropriate alkali metal hydroxide be convicted. According to an alternative procedure by sulfating the alkylated Dialkanolamine or alkylated dialkanolamine ethers prepared suIfo-acid with an aqueous base, such as aqueous sodium hydroxide, potassium hydroxide or ammonium hydroxide or a corresponding carbonate neutralized will.

According to a further embodiment, the invention therefore comprises a process for the production of new surface-active substances Agents, wherein in step (I) a dialka nolamine or bis (polyoxyalkyl) amine of the formula

(RO) _n H

in which each group R ^{1 is} an alkylene group having 1 to 4, preferably 2 carbon atoms and η and m are each integers from 1 to 20, which can be the same or different, with a compound of the formula R (OR ¹ ), in which R is an alkyl or aralkyl group with 8 to 23 carbon atoms and R ^{1 has} the meaning mentioned-

aJ-Kyj-

and q is a number from 0 to 20, preferably 0 to 5, / (II) any unreacted dialkanolamine or dialkanolamine ether is separated from the alkylated dialkanolamine or alkylated dialkanolamine ether, (III) optionally the product obtained is reacted with sufficient alkylene oxide, preferably ethylene oxide, up to a total of or there are up to 20 oxyalkylene units per mole and (IV) the product is sulfated to form a compound or a mixture of compounds of the formula or average formula

609883 / 138Ö

[RO) _n SO ₃ X

R (OR ') _q N

to form in which R, R ', q, η and m have the meanings mentioned have, ρ has the value 0 to 1 and X is sodium, potassium, lithium, ammonium or a substituted ammonium ion mean.

According to a further embodiment of the invention provided a hair shampoo containing the new products made according to the invention. Such In usual embodiments, shampoo formulations can also contain other surface-active ingredients, usually found in shampoos. The other ingredient that is in the shampoo formulation may be present includes detergents, especially the milder anionic or amphoteric detergents or cationic detergents. For example are alkyl ether sulfates such as sodium lauryl ethoxy or polyethoxysulfate because of its mild and non-irritating properties compared to alkyl sulfates such as sodium stearyl sulfate, preferred, although the latter detergent may also be present. Usually, alkylbenzenesulfonates, such as sodium dodecylbenzenesulfonate, alkylsulfonates and olefin sulfonates viewed as too rough, however, may optionally be present, preferably in small amounts. Alkyl betaines, such as lauryl myristyl-cocoyl-cetyl or oleyl dimethyl betaines are for use in the formulations of the invention very suitable, also the alkylamide betaines, alkylamine oxides, (e.g. coconut dimethylamine oxides), alkyl ether amine oxides and amido ether sulfates.

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The shampoo formulations according to the invention preferably contain cationic detergents, in particular when little or no anionic detergents are present. It can e.g. B. Alkyltrimethylammonium halides are used whose alkyl group has 8 to 22 carbon atoms, such as cetyl trimethyl ammonium chloride, Alkyl pyridinium halides, alkyl trimethylammonium methanosulfates or alkyl dimethyl benzyl ammonium halides. The new surfactants according to the invention are particularly compatible with high molecular weight cationic resins such as quaternized Polyvinyl pyrrolidone.

The shampoo formulations according to the invention can also contain nonionic detergents, although these are general are less preferred and usually only as minor components of the formulation, if at all, available. For example, fatty acid diethanolamides, such as coconut diethanolamide, or fatty acid monoethanolamides, such as stearic acid monoethanolamide or fatty acid isopropanolamide are present in the compounds. Other nonionic detergents that are useful are alkyl ethoxylates and polyethoxylates, fatty acid ethoxylates xind ethoxylated monoesters of ethylene glycol, glycerine or sorbitol.

The formulations can also contain opacifying agents, ethylene glycol monostearate, as well as inorganic salts such as Sodium chloride, perfumes, solvents such as ethylene glycol or isopropanol, dyes, lanolin and its Derivatives, formalin and other preservatives, antiseptics, Foam stabilizers, conditioning agents and oils contain.

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The pH of the formulation is preferably 4 to 7, most preferably 4.5 to 6, which can be achieved by adding weak acids such as acetic acid, citric acid or
Tartaric acid can be achieved.

The shampoo is usually used in the form of an aqueous solution containing 5 to 50 percent by weight of the surfactant Agent, preferably 10 to 35 percent by weight of these agents. The new surface-active Agents according to the invention represent, according to a typical embodiment, 20 to 80 percent by weight, e.g. B. 50 percent by weight of the active ingredients.

The invention is illustrated in more detail by the following examples:

EXAMPLE 1

300 g of chlorosulfonic acid were stirred over a period of 30 minutes to form 496 g of a mixture of 70 percent by weight of dodecyl alcohol and 30 percent by weight
Given myristyl alcohol. The mixture was stirred at 30 ⁰ C
For 30 minutes under a vacuum of 380 to 500 mm
Mercury (15 to 20 ") was held to strip off hydrogen chloride gas. 700 g of the sulphonic acid were recovered.

The sulfonic acid was added to 2192 g by slow addition
anhydrous diethanolamine at 30 ⁰ C neutralized. The mixture was stirred under a nitrogen atmosphere for 5 hours at 220 ^° C. and the product was then allowed to cool and allowed to separate into layers. The lower layer was discarded.

The top layer was isolated and washed with three 500 cubic meter portions of hot water. It was

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a small amount of ethanol was added to break the emulsion formed at this point. The washed alkylated dialkanolamine was dried under vacuum at 90 ⁰ C for 4 hours, yielding 653 g of intermediate versus a theoretical yield of 720 g, ie 91% yield. The intermediate product had a base value of 199 mg KOH / g.

The intermediate product was treated with 4 molar proportions of ethylene oxide and a katalytisehen amount of potassium hydroxide in a sealed reaction vessel was maintained at 110 ⁰ C, mixed. The temperature was allowed to ^{rise to 140 °} C. while the pressure was maintained at 3.5 kg / cm (50 psi). The base value of the ethoxylated amine ether obtained was 126 mg KOH / g compared to a theoretical value of 122. The compound contained 4 % polyethylene glycol.

There were 128 g of chlorosulfonic acid slowly to 445 g of the ethoxylated amine ether with stirring under a reduced pressure 380-635 mm Hg at 30 ⁰ C.

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added for a period of / 75 minutes. The mixture was ^{kept under reduced pressure at 30 °} C. for a further 30 minutes and the product was finally added slowly to a stirred solution of 95 g of 48% strength sodium hydroxide solution in 1000 g of water, which was kept below 30 ^° C. 1608 grams of the neutralized product was recovered which contained 22.7 percent by weight actives, 6.7 percent by weight free unsulfated ether, 1.6 percent by weight sodium sulfate, 3.4 percent by weight sodium chloride and 66 percent by weight water.

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EXAMPLE 2

75 grams of diethanolamine were placed in a sealed reactor. To this end, 176 g of ethylene oxide were added in the presence of sodium methoxide as a catalyst in an amount of 0.25 percent by weight, based on the diethanolamine. The temperature of the mixture rose to 140 ^° C. under a pressure of 3.5 kg / cm (50 psi) until the reaction was complete.

It was left for an 8-molar excess of alkoxylated Diäthanolamins in the reactor and the mixed dodecyl-myristyl-sulfonic acid, which had been prepared according to Example 1 was slowly added at 30 ⁰ C. The mixture was heated under nitrogen to 220 ° C. for 5 hours with stirring and then separated off and washed according to Example 1 with hot water. The product was then dried, sulfated and neutralized according to Example 1.

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Claims (3)

PATENT CLAIMS [1. Process for the preparation of an alkylamine-bis (polyoxyalkylene) sulfate by sulfating an alkyldialkanolamine, optionally after its alkoxylation,
characterized, that (a) a dialkanolamine is alkylated in a manner known per se, e.g. B. by converting excess Dialkanolamine with an alkylsulfuric acid, and (b) excess dialkanolamine removed, in particular by washing the alkylated phase with hot water, and the alkyldialkanolamine obtained optionally sulfated after alkoxylation in a manner known per se. 2. The method according to claim 1,
characterized, that in step (I) a dialkanolamine or bis (polyoxyalkyl) amine of the formula (RO) _n H in which each group R ^{1 is} an alkylene group having 1 to 4, preferably 2 carbon atoms and η and m are each integers from 1 to 20, which can be the same or different, with a compound of the formula R (OR ¹ ), in which R is an alkyl or aralkyl group with S to 23 carbon atoms and R ^{1 has} the meaning mentioned and q is a number from 0 to 20, preferably 0 to 5, alkylated, (II) any unreacted dialkanolamine or dialkanolamine 6 Ü 3 ^: - H 3? ί 3 8Π ether of the alkylated dialkanolamine or alkylated Dialkanolamine ether is separated off, (III) optionally the product obtained with sufficient Alkylene oxide, preferably ethylene oxide, is reacted up to a total of or up to 20 oxyalkylene units each Moles are present and (IV) the product is sulfated to give a compound or a mixture of compounds Formula or average formula R (OR ¹ - ( ^Rl °> mi ^S0 2F> p ^H (1-p) to form, in which R, R ¹ , q, η and m have the meanings mentioned, ρ has the value 0 to 1 and X is sodium, potassium, lithium, ammonium or a substituted ammonium ion. 3. Use of the alkylamine bis (polyoxyalkylene) sulfates prepared according to claim 1 or 2 as a surface-active agent Agents in shampoos. 609883/1380