NL8700035A - NEW SURFACE-ACTIVE AGENTS AND SHAMPOO PREPARATIONS CONTAINING THESE AGENTS. - Google Patents

Description

- * · - - * - New surfactants and shampoo preparations containing these agents -

This invention relates to new surfactants which are particularly useful as surfactants in shampoo formulations.

The invention provides a mixture of compounds of formula 1, wherein R is the remainder of a mixture of primary, aliphatic alcohols, at least 70 mole% of which are branched 1-decanols, the remainder consisting mainly of primary aliphatic alcohols having an average of 8- 12 carbon atoms exist, m = an integer from 2-13, n is an integer from 6-15, and M represents a cation.

Preferably R is R ', wherein R' is the residue of a mixture of primary aliphatic alcohols, at least 90 mol% of which are branched 1-decanols. It is more preferable that R = R ", wherein R" is the remainder of a mixture of primary, aliphatic alcohols, at least 95 mol% of which are branched 1-decanols. It is even more recommended that R = R'T ', where R *' * is the remainder of a mixture of primary, aliphatic alcohols, at least 95 mol% of which are branched 1-decanols and the major isomers are trimethyl-1-heptanols .

The variable m is preferably m ', where m' = 3-12, especially mM where m = 3-10 and especially m'fT, where m '' = 3-9.

The variable n is preferably n 'where n1 = 6-13, especially n ", where n" = 6-12 and especially n ", J where n" = 8-12.

M is preferably Mr, wherein Mr is a cation 8700033-2 - selected from alkali metals, alkaline earth metals, ammonium, mono-, di- and tri-C 2-6 alkanolammonium, mono-, di-, tri- and tetra-C 1-4. alkyl ammonium, pyridinium and morpholinium. It is especially recommended that M = M ", where M" be a cation selected from sodium, potassium, ammonium, mono-, di- and tri-C 1-4 alkanolammonium and mono-, di-, tri- and tetra-C 1-4 -alkylammonium. It deserves even more. recommendation that M - M '' in which M * 11 be a cation selected from sodium, potassium, ammonium and mono-, di- and tri-C ', alkanol ammonium.

2-4 - | 0 Recommended mixtures of compounds are those of formula 1a, wherein R ', m', n 'and M' have the previously defined meanings.

The more recommended mixtures of compounds are those of formula 1b wherein R ", m", n "and M" have the meanings defined above.

The most recommended mixtures of compounds are those of formula 1c, wherein R'm'11, n '”and M"' have the meanings defined above.

The compounds of formula 1. can be prepared by conventional methods. Thus, the new ether sulfates of this invention can be obtained by the adduct obtained by propoxylation and ethoxylation of a specific mixture of primary, aliphatic alcohols, as defined above, with a suitable sulfating agent, in a manner conventional for sulfating of corresponding primary alcohols, to sulfate.

The alkoxylation step is preferably carried out in the presence of a conventional catalyst, for example, an alkali metal hydroxide or alkaline earth metal oxide.

If desired, a small amount of a reducing agent, for example sodium borohydride, can be added to the alcohol mixture to prevent discoloration during the alkylation process.

8700035>? - - »- 3 -

An amount of propylene oxide calculated to provide the desired degree of propoxylation is added and the resulting mixture is reacted until the propylene oxide is used, as follows from the fact that the reaction pressure no longer increases with time. Corresponding addition and reaction of a calculated amount of ethylene oxide serves to provide the second block, which completes the alkoxylation. Preferably, the alkoxylated product is finally treated with a weak acid, for example glacial acetic acid, in order to neutralize any basic catalyst residues present.

It will be understood that any individual alkoxylation process serves to introduce a desired average number of alkylene oxide units per alcohol molecule.

For example, the initial treatment of an alcohol mixture with m moles of propylene oxide per mole of alcohol contemplates the propoxylation of each alcohol portion with propylene oxide to an average of m propylene oxide units per alcohol portion, although some alcohol portions will be combined with more than m propylene oxide portions and some will be combined by less than m. The variation in the number of alkylene oxide portions is not critical, as long as the average of the number of units in each block is within the limits for the m and n values in the above formula 1 gpnceni, 25 , which values, as mean values, are sometimes not integers.

Each alkoxylation is carried out under customary temperature and pressure conditions and preferably under anhydrous conditions.

The alkyl polyalkoxide intermediates obtained are then sulfated using a suitable sulfating agent, such as sulfuric acid, sulfamic acid, sulfur trioxide, and chlorosulfonic acid 8700035% by weight, using a batch process for the purposes of In this invention, it has been found to be most convenient to use chlorosulfonic acid by a batch process.

Typically, the alkyl polyalkoxide intermediate is placed in a reaction vessel, purged with nitrogen and heated under reduced pressure to remove traces of water. A 10-20% molar excess of chlorosulfonic acid is then added dropwise with stirring and the reaction temperature is maintained between 30 and 35 ° C until addition is complete. After allowing the reaction to proceed for 1.5 to 2 hours, the resulting mixture is poured on ice and the pH is adjusted to between 6.5 and 7.5 with sodium hydroxide.

The compounds of formula 1 are useful as surface-active agents, for example, emulsifiers, dispersants, detergents, wetting agents, leveling agents, etc., in the textile, leather, paper, lacquer, toilet, cosmetics and rubber fields. They can be used, for example, as wetting agents or detergents in the treatment and refining of textile materials and for the conversion of liquid or solid materials insoluble in water (such as hydrocarbons, high alcohols, oils, fats, waxes and resins) into cream-like emulsions, clear solutions or in fine, stable dispersions.

In addition, the compounds of formula t are useful emulsifying agents for insecticidal compositions and for agricultural spray applications; they are useful for use as additives in petroleum products, hydraulic fluids, lubricating oils, cutting oils and greases; they can be used as coating aids to be used in coating products containing a hydrophilic film-forming colloid and they can be used as adhesives in 8700035-5 - the adhesive layer of adhesive tapes in, for example, the photographic industry, and as foaming and emulsifying agents in a wide variety of food products are used.

The ether sulfates of the present invention are particularly useful as the essential surfactant ingredient in hair shampoo formulations.

The inclusion of these sulfates not only serves to improve the washability and foaming properties of the shampoo formulations, but also reduces their irritant effect and leads to extremely mild shampoo formulations, which also feel good. Such shampoo preparations will usually contain about 5% to about 50% of an ether sulfate mixture of formula I, preferably about 5% to about 40%, and especially about 10% to about 30%. As mentioned above, the ether sulfates can be used as the sole surfactant in the composition, completely replacing the conventional surfactants, such as alkyl-E0 sulfates, which is the more recommended embodiment of the present invention, although the ether sulfates can be used in combination with conventional surfactants, with only partial replacement of the latter.

The shampoo formulations may contain other ingredients commonly found in such formulations. For example, a high alkanol amide, or a mixture thereof, can be used to promote foam stabilization, foam stimulation and generation, and to obtain a cosmetically acceptable viscosity. Generally, a C 1 -g mono or dialkanolamide of the 1: 1 type (is prepared by reacting equimolar amounts of the methyl ester of a suitable S7 0 0 0 3 5 - 6 - Zr> * carboxylic acid and mono- or dialkanolamine). A suitable example of a monoalkanolamide is coconut monoethanolamide and typical examples of suitable dialkanol amides are lauric diethanolamide and coconut diethanol-5 amide.

Conditioning agents can also be used, such as quaternary ammonium compounds, for example dimethylsterylammonium chloride and cationic polymers, such as Cartaretine F-23 (Sandoz) and Polymer JR 10 (Union Carbide). These materials are used to improve the combability and manageability of affected hair and to reduce static build-up on dry hair.

To improve the shine of the hair, an oil can be present in the shampoo preparations. This can be a silicone oil, such as dimethyl polysiloxane or other conventional polysiloxanes, olive oil or a light mineral oil.

The amount of water or aqueous carrier 20 to be included depends on the desired consistency of the final product. It is possible to vary the amount of water present to formulate, for example, a thick liquid liquid, lotion or gel. Inorganic salts such as sodium chloride can also be included to control the viscosity.

Other conventional additives typically used in shampoo formulations can also be used. For example, scented oils that mask the odor and provide cosmetic appeal can be used. If desired, non-toxic and compatible dyes can be used to provide color to the compositions. Preservatives, such as methyl paraben, propyl paraben and formaldehydes 870 0 03 5 - 7, can also be used.

Furthermore, other ingredients which have a beneficial effect on providing shampoo compositions adapted for a special application can be included. For example, to protect the hair, a sun-filtering additive such as octyldimethyl para-aminobenzoic acid can be included. Likewise, dandruff protection products may be formulated with agents such as zinc omadine (Olin).

In the following examples, all parts are parts by weight.

Example I:

The sodium salt of hexapropoxy-dodeca-15-ethoxyisodecyl sulfate of formula iso-C ^ qH ^ (OCH ^) g (CC ^) ^ OSD ^ Na f, a) Preparation of hexapropoxy-dodecaethoxyisodanol.

2Q To the reaction vessel was added, with stirring, 327 parts of decyl alcohol (a mixture of primary aliphatic alcohols, at least 90 mol of which is 1-decanols, with a boiling range of 216-223 ° C, a density at 20/20 ° 20.

of 0.838, a refractive index nD of J ', 440, a pour point 22 of -53.5 ° C, a viscosity at 20 ° C of 22.5 centistokes and a water solubility at 20 ° C of 0.05 g / 100 g , available from Exxm Chemical Co.), 6.5 parts of potassium hydroxide and 0.21 parts of sodium borohydride. After the reaction mixture was heated to 60 ° C 3q under reduced pressure (66 mhar), the reaction mixture was purged with nitrogen to atmospheric pressure and the evacuation and rinsing repeated twice more in order to provide as little air as possible. Finally, the system was evacuated to a pressure of 66 mbar and then heated to 155 ° C with stirring.

© 70 0 035 * * - - 8 -

While maintaining the reaction temperature at 155 ° C, using a metering device from a pressurized cylinder, slowly add 720 parts of propylene oxide at such a rate that the pressure in the reaction vessel was close to about atmospheric pressure, then the reaction mixture was kept at about this pressure. Once the addition of propylene oxide was complete, the reaction mixture was allowed to react further until the pressure dropped to a value at which it remained constant for at least 30 minutes. The system was cooled to 60 ° C, after which evacuation and rinsing were repeated two more times. Finally, the system was evacuated to a pressure of 66 mbar and then 1092 parts of ethylene oxide was added according to the above procedure. After the post-reaction period, the system was cooled to 120 ° C and the reaction mixture at least adjusted. Expose for 1 hour to a reduced pressure of 66 mbar to remove unreacted alkylene oxide. The reaction mixture was cooled to 60 ° C, pressurized with nitrogen to atmospheric pressure and neutralized with about 6.3 parts of acetic acid to give a transparent, pale yellow liquid of the formula ° -C, OH (oc3h6) 6 ( oc2h4) 12 oh was obtained, which turned milky white on cooling and gave a white precipitate on standing.

b) Preparation of the Title Compound 50. 258.8 parts (0.25 mol) of the alcohol alkoxylate prepared according to a) was previously added to a three-necked flask and the system was purged with nitrogen for 10 min.

The reaction vessel was then placed under reduced pressure and the alcohol alkoxylate therein heated to 60 ° C to remove any traces of water. After cooling to room temperature, 40 parts (0.34 mol) of chlorosulfonic acid was added with stirring at such a rate that the reaction temperature during the addition remained between 5 and 35 ° C. The reaction mixture was then stirred for an additional 90 min, after which it was poured on ice and the pH was adjusted between 7.0 and 7.5 with a 50% solution of sodium hydroxide. Finally, sufficient water was added to bring the solids content between 40 and 45%.

Example II

Using in principle the method of Example Ia) and using the starting alcohol used in Example I, ie the decyl alcohol which is commercially available from Exxon

Chemical Co. and the appropriate amounts of propylene oxide and ethylene oxide, the following compounds were prepared;

a) iso-C1QH21 (OC3H6) 3 CO 2 H 4) 9 OH

B) iso-ClQH21 (QC3H6) 3 CO 2 H 4) 6 OH

c) iso-ClOH21 (0C3H6) 6 (0C2H4) 6 OH and d) iso-ClOH21 (O.C3H6) g (0C2H4) g OH.

Example III

25

Using essentially the procedure of Example 1 (b) and instead of the compound prepared in 1 (a), an approximately equivalent amount of the compounds (Ha) - lid) was obtained, respectively, 30 α -C10H21 (0C3V3 ( 0C2V) 0S03 Ha '»> ia ° -c, oB21 <0 ¥ Λ 0S ° 3 Ma c) iso-C10H2) (0C3H6) 6 (0C2H4) 6 0S03 Na and d) ieo-C10H2l (0C3E6) 9 COC2H4) 9 OSOj Na.

37 (50 <335

a

w 'w - 10 -

Example IV

A typical example of a formulation useful as a shampoo formulation is given below.

Percentage 5 A _B_ _G_

Example I (41.7% act.) 32.0 40.0 -

Example lilac) (40.7% act.) - - 35.5 lauramide diethanolamine 6.0 2.0 5.0 coconut amidohydroxypropylsultaine 10 (45% act.) - 6.0 dye 0.2 0.2 0.2 perfume 0 , 2 Q, 2 0.2 water qs q.s. q.s.

15 Total 100 100.0 100.0 pH (adjusted with citric acid or sodium hydroxide) 6.0 6.0 7.0 20 8700035

Claims (14)

A mixture of compounds according to claim 1 of formula 1a, wherein R 'is the remainder of a mixture of primary, aliphatic alcohols, of which at least 90 mol & are branched 1-decanols, 15 mT = an integer from 3-12, n T is an integer from 6-13 and M 'is a cation selected from alkali metals} alkaline earth metals, ammonium, mono-, di- and tri-C alkanol - 2 "4 ammonium and mono-, di-, tri- and tetra-C ^ _ ^ alkyl-20 represents ammonium. A mixture of compounds according to claim 2 of formula 1b, wherein R "is the balance of a mixture of primary, aliphatic alcohols, at least 95 mol% of which are branched 25 1-decanols, m11 is an integer from 3-10, an integer from 6 to 12 and M "is a cation selected from sodium, potassium, ammonium, mono-, di- and tri-C 1-4 alkanolammonium and mono-, di-, tri- and tetra-C 1-6 alkyl ammonium proposes. 8700335 - 12 - A mixture of compounds according to claim 3, of formula 1c, wherein R'11 is the balance of a mixture of primary, aliphatic alcohols, at least 95 mol% of which are branched ^ 1-decanols and the main isomers are trimethyl-1-heptanols , m "'is an integer from 3-9, n" "" is an integer from 8 - 12 and M "" is a cation selected from sodium, potassium, 10. ammonium and mono-, di- and tri- Ck represents alkanolammonium 2-4 A mixture of compounds according to claim 4 of formula iso-C, 0H2, (OC3H6) 6 (0C2H4) 120SO3Ha. 6. A mixture of compounds according to claim 4 of the formula iso? CioH2i (003H6) 3 (0C2H4) 9 OSOjNa. A mixture of compounds according to claim 3 of formula 2Q is ° -C, 0H2, «Wj (OC2H4> 6 ° S ° 3Na · A mixture of compounds according to claim 3 of formula Ie-C, OH 2, "SVi {Χΐ \\ 0S03Na · A mixture of compounds according to claim 4 of formula 25 is -C 10 H 21 (OC 3 H 6) 9 (0C 2 H 4) 9 SO 3 Na. A mild shampoo formulation containing, as the major surfactant component, 5-50% by weight of a mixture of compounds according to claim 1. 30 A preparation according to claim 10, characterized in that the essential surfactant component is present in an amount of 5 to 40% by weight. δ "7 Λ / ¾ η = 2 gr s j v y u o o - 13 - A formulation according to claim 11, characterized in that the essential surfactant component is present in an amount of 10 to 30% by weight. A composition according to claim 10, characterized in that the essential surfactant component is a mixture of compounds of formula iso-C 10 H 2, (0C 3 H 6) 6 (OC 2 H 4) 12 SO 3 Na U. A composition according to claim 10, 0 characterized in that the essential surfactant component is a mixture of compounds of formula iso-C 10 H 21 (OCgHg) ^ (OC ^ H ^) ^ OSO ^ Na. 15. A shampoo preparation according to any one of the examples VIA-C. 15 -ooooo- ^ §700035 * - ** ArR (0C3H4) m (0C2HJ,) n0S0j Μ 1 r '(ο c, Ht) "/ (ο oso3 μ' la R" (O Ci (0CeHi,) ^ "OS 03 M" 1bR (0 CjHfcV m (ΟΟίΗή) ^ '»0S03MW 1 C SANDOZ AG Basel, Switzerland 8700035