SECONDARY ALCOHOLIC SULPHATES

The present invention relates to the general field of alkoxylated secondary alcohols which are subjected to a sulfation reaction.

[0002] The sulfation of organic alcohols is a well-known route for obtaining organic alcohol sulfates. Fatty alcohol sulfates are known as surfactants in different applications. Indeed, they are endowed with a certain number of intrinsic properties in comparison with other cationic and anionic surfactants.

The main intermediate for the synthesis of organic alcohol sulfates is the organic alcohol itself. Different properties for an alcohol sulfate can be obtained, depending on the organic alcohol chosen as the raw material.

[0004] The organic alcohols used to synthesize these sulphates can be of very different nature, for example: linear or branched, of small or of large molar mass, mono or plurifunctional, among others.

[0005] They can also be organic alcohols which have undergone an alkoxylation step, in which one or more units of an alkyl oxide, for example of ethylene oxide, of propylene oxide, of butylene oxide, have been incorporated into said organic alcohol.

[0006] The synthesis of organic alcohol sulphates is of real industrial interest, especially when this synthesis is simple to implement and inexpensive, in particular from raw materials available and easily modifiable to obtain different properties.

[0007] In addition, at a time when the environmental stake is really important, the use of a bio-sourced or biodegradable reagent and having a good ecotoxicological profile is quite interesting to consider.

[0008] The alkoxylates of secondary alcohols represent a family of compounds offering a wide range of properties. Indeed, the applications are multiple. They can in particular be used as solvents, as hydrotopes or else as nonionic surfactants. They can also play the role of raw material for other compounds such as etheramines or anionic surfactants obtained by phosphatation or sulfation. Thus, the alkoxylates of secondary alcohols constitute a class of compounds of major industrial interest for many players.

[0009] De manière classique, les alcoxylats d'alcools secondaires sont synthétisés à l'aide d'une catalyse basique, en utilisant par exemple de l'hydroxyde de potassium. Un autre type de catalyseur peut également être employé, le catalyseur de type cyanure dimétallique, communément appelé catalyseur DMC. Divers documents font référence à l'alcoxylation de divers composés, dont les alcools, par une catalyse basique et/ou par une catalyse DMC.

[0010] Thus, a secondary alcohol sulfate is sought, said alcohol being short-chain and alkoxylated, the alkoxylation of which is carried out by a simple process and allows industrial and commercial development at low cost. It would also be advantageous to develop a process for preparing these sulfates using alkoxylated secondary alcohols, the starting compound of which is a bio-sourced and biodegradable reagent.

[0011] The object of the present invention is to provide a solution which makes it possible to solve the problems mentioned above.

The subject of the invention is the compounds of formula (I) below:

in which :

- the groups Ri and F¾, identical or different, represent, independently of one another, a linear, branched or cyclic, saturated or unsaturated hydrocarbon group comprising from 1 to 6 carbon atoms, it being understood that the sum of carbon atoms of the groups Ri and F¾ ranges from 2 to 7, Ri and R2 can form together and with the carbon atom which carries them, a ring with 6, 7 or 8 vertices,

- A represents a sequence of one or more units chosen from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, and

- n is an integer between, limits included, 1 and 100, preferably between 2 and 100, more preferably between 3 and 100, more particularly between 5 and 100, and very preferably between 10 and 100.

A subject of the present invention is also the salts of the compounds of formula (I) above with one or more cationic groups bearing at least one cation chosen from ammonium cation, metal cation, nitrogen cation, borated cation, cation phosphorus.

Examples of these salts euvent be described by the following formula (II):

in which :

- M x + represents a cationic group carrying at least one cation chosen from ammonium cation, metal cation, nitrogen cation, borated cation, phosphorus cation,

- x is an integer ranging from 1 to 7, and

- Ri, R2, A and n being as defined above.

A subject of the present invention is also a mixture of at least one compound of formula (I) and of at least one compound of formula (II). In the remainder of the present description, and unless otherwise indicated, the expression “compound of formula (I)” denotes at least one compound of formula (I) or at least one of its salts of formula (II) or a mixture of at least one compound of formula (I) with at least one of its salts of formula (II).

Another object of the invention is the use of the compound of formula (I) according to the invention, as a surfactant, low-foaming surfactant ("low-foaming surfactant" in French). English), wetting agent, foaming agent, hydrotrope, detergent, solvent, reactive solvent, coalescing agent, compatibilizer, emulsifying agent, dispersant, chemical intermediate, corrosion inhibitor, demulsifier, plasticizer, sequestering agent, mineral deposit inhibitor, ionic liquid , stabilizer, lubricant, additive for bitumen, additive for deinking, gelling agent in oils, flotation collector for ores, processing aid in the manufacture of plastic objects, antistatic agent, additive for fertilizer coatings,for plant protection, for textile processing and for enhanced oil recovery, for the production of electrodes and electrolytes for batteries.

[0017] Other advantages and characteristics of the invention will emerge more clearly on examination of the detailed description. It is specified that the expressions "from ... to ..." used in the present description must be understood as including each of the limits mentioned.

[0018] For the purposes of the present invention, the term “ethylene oxide unit” means the unit resulting from ethylene oxide after opening of the oxirane ring. Likewise, the term “propylene oxide unit” is understood to mean the unit resulting from propylene oxide after opening of the oxirane ring. Also similarly, the term “butylene oxide unit” is understood to mean the unit resulting from butylene oxide after opening of the oxirane ring.

The compound according to the invention is a compound of formula (I) as mentioned above or one of its salts of formula (II) as mentioned above.

In other words, the groups R 1 and F¾, with the carbon atom to which they are attached, denote a secondary radical comprising from 3 to 8 carbon atoms, preferably from 6 to 8 carbon atoms.

Preferably, the groups Ri and F¾, identical or different, are chosen, independently of one another, from methyl, ethyl, n-propyl, / ' so-propyl, n-butyl, sec -butyl, ie / f-butyl, pentyls, and hexyls.

Preferably, the radical formed by R 1, R 2 and the carbon atom to which they are attached is chosen from the 2-octyl radical and the 4-methyl-2-pentyl radical. More particularly, the radical formed by R 1, R 2 and the carbon atom to which they are attached is the 2-octyl radical.

Advantageously, n is between, limits included, 1 and 75, preferably between 2 and 75, more preferably between 3 and 75, more particularly between 5 and 75, and very preferably between 10 and 75.

Advantageously, n is between, limits included, 1 and 50, preferably between 2 and 50, more preferably between 3 and 50, more particularly between 5 and 50, and very preferably between 10 and 50.

Advantageously, n is between, limits included, 1 and 30, preferably between 2 and 30, more preferably between 3 and 30, more particularly between 5 and 30, and very preferably between 10 and 30.

[0026] Preferably, n is from 2 to 30.

As indicated above, A represents a sequence of one or more units chosen from ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof. According to a particular embodiment, when the compound of formula (I) comprises a mixture of said different units, they can be distributed randomly, alternately or in blocks.

According to a preferred embodiment, A represents a sequence of at least one ethylene oxide unit and at least one propylene oxide unit, distributed alternately, randomly or in blocks.

According to yet another preferred embodiment, A represents a sequence of at least one ethylene oxide unit and at least one butylene oxide unit, distributed alternately, randomly or in blocks.

According to yet another preferred embodiment, A represents a sequence of at least one propylene oxide unit and at least one butylene oxide unit, distributed alternately, randomly or in blocks.

According to a preferred embodiment of the invention, the group formed by Ri, F¾ and the carbon atom to which Ri and F¾ are attached represents the 2-octyl radical, n ranges from 3 to 15, and A represents a sequence of one or more units chosen from ethylene oxide, propylene oxide, butylene oxide units and mixtures thereof.

The invention also relates to the mixtures of secondary alcohol sulfates according to formula (I) as defined above.

A subject of the invention is also the salts of the compounds of formula (I) as defined above.

More precisely, the subject of the invention is the compound of formula (I) in the form of a salt with an alkali cation, an alkaline earth cation, a metal cation or with an organic compound, including organic bases.

As indicated above, these salts can be addition salts of a compound of formula (I) with a base, organic or inorganic.

These salts may be salts of organic amines, said amines possibly containing one or two or more amine groups. The amines which can be used for salifying the compounds of formula (I) as defined above are preferably chosen, and in a non-imitative capacity, from alkylamines, cycloalkylamines, aromatic amines and alkanolamines, said amines possibly being primary or secondary. or tertiary, and may also be alkoxylated.

[0037] The compounds of formula (I) can also be salts of heterocyclic amines or of urea. The salts of the compounds of formula (I) with the ammonium cation (NH4 + ) also form part of the invention.

These salts can be inorganic salts. Advantageously, they are the salts of the compounds of formula (I) with the elements of column 1 of the periodic table of the elements (alkali metals) such as for example lithium, sodium, potassium, rubidium and cesium.

[0039] According to another advantageous embodiment of the present invention, the salts of the compounds of formula (I) are the salts with the elements of column 2 of the periodic table of the elements (alkaline earth), for example magnesium and calcium.

[0040] According to yet another advantageous embodiment of the present invention, the salts of the compounds of formula (I) are the salts with the elements from columns 3 to 13 of the periodic table of the elements (transition metals), for example vanadium , manganese, cobalt, zirconium, yttrium, iron, cadmium, aluminum and zinc.

Yet according to another advantageous embodiment of the present invention, the salts of the compounds of formula (I) are those with rare earths (lanthanides and actinides), such as for example lanthanum, cerium, thorium, uranium and plutonium .

The compound of formula (I) according to the present invention can be obtained advantageously by sulfation of an alkoxylated secondary alcohol, according to methods well known to those skilled in the art. For example, sulfation consists in reacting the secondary alcohol with a sulfated compound chosen from sulfur trioxide, sulfuric acid, oleum, sulfur trioxide, sulfur trioxide complexes, sulfamic acid, chlorosulfonic acid, among others.

As indicated above, the synthesis of these sulfates and the characteristics of their preparation processes are known to those skilled in the art and are for example described by X. Domingo in “Anionic Surfactants”, vol. 5 HW Stache (1996), 224-279 pages, "Encyclopedia of Chemical Technology", Kirk Othmer, 4 th Edition, (1997), vol. 23, pp. 146-175; "Ullmann's Encyclopedia oflndustrial Chemistry", 5 th edition, Elvers, B., Hawkins, S. Schulz, G., (1994), vol. A25, pp. 778-783.

Preferably, the secondary alcohol used to synthesize the compound of formula (I) is chosen from 2-octanol and methyl isobutylcarbinol, preferably the secondary alcohol is 2-octanol.

This alcohol is of particular interest in several ways. Indeed, it is a bio-sourced, biodegradable product with a good ecotoxicological profile. In addition, the boiling point of 2-octanol is high and the cost price is quite reasonable.

[0046] According to a preferred embodiment, the alkoxylation of the secondary alcohol used to synthesize the compound of formula (I) is obtained using a catalyst of dimetallic cyanide type, also called DMC catalyst. Preferably, the catalyst of dimetallic cyanide type can be of any nature known to those skilled in the art. This catalyst is described in particular in patents US6429342, US6977236 and PL398518. Specifically, the catalyst used is zinc hexacyanocobaltate, for example marketed by Bayer Corporation under the name Arcol ® or by Mexeo under the name MEO-DMC ® .

Another object of the invention is the use of the compound of formula (I) according to the invention defined above, and / or one of its salts, alone or as a mixture, as a surfactant, a surfactant with low foaming power, wetting agent, foaming agent, hydrotrope, detergent, solvent, reactive solvent, coalescing agent, compatibilizer, emulsifying agent, dispersant, chemical intermediate, corrosion inhibitor, demulsifier, plasticizer, sequestering agent, mineral deposit inhibitor, liquid ionic, stabilizer, lubricant, additive for bitumens, additive for de-inking, gelling agent in oils, flotation collector for ores, processing aid in the manufacture of plastic objects, antistatic agent, additive for fertilizer coatings, for plant protection,for the treatment of textiles and for the enhanced recovery of petroleum, for the production of electrodes and electrolytes for batteries, to name only some of the most common applications known for this type of compound.

According to yet another object, the present invention relates to a composition comprising at least one compound of formula (I) as defined above, and / or one of its salts, alone or as a mixture, with one or more aqueous solvents, organic, hydroorganic, such as for example water, alcohols, glycols, polyols, mineral oils, vegetable oils, and others, alone or as mixtures of two or more of them, in all proportions.

The composition according to the invention may also contain one or more additives and fillers well known to a person skilled in the art, such as, for example, and without limitation, anionic, cationic, amphoteric or nonionic surfactants , rheology modifiers, de-emulsifiers, anti-deposit agents, anti-foam agents, dispersants, pH control agents, colorants, anti-oxidants, preservatives, corrosion inhibitors, biocides, and other additives such as for example sulfur products , nitrogenous borates, phosphates, and others. The natures and amounts of additives and fillers can vary widely depending on the nature of the envisaged application and can easily be adapted by those skilled in the art.

The invention is now illustrated by the following examples, which are in no way limiting.
CLAIMS

1. Compound of formula (I) below:

in which :

- the groups R 1 and R 2, identical or different, represent, independently of one another, a linear, branched or cyclic, saturated or unsaturated hydrocarbon group comprising from 1 to 6 carbon atoms, it being understood that the sum of carbon atoms of the groups R 1 and R 2 range from 2 to 7, R 1 and R 2 being able to form together and with the carbon atom which carries them, a ring with 6, 7 or 8 vertices,

- A represents a sequence of one or more units chosen from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, and

- n is an integer between, limits included, 1 and 100, preferably between 2 and 100, more preferably between 3 and 100, more particularly between 5 and 100, and very preferably between 10 and 100.

2. A compound according to claim 1, in the form of a salt with an alkali cation, an alkaline earth cation, a metal cation or with an organic compound, including organic bases.

3. A compound according to claim 1 or claim 2, in which the groups R 1 and R 2, which are identical or different, are chosen, independently of one another, from methyl, ethyl, n-propyl, / ' so -propyl, n-butyl, sec-butyl, ie / f-butyl, pentyls, and hexyls.

4. Compound according to any one of claims 1 to 3, in which the radical formed by R 1, R 2 and the carbon atom to which they are attached is chosen from the 2-octyl radical and the 4-methyl-2 radical. -pentyl, preferably the radical formed by R 1, R 2 and the carbon atom to which they are attached is the 2-octyl radical.

5. Compound according to any one of claims 1 to 4, in which n is between, limits included, 1 and 75, preferably between 2 and 75, more preferably between 3 and 75, more particularly between 5 and 75, and very preferably between 10 and 75.

6. Compound according to any one of claims 1 to 5, in which n is between, limits included, 1 and 50, preferably between 2 and 50, more preferably between 3 and 50, more particularly between 5 and 50, and very preferably between 10 and 50.

7. A compound according to any one of claims 1 to 5, in which the group formed by Ri, F¾ and the carbon atom to which they are attached represents the 2-octyl radical, n ranges from 3 to 15, and A represents a sequence of one or more units chosen from ethylene oxide, propylene oxide, butylene oxide units and mixtures thereof.

8. Salt of the compound according to any one of claims 1 to 7, corresponding to the following formula (II):

in which ;

- M x + represents a cationic group carrying at least one cation chosen from ammonium cation, metal cation, nitrogen cation, borated cation, phosphorus cation,

- x is an integer ranging from 1 to 7, and

- Ri, R2, A and n being as defined in any one of claims 1 to 7.

9. Use of a compound according to any one of the preceding claims, as a surfactant, low-foaming surface-active agent, wetting agent, foaming agent, hydrotrope, detergent, solvent, reactive solvent, coalescing agent, compatibilizer. , emulsifier, dispersant, chemical intermediate, corrosion inhibitor, demulsifier, plasticizer, sequestrant, mineral deposit inhibitor, ionic liquid, stabilizer, lubricant, additive for bitumen, additive for deinking, gelling agent in oils, flotation collector for ores, processing aid in the manufacture of plastic articles, antistatic agent, additive for fertilizer coatings, for plant protection, for the treatment of textiles and for enhanced oil recovery,for the production of electrodes and electrolytes for batteries.

10. Composition comprising at least one compound of formula (I) and / or one of its salts, alone or as a mixture, as defined in any one of claims 1 to 8, with one or more aqueous, organic or aqueous solvents. -organic, and optionally one or more additives and fillers.