SECONDARY ALCOHOLIC ALCOHOL

The present invention relates to the general field of alkoxylated secondary alcohols.

[0002] 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 a solvent, a hydrotrope or also a nonionic surfactant. 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.

[0003] Conventionally, the alkoxylates of secondary alcohols are synthesized using basic catalysis, for example using potassium hydroxide. Another type of catalyst can also be used: the catalyst of the dimetallic cyanide type, called the DMC catalyst.

[0004] Various documents refer to the alkoxylation of various compounds, including alcohols, by basic catalysis and / or by DMC catalysis.

[0005] For example, document WO 2012/071149 describes the ethoxylation of polybranched secondary alcohols by basic catalysis and / or DMC catalysis. In this document, the secondary alcohols comprise a large number of carbon atoms and numerous branches or branches on the main chain.

[0006] Furthermore, document WO 2009/000852 describes a process for the alkoxylation of various compounds via DMC catalysis. Propylene oxide and / or butylene oxide first react with said compounds, in the presence of a DMC catalyst, then ethylene oxide is grafted to the alkoxylate synthesized using the DMC catalyst present initially.

[0007] Document WO 2012/005897 discloses in particular alcohols alkoxylated using a propoxylated block, then an ethoxylated block, in the presence of a DMC catalyst.

[0008] It is also known that low molecular weight alcohols are poisons of the DMC catalyst.

This is one of the reasons why industrial players favor the alkoxylation of long chain or very strongly branched alcohols to avoid the formation of stable chelates, in the presence of the DMC catalyst.

It should also be noted that industrial players favor a first alkoxylation step with a propylene oxide and / or butylene oxide block, then a second alkoxylation step using ethylene oxide.

The alkoxylation processes described in the two documents WO 2009/000852 and WO 2012/005897 as cited above are moreover carried out according to this method.

[0012] It is also recognized that secondary alcohols exhibit low reactivity with respect to primary alcohols. As a result, the industrialization of products obtained by alkoxylating secondary alcohols has never been reasonably considered.

[0013] In addition, at a time when the environmental issue is truly important, the use of a bio-sourced or biodegradable reagent and having a good ecotoxicological profile is worth considering.

[0014] Thus, a short-chain alkoxylated secondary alcohol is sought, 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 alkoxylated secondary alcohols, the starting compound of which is a bio-sourced and biodegradable reagent.

The object of the present invention is to provide a solution making it possible to solve the problems mentioned above.

The invention relates to a compound of formula (I) below:

(IX

in which :

- The groups R 1 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; the groups R1 and R2 can also form together and with the carbon atom which carries them, a ring with 6, 7 or 8 vertices,

- n is an integer between, limits included, 1 and 100, preferably between 2 and 100, more preferably between 3 and 100, particularly between 4 and 100, more particularly between 5 and 100, preferably between 6 and 100 , more preferably between 7 and 100, preferably between 8 and 100, even more preferably between 9 and 100 and very preferably between 10 and 100,

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

- the group formed by Ri, F¾ and the carbon atom, to which Ri and F¾ are attached, has a degree of branching equal to 0, 1 or 2.

A subject of the present invention is also a process for preparing the compound of formula (I) according to the invention.

Another object of the invention is the use of a catalyst of dimetallic cyanide type (“DiMetallic Cyanide” or “DMC” in English) to carry out the alkoxylation of 2-octanol.

A subject of the present invention is also the use of the compound of formula (I) according to the invention, as nonionic surfactant, low foaming surfactant ("low-foaming surfactant" in French). English), wetting agent, foaming agent, hydrotrope, detergent, solvent, reactive solvent, coalescing agent, compatibilizer, emulsifier, 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 coatingsfertilizers, for plant protection, for textile processing and for enhanced oil recovery, for the production of electrodes and electrolytes for batteries

[0020] 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 ..." and "between ... and ..." used in the present description should be understood as including each of the limits mentioned.

For the purposes of the present invention, the term “ethylene oxide unit” is understood to mean a unit resulting from ethylene oxide after opening of the oxirane ring. For the purposes of the present invention, the term “propylene oxide unit” is understood to mean a unit derived from propylene oxide after opening of the oxirane ring. For the purposes of the present invention, the term “butylene oxide unit” is intended to mean a unit resulting from butylene oxide after opening of the oxirane ring.

The compound according to the invention is of formula (I) as mentioned above.

In other words, the groups Ri and F¾, and the carbon to which they are attached denote a secondary radical in C3-C8, preferably in C4-C8, more particularly in C5-C8, preferably in C6-C8 .

Preferably, the groups R 1 and F¾, identical or different, represent, independently of one another, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, pentyl, hexyl .

Preferably, the group formed by R 1, R 2 and the carbon atom, to which R 1 and R 2 are attached, is chosen from the 2-octyl radical and the 4-methyl-2-pentyl radical. More particularly, the group formed by R 1, R 2 and the carbon atom, to which R 1 and R 2 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, particularly between 4 and 75, more particularly between 5 and 75, preferably between 6 and 75, more preferably between 7 and 75, preferably between 8 and 75, even more preferably between 9 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, particularly between 4 and 50, more particularly between 5 and 50, preferably between 6 and 50, more preferably between 7 and 50, preferably between 8 and 50, even more preferably between 9 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, particularly between 4 and 30, more particularly between 5 and 30, preferably between 6 and 30, more preferably between 7 and 30, preferably between 8 and 30, even more preferably between 9 and 30 and very preferably between 10 and 30. Preferably, n is from 2 to 30.

The degree of branching designates, within the meaning of the present invention, the total number of terminal methyl groups (-CH3) present on the groups R 1 and R 2 minus 1. In other words, the degree of connection, denoted by D is an integer equal to the difference between the sum of the terminal methyl groups (-CH3) present on the groups R 1 and R 2 and 1. This equation can be expressed as follows:

Thus, if the groups R 1 and R 2 comprise 2 methyl groups, the degree of branching is then 1.

D = ∑ (Me in R1 and R2) - 1 = 2 - 1 = 1

Preferably, the degree of connection is 1 or 2.

[0033] For example, the degree of branching of the 2-octyl radical is 1 and the degree of branching of the 4-methyl-2-pentyl radical is 2.

The compound of formula (I) comprises n unit (s) ethylene oxide, and a sequence comprising one or more units chosen from the unit of 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.

In a preferred embodiment of the invention, the compound of formula (I) comprises n unit (s) ethylene oxide, and a sequence comprising one or more units chosen from the unit ethylene oxide, oxide of propylene, butylene oxide and mixtures thereof, said units possibly being distributed randomly, alternately or in blocks, at least one propylene oxide or butylene oxide unit being present in said sequence.

[0037] According to another preferred embodiment, A represents a sequence comprising at least one ethylene oxide unit and at least one propylene oxide unit, distributed alternately, randomly or in blocks.

[0038] According to yet another preferred embodiment, A represents a sequence comprising at least one ethylene oxide unit and at least one butylene oxide unit, distributed alternately, randomly or in blocks.

[0039] According to yet another preferred embodiment, A represents a sequence comprising at least one propylene oxide unit and at least one butylene oxide unit, distributed alternately, randomly or in blocks.

A subject of the invention is also a process for preparing a compound of formula (I) as defined above, comprising the following successive steps:

(a) reacting a secondary alcohol of the following formula (II): RiCH (OH) R2 (II), in which Ri and R2 are as defined above, with n ethylene oxide (s), where n is such that previously defined,

in the presence of at least one catalyst of dimetallic cyanide type;

(b) reacting the product resulting from step (a) with one or more oxides chosen from ethylene oxide, propylene oxide, butylene oxide and their mixtures, in the presence of at least a catalyst of the dimetallic cyanide type.

[0041] Optionally, the product resulting from step (a) can be isolated. The process according to the invention has the advantage of synthesizing the compound of formula (I) under good safety conditions, so that it can be carried out on an industrial scale. Indeed, the operating conditions in terms of temperature and pressure are controlled by the process according to the invention. The exothermicity of the reaction is in particular controlled.

The secondary alcohol of formula (II) has a degree of branching 0, 1 or 2. Advantageously, the secondary alcohol of formula (II) has an average molar mass by weight ranging from 70 to 200 g / mol, preferably from 80 to 180 g / mol. The secondary alcohol of formula (II) is C3-C8, preferably C6-C8.

The secondary alcohol of formula (II) can be chosen from 2-octanol and methyl isobutylcarbinol, preferably 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 its cost price is quite reasonable.

According to a preferred embodiment, the secondary alcohol of formula (II) is implemented after drying so that the water content in said alcohol is less than or equal to 200 ppm, preferably less than or equal at 100 ppm.

Preferably, the catalyst of dimetallic cyanide type can be of any nature known to those skilled in the art. These catalysts are described 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 ® .

Advantageously, the content of catalyst of dimetallic cyanide type ranges from 1 to 1000 ppm relative to the content of secondary alcohol of formula (II), preferably from 1 to 500 ppm, preferably from 2 to 300 ppm, more preferably from 5 to 200 ppm.

According to a preferred embodiment, the ethylene oxide / secondary alcohol molar ratio of formula (II) ranges from 1 to 100, preferably from 2 to 100, preferably from 3 to 100, preferably from 4 to 100, particularly from 5 to 100, more particularly from 6 to 100, preferably from 7 to 100, even more preferably from 8 to 100, preferably from 9 to 100, and preferably from 10 to 100.

Preferably, the reaction temperature during step (a) ranges from 80 to 200 ° C, preferably from 100 to 180 ° C. The pressure of the reaction during step (a) can range from 0.01 MPa to 3 MPa, preferably from 0.02 MPa to 2 MPa.

Preferably, the reaction temperature during step (b) ranges from 80 to 200 ° C, preferably from 100 to 180 ° C. The reaction pressure during step (b) can range from 0.01 MPa to 3 MPa, preferably from 0.02 MPa to 2 MPa.

The duration of each of steps (a) and (b) can range from a few minutes to a few hours, typically 5 minutes to 24 hours.

Preferably, the method according to the invention comprises a step of eliminating the residual oxides chosen from the oxides of ethylene, propylene, butylene and their mixtures used during the method according to the invention. Thus, this step can take place between step (a) and step (b) and also after step (b)

For the purposes of the present invention, “residual oxide” is understood to mean an oxide which has not reacted. Preferably, said step of removing the residual oxide is carried out by cooking, that is to say by maintaining a temperature ranging from 70 to 170 ° C, preferably from 100 to 160 ° C, to consume the residual oxide, and / or by a stripping step under a stream of inert gas. Alternatively, said stripping step can be carried out under vacuum.

Preferably, after said elimination step, the mass content of residual oxide is less than or equal to 0.1% relative to the weight of compound of formula (I) obtained, preferably less than or equal to 0.01% , more preferably less than or equal to 0.001%.

[0054] Preferably, the method according to the invention comprises the following successive steps:

(a1) Mix in a reactor at least one secondary alcohol of formula (II), preferably dried beforehand as described above, and at least one catalyst of dimetallic cyanide type;

(a2) gradually adding n ethylene oxide (s) to the mixture, to obtain the secondary alcohol of formula (I) ethoxylated;

(a3) maintaining at the reaction temperature until the pressure stabilizes;

(a4) Add to the mixture one or more oxides chosen from ethylene oxide, propylene oxide, butylene oxide and their mixtures,

(a5) maintaining at the reaction temperature until the pressure stabilizes;

(a6) recovery of the expected product after optional (but preferred) stripping.

Preferably, the method according to the invention comprises the following successive steps:

(a1) Mix in a reactor at least one secondary alcohol of formula (II), preferably dried beforehand as described above, and at least one catalyst of dimetallic cyanide type;

(a2) gradually adding n ethylene oxide (s) to the mixture, to obtain the secondary alcohol of formula (I) ethoxylated;

(a3) maintaining at the reaction temperature until the pressure stabilizes;

(a4) adding to the mixture one or more oxides selected from propylene oxide and butylene oxide and mixtures thereof;

(a5) maintaining at the reaction temperature until the pressure stabilizes;

(a6) Add to the mixture one or more oxides selected from ethylene oxide, propylene oxide, butylene oxide and mixtures thereof;

(a7) maintaining at the reaction temperature until the pressure stabilizes;

(a8) recovery of the expected product after optional (but preferred) stripping.

Furthermore, the method can be implemented in batch, semi-continuously or continuously. Those skilled in the art will know how to adapt the process for manufacturing the compound of formula

(I) according to the invention according to the random, alternating or block distribution of the sequence A.

A subject of the invention is also the use of a catalyst of dimetallic cyanide type for carrying out the alkoxylation of 2-octanol.

A subject of the present invention is also the use of the compound of formula (I) as defined above, as a nonionic surfactant, low foaming surfactant, 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 de-inking, gelling agent in oils, flotation collector for minerals, processing aid in the manufacture of plastic objects, 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.

A subject of the present invention is also a composition comprising at least one compound of formula (I) as defined above, and one or more aqueous, organic, hydro-organic solvents, such as for example water, alcohols, glycols , polyols, mineral oils, vegetable oils, and others, alone or in 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 those 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 illustrated by the following examples which are in no way limiting.

EXAMPLES

[0062] The 2-octanol (CAS RN 123-96-6) used is 2-octanol Oleris ® grade "Refined" (purity> 99%), marketed by Arkema France.

Example 1: Ethoxylation of 2-octanol

In an autoclave of 4 L, clean and dry, 619 g (4.76 M) of 2-octanol dried at less than 200 ppm of water and 0.06 g (100 ppm) of DMC Arcol catalyst are charged ® . The reactor is closed, purged with nitrogen and the tightness under pressure is checked. The reactor is pressurized with nitrogen at 0.269 MPa at 20 ° C.

The reaction medium is brought to 120 ° C with stirring. At this temperature of 120 ° C., 40 g of ethylene oxide are introduced. When the initiation of the reaction is observed, the remainder of the ethylene oxide is introduced, ie in all 628 g (14.27 M) over 60 min at a temperature of 140-150 ° C. At the end of the addition, the temperature is maintained for 30 min and then the residual ethylene oxide is stripped with nitrogen. The reactor is cooled to 60 ° C. and 1240 g of alkoxylated 2-octanol comprising 3 ethylene oxide units are recovered. The hydroxyl number (IOH) is 210 mg KOH / g and the coloration is 26 Hz.

Example 2: Ethoxylation of methyl isobutylcarbinol (MIBC)

[0065] In a 4 L autoclave, clean and dry, was charged 441 g (4.32 M) of MI BC dried at less than 200 ppm of water and 0.044 g (100 ppm) of DMC catalyst Arcol ® . The reactor is closed, purged with nitrogen and the tightness under pressure is checked. The reactor is pressurized with nitrogen at 0.246 MPa at 28 ° C.

The reaction medium is brought to 120 ° C with stirring. At this temperature of 120 ° C., 40 g of ethylene oxide are introduced. When the initiation of the reaction is observed at 141 ° C, the remainder of the ethylene oxide is introduced, ie in all 380 g (8.64 M) over 40 min at a temperature of 140 ° C-150 ° vs. At the end of the addition, the temperature is maintained for 60 min, then the residual ethylene oxide is stripped with nitrogen. The reactor is cooled to 60 ° C. and 815 g of alkoxylated methylisobutylcarbinol comprising 2 ethylene oxide units are recovered. (IOH: 290 mg KOH / g and staining: 3 Hz).

Example 3: Ethoxylation-propoxylation of 2-octanol

In an autoclave of 10 L, clean and dry, 1034 g (7.95 M) of 2-octanol dried at less than 200 ppm of water and 0.15 g (145 ppm) of DMC Arcol catalyst are charged ® . The reactor is closed, purged with nitrogen and the tightness under pressure is checked. The reactor is pressurized with nitrogen under 0.12 MPa at 27 ° C.

The reaction medium is brought to 120 ° C with stirring. At this temperature of 120 ° C., 35 g of ethylene oxide are introduced. When the initiation of the reaction is observed, the remainder of the ethylene oxide is introduced, ie a total of 2098 g (47.68 M) over 4 hours at a temperature of 140 ° C-150 ° C. At the end of the addition, the temperature is maintained for 30 min to consume the residual ethylene oxide. An analytical sample of the intermediate product indicates the following characteristics: IOH = 136 mg of KOH / g and staining of 39 Hz.

The reaction is continued by introducing propylene oxide, or a total of 1844 g (31, 18 M) over 3 hours. At the end of the reaction, the mixture is maintained at 140 ° C. for 30 min to consume the residual propylene oxide, then a purge and degassing is carried out, 4910 g of 2-octanol-60E-40P are recovered. IOH = 86 mg KOH / g and 44 Hz stain.
CLAIMS

1. Compound of formula (I) below:

in which :

- The groups R 1 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; the groups R1 and R2 can also form together and with the carbon atom which carries them, a ring with 6, 7 or 8 vertices,

- n is an integer between, limits included, 1 and 100, preferably between 2 and 100, more preferably between 3 and 100, particularly between 4 and 100, more particularly between 5 and 100, preferably between 6 and 100 , more preferably between 7 and 100, preferably between 8 and 100, even more preferably between 9 and 100 and very preferably between 10 and 100,

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

- the group formed by R 1, R 2 and the carbon atom to which R 1 and R 2 are attached, has a degree of branching equal to 0, 1 or 2.

2. Compound according to claim 1, characterized in that the group formed by R 1, R 2 and the carbon atom to which R 1 and R 2 are attached has a degree of branching of 1 or 2.

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

4. Process for preparing a compound of formula (I) as defined in any one of claims 1 to 3, comprising the following successive steps:

(a) reacting a secondary alcohol of the following formula (II): RiCH (OH) R2 (II), in which R1 and R2 are as defined in claim 1, with n ethylene oxide (s), where n is as defined in claim 1, in the presence of at least one catalyst of dimetallic cyanide type;

(b) reacting the product resulting from step (a) with one or more oxides chosen from ethylene oxide, propylene oxide, butylene oxide and their mixtures, in the presence of at least a double metallic cyanide type catalyst.

5. Method according to claim 4, characterized in that the secondary alcohol of formula (II) has an average molar mass by weight ranging from 70 to 200 g / mol, preferably from 80 to 180 g / mol.

6. Method according to claim 4 or 5, characterized in that the secondary alcohol of formula (II) is chosen from 2-octanol and methyl isobutylcarbinol, preferably 2-octanol.

7. Process according to any one of claims 4 to 6, characterized in that the catalyst of dimetallic cyanide type is zinc hexacyanocobaltate.

8. Method according to any one of claims 4 to 7, characterized in that the content of catalyst of dimetallic cyanide type ranges from 1 to 1000 ppm relative to the content of secondary alcohol of formula (II), preferably 2. at 300 ppm, more preferably from 5 to 200 ppm.

9. Method according to any one of claims 4 to 8, characterized in that the molar ratio of ethylene oxide / secondary alcohol of formula (II) ranges from 2 to 100, preferably from 3 to 100, more preferably from 4 to 100, particularly 5 to 100, more particularly 6 to 100, preferably 7 to 100, even more preferably 8 to 100, preferably 9 to 100, and preferably 10 to 100.

10. Use of a catalyst of dimetallic cyanide type to effect the alkoxylation of 2-octanol.

11. Use of the compound of formula (I) as defined in any one of claims 1 to 3, as nonionic surfactant, low foaming surfactant, 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, bitumen additive, de-inking additive , gelling agent in oils, flotation collector for minerals, 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.

12. Composition comprising at least one compound of formula (I) as defined in any one of claims 1 to 3, and one or more aqueous, organic or hydro-organic solvents, optionally with one or more additives and fillers.