0001] The present invention relates to the general field of ether amines. The family of ether amines is a unique family of chemicals with a wide range of properties. Indeed, they can be used in particular as lubricant, cationic surfactant, flotation collector for minerals or as a corrosion inhibitor. Thus, they are a class of materials which are of major industrial interest for many actors. The ether amines market is already largely developed over several decades.

[0002] etheramines are conventionally synthesized by first reacting an alcohol with a nitrile compound, generally acrylonitrile, in the presence of a basic catalyst. A hydrogenation step the product obtained is then performed to isolate the etheramine referred.

[0003] For example, the US5196589 patent discloses a method for producing etheramine by reacting a first alcohol with acrylonitrile in the presence of an alkaline catalyst. A hydrogenation step is then performed to obtain the desired etheramine. The feature of this process resides in the fact that the alcohol, a compound comprising a number of carbon atoms ranging from 6 to 36, in the presence of a stable free radical compound, thereby reducing considerably obtaining particular unwanted side products.

[0004] Patent EP1219597 discloses in turn a process for preparing an etheramine comprising a first step of reacting a primary or secondary alcohol with acrylonitrile in the presence of an alkali metal hydroxide, then a second step hydrogenation product obtained. The primary or secondary alcohol is a compound comprising a number of carbon atoms ranging from 6 to 24.

[0005] In contrast, at a time when the environmental issue is really important, none of these documents suggests using any bio-based or biodegradable reactive and has a good ecotoxicological profile.

[0006] Furthermore, it is known that special ether amines, including products marketed Tomamine® PA-14 and Tomamine® DA-14, are used for the selective removal of silicates in ore flotation.

[0007] It would be interesting to provide an ether amine obtained from at least one bio-based and biodegradable reagent. It would also be advantageous for the use of such etheramine lead to a more selective removal of silicates in the ore flotation that commercial ether amines.

[0008] The present invention relates to a compound of formula (I):

(I) wherein:

Ri and R2, identical or different, represent, independently of one another, a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms;

R3 and groups R 4 , identical or different, are chosen, independently of each other, from a hydrogen atom, methyl group and ethyl group;

the groups R 5, R 6, and R 7 , identical or different, are chosen, independently of each other, from a hydrogen atom and an alkyl group comprising from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms;

n is an integer from 0 to 20;

m is an integer from 1 to 6.

[0009] According to a preferred embodiment, when Ri is a group hexyl, R2 is methyl, n is 0, R5, R6 and R 7 denote a hydrogen atom, then m is different from 1.

[0010] According to another preferred embodiment, the total number of carbon atoms of Ri and R2 is between 5 and 20 carbon atoms, preferably between 6 and 20 carbon atoms.

[0011] The present invention also relates to a method of manufacturing the compound of formula (I) according to the invention.

[0012] Another object of the invention is a compound of formula (V):

in which :

Ri, R2, R3, R 4 , R 5, R 6 and R 7 are as defined above and n is as defined above.

[0013] The résente invention also relates to a compound of formula (VI):

in which :

Ri, R2, R3, R 4 , R 5, R 6 and R 7 are as defined above, and n and m are as defined above.

[0014] Another object of the present invention relates to the use of the compound according to the invention as including flotation collector for minerals.

[0015] Other advantages and features of the invention will become apparent on examining the detailed description.

[0016] It is also specified that the terms "between ... and ..." and "... to ..." used herein shall be construed as including each of the mentioned limits.

[0017] The compound of the invention is of formula (I) mentioned above.

[0018] Preferably, n is an integer from 0 to 10, more preferably from 0 to 5, more preferably from 0 to 1.

[0019] Advantageously, the groups R3 and R 4 , identical or different, are chosen, independently of each other, from a hydrogen atom and the methyl group.

[0020] Preferably, m is an integer from 1 to 4, more preferably m is 1, 2 or 3.

[0021] The invention also relates to a method of manufacturing the compound of formula (I) according to the invention, comprising successively:

a step of reactio a compound of formula (II):

(II)

wherein Ri, R2, R3 and R 4 and n are as defined above; a nitrile with α, β-unsaturated;

a hydrogenation reaction;

the product of these steps being capable of reacting in series (m-1) times with the nitrile α, β-unsaturated and dihydrogen, m being as defined previously.

[0022] According to a preferred embodiment, the nitrile α, β-unsaturated carboxylic acid is selected from acrylonitrile and methacrylonitrile, preferably acrylonitrile.

[0023] Thus, when n is 0, the compound of formula (II) can be 2-octanol. This alcohol is of particular interest for several reasons. Indeed, it is a bio-based, biodegradable and has a good ecotoxicological profile. In addition, the boiling point of 2-octanol is high and the cost is quite reasonable.

[0024] Advantageously, the molar ratio of the nitrile α, β-unsaturated compound of the formula (II) varies from 0.8 to 1, 2, preferably from 0.9 to 1, 2.

[0025] In a particularly advantageous manner, the molar ratio of the nitrile α, β-unsaturated compound of the formula (II) ranges from 1 01 to 1, 1, that is to say the reaction of the compound of formula (II) with the nitrile α, β-unsaturated carboxylic acid is carried out with a slight excess of nitrile α, β-unsaturated.

[0026] Preferably, the reaction of the compound of formula (II) with the nitrile α, β-unsaturated carboxylic acid is conducted in the presence of at least one basic catalyst CB.

[0027] Preferably, the CB basic catalyst is selected from alkali metal hydroxides and alkaline earth, alkali metal alkoxides, alkali hydrides, basic resins and quaternary ammonium hydroxides.

[0028] Particularly preferably, the basic catalyst CB is selected from sodium hydroxide, potassium hydroxide, sodium hydride and potassium hydride.

[0029] According to a particular embodiment of the invention, the amount of basic catalyst used varies CB from 0.1% to 2% by weight, preferably from 0.5% to 1% by weight, based on the weight total of the compound of formula (II).

[0030] The temperature of the reaction of the compound of formula (II) with the nitrile α, β-unsaturated may vary in large proportions. Preferably it ranges from 20 to 75 ° C, more preferably from 25 to 70 ° C, more preferably 25 to 65 ° C.

[0031] Advantageously, the reaction of the compound of formula (II) with the nitrile α, β-unsaturated carboxylic acid is carried out without solvent but it is also possible to use a solvent neutral vis-à-vis the reaction of the compound of formula ( II) with the nitrile α, β-unsaturated.

[0032] The term "solvent neutral vis-à-inert solvent" means any solvent which does not interact chemically with the reactants of the reaction of the compound of formula (II) with the nitrile α, β-unsaturated.

[0033] Preferably, the solvent neutral vis-à-vis the reaction are selected from ethers, dimethylformamide and aromatic solvents solubilizing reagents selected from toluene and xylenes.

[0034] Where appropriate, the CB basic catalyst can be neutralized at the end of reaction by any means known to those skilled in the art, such as, for example, and without limitation, an organic or inorganic acid, preferably selected from hydrochloric acid and acetic acid or, alternatively, the catalyst may be removed, for example by filtration when it is solid in nature.

[0035] Preferably, the hydrogenation reaction is carried out in the presence of at least one CT catalyst.

[0036] According to a particular embodiment, said CT catalyst is selected from Raney nickel and Raney cobalt.

[0037] Advantageously, the amount of CT catalyst varies from 0.5 to 10% by weight, preferably from 2 to 8% by weight, based on the weight of the product of the reaction of the compound of formula (II) with nitrile α, β-unsaturated.

[0038] Preferably, the pressure during the hydrogenation reaction is from 1 to

10 MPa, preferably from 1 5 to 5 MPa.

[0039] Preferably, the temperature of hydrogenation reaction ranges from 50 to 170 ° C, preferably from 70 to 150 ° C.

[0040] According to a particular embodiment of the invention, in order to promote the formation of the primary amine, it is possible to add an amount of ammonia that can generate ammonia partial pressure. Advantageously, a molar ratio ammonia / nitrile function ranging from 0.5 to 2 is adapted. Alternatively,

11 is also possible to add a strong base, preferably selected from sodium hydroxide and potassium hydroxide, in an amount ranging from 100 ppm to 5000 ppm, preferably from 500 to 5000 ppm, more preferably from 500 to 2500 ppm, relative to the amount of product obtained by reacting the compound of formula (II) with the nitrile α, β-unsaturated.

[0041] Particularly advantageously, the addition of said amount of ammonia that can generate ammonia partial pressure and the addition of said strong base are combined.

[0042] Preferably, the successive steps of reacting the compound of formula (II) with the nitrile α, β-unsaturated and hydrogenation reaction are carried out in the same reactor.

[0043] It is also possible to work in a solvent medium with organic solvents or aqueous-organic, such as for example alcohols (methanol, ethanol, isopropanol) and any other solvent used for hydrogenation reactions and solubilizing reagents and the final products.

[0044] It is possible to work in batch by introducing all reactants and carrying out the hydrogenation reaction. It is also possible to operate in semi-batch by charging the solvent, ammonia and / or strong base, catalyst and hydrogen, and by continuously feeding the condensation product obtained by reacting the compound of formula ( II) with the nitrile α, β-unsaturated.

[0045] Advantageously, the reaction of the compound of formula (II) with the nitrile α, β-unsaturated and hydrogenation reaction are carried out in different reactors.

[0046] Preferably, the method according to the invention comprises, prior to the successive steps of reacting the compound of formula (II) with a nitrile α, β-unsaturated and hydrogenation, a step of reacting an alcohol of formula ( III)

where Ri and R2 are as defined above,

with n compound (s) formulated

in which :

the groups R3 and R 4 are as defined above, and

n is as defined above.

[0047] The invention also relates to the use of a compound of formula (I) as defined above, as a lubricant, cationic surfactant, flotation collector for minerals, corrosion inhibitor, fuel additive and curing agent for epoxy resins.

[0048] The use of the compound of formula (I), as a collector for flotation of ores is particularly preferred.

[0049] The invention is illustrated by the following examples which are in no way limiting.

EXAMPLES

[0050] The 2-octanol used is grade Refined product sold by Arkema. Example 1: Synthesis of 3- (2-octyloxy) -propanamine

1) Synthesis of 3- (2-octyloxy) -propionitrile

a) Using potassium hydroxide

[0051] In a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, an inerting system with nitrogen, and a jacket for heating, 130 g (1 M) of 2-octanol and 2 g of potassium hydroxide in 50% aqueous solution, are loaded. The reaction medium is brought to 45 ° C with stirring and under an inert atmosphere and then 55 g (1, 04 M) of acrylonitrile are added dropwise. The temperature is maintained following casting until complete reaction. End of the reaction, the basic catalyst is neutralized by hydrochloric acid stoichiometry. Propionitrile The ether is isolated by distillation on thin film with a molar yield of 90%.

b) Use of sodium hydride

[0052] In a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, an inerting system with nitrogen, and a jacket for heating, 130 g (1 M) of 2-octanol and 0.6 g of sodium hydride are loaded. The reactor is purged with nitrogen to remove the hydrogen formed. The reaction medium is brought to 35 ° C under stirring and under an inert atmosphere and then 55 g (1, 04 M) of acrylonitrile are added dropwise. The temperature is maintained following casting until complete reaction. End of the reaction, the basic catalyst is neutralized by hydrochloric acid stoichiometry. Propionitrile The ether is isolated by distillation on thin film with a molar yield of 91%.

2) Hydrogenation of 3- (2-octyloxy) -propionitrile

[0053] In an autoclave of 300 cm 3, Type Autoclave Engineer, provided with a type of stirring impeller self-priming system, of a cooling coil and a pressure control system and the temperature, 183 g (1 M) 3 - (2-octyloxy) -propionitrile obtained according to the methods 1) a) or 1) b), 14 g of Raney nickel and 2000 ppm of KOH in 50% aqueous solution, are loaded. The autoclave is locked and purged with nitrogen. Then, hydrogen was introduced when the temperature rises such that a total pressure of 3 MPa to 1 10 ° C is obtained. The reaction is continued until no more hydrogen consumption. When the reaction, the catalyst is recovered parfiltration.

Example 2 Synthesis of a étherdiamine

1) Synthesis of 3- [3- (2-octyloxy) propylaminel-propionitrile

[0054] In a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, an inerting system with nitrogen, and a jacket for heating, 225 g (1 , 2 M) of 3- (2-octyloxy) -propanamine and 2.25 g of water are charged.

[0055] The reaction medium is brought to 60 ° C with stirring and under an inert atmosphere and then 65 g (1, 226 M) of acrylonitrile are added dropwise. The temperature is maintained following casting until complete reaction, about 2 hours. 3- [3- (2-octyloxy) propyl] -propionitrile is obtained with a molar yield of 87%.

2) Hydrogenation of 3- [3- (2-octyloxy) propylaminel-propionitrile

[0056] In an autoclave of 500 cm 3, Type Autoclave Engineer, provided with a system type stirring impeller self-priming, a cooling coil and a pressure control system and the temperature, 200 g (1 M) 3 - [3- (2-octyloxy) propyl] -propionitrile obtained according to the above method and 3.6 g of Raney Nickel are loaded. The autoclave is locked and purged with nitrogen. Then, the reaction mixture is heated to 75 ° C. Ammonia is introduced until a total pressure of 0.8 MPa. Hydrogen is then introduced during the rise in temperature such that a total pressure of 3 MPa at 120 ° C is obtained. The reaction is continued until no more hydrogen consumption. When the reaction, the autoclave is degassed and the catalyst is recovered by filtration. The crude étherdiamine is obtained with a molar yield of 83%.

Example 3 Synthesis of a polyetheramine

1) Synthesis of tris (ether) propionitrile

[0057] In a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, an inerting system with nitrogen, and a jacket for heating, 262 g (1 M) of 2-octanol tris (ethoxylated) and 2 g of potassium hydroxide in 50% aqueous solution, are loaded. The reaction medium is brought to 55 ° C with stirring under inert atmosphere, then 55.6 g (1 05 M) of acrylonitrile are added dropwise. The temperature is maintained following casting until complete reaction. End of the reaction, the basic catalyst is neutralized by hydrochloric acid stoichiometry. Tris (ether) propionitrile is obtained with a molar yield of 89%.

2) Hydrogenation of tris (ether) propionitrile

[0058] In an autoclave of 500 cm 3, Type Autoclave Engineer, provided with a system type stirring impeller self-priming, a cooling coil and a pressure control system and the temperature, 252 g (0.8 M) tris (ether) propionitrile, obtained according to the above method, 20 g of Raney nickel and 2000 ppm of potassium hydroxide in 50% aqueous solution, are loaded. The autoclave is locked and purged with nitrogen. Then, hydrogen was introduced when the temperature rises such that a total pressure of 3 MPa at 120 ° C is obtained. The reaction is continued until no more hydrogen consumption. At the end of reaction, the autoclave is degassed and the catalyst is recovered by filtration. Tris (ether) amine is obtained with a molar yield of 81%.

EXAMPLE 4 Use of compound according to the invention as a flotation collector

[0059] A phosphate ore containing silicates is purified by reverse flotation. Tests are carried out in Outotec flotation cell.

[0060] At first, 2.5 liters of tap water and 340 g of ground phosphate ore (having a particle size from 30 to 300 μηι) are introduced. The pan speed was adjusted to 1500 rev / min to ensure an ore suspension in the whole volume of the cell. 0.34 g of phosphoric acid in 85% aqueous solution, are then added and stirring is maintained for three minutes.

[0061] Then, 0.17 g of an ECSC supplied by the Company carbonate collector Melioran under the tradename ® P312 is added and stirring is maintained for two minutes. The air is then fed into the cell at a flow rate of 3 L / min, and the flotation is carried out for two minutes. A regular collection of foams with a spatula is made.

[0062] The air supply is switched off at the end of flotation and 10.2 g of cationic collector for silicates are added. Agitation is maintained for two minutes before restoring air supply. The flotation was carried out for four minutes.

[0063] Following these two steps, the remaining ore in the flotation cell is filtered on Buchner and dried in an oven overnight. The dried ore is then weighed to determine the amount recovered and sent to analysis to determine its composition.

[0064] The comparative tests cover five cationic collectors for the silicates used in the second flotation step.

[0065] The starting ore is fluoroapatite type containing 43% by weight of calcite and 17% by weight of quartz, based on the total weight of the ore, as impurities. P2O5 compound content was 13.8% by weight based on the weight of the ore.

[0066] Compound A is a comparative compound. This is the Noramac ® C26 (acetate N-alkyl amino coconut) marketed by CECA.

[0067] Compound B is a comparative compound. This is the Tomamine ® PA-14 (isodécyloxypropylamine) sold by Air Products.

[0068] Compound C is a comparative compound. This is the Tomamine ® DA-14 (isodecyloxypropyl-1, 3-diaminopropane) sold by Air Products.

[0069] Compound D is a compound of the invention of formula (VII):

[0070] The compound E is a compound of the invention of formula (VIII):

[0071] The results of analysis of the ore after flotation are summarized in Table 1 below:

- Table 1 -

[0072] Table 1 clearly shows that the compounds D and E according to the invention make it possible to remove a greater amount of silicates that three comparison compounds A, B and C.

[0073] In addition, the final content of P2O5 is more important due to the use of compounds D and E than that associated with the use of the comparative compounds.

[0074] Thus, it has been demonstrated that the use of compound according to the invention led to selective removal in the flotation of phosphate ore. This property is even improved compared to commercial products.

CLAIMS

1. A compound of formula (I):

in which :

the groups Ri and F¾, identical or different, represent, independently of one another, a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms;

R3 and groups R 4 , identical or different, are chosen, independently of each other, from a hydrogen atom, methyl group and ethyl group;

the groups R 5, R 6 and R 7 , identical or different, are chosen, independently of each other, from a hydrogen atom and an alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms;

n is an integer from 0 to 20;

m is an integer from 1 to 6.

2. A compound according to claim 1, characterized in that n is an integer from 0 to 10, more preferably from 0 to 5, more preferably from 0 to 1.

3. A compound according to claim 1 or claim 2, characterized in that the groups R 3 and R 4 , identical or different, are chosen, independently of each other, from a hydrogen atom and a methyl group .

4. A compound according to any one of claims 1 to 3, characterized in that m is an integer from 1 to 4, preferably m is 1, 2 or 3.

5. A method of making a compound of formula (I) as defined in any one of claims 1 to 4, comprising successively:

a step of reactio a compound of formula (II):

wherein the groups R, F¾, R 3 and R 4 and n are as defined in claim 1;

a nitrile with α, β-unsaturated;

a hydrogenation reaction;

the product of these steps being capable of reacting in series (m-1) times with the nitrile α, β-unsaturated and dihydrogen, m being as defined in claim 1.

6. A method according to claim 5, characterized in that the nitrile α, β-unsaturated carboxylic acid is selected from acrylonitrile and methacrylonitrile, preferably acrylonitrile.

7. The method of claim 5 or 6, characterized in that the molar ratio of the nitrile α, β-unsaturated compound of the formula (II) varies from 0.8 to 1, 2, preferably from 0.9 to 1 2.

8. Method according to one of Claims 5 to 7, characterized in that the molar ratio of the nitrile α, β-unsaturated compound of the formula (II) ranges from 1 01-1, 1.

9. Method according to one of Claims 5 to 8, characterized in that the reaction of said compound of formula (II) with the nitrile α, β-unsaturated carboxylic acid is conducted in the presence of at least one basic catalyst (CB).

10. The method of claim 9, characterized in that the basic catalyst (CB) is selected from alkali metal hydroxides and alkaline earth, alkali metal alkoxides, alkali hydrides, basic resins and hydroxides quaternary ammonium, and preferably, the basic catalyst (CB) is selected from sodium hydroxide, potassium hydroxide, sodium hydride and potassium hydride.

11. A method according to any one of claims 5 to 10, characterized in that said method comprises, prior to the successive steps of reacting the compound of formula (II) as defined in claim 5, with a nitrile α, β -unsaturated and hydrogenation, a step of reacting an alcohol of formula (III):

where Ri and R2 are as defined in claim 1,

with n compound (s) of formula (IV):

(IV)

in which :

the groups R3 and R 4 are as defined in claim 1 and n is as defined in claim 1.

12. A compound of formula (V)

(V)

in which :

Ri, R2, R3, 4 , R5, R 6 and 7 are as defined in claim 1;

n is as defined in claim 1.

13. A compound of formula (VI):

(WE)

in which :

Ri, R2, R3, R 4 , R 5, R 6 and R 7 are as defined in claim 1;

n and m are as defined in claim 1.

14. Use of a compound of formula (I) as defined in any one of claims 1 to 4, as a lubricant, cationic surfactant, flotation collector for minerals, corrosion inhibitor and fuel additive agent for crosslinking epoxy resins.