ETHER AMINE COMPOUNDS AND USE THEREOF AS FLOTATION COLLECTOR

Abstract

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

##STR00001##

in which: the R.sub.1 and R.sub.2 groups, which may be identical or different, are, independently of one another, a saturated or unsaturated, linear, branched or cyclic hydrocarbon group having from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms; the R.sub.3 and R.sub.4 groups, which may be identical or different, are selected, independently of one another, from a hydrogen atom, a methyl group or an ethyl group; the R, R.sub.6 and R.sub.7 groups, which may be identical or different, are selected, independently of one another, from a hydrogen atom or an alkyl group comprising from 1 to 6 carbon atoms; n is an integer of 0 to 20; and m is an integer of 1 to 6.

Claims

1. A compound of formula (I): ##STR00009## wherein: the groups R.sub.1 and R.sub.2, which may be identical or different, represent, independently of each other, a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group, comprising from 1 to 15 carbon atoms; the groups R.sub.3 and R.sub.4, which may be identical or different, selected, independently of each other, from a hydrogen atom, a methyl group or an ethyl group; the groups R.sub.5, R.sub.6 and R.sub.7, which may be identical or different, are selected, independently of each other, from a hydrogen atom or an alkyl group comprising from 1 to 6 carbon atoms; n is an integer ranging from 0 to 20, inclusive; and m is an integer ranging from 1 to 6, inclusive.

2. The compound according to claim 1, wherein n is an integer ranging from 0 to 10, inclusive.

3. The compound according to claim 1, wherein the groups R.sub.3 and R.sub.4, which may be identical or different, are selected, independently of each other, from a hydrogen atom or a methyl group.

4. The compound according to claim 1 wherein m is an integer ranging from 1 to 4, inclusive.

5. A process for manufacturing a compound of formula (I) according to claims 1 the steps of: a) a step of reacting a compound of formula (II): ##STR00010## in which the groups R.sub.1, R.sub.2, R.sub.3, R.sub.4 and n are as defined in claim 1; with an ?,?-unsaturated nitrile; b) a step of hydrogenation of the product of step a); and c) when m is an integer greater than 1, reacting the product derived from step a) and step b) in series (m-1) times with the ?,?-unsaturated nitrile, and then with dihydrogen, m being as defined in claim 1.

6. The process according to claim 5, wherein the ?,?-unsaturated nitrile is selected from acrylonitrile or methacrylonitrile.

7. The process according to claim 5 wherein the mole ratio of the ?,?-unsaturated nitrile to the compound of formula (II) ranges from 0.8 to 1.2, inclusive.

8. The process according to claims 5 wherein the mole ratio of the ?,?-unsaturated nitrile to the compound of formula (II) ranges from 1.01 to 1.1, inclusive.

9. The process according to claim 5 wherein the step a) reaction of said compound of formula (II) with the ?,?-unsaturated nitrile is performed in the presence of at least one basic catalyst (BC).

10. The process according to claim 9, wherein the basic catalyst (BC) is selected from the group consisting of alkali metal hydroxides, alkaline-earth metal hydroxides, alkali metal alkoxides, alkali metal hydrides, basic resins, quaternary ammonium hydroxides, and mixtures thereof.

11. The process according to claim 5 wherein said process comprises, prior to the step a), a step of reacting an alcohol of formula (III):
R.sub.1CH(OH)R.sub.2 (III), wherein the groups R.sub.1 and R.sub.2, which may be identical or different, represent, independently of each other, a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group, comprising from 1 to 15 carbon atoms with n compound(s) of formula (IV): ##STR00011## in which: the groups R.sub.3 and R.sub.4, which may be identical or different, are selected, independently of each other, from a hydrogen atom, a methyl group or an ethyl group, and n is an integer ranging from 0 to 20, inclusive, whereby the compound of Formula (II) is produced.

12. A compound of formula (V): ##STR00012## wherein: the groups R.sub.1 and R.sub.2, which may be identical or different, represent, independently of each other, a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group, comprising from 1 to 15 carbon atoms; the groups R.sub.3 and R.sub.4, which may be identical or different, are selected, independently of each other, from a hydrogen atom, a methyl group or an ethyl group; the groups R.sub.5, R.sub.6 and R.sub.7, which may be identical or different, are selected, independently of each other, from a hydrogen atom or an alkyl group comprising from 1 to 6 carbon atoms; and n is an integer ranging from 0 to 20, inclusive.

13. A compound of formula (VI): ##STR00013## wherein: the groups R.sub.1 and R.sub.2, which may be identical or different, represent, independently of each other, a linear, branched or cyclic, saturated or unsaturated hydrocarbon-based group, comprising from 1 to 15 carbon atoms; the groups R.sub.3 and R.sub.4, which may be identical or different, are selected, independently of each other, from a hydrogen atom, a methyl group or an ethyl group; the groups R.sub.5, R.sub.6 and R.sub.7, which may be identical or different, are selected, independently of each other, from a hydrogen atom or an alkyl group comprising from 1 to 6 carbon atoms; n is an integer ranging from 0 to 20, inclusive; m is an integer ranging from 1 to 6, inclusive.

14. A method of manufacturing a lubricant, a cationic surfactant, an ore flotation collector, a corrosion inhibitor, a fuel additive, or a crosslinking agent for epoxy resins comprising incorporating the compound of formula (I) according to claim 1 into a lubricant, a cationic surfactant, an ore flotation collector, a corrosion inhibitor, a fuel additive, or a crosslinking agent for epoxy resins.

Description

EXAMPLES

[0066] The 2-octanol used is the refined-grade product sold by Arkema.

Example 1

Synthesis of 3-(2-octyloxy)propanamine

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

a) Use of Potassium Hydroxide

[0067] 130 g (1 M) of 2-octanol and 2 g of potassium hydroxide, as a 50% aqueous solution, are placed in a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, a system for inertizing with nitrogen and a heating jacket. The reaction medium is brought to 45? C. with stirring and under an inert atmosphere, and 55 g (1.04 M) of acrylonitrile are then added dropwise. The temperature is maintained after the addition until the reaction is complete. At the end of the reaction, the basic catalyst is neutralized by stoichiometry with hydrochloric acid. The propionitrile ether is isolated by thin-film distillation, in a molar yield of 90%.

b) Use of Sodium Hydride

[0068] 130 g (1 M) of 2-octanol and 0.6 g of sodium hydride are placed in a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, a system for inertizing with nitrogen and a heating jacket. The reactor is purged with nitrogen to remove the hydrogen formed. The reaction medium is brought to 35? C. with stirring and under an inert atmosphere, and 55 g (1.04 M) of acrylonitrile are then added dropwise. The temperature is maintained after the addition until the reaction is complete. At the end of the reaction, the basic catalyst is neutralized by stoichiometry with hydrochloric acid. The propionitrile ether is isolated by thin-film distillation, in a molar yield of 91%.

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

[0069] 183 g (1 M) of 3-(2-octyloxy)propionitrile obtained according to processes 1)a) or 1)b), 14 g of Raney nickel and 2000 ppm of KOH, as an aqueous 50% solution, are placed in a 300 cm.sup.3 Autoclave Engineer autoclave equipped with a stirring system of auto-suction turbomixer type, a cooling coil and a pressure and temperature regulation system. The autoclave is locked and purged with nitrogen. Hydrogen is then introduced during the temperature increase so that a total pressure of 3 MPa at 110? C. is obtained. The reaction is continued until there is no more consumption of hydrogen. At the end of the reaction, the catalyst is recovered by filtration. The crude reaction product is thin-film distilled to obtain 3-(2-octyloxy)propanamine in a molar yield of 85%.

Example 2

Synthesis of an Etherdiamine

1) Synthesis of 3-[3-(2-octyloxy)propylamine]propionitrile

[0070] 225 g (1.2 M) of 3-(2-octyloxy)propanamine and 2.25 g of water are placed in a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, a system for inertizing with nitrogen and a heating jacket.

[0071] The reaction medium is brought to 60? C. With stirring and under an inert atmosphere, and 65 g (1.226 M) of acrylonitrile are then added dropwise. The temperature is maintained after the addition until the reaction is complete, i.e. about 2 hours. The 3-[3-(2-octyloxy)propylamine]propionitrile is obtained in a molar yield of 87%.

2) Hydrogenation of 3-[3-(2-octyloxy)propylaminelpropionitrile

[0072] 200 g (1 M) of 3-[3-(2-octyloxy)propylamine]propionitrile obtained according to the above process and 3.6 g of Raney nickel are placed in a 500 cm.sup.3 Autoclave Engineer autoclave equipped with a stirring system of auto-suction turbomixer type, a cooling coil and a pressure and temperature regulation system. The autoclave is locked and purged with nitrogen. The reaction medium is then heated to 75? C. Ammonia is introduced up to a total pressure of 0.8 MPa. Hydrogen is then introduced during the temperature increase so that a total pressure of 3 MPa at 120? C. is obtained. The reaction is continued until there is no more consumption of hydrogen. At the end of the reaction, the autoclave is degassed and the catalyst is recovered by filtration. The crude etherdiamine is obtained in a molar yield of 83%.

Example 3

Synthesis of a Polyether Amine

1) Synthesis of a tris(ether) propionitrile

[0073] 262 g (1 M) of tris(ethoxyl) 2-octanol and 2 g of potassium hydroxide, as a 50% aqueous solution, are placed in a reactor equipped with a stirrer and fitted with a dropping funnel, a condenser, a system for inertizing with nitrogen and a heating jacket. The reaction medium is brought to 55? C. with stirring and under an inert atmosphere, and 55.6 g (1.05 M) of acrylonitrile are then added dropwise. The temperature is maintained after the addition until the reaction is complete. At the end of the reaction, the basic catalyst is neutralized by stoichiometry with hydrochloric acid. The tris(ether) propionitrile is obtained in a molar yield of 89%.

2) Hydrogenation of the tris(ether) propionitrile

[0074] 252 g (0.8 M) of the tris(ether) propionitrile obtained according to the above process, 20 g of Raney nickel and 2000 ppm of potassium hydroxide, as an aqueous 50% solution, are placed in a 500 cm.sup.3 Autoclave Engineer autoclave equipped with a stirring system of auto-suction turbomixer type, a cooling coil and a pressure and temperature regulation system. The autoclave is locked and purged with nitrogen. Hydrogen is then introduced during the temperature increase so that a total pressure of 3 MPa at 120? C. is obtained. The reaction is continued until there is no more consumption of hydrogen. At the end of the reaction, the autoclave is degassed and the catalyst is recovered by filtration. The tris(ether)amine is obtained in a molar yield of 81%.

Example 4

Use of the Compound According to the Invention as a Flotation Collector

[0075] A phosphate ore containing silicates is purified by reverse flotation. The tests are performed in an Outotec flotation cell.

[0076] In a first stage, 2.5 liters of tap water and 340 g of a ground phosphate ore (the particle size of which ranges from 30 to 300 ?m) are introduced. The turbomixer speed is adjusted to 1500 rpm to ensure suspension of the ore in the entire volume of the cell. 0.34 g of phosphoric acid, as an aqueous 85% solution, is then added and stirring is continued for three minutes.

[0077] Next, 0.17 g of a carbonate collector provided by the company CECA under the trade name Melioran? P312 is added and stirring is continued for two minutes. Air is then fed into the cell at a flow rate of 3 L/minute and flotation is performed for two minutes. The foam is collected regularly with a spatula.

[0078] The air supply is switched off at the end of flotation and 10.2 g of cationic silicate collector are added. Stirring is continued for two minutes before switching the air supply back on. Flotation is performed for four minutes.

[0079] On conclusion of these two steps, the ore remaining in the flotation cell is filtered off on a B?chner funnel and dried in an oven overnight. The dried ore is then weighed to io determine the amount recovered and sent for analysis to determine its composition.

[0080] The comparative tests relate to five cationic silicate collectors used in the second flotation step.

[0081] The starting ore is of fluoroapatite type containing 43% by weight of calcite and 17% by weight of quartz, relative to the total weight of the ore, as impurities. The content of P.sub.2O.sub.5 compound is 13.8% by weight relative to the weight of the ore.

[0082] Compound A is a comparative compound. It is Noramac? C26 (N-alkyl coconut amine acetate) sold by the company CECA.

[0083] Compound B is a comparative compound. It is Tomamine? PA-14 (isodecyloxypropylamine) sold by the company Air Products.

[0084] Compound C is a comparative compound. It is Tomamine? DA-14 (isodecyloxypropyl-1,3-diaminopropane) sold by the company Air Products.

[0085] Compound D is a compound according to the invention corresponding to formula (VII) below:

##STR00007##

[0086] Compound E is a compound according to the invention corresponding to formula (VIII) below:

##STR00008##

[0087] The analysis results for the ore after flotation are collated in Table 1 below:

TABLE-US-00001 TABLE 1 Calcite Final content Silicates removed removed of P.sub.2O.sub.5 (mass %) (mass %) (mass %) Compound A (comp.) 12.1 65.2 20.5 Compound B (comp.) 29.4 76.4 22.8 Compound C (comp.) 78.5 64.9 25.6 Compound D (inv.) 81 86.6 29.6 Compound E (inv.) 81.6 82.9 28.6

[0088] Table 1 clearly shows that compounds D and E according to the invention make it possible to remove a larger amount of silicates than the three comparative compounds A, B and C.

[0089] In addition, the final content of P.sub.2O.sub.5 is greater by means of the use of compounds D and E than that associated with the use of the comparative compounds.

[0090] Thus, it has been demonstrated that the use of a compound according to the invention led to selective removal during the flotation of a phosphate ore. This property is even improved relative to the commercial products.