• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a compound of formula (I): in which: the groups R 1 and R 2, which are 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; the groups R3 and R4, which are identical or different, are chosen, independently of one another, from among the hydrogen atom, the methyl group and the ethyl group; the groups R5, R6 and R7, which are identical or different, are chosen, independently of one another, from a hydrogen atom and an alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms; n is an integer from 0 to 20; m is an integer ranging from 1 to 6.
    公开号:FR3040994A1
    申请号:FR1558435
    申请日:2015-09-10
    公开日:2017-03-17
    发明作者:Jean-Philippe Gillet；Eric Jorda
    申请人:Carbonisation et Charbons Actifs CECA SA；
    IPC主号:
    专利说明:

    Etheramine compounds and its use as a flotation collector
    The present invention relates to the general field of etheramines.
    The family of etheramines represents a unique family of chemicals offering a wide range of properties. Indeed, they can be used in particular as a lubricant, cationic surfactant, flotation collector for ores or as a corrosion inhibitor. Thus, they constitute a class of materials of major industrial interest for many actors. The etheramine market has already been widely developed for several decades.
    Etheramines are conventionally synthesized by first reacting an alcohol with a nitrile compound, usually acrylonitrile, in the presence of a basic catalyst. A hydrogenation step of the product obtained is then carried out in order to isolate the targeted etheramine.
    Thus, US Pat. No. 5,196,589 describes a process for producing an etheramine by first reacting an alcohol with acrylonitrile in the presence of an alkaline catalyst. A hydrogenation step is then performed to obtain the desired etheramine. The peculiarity of this process lies in the fact that the alcohol, a compound comprising a number of carbon atoms ranging from 6 to 36, is in the presence of a stable free radical compound, thus making it possible in particular to considerably reduce the amount of unwanted side products.
    The patent EP 1 219 597 discloses a process for the preparation of an etheramine comprising a first step of reacting a primary or secondary alcohol with acrylonitrile, in the presence of an alkali metal hydroxide, and then a second step hydrogenation of the product obtained. The primary or secondary alcohol is a compound comprising a number of carbon atoms ranging from 6 to 24.
    However, at a time when the environmental issue is really important, none of these documents indicate using any bio-based or biodegradable reagent with a good ecotoxicological profile.
    In addition, it is known that particular etheramines, including the commercial products Tomamine® PA-14 and Tomamine® DA-14, are used for the selective removal of silicates during the flotation of ores.
    It would therefore be advantageous to provide an etheramine obtained from at least one bio-sourced and biodegradable reagent. It would also be advantageous for the use of such an etheramine to lead to a more selective removal of silicates during the flotation of ores than commercial etheramines.
    The present invention relates to a compound of formula (I):
    in which: the groups R 1 and R 2, which are identical or different, represent, independently of each other, a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms; the groups R3 and R4, which are identical or different, are chosen, independently of one another, from among the hydrogen atom, the methyl group and the ethyl group; the groups R 5, R 6, and R 7, which are identical or different, are chosen, independently of one another, from a hydrogen atom and an alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to to 4 carbon atoms, more preferably 1 to 3 carbon atoms; n is an integer from 0 to 20; m is an integer ranging from 1 to 6.
    According to a preferred embodiment, when R 1 is a hexyl group, R 2 is a methyl group, n is 0, R 5, R 6 and R 7 denote a hydrogen atom, then m is different from 1.
    According to another preferred embodiment, the total number of carbon atoms of the groups R 1 and R 2 is between 5 and 20 carbon atoms, preferably between 6 and 20 carbon atoms.
    The subject of the present invention is also a process for producing the compound of formula (I) according to the invention.
    Another subject of the invention is a compound of formula (V):
    in which: the groups R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are as defined previously; n is as defined above;
    The subject of the present invention is also a compound of formula (VI):
    in which: the groups R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are as defined previously; n and m are as defined previously;
    Another object of the present invention relates to the use of the compound according to the invention as a particular flotation collector for ores. Other advantages and features of the invention will emerge more clearly from the detailed description.
    It is furthermore specified that the expressions "between ... and ..." and "from ... to ..." used in the present description must be understood as including each of the mentioned terminals.
    The compound according to the invention is of formula (I) mentioned above.
    Preferably, n is an integer ranging from 0 to 10, more preferably from 0 to 5, even more preferably from 0 to 1.
    Advantageously, the groups R3 and R4, which are identical or different, are chosen, independently of one another, from a hydrogen atom and a methyl group.
    Preferably, m is an integer ranging from 1 to 4, more preferably m is equal to 1, 2 or 3. The subject of the invention is also a process for the manufacture of the compound of formula (I) according to the invention, comprising successively: - a reaction step of a compound of formula (II):
    wherein the groups R 1, R 2, R 3 and R 4 and n are as previously defined; with an α, β-unsaturated nitrile; a hydrogenation reaction; the product resulting from these steps being capable of reacting in series (m-1) times with the α, β-unsaturated nitrile and then with dihydrogen, m being as defined previously.
    According to a preferred embodiment, the α, β-unsaturated nitrile is chosen from acrylonitrile and methacrylonitrile, preferably acrylonitrile.
    Thus, when n is 0, the compound of formula (II) may be 2-octanol. This alcohol is of particular interest in many 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 is quite reasonable.
    Advantageously, the molar ratio of the α, β-unsaturated nitrile on the compound of formula (II) varies from 0.8 to 1.2, preferably from 0.9 to 1.2.
    Particularly advantageously, the molar ratio of the α, β-unsaturated nitrile on the compound of formula (II) varies from 1.01 to 1.1, that is to say that the reaction of the compound of formula (II) with the α, β-unsaturated nitrile is conducted with a slight excess of α, β-unsaturated nitrile.
    Preferably, the reaction of the compound of formula (II) with the α, β-unsaturated nitrile is carried out in the presence of at least one basic catalyst CB.
    Preferably, the basic catalyst CB is chosen from alkali and alkaline earth hydroxides, alkali alkoxides, alkali hydrides, basic resins and quaternary ammonium hydroxides.
    In a particularly preferred manner, the basic catalyst CB is chosen from sodium hydroxide, potassium hydroxide, sodium hydride and potassium hydride.
    According to a particular embodiment of the invention, the amount of basic CB catalyst used varies from 0.1% to 2% by weight, preferably from 0.5% to 1% by weight, relative to the total weight of the compound. of formula (II).
    The temperature of the reaction of the compound of formula (II) with the α, β-unsaturated nitrile can vary in large proportions. Preferably, it ranges from 20 to 75.degree. C., more preferably from 25 to 70.degree. C., even more preferably from 25 to 65.degree.
    Advantageously, the reaction of the compound of formula (II) with the α, β-unsaturated nitrile is carried out without solvent but it is also possible to use a neutral solvent with respect to the reaction of the compound of formula (II) with the α, β-unsaturated nitrile.
    "Solvent neutral to the reaction" is understood to mean any solvent which does not chemically interact with the reagents of the reaction of the compound of formula (II) with the α, β-unsaturated nitrile.
    Preferably, the reaction-neutral solvents are chosen from ethers, dimethylformamide and aromatic solvents solubilizing the reagents chosen from toluene and xylenes.
    Where appropriate, the basic catalyst CB may be neutralized at the end of the 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 the acid hydrochloric acid and acetic acid or, alternatively, the catalyst can be removed, for example by filtration when it is of a solid nature.
    Preferably, the hydrogenation reaction is carried out in the presence of at least one CT catalyst.
    According to a particular embodiment, said catalyst CT is selected from Raney nickel and Raney cobalt.
    Advantageously, the amount of catalyst CT varies from 0.5 to 10% by weight, preferably from 2 to 8% by weight, relative to the weight of the product resulting from the reaction of the compound of formula (II) with the nitrile α, β-unsaturated.
    Preferably, the pressure during the hydrogenation reaction ranges from 1 to 10 MPa, preferably from 1.5 to 5 MPa.
    Preferably, the temperature of the hydrogenation reaction ranges from 50 to 170 ° C, preferably from 70 to 150 ° C.
    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 capable of generating a partial pressure of ammonia. Advantageously, a molar ratio ammonia / nitrile function ranging from 0.5 to 2 is suitable. Alternatively, it 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 resulting from the reaction of the compound of formula (II) with the α, β-unsaturated nitrile.
    Particularly advantageously, the addition of said amount of ammonia capable of generating a partial pressure of ammonia and the addition of said strong base are combined.
    Preferably, the successive reaction steps of the compound of formula (II) with the α, β-unsaturated nitrile and of hydrogenation reaction are carried out in the same reactor.
    It is also possible to work in a solvent medium with organic or hydro-organic solvents, such as, for example, alcohols (methanol, ethanol, isopropanol) and any other solvent used for the hydrogenation reactions and solubilizing the reagents and the final products. .
    It is possible to work in batch by introducing all the reagents and conducting the hydrogenation reaction. It is also possible to work in semi-batch by charging the solvent, the ammonia and / or the strong base, the catalyst and the hydrogen, then continuously introducing the condensation product resulting from the reaction of the compound of formula ( II) with the α, β-unsaturated nitrile.
    Advantageously, the reaction of the compound of formula (II) with the α, β-unsaturated nitrile and the hydrogenation reaction are carried out in different reactors.
    Preferably, the process according to the invention comprises, prior to the successive reaction steps of the compound of formula (II) with an α, β-unsaturated nitrile and of hydrogenation, a reaction step of an alcohol of formula (III): R 1 -C (OH) -R 2 (III) with n compound (s) of formula (IV): in which:
    the groups R3 and R4 are as defined previously; - n is as defined above. The subject of the invention is also the use of a compound of formula (I) as defined above, as a lubricant, a cationic surfactant, a flotation collector for ores, a corrosion inhibitor, a fuel additive and a crosslinking agent. for epoxy resins. The use of the compound of formula (I) as a flotation collector for ores is particularly preferred. The invention is illustrated by the following examples which are in no way limiting.
    EXAMPLES
    The 2-octanol used is the Refined grade product marketed by Arkema.
    Example 1 Synthesis of 3- (2-octyloxy) -propanamine 1) Synthesis of 3- (2-octyloxy) -propionitrile a) Use of potassium hydroxide
    In a reactor equipped with a stirrer and equipped with a dropping funnel, a condenser, a nitrogen inerting system and a jacket for heating, 130 g (IM) of 2 octanol and 2 g of potassium hydroxide in a 50% aqueous solution are charged. The reaction medium is heated 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 after casting until complete reaction. At the end of the reaction, the basic catalyst is neutralized with hydrochloric acid stoichiometry. The propionitrile ether is isolated by thin-film distillation with a molar yield of 90%. b) Use of sodium hydride
    In a reactor equipped with a stirrer and equipped with a dropping funnel, a condenser, a nitrogen inerting system and a jacket for heating, 130 g (IM) of 2 octanol and 0.6 g of sodium hydride are charged. 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 then 55 g (1.04 M) of acrylonitrile are added dropwise. The temperature is maintained after casting until complete reaction. At the end of the reaction, the basic catalyst is neutralized with hydrochloric acid stoichiometry. The propionitrile ether is isolated by thin-film distillation with a molar yield of 91%. 2) Hydrogenation of 3- (2-octyloxy) propionitrile
    In a 300 cm3 Autoclave Engineer autoclave equipped with a self-aspirating turbine type stirring system, a cooling coil and a pressure and temperature control system, 183 g (IM) of 3- (2-octyloxy) -propionitrile obtained according to processes 1) a) or 1) b), 14 g of Raney nickel and 2000 ppm of KOH in 50% aqueous solution are charged. The autoclave is locked and purged with nitrogen. Then, the hydrogen is introduced during the rise in temperature so that a total pressure of 3 MPa at 110 ° C is obtained. The reaction is continued until there is no more hydrogen consumption. At the end of the reaction, the catalyst is recovered by filtration. The reaction crude is distilled on a thin film to obtain 3- (2-octyloxy) -propanamine with a molar yield of 85%.
    Example 2 Synthesis of an ether diamine 1) Synthesis of 3- [3- (2-octyloxy) propylaminelpropionitrile
    In a reactor equipped with a stirrer and equipped with a dropping funnel, a condenser, a nitrogen inerting system and a jacket for heating, 225 g (1.2 M ) of 3- (2-octyloxy) propanamine and 2.25 g of water are charged. The reaction medium is heated to 60 ° C. with stirring and under an inert atmosphere, then 65 g (1.226 M) of acrylonitrile are added dropwise. The temperature is maintained after casting until complete reaction, about 2 hours. 3- [3- (2-octyloxy) propylamine] -propionitrile is obtained with a molar yield of 87%. 2) Hydrogenation of 3- [3- (2-octyloxy) propylaminelpropionitrile
    In a 500 cm3 Autoclave Engineer autoclave equipped with a self-aspirating turbine type stirring system, a cooling coil and a pressure and temperature control system, 200 g (IM) of 3- [3- (2-octyloxy) propylamine] -propionitrile obtained according to the above process and 3.6 g of Raney nickel are charged. The autoclave is locked and purged with nitrogen. Then, the reaction medium is heated to 75 ° C. Ammonia is introduced to a total pressure of 0.8 MPa. The hydrogen is then introduced during the rise in temperature so that a total pressure of 3 MPa at 120 ° C is obtained. The reaction is continued until there is no more hydrogen consumption. At the end of the reaction, the autoclave is degassed and the catalyst is recovered by filtration. The crude ether-diamine is obtained with a molar yield of 83%.
    Example 3 Synthesis of a Polyetheramine 1) Synthesis of a tris (ether) propionitrile
    In a reactor equipped with a stirrer and equipped with a dropping funnel, a condenser, a nitrogen inerting system and a jacket for heating, 262 g (1 M) of 2-octanol tris (ethoxylated) and 2 g of potassium hydroxide, in aqueous solution at 50%, are charged. The reaction medium is brought to 55 ° C. with stirring and under an inert atmosphere, then 55.6 g (1.05 M) of acrylonitrile are added dropwise. The temperature is maintained after casting until complete reaction. At the end of the reaction, the basic catalyst is neutralized with hydrochloric acid stoichiometry. The tris (ether) propionitrile is obtained with a molar yield of 89% 2) Hydrogenation of the tris (ether) propionitrile
    In a 500 cm3 Autoclave Engineer autoclave equipped with a self-aspirating turbine type stirring system, a cooling coil and a pressure and temperature control system, 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 KOH, in 50% aqueous solution, are charged. The autoclave is locked and purged with nitrogen. Then, the hydrogen is introduced during the rise in temperature so that a total pressure of 3 MPa at 120 ° C is obtained. The reaction is continued until there is no more hydrogen consumption. At the end of the reaction, the autoclave is degassed and the catalyst is recovered by filtration. The tris (ether) amine is obtained with a molar yield of 81%.
    Example 4 Use of a compound according to the invention as a flotation collector
    A phosphate ore containing silicates is purified by reverse flotation.
    The tests are performed in an Outotec flotation cell.
    First, 2.5 liters of tap water and 340 grams of ground phosphate ore (ranging in particle size from 30 to 300 μm) are introduced. The speed of the turbine is adjusted to 1500 rpm to ensure a suspension of the ore in the entire volume of the cell. 0.34 g of phosphoric acid in 85% aqueous solution are then added and stirring is continued for three minutes.
    Then, 0.17 g of a carbonate collector supplied by CECA under the trade name Melioran 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. Regular collection of mosses with a spatula is performed. The air supply is cut at the end of flotation and 10.2 g of cationic collector for silicates are added. Stirring is maintained for two minutes before restoring the air supply. Flotation is carried out for four minutes. At the end of these two steps, the ore remaining 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 for analysis to determine its composition.
    The comparative tests relate to five cationic collectors for the silicates used in the second flotation step.
    The starting ore is of the 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 P2O5 compound is 13.8% by weight relative to the weight of the ore.
    Compound A is a comparative compound. This is Noramac® C26 (N-alkyl cocoamine acetate) marketed by CECA.
    Compound B is a comparative compound. It's about the
    Tomamine® PA-14 (isodecyloxypropylamine) sold by the company Air Products.
    Compound C is a comparative compound. It's about the
    Tomamine® DA-14 (isodecyloxypropyl-1,3-diaminopropane) sold by the company Air Products.
    Compound D is a compound according to the invention corresponding to the following formula (VII):
    Compound E is a compound according to the invention corresponding to the following formula (VIII):
    The results of analysis of the ore after flotation are summarized in Table 1 below:
    Table 1
    Table 1 clearly shows that the compounds D and E according to the invention make it possible to eliminate a larger quantity of silicates than the three comparative compounds A, B and C.
    In addition, the final P2O5 content is greater due to the use of the compounds D and E than that associated with the use of the comparative compounds.
    Thus, it has been demonstrated that the use of the compound according to the invention leads to a selective elimination during the flotation of a phosphate ore. This property is even better compared to commercial products.
    权利要求:
    Claims (17)
    [1" id="c-fr-0001]
    1. Compound of formula (I):

    in which: the groups R 1 and R 2, which are identical or different, represent, independently of each other, a hydrocarbon group, linear, branched or cyclic, saturated or unsaturated, comprising from 1 to 15 carbon atoms, preferably from 1 to 10 carbon atoms; the groups R3 and R4, which are identical or different, are chosen, independently of one another, from among the hydrogen atom, the methyl group and the ethyl group; the groups R 5, R 6 and R 7, which are identical or different, are chosen, independently of one another, from a hydrogen atom and an alkyl group comprising from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms; n is an integer from 0 to 20; m is an integer ranging from 1 to 6.
    [2" id="c-fr-0002]
    2. Compound according to claim 1, characterized in that n is an integer ranging from 0 to 10, more preferably from 0 to 5, even more preferably from 0 to 1.
    [3" id="c-fr-0003]
    3. Compound according to claim 1 or 2, characterized in that the groups R3 and R4, identical or different, are chosen, independently of one another, from the hydrogen atom and the methyl group.
    [4" id="c-fr-0004]
    4. Compound according to any one of claims 1 to 3, characterized in that m is an integer ranging from 1 to 4, preferably m is equal to 1, 2 or 3.
    [5" id="c-fr-0005]
    5. A process for producing a compound of formula (I) as defined in any one of claims 1 to 4, comprising successively: a reaction step of a compound of formula (II):

    wherein the groups R 1, R 2, R 3 and R 4 and n are as defined in claim 1; with an α, β-unsaturated nitrile; a hydrogenation reaction; the product resulting from these steps being capable of reacting in series (m-1) times with the α, β-unsaturated nitrile and then with dihydrogen, m being as defined in claim 1.
    [6" id="c-fr-0006]
    6. Process according to claim 5, characterized in that the α, β-unsaturated nitrile is chosen from acrylonitrile and methacrylonitrile, preferably acrylonitrile.
    [7" id="c-fr-0007]
    7. Method according to claim 5 or 6, characterized in that the molar ratio of the α, β-unsaturated nitrile on the compound of formula (II) varies from 0.8 to 1.2, preferably from 0.9 to 1 2.
    [8" id="c-fr-0008]
    8. Method according to one of claims 5 to 7, characterized in that the molar ratio of α, β-unsaturated nitrile on the compound of formula (II) varies from 1.01 to 1.1.
    [9" id="c-fr-0009]
    9. Process according to one of Claims 5 to 8, characterized in that the reaction of said compound of formula (II) with the α, β-unsaturated nitrile is carried out in the presence of at least one basic catalyst (CB).
    [10" id="c-fr-0010]
    10. Process according to claim 9, characterized in that the basic catalyst (CB) is chosen from alkali and alkaline-earth hydroxides, alkali alkoxides, alkali hydrides, basic resins and hydroxides. quaternary ammonium.
    [11" id="c-fr-0011]
    11. The method of claim 9 or 10, characterized in that the basic catalyst (CB) is selected from sodium hydroxide, potassium hydroxide, sodium hydride and potassium hydride.
    [12" id="c-fr-0012]
    12. Process according to any one of claims 5 to 11, characterized in that the hydrogenation reaction is carried out in the presence of at least one catalyst (CT).
    [13" id="c-fr-0013]
    13. The method of claim 12, characterized in that the catalyst (CT) is selected from Raney nickel and Raney cobalt.
    [14" id="c-fr-0014]
    14. Process according to any one of Claims 5 to 13, characterized in that the said process comprises, prior to the successive reaction steps of the compound of formula (II), as defined in Claim 5, with an α, β nitrile. unsaturated and hydrogenation, a reaction step of an alcohol of formula (III): R 1 -C (OH) -R 2 (III), with n compound (s) of formula (IV): in which:

    the groups R3 and R4 are as defined in claim 1; n is as defined in claim 1.
    [15" id="c-fr-0015]
    15. Compound of formula (V):

    wherein: - the groups R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are as defined in claim 1; n is as defined in claim 1.
    [16" id="c-fr-0016]
    16. Compound of formula (VI):

    wherein: - the groups R 1, R 2, R 3, R 4, R 5, R 6 and R 7 are as defined in claim 1; n and m are as defined in claim 1.
    [17" id="c-fr-0017]
    17. 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 ores, corrosion inhibitor, fuel additive and agent. crosslinking agent for epoxy resins.
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    法律状态:
    2016-08-16| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-17| PLSC| Publication of the preliminary search report|Effective date: 20170317 |
    2017-08-10| PLFP| Fee payment|Year of fee payment: 3 |
    2017-10-27| TP| Transmission of property|Owner name: ARKEMA FRANCE, FR Effective date: 20170922 |
    2018-08-13| PLFP| Fee payment|Year of fee payment: 4 |
    2019-08-15| PLFP| Fee payment|Year of fee payment: 5 |
    2020-08-12| PLFP| Fee payment|Year of fee payment: 6 |
    2021-08-12| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1558435|2015-09-10|
    FR1558435A|FR3040994B1|2015-09-10|2015-09-10|ETHERAMINE COMPOUNDS AND ITS USE AS A FLOTATION COLLECTOR|FR1558435A| FR3040994B1|2015-09-10|2015-09-10|ETHERAMINE COMPOUNDS AND ITS USE AS A FLOTATION COLLECTOR|
    CN202111271206.4A| CN113943226A|2015-09-10|2016-09-09|Ether amine compounds and their use as flotation agents|
    MA042781A| MA42781A|2015-09-10|2016-09-09|ETHERAMINE COMPOUNDS AND THEIR USE AS A FLOTATION COLLECTOR|
    PCT/FR2016/052277| WO2017042514A1|2015-09-10|2016-09-09|Ether amine compounds and use thereof as flotation collector|
    CN201680052404.2A| CN108137481A|2015-09-10|2016-09-09|Ether amines compound and its purposes as flotation agent|
    US15/756,116| US10815337B2|2015-09-10|2016-09-09|Ether amine compounds and use thereof as flotation collector|
    EP16775296.3A| EP3347339A1|2015-09-10|2016-09-09|Ether amine compounds and use thereof as flotation collector|
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