Method for the synthesis of a rare-earth organophosphate and use thereof for preparing a preformed catalytic system
View Patent ↗A process for preparing a rare-earth organophosphate in the form of a gel that can be used as is for the preparation of a “preformed” catalyst system intended, in particular, for the cis-1,4 stereospecific polymerization of conjugated dienes.
1. A process for the synthesis of a rare-earth organophosphate comprising the steps of:
dispersion, under high shear, in a mixer having agitator impellers, of a rare-earth oxide in a two-phase reaction medium comprising at least one organophosphoric acid and a mixture of at least two immiscible solvents and, simultaneously or sequentially; and
reaction of the rare-earth oxide with the organophosphoric acid,
the reaction medium being driven, during the dispersion, by a shear rate of greater than 200 s −1 , expressed by the equation:
Γ average =kN
in which k is a constant ranging from 10 to 13 and N is the speed of the agitator impellers, by a blade tip peripheral speed of greater than 4 m·s −1 , expressed by the equation:
V periph πND
in which D is the diameter of the agitator impellers expressed in meters and N is their rotational speed expressed in s −1 .
2. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the reaction medium is driven, during the dispersion, by a shear rate between 200 s −1 and 20 000 s −1 .
3. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the blade tip peripheral speed is between 10 m·s −1 and 40 m·s −1 .
4. The process for the synthesis of a rare-earth organophosphate according to claim 1 , the rare-earth oxide is chosen from lanthanide oxides.
5. The process for the synthesis of a rare-earth organophosphate according to claim 4 , wherein the rare-earth oxide is neodymium oxide.
6. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the rare-earth oxide has a degree of hydration greater than or equal to 25%.
7. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the organophosphoric acid is chosen from phosphoric acid diesters of general formula (RO)(R′O)PO(OH), in which R is an n-butyl, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl, tolyl, nonylphenoxy radical and R′ is an n-butyl, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl, tolyl, nonylphenoxy radical; phosphoric acid monoesters of general formula (RO)PO(OH) 2 in which R is an n-butyl, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl, tolyl, nonylphenoxy radical; phosphonates of general formula (RO)R′P(O) or RP(O)(OH) 2 in which R is an n-butyl, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl, tolyl, nonylphenoxy radical; phosphinates of general formula R(R′)P( 0 )OH or R(H)P(O)OH in which R is an n-butyl, isobutyl, pentyl, amyl, isopentyl, 2,2-dimethylhexyl, 2-ethylhexyl, 1-ethylhexyl, tolyl, nonylphenoxy radical; and mixtures thereof.
8. The process for the synthesis of a rare-earth organophosphate according to claim 7 , wherein the organophosphoric acid is a phosphoric acid diester.
9. The process for the synthesis of a rare-earth organophosphate according to claim 8 , wherein the organophosphoric acid is di(2-ethylhexyl)phosphoric acid.
10. The process for the synthesis of a rare-earth organophosphate according to claim 8 , wherein the molar ratio of the phosphoric acid diester to the rare earth is from 2.9 to 6.
11. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the mixture of immiscible solvents comprises at least one inert hydrocarbon solvent and water.
12. The process for the synthesis of a rare-earth organophosphate according to claim 9 , wherein the inert hydrocarbon solvent is cyclohexane or methylcyclohexane or a mixture thereof.
13. The process for the synthesis of a rare-earth organophosphate according to claim 11 , wherein the volume ratio of the water of synthesis relative to the inert hydrocarbon solvent is strictly greater than 0 and strictly less than 1.
14. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the process takes place, in its entirety, within a single reactor.
15. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the process is carried out successively in two different reactors, in a first reactor that is suitable for the dispersion, under high shear, of the rare-earth oxide in the reaction medium, then in a second reactor, into which the reaction mixture obtained in the first reactor is decanted, in order to continue the process.
16. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the process comprises, after the step of reacting the rare-earth oxide with the organophosphoric acid, a step of removing water by azeotropic distillation.
17. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein the process comprises the addition to the reaction medium, before, during and/or after the steps of dispersion of the rare-earth oxide and of reacting it with the organophosphoric acid, of a fluidizing agent.
18. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein, once the synthesis of the rare-earth organophosphate has been carried out, the process does not comprise a subsequent step of treating the effluents.
19. The process for the synthesis of a rare-earth organophosphate according to claim 1 , wherein, once the synthesis of the rare-earth organophosphate has been carried out, the effluents of the reaction possibly containing unreacted organophosphoric acid are recycled upstream of the process.