# Patent

## Title
Method for the synthesis of a rare-earth organophosphate and use thereof for preparing a preformed catalytic system

## Abstract

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.

## Background
RELATED APPLICATIONS
This is a U.S. national stage under 35 USC §371 of application No. PCT/EP2008/067920, filed on Dec. 18, 2008.
This application claims the priority of French application Ser. No. 07/8913 filed Dec. 20, 2007, the entire content of which is hereby incorporated by reference.
FIELD OF THE INVENTION
The invention relates to a process for preparing a rare-earth organophosphate in the form of a gel that can be used as is in a catalyst system intended, in particular, for the cis-1,4 stereospecific polymerization of conjugated dienes.
BACKGROUND OF THE INVENTION
In the 1980s, the first rare-earth-based catalyst systems saw the light of day and interest in them has been growing, on the one hand due to the non-toxicity of the metal and on the other hand due to the fact that non-aromatic solvents, such as hexane, cyclohexane, cuts of isomers of hexane or methylcyclohexane can be used as the polymerization solvent. More particularly, neodymium catalysis is currently experiencing a real expansion.
Rare-earth catalysts are multicomponent catalysts and are generally constituted of at least:
a conjugated diene monomer,
a salt of one or more rare-earth metals of an organic phosphoric acid or of an organic carboxylic acid,
an alkylating agent constituted of an alkylaluminium corresponding to the formula AlR3 or HAlR2, and
a halogen donor constituted of an alkylaluminium halide.
This type of catalyst is described, in particular, in International Patent Applications WO 02/38635, WO 02/38636 and WO 03/097708 in the name of the applicants.
Among the rare-earth salts, the rare-earth salts known as phosphates and of general formula Ln[OP(═O)x(OR)3-x]3 (Ln being a metal from the lanthanide family, scandium or yttrium, x being equal to 1 or 2, R being identical or different, linear or branched, aliphatic or alicyclic alkyl radicals comprising 1 to 20 carbon atoms) are significant compounds for the preparation of highly active catalyst systems for the cis-1,4 stereospecific polymerization of conjugated dienes, more particularly butadiene and isoprene. These systems have the advantage of resulting in elastomers that have a narrow molecular weight distribution.
Due to their nature, these salts are not very soluble and have a high tendency to associate in a hydrocarbon solvent medium and generally result in the formation of gel, as described by Suglobov in document “DEHP Complexes of Lanthanides (III) and Actinides (III)”, Journal of Alloys and Compounds, 213/214, 1994, p. 523-527). This leads to practical difficulties, whether during the synthesis thereof or the use thereof as a polymerization catalyst precursor.
Several methods of synthesis are described in the literature. Most consist of the reaction of a rare-earth salt of rare-earth halide or nitrate type with an organophosphate salt (Korovin et al., Russian Journal of Inorganic Chemistry, 22(5), 1977; Chen Tien et al. “Preparation and characterization of bis(2-ethylhexyl)phosphate(P204) rare earth”, K'o Hsueh T'ung Pao 1981, 26(13), 794-6; JP 60023406 in the name of Asahi, page 4).
Patent document EP 1 509 557 B1 in the name of the applicants describes the synthesis of a powder of neodymium tris(organophosphate) [(RO)2P(═O)O]3Nd by reaction of:

    
    
        a) an aqueous solution of neodymium chloride NdCl3(H2O)6, prepared by reaction of HCl with Nd2O3, and
        b) a water/acetone solution of sodium di(2-ethylhexyl)phosphate.
    
    


This synthesis process, in several steps, allows a complete reaction and results in the formation of the neodymium tris[di(2-ethylhexyl)phosphate] salt in the form of a solid. After washing this solid with water a certain number of times, the qualitative test for the determination of chloride ions is almost negative, which indicates that an almost pure product is obtained. Once dry, the product is in the form of a pink-mauve powder.
Patent document U.S. Pat. No. 6,767,927 B1 describes a process for the synthesis, in three steps, of a stable solution of rare-earth tris(organophosphate) in a hydrocarbon solvent:

    
    
        1) preparation of an organophosphate salt by reaction of the corresponding acid and a base,
        2) reaction of the organophosphate obtained previously with a rare-earth salt,
        3) adjustment of the concentration of free acid.
    
    


This synthesis is carried out in a two-phase water/hydrocarbon solvent medium. At the end of the reaction, the water is removed by decantation and azeotropic distillation. The product of this synthesis process is a fluid solution that can be used directly for the preparation of a polymerization catalyst. Nevertheless, the process comprises a certain number of synthesis steps in order to result in the desired solution. This process furthermore generates aqueous effluents that contain ions, for example ammonium nitrate, which from an environmental point of view requires a supplementary step for the subsequent treatment of these waste products.
The preceding synthesis processes may be defined as being indirect processes. That is to say that the synthesis of the rare-earth phosphate salt is carried out starting from a rare-earth salt, obtained by reaction of the rare-earth oxide and an acid, and from an organophosphate salt, obtained by reaction of the corresponding acid and a base. The number of steps generally produces, for this type of process, complex and not very economical synthesis pathways. A drawback of these processes is that they generate aqueous waste products, which makes it necessary to introduce a supplementary step for treating these waste products.
Rare-earth tris(carboxylates), such as for example rare-earth versatates, are compounds that themselves can also be used as a precursor in the synthesis of catalysts for the cis-1,4 stereospecific polymerization. They can be synthesized according to the same pathway as before, that is to say by reaction of a carboxylate salt with a rare-earth salt (for example, reaction of sodium versatate with neodymium nitrate as described in patent document U.S. Pat. No. 6,111,082).
Alternative synthesis pathways have been developed for the synthesis of organometallic salts of this family in order to reduce the cost of the synthesis by limiting the number of steps. In these syntheses, the carboxylate salt or the rare-earth salt is replaced by the precursor thereof, that is to say the corresponding carboxylic acid or the corresponding rare-earth oxide.
Patent document U.S. Pat. No. 6,482,906 B1 describes a process for preparing neodymium tris(neodecanoate) also known as neodymium tris(versatate), in four steps:

    
    
        1) preparing a sludge by dispersion of Nd2O3 in a hydrocarbon solvent and reaction with a deficiency of HCl relative to the neodymium,
        2) adding neodecanoic acid in an amount of 3.25 equivalents relative to the neodymium,
        3) settling of the reaction medium,
        4) separating the neodymium tris(neodecanoate) from the residual reactants.
    
    


This synthesis pathway has the advantage of not comprising the step of synthesis of the neodecanoate salt by reaction with a base, which removes one step. The drawback is that the reaction is not complete and that a step of separating the unreacted neodymium oxide from the solution of neodymium tris(neodecanoate) is necessary with a view to using the neodymium tris(neodecanoate) for other applications, especially for the preparation of a catalyst system.
U.S. Pat. No. 5,220,045 describes a process for the synthesis of neodymium neodecanoate in one step comprising the reaction, in a two-phase medium, of an aqueous solution of neodymium nitrate with an organic solution of versatic acid in the presence of a base of amine, ammonia or quaternary ammonium hydroxide type. During this synthesis, the ammonium neodecanoate salt is generated in situ in order to react with the neodymium nitrate. This synthesis pathway has the advantage of taking place in a single reactor and of being complete. It has the drawback of requiring the addition of a base to the reaction medium and of involving a certain number of washes with water and of decantation steps in order to rid the gel of its impurities, which is detrimental from an economical viewpoint: Furthermore, this process generates aqueous effluents that contain ions, for example ammonium nitrate, which, from the environmental point of view, requires a supplementary step for the subsequent treatment of these waste products.
Unlike the synthesis pathways described above, a direct synthesis consists in directly reacting the rare-earth oxide with the phosphoric or carboxylic acid, without going via the rare-earth salt and/or via the phosphate or carboxylate salt.
Patent EP 0 924 214 B1 relates to a process for fluidizing organic solutions of rare-earth compounds, such as rare-earth phosphates or carboxylates, by addition of a Lewis acid. Example 1 of this patent describes the preparation of lanthanum di(2-ethylhexyl)phosphate by reaction of lanthanum oxide La2O3 with di(2-ethylhexyl)phosphoric acid in hexane and a small amount of water. The mixture is stirred and brought to reflux until a clear yellow solution is obtained. The water is then removed by azeotropic distillation. The gel obtained is very viscous, the viscosities measured being greater than 90 000 cps, and has a brittle structure. Indeed, it is stated in this patent that holes (fracture zones) appear in the gel during the viscosity measurement. This gelatinous and “brittle” characteriztic makes it difficult to handle such a product, especially during processing steps for the preparation of a catalyst system for the cis-1,4 stereospecific polymerization of conjugated dienes, and prevents its characterization. This involves taking precautions for the handling and characterization of this product, especially during the use of this gel in an industrial process.
SUMMARY OF THE INVENTION
One object of the present invention is to overcome the drawbacks encountered with the synthesis processes of the prior art. More particularly, one object of the present invention is to propose a process for the synthesis of a rare-earth organophosphate that only comprises a few steps and the product of which is free from residual rare-earth precursor. Another object of the invention is a synthesis of a rare-earth organophosphate which can be used directly and easily for a subsequent application, especially for the preparation of a catalyst system. Another objective of the invention is to implement a process that generates no or few aqueous effluents that require a subsequent treatment in order to respond to an environmental problem.
This objective is achieved in that the inventor has just discovered, during his research, a method for the synthesis of a rare-earth organophosphate via a direct pathway, the product of which is, unexpectedly, free of residual rare-earth oxide or of any impurity, in amounts that are detrimental to any subsequent use. The direct synthesis process results in a product, the handling of which is not hindered by a “brittle” character which would restrict the processing thereof and the use thereof during the preparation of a catalyst system for the cis-1,4 polymerization of conjugated dienes. The rare-earth organophosphate obtained via this process is in the form of a gel that is not very viscous. Just as unexpectedly, it turns out that this gel can be easily used, as is, in particular as a precursor for a catalyst system intended for the cis-1,4 stereospecific polymerization of conjugated dienes without impairing the catalytic activity of the system or the characteriztics of the polymer synthesized. The synthesis process according to the invention does not generate aqueous effluents that require subsequent treatment.
One aspect of the invention is a process for the synthesis, via a direct pathway, of a rare-earth organophosphate from the rare-earth oxide and an organophosphoric acid in a single step.
One aspect of the invention is directed to a synthesis process that makes it possible to prepare a rare-earth organophosphate, wherein the process is a direct synthesis process which comprises:
the dispersion, under high shear, of a rare-earth oxide in a two-phase reaction medium comprising at least one organophosphoric acid and two immiscible solvents, and simultaneously or sequentially in a separate manner
the reaction of the rare-earth oxide with the organophosphoric acid.
The high shear dispersion according to an embodiment of the invention may be carried out by any suitable means using any dynamic mixer known to a person skilled in the art. Particularly suitable are the devices constituted of a rotating stirrer comprising one or more impellers fixed to a shaft, which dissipate power densities of the order of 0.1 to 250 kW/m3/unit of dynamic viscosity of the reaction mixture, more particularly of the order of 1 to 150 kW/m3/Pa·s. The shear depends on the characteristics of the impeller, in particular on its geometry. Devices of this type are, for example, rotor/stator mixers, especially those sold by VMI Rayneri under the trademark “Ultramix” and by IKA under the trademark “Ultra Turrax”.
The expression “high shear” should be understood to mean a “high shear rate” or a “high velocity gradient”, which are two synonymous expressions for a person skilled in the art. The term “high” is understood, in the present case, to mean high enough to attain the desired properties of the rare-earth organophosphates prepared according to the process of the invention.
The concept of “average velocity gradient” in a stirred chamber is defined, for example, in the article “Agitation Mélange—concepts théoriques de base” [Stirring/Mixing—basic theoretical concepts], written by Michel Roustan, Jean-Claude Pharamond and Alain Liné from the work “Techniques de l'ingénieur, traité Génie des Procédés [Engineering Techniques, treatise on Process Engineering]—J3 800, page 13”. This concept is, for example, used in U.S. Pat. No. 6,638,918, which describes it in the same manner as in the preceding reference. Thus, the average shear (Γaverage) in the reaction medium can be expressed by the equation:

Γaverage=kN 

in which k is a proportionality constant which depends on the type of mixer blade and on the configuration of the chamber of the mixer and N is the speed of the agitator impellers (in s−1). Γaverage is expressed in s−1. The mixers that can be used for carrying out the process according to the invention have a constant k that varies between 10 and 13.

Associated with this concept of shear is a blade tip peripheral speed, expressed by the equation:

Vperiph=πND 

in which D is the diameter of the agitator impellers expressed in meters and N is their rotational speed expressed in s−1.

According to an embodiment of the invention, the expression “high shear dispersion” is understood to mean a dispersion carried out with stirring at high blade tip speed, typically greater than 4 m·s−1, preferably greater than or equal to 10 m·s−1, and more preferably still between 10 m·s−1 and 40 m·s−1, which gives the reaction medium a shear typically greater than 200 s−1, preferably between 200 s−1 and 20 000 s−1.
As a function of the desired shear level, a person skilled in the art will know how to use a stirring system that has a suitable geometry and how to apply it at a sufficient rotational speed to achieve the desired blade tip rotational speed and shear level. Depending on the nature of the stirring system and the size of the synthesis reactor, the rotational speed may, by way of example, be between 100 rpm and 30 000 rpm.
The temperature of the reaction medium during the high shear dispersion of the rare-earth oxide in this medium and the reaction of the rare-earth oxide with the organophosphoric acid is defined as a function of the nature of the solvents used and of the total amount of phosphoric acid introduced into the medium. The temperature of the reaction medium is generally between 0 and 130° C. This temperature is preferably between 50 and 110° C.
The duration of the dispersion of the rare-earth oxide in the reaction medium may vary from 1 to 400 minutes; preferably it is from 1 to 60 minutes. The total duration of the dispersion of the rare-earth oxide and of its reaction with the organophosphoric acid is from 1 to 400 minutes.
According to an embodiment of the invention, the expression “rare earth” is understood to mean a metal chosen from yttrium, scandium and the lanthanides, metals that have an atomic number ranging from 57 to 71 inclusive in Mendeleev's periodic table of the elements. Preferably, the rare-earth metal is chosen from lanthanides, such as, in particular, lanthanum, praseodymium, gadolinium or neodymium, neodymium being more particularly preferred.
Although the process according to an embodiment of the invention also applies to yttrium and scandium, the invention will be described in the following paragraph by reference to lanthanides for reasons of simplification of writing.
One of the reactants of the process according to an embodiment of the invention is lanthanide oxide. According to the invention, the expression “lanthanide oxide” is understood to mean any species of lanthanide sesquioxide type corresponding to the formula Ln2O3, but also any partially or completely hydrated form of lanthanide oxide containing Ln-OH functions. Indeed, due to their hygroscopic character, lanthanide oxides may absorb a certain amount of water under the effect of the humidity of the ambient air. This water may lead to the hydration of the lanthanide oxide and to the formation of other lanthanide-based species, such as lanthanide trihydroxide, according to the equation:

Ln2O3+3H2OLn(═O)OH+2H2O2Ln(OH)3 

By way of illustration, in the case where the lanthanide metal is neodymium, the theoretical neodymium weight content of neodymium sesquioxide, denoted by % Nd[Nd2O3]theo, is 85.74%. The theoretical neodymium weight content of neodymium trihydroxide, denoted by % Nd[Nd(OH)3]theo, is 73.87%.

The neodymium weight content of the raw material used, denoted by % Nd[Nd2O3], is determined according to any characterization method known to a person skilled in the art. For example, the assay methods described in patent application WO 03/097708 in the name of the applicants may be used.

Thus, the degree of hydration Dhydration of a lanthanide oxide is defined as being:





  
    D
    Hydration
  
  =
  
    
      
        %
        ⁢
        
          
        
        ⁢
        
          Nd
          ⁡
          
            [
            
              
                Nd
                2
              
              ⁢
              
                O
                3
              
            
            ]
          
        
      
      -
      
        %
        ⁢
        
          
        
        ⁢
        
          
            Nd
            ⁡
            
              [
              
                
                  Nd
                  ⁡
                  
                    (
                    OH
                    )
                  
                
                3
              
              ]
            
          
          theo
        
      
    
    
      
        %
        ⁢
        
          
        
        ⁢
        
          
            Nd
            ⁡
            
              [
              
                
                  Nd
                  2
                
                ⁢
                
                  O
                  3
                
              
              ]
            
          
          theo
        
      
      -
      
        %
        ⁢
        
          
        
        ⁢
        
          
            Nd
            ⁡
            
              [
              
                
                  Nd
                  ⁡
                  
                    (
                    OH
                    )
                  
                
                3
              
              ]
            
          
          theo
        
      
    
  




Thus, the degree of hydration Dhydration according to the invention of pure neodymium sesquioxide of formula Nd2O3 is 0%, whilst the degree of hydration of neodymium trihydroxide of formula Nd(OH)3 is 100%.

Preferably, the synthesis process according to an embodiment of the invention involves a rare-earth oxide having a degree of hydration greater than or equal to 5%, preferably greater than or equal to 25% and more preferably still greater than 50%. The inventor has demonstrated that, under certain reaction conditions, especially for short reaction times, a high degree of hydration of the rare-earth oxide proves to be advantageous.
The organophosphoric acid, the second reactant of the process according to the invention, is chosen from the following compounds: phosphoric acid diesters of general formula (RO)(R′O)PO(OH), in which R is an alkyl, aryl or alkylaryl radical and R′ is an alkyl, aryl or alkylaryl radical; phosphoric acid monoesters of general formula (RO)PO(OH)2 in which R is an alkyl, aryl or alkylaryl radical; phosphonates of general formula (RO)R′P(O) or RP(O)(OH)2 in which R is an alkyl, aryl or alkylaryl radical; phosphinates of general formula R(R′)P(O)OH or R(H)P(O)OH in which R is an alkyl, aryl or alkylaryl radical; and mixtures thereof.
Preferably, 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, 1-ethylhexyl, 2-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, 1-ethylhexyl, 2-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(O)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. More preferably still, the organophosphoric acid according to the invention is chosen from di(2-ethylhexyl)phosphoric acid.
The molar ratio of the organophosphoric acid to the rare-earth oxide is a function of the nature of the organophosphoric acid. A person skilled in the art will adjust the amount of organophosphoric acid to be introduced into the reaction medium as a function of its nature.
When the organophosphoric acid is a phosphoric acid diester, the molar ratio of the organophosphoric acid to the rare earth is from 2.9 to 6, preferably from 2.95 to 5 and more preferably still from 3 to 3.4.
According to the process of an embodiment of the invention, the reaction medium comprises at least two immiscible solvents. The expression “immiscible solvents” is understood to mean, within the context of the invention, a mixture comprising at least one inert hydrocarbon solvent, the other solvent preferably being water. According to one preferred embodiment of the invention, the inert hydrocarbon solvent is an aliphatic and alicyclic solvent of low molecular weight such as, by way of indication, n-pentane, iso-pentane, cyclopentane, a cut of C5 compounds, a C5 cut from the steam cracking of naphtha, hexane, cyclohexane, a cut of hexane isomers, methylcyclohexane, heptane, isomers thereof or a mixture of these solvents. More preferably still, use is made of cyclohexane, methylcyclohexane or a mixture thereof as inert hydrocarbon solvents.
According to one preferred implementation of the invention, the volume ratio of water relative to the inert hydrocarbon solvent is strictly greater than 0 and strictly less than 1.
According to one variant of the process of the invention, the reaction medium may also comprise other components capable of acting on the implementation of the process or else on the properties of the product obtained. Thus, with a view to further reducing the viscosity of the solution of rare-earth organophosphate prepared according to the invention, it is possible to add a fluidizing agent before, during and/or after the synthesis of this salt. According to one particular implementation, the fluidizing agent is added at the very start of the synthesis. Among these fluidizing agents, mention may be made, for example, of Lewis acids, alcohols such as methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, polyalcohols such as glycols, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol or 1,4-butanediol, glycol ethers, or mixtures thereof.
According to one variant of the synthesis process of the invention, the steps of high shear dispersion of the rare-earth oxide in the reaction medium and of reaction of the rare-earth oxide and of the organophosphoric acid may be carried out in one and the same reactor (“one-pot” synthesis). In this case, the dispersion of the rare-earth oxide in the reaction medium and the reaction of the rare-earth oxide and of the organophosphoric acid may take place simultaneously or sequentially. The simultaneity of these two steps constitutes a preferred implementation of the invention in so far as the overall duration of the synthesis process is reduced.
According to another variant of the synthesis process of the invention, the steps of high shear dispersion of the rare-earth oxide in the reaction medium and of reaction of the rare-earth oxide with the organophosphoric acid may be carried out in two different reactors. After the high shear dispersion of the rare-earth oxide in the reaction medium, the mixture is transferred into a second reactor. This second reactor may be equipped with a conventional blade-type mechanical stirring system and the reaction may be carried out with mechanical stirring. The reaction medium in the two reactors is generally heated at a temperature from 0 to 100° C. for a total duration of the process that varies from 0 to 400 minutes. According to this variant, the steps of the process of the invention may take place sequentially or simultaneously, the reaction of the rare-earth oxide with the organophosphoric acid possibly, for example, having started during the high shear dispersion of the rare-earth oxide in the reaction medium, in the first reactor, and being continued in the second reactor.
After reaction of the phosphoric acid with the lanthanide oxide, the lanthanide phosphate gel obtained comprises water and must therefore be dried, in particular in view of the subsequent use of the lanthanide phosphate gel for the preparation of a catalyst for the polymerization of conjugated dienes. This removal may be carried out by any process known to a person skilled in the art. According to one preferred variant of the invention, the water is removed by azeotropic distillation.
The implementation according to an embodiment of the process of the invention allows the synthesis of a rare-earth organophosphate in the form of a gel with a high degree of conversion of the rare-earth oxide. No supplementary washing or purification step is necessary. This does not however rule out such steps, while remaining within the scope of the invention. When such a supplementary washing or purification step is carried out, the implementation of a subsequent treatment of the aqueous waste products is not necessary, since these are either free of any by-product of the reaction, or can be recycled to the synthesis process.
Specifically, according to another variant of the synthesis process of the invention, an optional step of washing the lanthanide phosphate gel is carried out immediately after the reaction of the phosphoric acid with the lanthanide oxide. This washing step consists in introducing into the reaction medium, composed of the lanthanide organophosphate, a supplementary volume of water, then in stirring the thus resulting two-phase medium so as to wash the gel, then finally in separating, by any method known to a person skilled in the art, the aqueous phase from the lanthanide phosphate organic gel. This washing step makes it possible, in particular, to remove the excess reactants that have not reacted, such as for example the organophosphoric acid. A person skilled in the art will adjust the washing conditions, in terms of the volume of water used, stirring conditions used and number of consecutive washing operations in order to achieve the desired characteriztics of the product.
This additional amount of water must be removed at the end of the washing operation, in particular in view of the subsequent use of the lanthanide phosphate gel for preparing a catalyst for the polymerization of conjugated dienes. This amount of water does not have ions in solution, such as nitrate or ammonium ions, that would require a specific subsequent treatment. This amount of water may optionally be recycled upstream of the synthesis process, so as to reuse the organophosphoric acid, such as the di(2-ethylhexyl)phosphoric acid, that has not reacted.
The gel obtained by the synthesis process of the invention comprises at least one rare-earth organophosphate and an inert hydrocarbon solvent as defined previously. It may also comprise residual free acid, and also a tiny amount of water.
According to one preferred variant, the process of the invention allows the synthesis of a lanthanide organophosphate, and more particularly a neodymium organophosphate in the form of a gel. The synthesis, in accordance with the process of the invention, of neodymium tris[di(2-ethylhexyl)phosphate] constitutes one particularly preferred aspect of this variant.
The neodymium organophosphate gel obtained preferably by the implementation of the synthesis process according to the invention advantageously has the following characteriztics:
the weight content of Nd is between 1.5 and 5%, preferably between 2 and 5%;
the number of moles of free organophosphoric acid is between 15 and 200% relative to the number of moles of neodymium, preferably between 30 and 100%;
the amount of residual water in the gel is less than 500 ppm, preferably less than 200 ppm and more preferably still less than 100 ppm;
the viscosity of the gels is strictly between 2000 and 90 000 cP, the value of 90 000 being excluded from this range.
The rare-earth organophosphate gel obtained by the process according to the invention may advantageously be used as is or it may undergo modifications after its preparation and before any subsequent use, without this departing from the scope of the invention. In the present application, the term “modification” is understood to mean any treatment that the gel obtained directly by the process of the invention could undergo, for example the removal of all or some of the residual free acid by any method known to a person skilled in the art, such as, in particular, washing with an aqueous solution, washing with an aqueous solution containing a base, such as ammonium hydroxide or sodium hydroxide, washing with an aqueous solution containing an acid or else the addition of various agents, such as for example a fluidizing agent with a view to reducing the viscosity of the product. Among these fluidizing agents, mention may be made, for example, of Lewis acids, alcohols such as methanol, ethanol, propan-1-ol, propan-2-ol, butan-1-ol, butan-2-ol, polyalcohols such as glycols, 1,2-ethanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol or 1,4-butanediol, glycol ethers, or mixtures thereof. Mention may also be made of certain aluminium derivatives corresponding to the formula Al(R)3-nHn, where n has the value 0, 1 or 2 and R is a hydrocarbon comprising 1 to 8 carbon atoms, such as for example, in particular, triethylaluminium, triisobutylaluminium, trioctylaluminium or else diisobutylaluminium hydride.
The rare-earth organophosphate gel obtained by the process according to the invention may be used as is, for example for the preparation of catalyst systems for the stereospecific polymerization of conjugated dienes. In particular, it may be used as is, together with an alkylating agent, for example an alkylaluminium, and together with a halogen donor, for example a dialkylaluminium chloride, without this being detrimental to the preparation of the catalyst, or to its activity.
The rare-earth organophosphate, particularly the neodymium tris(organophosphate), prepared according to the process in accordance with the invention may advantageously be used during the preparation of a “preformed” catalyst system for the stereospecific polymerization of conjugated dienes based on at least:
a conjugated diene monomer,
the rare-earth organophosphate gel described previously and obtained by the synthesis process of the invention, which is modified or unmodified
an alkylating agent constituted of an alkylaluminium of formula AlR3 or HAlR2 and
a halogen donor which belongs to the family of alkylaluminium halides with the exclusion of alkylaluminium sesquihalides.
This use is carried out without impairment linked to the nature of the rare-earth organophosphate and/or to its production process. This is why this particularly advantageous use is also the subject of the invention.
The process for preparing this “preformed” catalyst system according to an embodiment of the invention implements the following steps:
in a first step, the rare-earth organophosphate, more particularly the neodymium organophosphate is prepared according to the process described above;
in a second step, a conjugated diene monomer is added to the rare-earth organophosphate obtained;
in a third step, an alkylating agent is added to the solution obtained at the end of the second step in order to obtain an alkylated salt; and
in a fourth step, a halogen donor is added to the alkylated salt obtained previously.
The conjugated diene monomers, the alkylating agents and the halogen donors that can be used within the context of the process for preparation of the catalyst system of the invention are as defined, in particular, in patent EP 1 509 557 B1 in the name of the applicants.
The catalyst system according to the invention is particularly suitable for the cis-1,4 stereospecific polymerization of conjugated dienes, in particular of butadiene and of isoprene.
The process for polymerization of conjugated dienes consists in reacting at least one conjugated diene monomer in the presence of the catalyst system of the invention in an inert hydrocarbon polymerization solvent, for example cyclohexane, methylcyclohexane or mixture thereof. This process is preferably carried out at a temperature ranging from 0° C. to 100° C.
The polymer thus prepared has a high content of cis-1,4 units, preferably greater than 97%, and a macrostructure that has a narrow molar mass distribution.
By way of example, mention may be made of the preparation of polybutadiene by batch polymerization with a catalyst system based on neodymium organophosphate of the invention, having a polydispersity index Ip, measured by the “SEC” technique, of less than 2, or else the batch preparation of polyisoprene having a polydispersity index of less than 2.7. Continuous polymerization with the same catalyst system makes it possible to obtain polybutadiene and polyisoprene having Ip values of less than 2.7 and 3.5 respectively.
The aforementioned features of an embodiment of the present invention, and also other features, will be better understood on reading the following description of several exemplary embodiments of the invention, given by way of illustration and non-limitingly, and also diagrams which represent the catalytic activity of catalyst systems in accordance with the invention and of the prior art, evaluated by measuring the conversion rate of the monomer to polymer as a function of the reaction time.
I. Synthesis of Organic Phosphate Salts of Neodymium
Neodymium tris(di(2-ethylhexyl)phosphate) was synthesized. The synthesis conditions which are explained in detail below were used for each test.
Raw Materials
1—Neodymium Oxide
A neodymium oxide with a weight content of neodymium equal to 73.6% (type A) or a neodymium oxide with a weight content of neodymium equal to 82.4 wt % (type B) is used.
2—Other Reactants
Di(2-ethylhexyl)phosphoric acid, cyclohexane, methylcyclohexane and the other reactants were obtained from conventional suppliers.
Characterization Techniques.
1—Nd and P Assay
The weight contents of neodymium and of phosphorus are determined by elemental analyses via complexometry.
2—Free Acid Assay
The amount of free organophosphoric acid is determined by potentiometric assay via acid-base reaction.
3—Water Assay
The Karl Fischer method is used.
4—Content of Insoluble Species
The amount of insoluble species present in the neodymium tris(di(2-ethylhexyl)phosphate) gel is determined by centrifuging the gel at a temperature of 20° C. at a speed of 3500 rpm and is expressed as a weight percentage of solid relative to the gel.
1) Synthesis of an Organic Phosphate Salt of Neodymium According to the Process Described in Patent EP 0 924 214 B1:
The following counterexamples make it possible to demonstrate the advantage of high shear stirring.
COUNTEREXAMPLE 1
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 15.59 g of Nd2O3 of type A (0.040 mol), 83.8 g of di(2-ethylhexyl)phosphoric acid (DEHPA) (0.249 mol), 560 ml of methylcyclohexane and 20 ml of water. The mixture was brought to reflux and stirred for 300 minutes. The presence of a solid in suspension was observed. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 490 g were obtained of a viscous and brittle cloudy gel which had solid particles in suspension. The solid could not be separated from the gel by centrifuging, due to the viscosity of the gel being too high.
This test shows that the synthesis conditions described in Example 1 of patent EP 0 924 214 B1, applied to neodymium oxide and to an alicyclic solvent, do not make it possible to obtain a tris(organophosphate) gel that is clear and free of solid residue in suspension.
COUNTEREXAMPLE 2
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 13.99 g of Nd2O3 of type B (0.040 mol), 83.8 g of di(2-ethylhexyl)phosphoric acid (DEHPA) (0.249 mol), 560 ml of methylcyclohexane and 20 ml of water. The mixture was brought to reflux and stirred for 300 minutes. The presence of a solid in suspension was observed. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 497 g were obtained of a viscous and brittle gel which had a solid in suspension. The solid could not be separated from the gel by centrifuging, due to the viscosity of the gel being too high.
This test shows that the synthesis conditions described in Example 1 of patent EP 0 924 214 B1, applied to neodymium oxide and to an alicyclic solvent, do not make it possible to obtain a tris(organophosphate) gel that is clear and free of solid residue in suspension.
COUNTEREXAMPLE 3
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 15.59 g of Nd2O3 of type A (0.040 mol), 92.3 g of di(2-ethylhexyl)phosphoric acid (DEHPA) (0.275 mol), 550 ml of methylcyclohexane and 20 ml of water. The mixture was brought to reflux and stirred for 120 minutes. The presence of a solid in suspension was observed. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 480 g were obtained of a gel having a solid in suspension (weight content of solid=0.3%).
This test shows, by fluidizing the gel obtained for better centrifugation owing to the addition of a supplementary amount of DEHPA, that the gel contains a sizeable amount of residual solid.
COUNTEREXAMPLE 4
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 16.82 g of Nd2O3 of type A (0.043 mol), 105 g of di(2-ethylhexyl)phosphoric acid (DEHPA) (0.314 mol), 685 ml of methylcyclohexane and 20 ml of water. The mixture was brought to reflux and stirred for 210 minutes. The presence of a solid in suspension was observed. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 595.5 g were obtained of a gel having a solid in suspension (weight content of solid=0.38%).
This test shows, by further fluidizing the gel obtained for better centrifugation owing to the addition of a supplementary amount of DEHPA, that the gel contains a sizeable amount of residual solid.
All of these examples show that the synthesis conditions described in patent document EP 0 924 214 B1, applied to neodymium metal and to an alicyclic solvent, do not make it possible to obtain a clear neodymium organophosphate gel.
3) Synthesis of an Organic Phosphate Salt of Neodymium According to the Process of the Invention:


EXAMPLE 1
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 15.59 g of Nd2O3 of type B (0.040 mol), 83.7 g of di(2-ethylhexyl)phosphoric acid (DEHPA) (0.250 mol), 560 ml of methylcyclohexane and 20 ml of water. The mixture underwent treatment with a rotor-stator of Ultra-Turrax brand for 20 minutes, so as to disperse the neodymium oxide in the reaction medium. The mixture was brought to reflux for 280 minutes. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 440 g of a translucent violet gel were obtained.
EXAMPLE 2
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 15.59 g of Nd2O3 of type B (0.040 mol), 92.2 g of DEHPA acid (0.275 mol), 550 ml of methylcyclohexane and 20 ml of water. The mixture underwent treatment with a rotor-stator of Ultra-Turrax brand for 20 minutes, so as to disperse the neodymium oxide in the reaction medium. The mixture was brought to reflux for 100 minutes. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 463 g of a translucent violet gel were obtained.
EXAMPLE 3
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 14.21 g of Nd2O3 of type B (0.036 mol), 88.3 g of DEHPA (0.264 mol), 560 ml of methylcyclohexane and 20 ml of water. The mixture underwent treatment with a rotor-stator of Ultra-Turrax brand for 45 minutes, so as to disperse the neodymium oxide in the reaction medium and to carry out the reaction of DEHPA with the neodymium oxide. During this treatment, the mixture was brought to reflux. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 463 g of a translucent violet gel were obtained.
EXAMPLE 4
Introduced into a jacketed 1-liter reactor equipped with a Dean-Stark trap, a condenser and a blade-type mechanical stirring system were 17.3 g of Nd2O3 of type B (0.044 mol), 107.7 g of DEI PA (0.322 mol), 680 ml of methylcyclohexane and 30 ml of water. The mixture underwent treatment with a rotor-stator of VMI Rayneri TRIMIX brand for 45 minutes, so as to disperse the neodymium oxide in the reaction medium. The water of the reaction medium was then removed by azeotropic distillation. After decanting from the reactor, 650 g of a translucent violet gel were obtained
Table 1 below gives the significant experimental data and presents the features of the various gels synthesized.
It is observed that the neodymium tris[di(2-ethylhexyl)phosphate] gels obtained with the process according to the invention are free of insoluble solid and therefore of residual neodymium oxide.















TABLE 1






C.-Ex. 1
C.-Ex. 2
C.-Ex. 3
C.-Ex. 4
Ex. 1
Ex. 2
Ex. 3
Ex. 4























Initial DEHPA/Nd stoichiometry
3.12
3.12
3.44
3.65
3.12
3.44
3.63
3.63


Apparatus used for the dispersion
No
No
No
No
Ultra-Turrax
Ultra-Turrax
Ultra-Turrax
Trimix


Diameter of the impeller (m)
0.04
0.04
0.04
0.04
0.016
0.016
0.016
0.069


Rotational speed (rpm)
8.3
8.3
8.3
8.3
400
400
400
50


Blade tip peripheral speed (m · s−1)
1
1
1
1
20
20
20
10.7


Shear calculated with k = 10 (s−1)
83
83
83
83
4000
4000
4000
500


Dispersion time in minutes




20
20
45
45


Reflux time in minutes
300
300
120
220
280
100




Azeotropic distillation time in minutes
180
180
180
180
180
180
120
180


Total duration of the synthesis in minutes
480
480
400
400
480
400
165
225


Appearance of the gel
Cloudy
Cloudy
Cloudy
Cloudy
Translucent
Translucent
Translucent
Translucent


Presence of solid
yes
yes
yes
yes
no
no
no
no


Content of insoluble species
Non-det.
Non-det.
0.3%
0.38%
0
0
0
0


% Nd
2.42%
2.34%
2.26%
1.90%
2.33%
2.35%
2.52%
2.77%


% free acid
1.80%
1.65%
3.77%
6.64%
1.89%
3.61%
4.32%
4.18%


Viscosity in cP
92000
96000
34000
Non det.
39000
44000
32000
53000





Non-det.: value not determined






On reading the results described in the preceding table, a person skilled in the art will conclude that the gels prepared in the counterexamples 1 to 4 are not satisfactory, on the one hand due to the high viscosity and on the other hand due to the presence of a solid residue in suspension, these parameters both being detrimental in view of a subsequent use for the preparation of a catalyst system for the polymerization of conjugated dienes.
4) Larger-Scale Synthesis of an Organic Phosphate Salt of Neodymium According to the Process of the Invention:
The syntheses described in Examples 5 to 8 were carried out in a VMI Rayneri TRIMIX brand 50-liter conical reactor possessing a wall scraper and a central shaft, the base of which is equipped with a rotor-stator, equipped at its centre with three counter-blades. The three agitator impellers are independent and have their own stirring speed, 3100 rpm for the rotor-stator, 200 rpm for the counter-blades and 67 rpm for the scrapers. The reactor is equipped with a distillation column surmounted by a condenser and a decanter that makes it possible to separate the water from the solvent.
EXAMPLE 5
Synthesis in MCH of a 2.3 wt % Gel
Introduced into the reactor were 0.88 kg of Nd2O3 of type B, 1.2 liters of water, 5.37 kg of DEHPA and 33 liters of methylcyclohexane. The reaction medium was stirred using the three agitator impellers and the temperature of the medium was brought to 75° C. in 35 minutes. Once the temperature of the system had stabilized, the water of the reaction medium was removed by azeotropic distillation. After 2 hours, the reaction medium was cooled to 40° C., then poured into a suitable container. Thus, 29.5 kg were obtained of clear gel having the features listed in Table 2.
EXAMPLE 6
Synthesis in Cyclohexane of a 2.3 wt % Gel
Introduced into the reactor were 0.875 kg of Nd2O3 of type B, 1.2 liters of water, 5.32 kg of DEHPA and 33 liters of cyclohexane. The reaction medium was stirred using the three agitator impellers and the temperature of the medium was brought to 66° C. in 20 minutes. Once the temperature of the system had stabilized, the water of the reaction medium was removed by azeotropic distillation. After 3 hours and 30 minutes, the reaction medium was cooled to 30° C., then poured into a suitable container. Thus, a clear gel was obtained having the features listed in Table 2.
EXAMPLE 7
Synthesis in Pentane of a 2.3 wt % Gel
Introduced into the reactor were 0.875 kg of Nd2O3 of type B, 1.45 liters of water, 5.32 kg of DEHPA and 40 liters of pentane. The reaction medium was stirred using the three agitator impellers and the temperature of the medium was brought to 40° C. in 15 minutes. Once the temperature of the system had stabilized, the water of the reaction medium was removed by azeotropic distillation. After 6 hours, the reaction medium was cooled to 20° C., then poured into a suitable container. Thus, a clear gel was obtained having the features listed in Table 2.
EXAMPLE 8
Synthesis in MCH of a Concentrated Gel
Introduced into the reactor were 0.875 kg of Nd2O3 of type B, 0.45 liters of water, 5.374 kg of DEHPA and 13 liters of methylcyclohexane. The reaction medium was stirred using the three agitator impellers and the temperature of the medium was brought to 75° C. in 35 minutes. Once the temperature of the system had stabilized, the water of the reaction medium was removed by azeotropic distillation. After 2 hours, the reaction medium was cooled to 40° C., then poured into a suitable container. Thus, a clear gel was obtained having the features listed in Table 2.
EXAMPLE 9
Synthesis in CH of a Concentrated Gel
Introduced into the reactor were 1.75 kg of Nd2O3 of type B, 1.5 liters of water, 10.6 kg of DEHPA and 33 liters of cyclohexane. The reaction medium was stirred using the three agitator impellers and the temperature of the medium was brought to 66° C. in 30 minutes. Once the temperature of the system had stabilized, the water of the reaction medium was removed by azeotropic distillation. After 4 hours, the reaction medium was cooled to 30° C., then poured into a suitable container. Thus, a clear gel was obtained having the features listed in Table 2.












TABLE 2






Ex 5
Ex 6
Ex 7
Ex 8
Ex 9




















Initial DEHPA/Nd stoichiometry
3.18
3.16
3.17
3.20
3.16


Solvent
Methylcyclohexane
Cyclohexane
Pentane
Methylcyclohexane
Cyclohexane


Total duration of the synthesis in
155
230
375
155
270


Appearance of the gel
Translucent
Translucent
Translucent
Translucent
Translucent


Presence of solid
no
no
no
no
no


Content of insoluble species
0
0
0
0
0


% Nd
2.19%
2.50%
2.61%
4.14%
4.4%


% P
1.55%
1.71%
1.99%
3.03%
3.3%


% free acid
1.90%
2.61%
2.07%
3.66%
3.50%


% H2O in ppm
450
34
424
800
45


Viscosity in cP
59000
—
9000
1600
—









II Preparation of Catalyst Systems
Synthesis of “Control” Catalyst Systems and Catalyst Systems According to the Invention from these Salts:
In view of obtaining each catalyst system, the corresponding salt of neodymium in gel form was poured into a reactor that had previously been cleaned of its impurities. The control gel was prepared according to U.S. Pat. No. 6,767,927. The gels according to the invention were those prepared in the preceding examples.
First Step of “Preforming” Each Catalyst System:
Introduced next, into the reactor at a temperature of 30° C., were butadiene and also a certain amount of the inert hydrocarbon solvent of the synthesis of the neodymium salt.
Second Step of Alkylation:
Introduced next into the reactor was diisobutylaluminium hydride (HDiBA) as an alkylating agent of the neodymium salt, at a concentration of around 1M. The alkylation time was 15 min. The temperature of the alkylation reaction was equal to 30° C.
Third Step of Halogenation:
Introduced next into the reactor was diethylaluminium chloride (CDEA) as a halogen donor, at a concentration of around 1M. The temperature of the reaction medium was brought to 60° C. The halogenation time was 70 minutes.
Fourth Step of Ageing:
An ageing of the mixture thus obtained was then carried out by maintaining this temperature of 60° C. for a time of 120 min.
Finally, the catalyst solution, under a nitrogen atmosphere, was stored in a freezer at a temperature of −15° C.
The molar ratios of the various constituents (butadiene, alkylating agent and halogen donor) relative to the neodymium salt of the catalyst systems thus prepared are given in the following tables.
These catalyst systems were then tested in the polymerization of butadiene and of isoprene in accordance with the processes described below.
III. Polymerization of Butadiene and of Isoprene Using the Prepared Catalyst Systems
The polymer characterization techniques are described in Appendix 1.
1) Polymerization of Butadiene:
A 250 ml “Steinie” bottle, previously washed and dried, and equipped with pierced caps and with a rubber septum was used as a polymerization reactor. Each butadiene polymerization reaction was carried out under an inert (nitrogen) atmosphere.
For each polymerization, 122 ml of methylcyclohexane was introduced into said bottle as a polymerization solvent. This methylcyclohexane was sparged with nitrogen for 10 minutes in order to remove the impurities.
16 ml (10.4 g) of freshly distilled butadiene was then introduced into the bottle using a syringe.
An amount of 582 μmol of HDiBA per 100 g of butadiene was then introduced into the bottle so as to cleanse the reaction medium of the impurities and so as to play the role of transfer agent for the control of the molar masses of the polymer.
A “polymerization solvent (methylcyclohexane)/monomer (butadiene)” weight ratio of 9 was used.
The [Nd/butadiene/HDiBA/CDEA] catalyst prepared previously was introduced into the bottle in an amount of 192 μmol of neodymium per 100 g of butadiene. This is the value of the catalytic base.
The bottle was then placed in a thermostated bath at the desired temperature of 90° C.
1 ml of methanol was used to stop the polymerization reactions.
The polybutadienes were then extracted from the polymer solutions thus obtained, either by steam stripping and drying on rolls at 100° C. or drying in an oven at 60° C. under vacuum with a slight stream of nitrogen, or by devolatilization by drawing the vacuum under nitrogen at 60° C.
The key parameters are the polymerization kinetics and the molar mass distribution of the elastomers obtained, and also the content of cis-1,4 units. The measurement of the degree of conversion of the monomer to polymer as a function of the reaction time is used to describe the polymerization kinetics. The characterization of the macrostructure of the polymers was carried out by the SEC method. The characterization of the microstructure of the polymers was carried out by the “near infrared” (NW) method.
The test results are summarized in Table 3 below:












TABLE 3






Molar ratios of the


Mn in




Nd/Bd/HDiBA/CDEA
% conversion
ηinh
g/mol
cis-1,4


TEST
catalyst system
(time in min.)
(dl/g)
(IP)
content





















With the Nd salt of
1/30/3/2.9
98
(30)
2.32
130000
99.0


Ex. 3




(1.85)



With the Nd salt of
1/30/3/2.9
100
(30)
2.39
128000
98.0


Ex. 4




(1.90)



With the Nd salt of
1/30/3.5/2.9
100
(30)
2.41
131000
98.0


Ex. 5




(1.85)



With the Nd salt of
1/30/3.5/2.9
98
(30)
2.23
133000
98.0


Ex. 6




(1.70)



With the Nd salt of
1/30/3.5/2.9
99
(30)
2.82
152000
99.0


Ex. 8




(1.80)



With the Nd salt of
1/30/3.5/2.9
100
(30)
2.63
143000
98.0


Ex. 9




(1.75)



Control “3.5”
1/30/3.5/2.9
100
(30)
2.55
137000
98.0







(1.90)



Control “3”
1/30/3/2.9
99
(30)
2.80
153000
98.0







(1.90)









Furthermore, the catalytic activity of these catalyst systems was also evaluated.
The results of the tests show that the gels prepared via a direct pathway according to the synthesis process of the invention can be used as is for the preparation of catalysts that are effective for the cis-1,4 stereospecific polymerization of butadiene.
The kinetics of the polymerizations are equivalent or even slightly superior to those observed with a catalyst prepared from a control commercial gel. The molecular weight distributions are narrow, as shown by the values of the polydispersity index, which are all below 2. The polybutadienes formed have a content of cis-1,4 units that is high and greater than 97%.
2) Polymerization of Isoprene:
A 250 ml “Steinie” bottle, previously washed and dried, and equipped with pierced caps and with a rubber septum was used as a polymerization reactor. Each isoprene polymerization reaction was carried out under an inert (nitrogen) atmosphere.
For each polymerization, 122 ml of methylcyclohexane was introduced into said bottle as a polymerization solvent. This methylcyclohexane was sparged with nitrogen for 10 minutes in order to remove the impurities.
15 ml (10.2 g) of freshly distilled isoprene was then introduced into the bottle using a syringe.
A “polymerization solvent (methylcyclohexane)/monomer (isoprene)” weight ratio of 9 was used.
The [Nd/butadiene/HDiBA/CDEA] catalyst obtained previously was introduced into the bottle in an amount of 431 μmol of neodymium per 100 g of isoprene.
The bottle was then placed in a thermostated bath at the desired temperature of 50° C.
1 ml of methanol was used to stop the polymerization reactions.
The polyisoprenes were then extracted from the polymer solutions thus obtained by drying in an oven at 60° C. under vacuum with a slight stream of nitrogen.
The key parameters are the polymerization kinetics and the molecular weight distribution of the elastomers obtained, and also the content of cis-1,4 units. The measurement of the degree of conversion of the monomer to polymer as a function of the reaction time is used to describe the polymerization kinetics.
The test results are summarized in Table 4 below:












TABLE 4






Molar ratios of the


Mn in




Nd/Bd/HDiBA/CDEA
% conversion
ηinh
g/mol
cis-1,4


TEST
catalyst system
(time in min.)
(dl/g)
(IP)
content





















With the Nd salt of
1/30/2/2.6
100
(90)
3.92
408000
97.2


Ex. 3




(2.50)



With the Nd salt of
1/30/2/2.6
95
(90)
4.44
479000
97.2


Ex. 4




(2.65)



Control
1/30/2/2.6
99
(90)
4.31
454000
97.4







(2.55)









Furthermore, the catalytic activity of these catalyst systems was also evaluated.
The results of these tests show that the gels prepared via a direct pathway according to the synthesis process of the invention can be used as is for the preparation of catalysts that are effective for the cis-1,4 stereospecific polymerization of isoprene.
The kinetics of the polymerizations are equivalent to those observed with a catalyst prepared from a control commercial gel. The molecular weight distributions are narrow, as shown by the values of the polydispersity index. The polymers formed have a content of cis-1,4 units that is high and greater than 97%.
It emerges from these tests that the gels prepared according to the direct synthesis process of the invention can be used for the cis-1,4 stereospecific polymerization of conjugated dienes, with catalytic activities comparable to those generally observed with this type of gel. The elastomers obtained have a high content of cis-1,4 units and a macrostructure that has a narrow molecular weight distribution.
APPENDIX 1
Measurement of the Intrinsic Viscosity
The intrinsic viscosity ηinh is measured at 25° C. at 0.1 g/dL in toluene and characterizes the macrostructure of the elastomer.
The viscosity is calculated from the equation:




  η
  =
  
    
      1
      C
    
    ×
    
      ln
      ⁡
      
        (
        
          
            T
            1
          
          
            T
            2
          
        
        )
      
    
  




where η is the intrinsic viscosity (dL/g), C the concentration of polymer in toluene (g/dL), T1 the flow time of the polymer solution (s) and T2 the flow time of the toluene (s).

Characterization of the Macrostructure by SEC

a) Measurement Principle:
Size exclusion chromatography (SEC) makes it possible to physically separate the macromolecules according to their size in the swollen state through columns filled with a porous stationary phase. The macromolecules are separated according to their hydrodynamic volume, those with the largest volumes being eluted first.
Without being an absolute method, SEC allows the molecular weight distribution of a polymer to be assessed. The various number-average (Mn) and weight-average (Mw) molecular weights may be determined, and the polydispersity index (Ip=Mw/Mn) calculated, from commercial standards.
b) Preparation of the Polymer:
There is no particular treatment of the polymer sample before analysis. It is simply dissolved in tetrahydrofuran at a concentration of around 1 g/l.
c) SEC Analysis:
Case c1) The equipment used is a WATERS Alliance chromatograph. The eluting solvent is tetrahydrofuran, the flow rate is 1 ml/min, the temperature of the system is 35° C. and the analysis time is 90 min. A set of two columns having the trade name STYRAGEL HT6E is used.
The injected volume of the polymer sample solution is 100 μl. The detector is a WATERS 2140 differential refractometer and the software for processing the chromatographic data is the WATERS Millennium system.
Case c2) The equipment used is a WATERS model 150C chromatograph. The eluting solvent is tetrahydrofuran, the flow rate is 0.7 ml/min, the temperature of the system is 35° C. and the analysis time is 90 min. A set of four columns in series is used, the columns having the trade names SHODEX KS807, WATERS STYRAGEL HMW7 and two WATERS STYRAGEL HMW6E.
The injected volume of the polymer sample solution is 100 μl. The detector is a WATERS model RI32X differential refractometer and the software for processing the chromatographic data is the WATERS MILLENNIUM system (version 3.00).
Characterization of the Microstructure (Cis-1,4 Content) by Near-Infrared (NIR)
The “near-infrared” (NIR) assay technique was used. This is an indirect method requiring “control” elastomers whose microstructure has been measured by the 13C NMR technique. The quantitative relationship (Beer-Lambert law) that exists between the distribution of monomers in an elastomer and the shape of the elastomer NIR spectrum is used. This technique is carried out in two steps:
1) Calibration:
The respective spectra of the “control” elastomers were acquired. A mathematical model is established that associates one microstructure with a given spectrum, this being done using the method of partial least squares (PLS) regression that is based on a factorial analysis of the spectral data. The following two documents relate, in an in-depth manner, to the theory and use of this method for analysing “multivariant” data:

    (1) P. GELADI and B. R. KOWALSKI, “Partial Least Squares regression: a tutorial”, Analytica Chimica Acta, vol. 185, 1-17 (1986).
    (2) M. TENENHAUS, “La régression PLS—Théorie et pratique” [PLS regression—theory and practice], Paris, Editions Technip (1998).


2) Measurement:
The spectrum of the sample was recorded. Then the microstructure was calculated.

## Claims

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:


Γaverage=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:


VperiphπND 


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.