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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
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• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F17/00—Compounds of rare earth metals
  • C01F17/20—Compounds containing only rare earth metals as the metal element
  • C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
  • C01F17/224—Oxides or hydroxides of lanthanides
  • C01F17/235—Cerium oxides or hydroxides
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  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F17/00—Compounds of rare earth metals
  • C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
  • C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
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  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
  • C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2237—Oxides; Hydroxides of metals of titanium
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2244—Oxides; Hydroxides of metals of zirconium

Definitions

• the present invention relates to a suspension of cerium oxide particles in a mixture of polar solvents.
• the invention also relates to the process for preparing this suspension and to the use thereof for dispersing cerium oxide particles in at least one polymer.
• Cerium oxide particles have anti-UV properties. Their incorporation into a polymer may be carried out by extrusion, but for some polymers difficult to extrude, the incorporation may consist in dissolving the polymer in a solvent or a mixture of solvents, in adding a suspension comprising particles of cerium oxide in a polar solvent, and then evaporate the solvent.
• polar polymers such as polyimide
• N-methyl pyrrolidone NMP or 1-methyl-2-pyrrolidone
• NMP N-methyl pyrrolidone
• NMP 1-methyl-2-pyrrolidone
• the technical problem to be solved is therefore to develop a stable suspension of cerium oxide particles in a polar solvent.
• No. 9,193,850 discloses a composite in the form of a polyimide matrix in which particles of an oxide whose surface has been modified are dispersed.
• the latter comprises particles of cerium oxide in a mixture of DMSO and of at least one Si compound of formula (I):
• ⁇ A denotes a group (C 2 -C 5) -alkylene
• ⁇ R is a (dC 4) -alkyl
• R 2 and R 3 are both groups (-C 4) -alkyl, which are identical or different.
• the particles are advantageously nanometric particles. They have an average size of less than or equal to 200 nm. They may have at least one of the following characteristics:
• ⁇ a mean size determined by ODR diffraction technique of less than X-ray or equal to 100 nm;
• ⁇ a mean size DMET determined using transmission electron microscopy (TEM) of less than or equal to 200 nm;
• dDRx is the size t of the coherent domain calculated from the width of one or more most intense diffraction lines and using the Scherrer model. According to this model, we use the following formula:
• ODRX corresponds to the arithmetic mean of three sizes ti, t 2 and t 3 determined from Scherrer's formula above on the three peaks at the following 2 ⁇ (2 theta) angles: 28.6 °; 47.5 ° and 56.4 ° or at the following angles: 28.6 ° ⁇ 0.1; 47.5 ⁇ 0.1 and 56.4 ⁇ 0.1.
• ⁇ Rx can vary over a wide range from 0.1 to 200 nm, even from 0.1 to 100 nm, preferably from 0.5 to 100 nm.
• ODX may be between 80 and 100 nm; or between 45 and 65 nm; or between 25 and 45 nm; or between 15 and 30 nm; or between 6 and 15 nm; or between 2 and 4 nm.
• di iET is calculated from a particle size distribution determined using transmission electron microscopy (TEM).
• the particles have a dMET of less than or equal to 200 nm, dMET being calculated from a particle size distribution determined using transmission electron microscopy (TEM). It is also possible to characterize the particles using the SMET standard deviation which is less than 35% of said average diameter, SMET being calculated from a particle size distribution determined using microscopy.
• transmission electronics MET
• the method for obtaining the distribution consists of measuring the diameter of at least 300 particles on one or more electron microscope slides.
• the enlargement of the microscope which is retained must make it possible to clearly distinguish the images of the particles on a snapshot.
• the enlargement can be for example between 50 000 and 500 000.
• the diameter of a particle which is retained is that of the minimum circle making it possible to circumscribe the entirety of the image of the particle as it is visible on a surface.
• MET snapshot The term "minimum circle” has the meaning given to it in mathematics and represents the circle of minimum diameter to contain a set of points of a plane. Only particles with at least half of the perimeter are defined.
• ImageJ software can be used to do more simple processing; this open source software was originally developed by the NIH American Institute and is available at http://rsb.info.nih.gov or http://rsb.info.nih.gov/ij/ dovvnload.html.
• said diameters are grouped into several size classes ranging from 0 to 500 nm, the width of each class being 1 nm.
• Number of particles in each class is the basic data to represent the (cumulative) number distribution. From the distribution, the mean diameter dMET is determined which corresponds to the median diameter as conventionally understood in statistics.
• dMET is such that 50% of the particles (in number) taken into account on the plate (s) MET have a diameter smaller than this value. From this distribution, it is also possible to determine the standard deviation SMET which has the usual meaning used in mathematics and which can be defined as the square root of the variance:
• n is the number of (so-called primary) particles taken into account on the SEM image (s);
• X is the diameter of a particle i on the SEM image (s);
• dMET may be between 150 and 200 nm; or between 70 and 110 nm; or between 35 and 70 nm; or between 15 and 35 nm; or between 6 and 15 nm; or between 2 and 5 nm.
• d 5 o corresponds to the median diameter as conventionally understood in statistics, determined from a volume distribution of the diameters of the particles obtained using the dynamic light scattering technique (also called DLS for dynamic light scattering). This technique is particularly suitable for submicron particles. It is therefore the value for which on the cumulative volume distribution curve, 50% of the particles have a diameter greater than d 5 o and 50% of the particles have a diameter less than d 5 o.
• the Zetasizer Nano ZS from Malvern Instruments can be used according to the recommendations and using the manufacturer's software to obtain such a distribution. It should be noted that d 5 o is generally greater than dMET because the particles can agglomerate.
• the specific surface is determined for its part by nitrogen adsorption on a powder dried at 100 ° C. overnight and placed in a study at 200 ° C. for 2 hours just before the measurement, according to the Brunauer-Emmet-Teller method. which has been described in J. Am. Chem. Soc. 1938, 60, p.309. The principle of this method is also described in ASTM D3663-03.
• the Shimadzu Flowsorb II 2300 can be used to automatically determine the BET surface area according to the manufacturer's recommendations. It is possible from the BET specific surface of the powder thus measured to determine an equivalent diameter denoted dBET calculated from the following formula:
• a density of 7200 kg / m 3 is retained for the particles of the invention.
• BET - 59.5 nm is used.
• the particles are characterized by a mean dMET size of less than or equal to 200 nm and an average size of ⁇ RDX of less than or equal to 100 nm. More particularly, the particles may have the following characteristics:
• the particles may also have a SMET standard deviation of at most 30% (SMET ⁇ 30% x dMET) - it may be preferably less than 25%, more particularly less than 20%, of said diameter dMET-
• the particles can have a volume distribution obtained using the dynamic light scattering technique which is narrow and which is characterized by a dispersion index of at most 0.5. This index may more particularly be at most 0.4 and even more particularly at most 0.3.
• the dispersion index is the ratio:
• - ds 4 is the particle diameter for which 84% of the particles have a diameter less than ds 4 ;
• - d i6 is the particle diameter for which 1 6% of the particles have a diameter less than d i6- If is a compound chosen from the compounds of formula (I) below:
• ⁇ A denotes a group (C 2 -C 5) -alkylene
• Ri is a (dC 4 ) -alkyl group
• R 2 and R 3 are both groups (dC 4) -alkyl, which are identical or different.
• A may for example be chosen from the following group: -CHMe-CH 2 CH 2 -; - CH 2 CH 2 -CHMe-; -CHEt-CH 2 CH 2 - or -CH 2 CH 2 -CHEt-.
• R1 can for example be selected from the following group: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl.
• MeOOC-Ai-CONMe 2 wherein Ai designates the alkylene group of formula -CHMe-CH 2 CH 2 - or -CH 2 CH 2 -CHMe-;
• a 2 is the alkylene group of formula -CHEt-CH 2 CH 2 - or -CH 2 CH 2 -CHEt-.
• Si may be in the form of a mixture of the following two compounds: MeOOC-CHMe-CH 2 CH 2 -CONMe 2 and MeOOC-CH 2 CH 2 -CHME-CONME 2 .
• the mass proportion S1 / DMSO can vary from 1/99 to 60/40, more particularly between 40/60 and 60/40.
• Si and the proportion of Si and DMSO it is possible to modify the physicochemical properties of the mixture in order to adapt them to the end use.
• the nature and the proportion of Si are advantageously adapted from so that Si and DMSO are compatible and form a homogeneous liquid phase at room temperature (15-25 ° C).
• the mixture of the suspension makes it possible to keep the particles in suspension. It has been found that other mixtures associating an Si compound with another polar solvent such as DMSO such as PGMEA or propylene glycol monomethyl ether acetate do not make it possible to obtain such stability. Thus, advantageously, the suspension therefore does not include a chemical compound that would destabilize the suspension and cause precipitation of the particles.
• the invention also relates to a suspension consisting of:
• ⁇ A denotes a group (C 2 -C 5) -alkylene
• ⁇ R is a (dC 4) -alkyl
• R 2 and R 3 are both groups (dC 4) -alkyl, which are identical or different.
• the proportion by weight of the cerium oxide in the suspension is generally at most 25% by weight, preferably at most 10% by weight and even more preferably at most 3% by weight with respect to whole suspension.
• the suspension may advantageously also comprise at least one anionic surfactant in order to improve the stability of the suspension, especially in contact with a polymer to be dissolved.
• the surfactant may be more particularly chosen from those of general formula (II):
• ⁇ A denotes a group (d-C20) -alkyl, linear or branched
• B denotes a group of formula - (CH 2 CH 2 O) n -;
• ⁇ n denotes an integer between 2 and 60.
• the anionic surfactant may be that of formula
• the anionic surfactant may for example be selected from Rhodafac RS 960, Rhodafac RS 710 E, Rhodafac ASI 100, Rhodasurf TR 4070, Rhodasurf CET 55, Abex 18 S or Geropon ACR-4.
• the anionic surfactant may also be more particularly chosen from those of general formula (III):
• ⁇ M counter-cation as described previously;
• R 4 denotes a group (C 4 -C 17) -alkyl, linear or branched; a - (CH 2 CH 2 O) n -X group or a counter-cation M as previously described;
• ⁇ n is an integer between 2 and 20;
• X denotes a linear or branched (C 4 -C 17) -alkyl group.
• the anionic surfactant is in sufficient quantity to obtain the desired stability.
• the proportion by weight of the surfactant is generally at most 10% relative to the entire suspension and may be between 1 and 7%.
• the mixture has a lower volatility than DMSO, which allows easier handling;
• the particles are cerium oxide particles but it is also possible that it is hydrated oxide (hydroxide).
• the composition of the particles may thus correspond to an oxide and / or a hydroxide and / or an oxyhydroxide of cerium.
• the particles may also be composed of a mixed oxide of cerium and at least one other element E selected from La, Pr, Nd, Sr, Y, Al, Ti or Zr.
• the invention as previously described in all embodiments and variants therefore also relates to particles of cerium oxide hydrate or a mixed cerium oxide and at least one other element E.
• the proportion by weight the oxide of the element E is at most 10%, more particularly between 1% and 10%, this proportion being determined relative to the mixed oxide.
• the method comprises contacting an aqueous slurry of cerium oxide and the anionic surfactant, to evaporate water by heating to obtain a powder, shaking together the powder and the solvents, DMSO and Si, and then heating the resulting mixture to a temperature between 50 ° C and 150 ° C, preferably between 50 ° C and 100 ° C.
• the contacting of the powder and the solvents can be carried out according to different embodiments. Thus, it is possible to add the powder to the mixture of the two solvents or to add to the powder the mixture of the two solvents. It is also possible to first contact the powder and one of the solvents, then add the other solvent.
• the embodiment chosen depends on the nature of the anionic surfactant, the S 1 / DMSO ratio and the cerium oxide particles (size, surface state) and must ensure a stable suspension without precipitation of the particles.
• the heating of the last stage of the process makes it possible to deaglomerate the optionally aggregated particles. This step can be carried out by increasing the temperature either in steps or progressively.
• the process consists in bringing into contact an aqueous suspension of cerium oxide, the two solvents, DMSO and Si, and, if appropriate, the anionic surfactant, then to remove water by vacuum distillation.
• the surfactant can be advantageously premixed with one of the two solvents or with the mixture of the two solvents. In the case where the suspension is not brought into contact with the mixture of the two solvents, it may be advantageous to first bring the suspension into contact with the DMSO.
• the mixtures are preferably constantly agitated to prevent settling of the particles that can lead to agglomeration thereof.
• the stirring retained also depends on the variables already described, namely the nature of the anionic surfactant, the S1 / DMSO ratio and the cerium oxide particles (size, state of the surface). At the laboratory scale, it has been possible to obtain suspensions according to the invention using stir bar stirring.
• This process for preparing the suspension is carried out identically in its two embodiments for a hydrated oxide (hydroxide) or for a mixed oxide of cerium and at least one other element E. It also applies to case of a composition corresponding to an oxide and / or a hydroxide and / or an oxyhydroxide of cerium.
• the aqueous suspension of cerium oxide may in turn be prepared by a precipitation process by contacting an aqueous solution of a cerium salt and a basic solution.
• the cerium salt may in particular be a nitrate.
• the basic solution may in particular be an ammonia solution.
• An example of a process for preparing an aqueous suspension of cerium oxide is that described in EP 208580. This process consists in bringing an aqueous solution of a salt of Ce lv into contact with a base in order to obtain the aqueous suspension. .
• the aqueous solution of this lv salt may be an aqueous solution of ceric nitrate or an aqueous solution of ceric ammonium nitrate.
• the aqueous solution of Ce lv salt may also comprise Ce "but it is desirable that the molar ratio of Ce lv is at least 85% (That lv / Ce to tai) -
• the aqueous solution preferably contains no or Few impurities in the form of covalent anions such as sulphate ions
• the concentration of the salt solution of Ce lv is not critical and may vary between 0.1 and 2 mol / L. This solution generally has a certain initial acidity.
• the concentration of H + ions is not critical.
• it is between 0.1 N and 4 N. It may advantageously be used a solution of ceric nitrate obtained by the electrolytic oxidation process described in application FR 2570087.
• the basic solution may be an aqueous solution of ammonia, soda or potash. This basic solution can have a concentration of between 0.1 and 1 1 N, or even between 0.1 and 5 N.
• the proportion between the basic solution and the salt solution of Ce IV may be such that the degree of neutralization T is greater than or equal to 0.01 and less than or equal to 3.0.
• T is defined by the formula (n 3 -n 2 ) / n wherein:
• ⁇ represents the number of moles of Ce lv present in the final colloidal suspension
• ⁇ n 2 represents the number of moles OH "needed to neutralize the acidity introduced by the aqueous solution of salt of Ce lv;
• ⁇ n 3 represents the number of moles OH "made by the basic solution.
• the reaction between the aqueous solution of Ce lv and the basic solution is performed at a temperature between 10 ° C and 60 ° C or between 15 ° C and 25 ° C.
• the mixture can be carried out of the two solutions according to several variants. for example, one can make a simultaneous mixing, with stirring, of two solutions or continuously introducing the basic solution in the aqueude solution of Ce lv or vice versa.
• the aqueous suspension of cerium oxide may be prepared by the process described in application WO 2008/043703 from a mixture of Ce '' and Ce lv, This process comprises the following steps:
• the medium obtained in the preceding step is heated under an inert atmosphere at a temperature between 60 and 95 ° C, at least one of the steps (a) or (b) being conducted in the presence of nitrate ions; - (c) is carried out successively but in any order acidification and washing of the medium thus obtained, whereby the suspension is obtained.
• the first step (a) is prepared from a solution which is a solution of a salt of Ce "further comprising Ce lv.
• Ce lv is provided by a salt which may be for example the cerium IV nitrate.
• the amount of Ce lv is such that the molar ratio Ce lv / Ce to tai in the starting solution may be between 1/100 and 1 / 50. It can be between 1/70 and 1/50, particularly between 1/65 and 1/50. This report lv / This is to re adapted and modified if necessary to achieve the particle size DurX desired.
• the starting solution may be degassed beforehand by contact with an inert gas.
• inert gas or “inert atmosphere” is meant for the present description an oxygen-free atmosphere or gas, the gas being, for example, nitrogen or argon.
• the contacting may be a bubbling of the inert gas in the solution.
• the starting solution is reacted with a base.
• a base the products of the hydroxide type can be used in particular.
• alkali or alkaline earth hydroxides and ammonia There may be mentioned alkali or alkaline earth hydroxides and ammonia. It is also possible to use secondary, tertiary or quaternary amines. However, amines and ammonia are preferred insofar as this makes it possible to reduce the risks of pollution by alkaline or alkaline-earth cations.
• the base may also be degassed beforehand by contact with an inert gas. The amount of base used is in excess of the cations present in the starting solution, so as to precipitate all the cerium present.
• the contacting can be done in any order of introduction of the reagents. However, it is preferable to introduce the starting solution in a medium containing the base.
• This step (a) must be conducted under an inert atmosphere. It can be conducted either in a closed reactor or in a semi-closed reactor with inert gas scavenging.
• the contacting is generally carried out in a stirred reactor. This step is generally carried out at room temperature (20-25 ° C) or at a temperature of at most 50 ° C.
• the 2nd step (b) of the process is a heat treatment of the reaction mixture obtained at the end of the previous step.
• This treatment consists in heating the mixture and maintaining it at a temperature which is generally at most 95 ° C. and more particularly between 60 ° C. and 95 ° C.
• the duration of this treatment can be between a few minutes and a few hours.
• This treatment is also carried out under an inert atmosphere, which has been described with respect to this atmosphere for step (a) applying likewise here.
• at least one of the steps (a) or (b) must be conducted in the presence of nitrate ions.
• the nitrate ions are provided by the addition of nitric acid, more particularly in step (a), during the preparation of the Ce '' solution.
• the amount of nitrate ions expressed by the molar ratio This is generally between 1/6 and 5/1, rather between 1/3 and 5/1.
• Step (c) actually comprises two successive operations that can be performed in any order. These operations are on the one hand an acidification and on the other hand a washing. These operations will be described below more precisely in the case of a sequence of acidification and then washing.
• Acidification generally takes place after cooling of the medium obtained at the end of step (b) by addition of an acid. Any mineral or organic acid can be used. Nitric acid is more particularly used. The amount of acid added is such that the pH of the medium after acidification is between 1 and 5. This operation can be conducted in air, it is no longer necessary to operate under an inert atmosphere at this stage of the process.
• the acidification is followed by a washing which aims to remove from the suspension the soluble species, mainly salts.
• the washing can be done in different ways with or without solid / liquid separation. It can thus be carried out by separating the solid particles from the liquid phase, for example by frontal filtration, decantation or centrifugation. The solid obtained is handed then suspended in an aqueous phase. One can also proceed by tangential filtration. This washing may be optionally renewed if necessary, for example until a given conductivity of the suspension is obtained, the conductivity measuring the level of impurities present in this suspension. As indicated above, the order of operations can be reversed with respect to what has just been described.
• step (c) at the end of step (c) and, again, generally after cooling the medium obtained, it is then possible to carry out a washing as described above. At the end of the washing, the acidification of the medium obtained is then carried out.
• the advantage of this process is to obtain a suspension of cerium oxide without calcination step at high temperature.
• the suspension of nonfunctionalized cerium oxide is thus obtained.
• the cerium oxide can be described here as non-functionalized because it is not necessary that the suspension comprises an organic stabilizer, including a stabilizer comprising at least one carboxylic acid or carboxylate function.
• the suspension nevertheless remains stable, the stability being able to be ensured by the residual amounts of inorganic ions present in the suspension, such as nitrate or ammonium ions.
• Steps (a), (b) and (c) may be more particularly the following:
• step (c) is carried out successively but in any order acidification and washing of the medium thus obtained, whereby the suspension according to the invention is obtained.
• the solutions used in step (a) are preferably degassed with a neutral gas, such as, for example, nitrogen.
• the acidic solution can be a nitrate solution of Ce "and Ce lv and nitric acid.
• the amount of ammonia used is in excess of the cations present in the starting solution and to precipitate the throughout this cerium.
• One can use an amount of ammonia being such that the molar ratio NH OH / cations present in the starting solution is greater than 1, 30.
• the ratio Ce lv / Ce to tai is adapted and modified if necessary, to reach the desired particle size dDRx.It can be between 1/100 and 1/50, more particularly between 1/70 and 1/50, even more particularly between 1/65 and 1/50.
• the solution of Ce '' and Cev is added to the ammonia solution.
• the duration of the addition can be between 20 minutes and 1 hour.
• step (c) one carries out successively but in any order an acidification and a washing of the medium thus obtained, whereby one obtains the suspension according to the invention.
• the process may comprise contacting an aqueous solution comprising nitrate anions, a cerium (III) salt, a cerium (IV) salt and a salt of the element E and causing the particles to precipitate at room temperature. using a basic solution under an inert atmosphere and subjecting the resulting mixture to heating under an inert atmosphere. This is for example an aqueous solution of nitrates.
• suspension according to the invention it may be used to disperse cerium oxide particles in at least one polymer.
• the method of dispersing cerium oxide particles in at least one polymer comprises a 1 st step in which is contacted stirring the suspension according to the invention with at least one polymer and optionally at least one organic solvent ( S i p0) of the polymer to disperse the cerium oxide particles in the polymer, then a 2 nd step during which DMSO, the compound Si and optionally S p0 i are totally or partially removed.
• the solvent S p0 ia operable to partially or completely dissolve and / or swell the polymer.
• S p0 i therefore denotes an organic solvent which can effectively partially or completely dissolve the polymer, but it is also possible to use an organic solvent which, without dissolving the polymer, makes it possible to swell it.
• S p0 ia operable to reduce mix viscosity and improve the dispersion of cerium oxide particles.
• S p0 i is chosen according to the nature of the polymer.
• the solvent may be decalin.
• S p0 i may be a polar solvent such as NMP.
• the 1 st step may be carried out according to several variants.
• the suspension according to the invention, the polymer and optionally the solvent S p0 i are mixed together.
• the suspension according to the invention and the polymer which has been previously totally or partially dissolved in the solvent S p0 i and / or swollen with the solvent S p0 i are mixed together.
• the 1 st step is conducted at a temperature which depends on the nature of the polymer.
• the mixture formed of the suspension according to the invention, the polymer and the optional solvent S p0 i is preferably heated to a temperature at which the viscosity of the mixture is not too high and compatible with the liquid compounds present in the mixture. It is generally between room temperature and 250 ° C, or even between room temperature and 200 ° C.
• the mixture can be carried out in a closed chamber, possibly under pressure to maintain some of the liquid compounds.
• the 2 nd step is to eliminate totally or partially, DMSO, Si compound and optionally i S p0. To do this, it may submit the mixture from the 1 st stage at a pressure lower than atmospheric pressure. In particular, it is also possible to form a film of the mixture from the 1 st step so as to promote the elimination of volatile compounds.
• the applicable industrial techniques in this case are the spin-coating or the "slot die coating". By these techniques, the polymer is applied on a moving support and the solvent is evaporated in a vacuum chamber. We can rest in Progr Colloid Polym Sci 2005, 130, 1-14 which describes techniques for preparing polymer films.
• the removal of DMSO compounds, Si compound and optionally S p0 i may be greater or lesser degree as required. They can be eliminated completely under the effect of a very high vacuum. According to one embodiment, it is possible to first apply a light vacuum to remove a part of the volatile compounds, then a higher vacuum to complete the removal of the volatile compounds. This embodiment can in particular make it possible to prevent the formation of holes in a polymer film by bursting of the gas bubbles that would have formed under the effect of a high vacuum.
• the volatile compounds can also be partially removed so as to allow the handling of the polymer, for example in the form of a film, then to allow the residue of the volatile compounds to be eliminated.
• the operating conditions eg, the presence of S p0 i or the polymer
• S p0 i or the polymer used for one of the steps of the dispersion process could theoretically destabilize the suspension according to the invention.
• the particles disperse in the polymer and the aggregation of particles is limited or prevented.
• the polymer may be a thermoplastic polymer, such as for example a polyolefin, a polyamide, an acrylic polymer, a polyester, a fluorinated polymer such as PVDF, a chlorinated polymer such as for example PVC.
• the proportion of cerium oxide in the polymer may be between 1% and 10%, or even between 1% and 7%, this proportion being expressed by weight of cerium oxide relative to the total weight of the polymer and of the cerium oxide.
• the techniques for preparing a polymer film are particularly suitable for the case where the extrusion technique in the molten state is not adapted to the polymer or to one of the polymers, which is the case for a polyimide that is, a polymer whose polymer chains comprise imide functions.
• the polyimide may be obtained by the polymerization of at least one aromatic dianhydride and at least one aromatic diamine.
• An example of polyimide is that obtained by the polymerization of dianhydride pyromellitic and 4,4'-oxydianiline. This polyimide comprises
• the aromatic dianhydride may correspond to a product of general formula (IV):
• R 5 denotes a tetravalent organic group containing at least one aromatic ring and preferably having at most 25 carbon atoms.
• R 5 can for example be chosen from the following list:
• R 5 may be more particularly chosen from the following list
• the aromatic dianhydride may be chosen from the following compounds: pyromellitic dianhydride; 3,3 ', 4,4'-biphenyl tetraacarboxylic dianhydride; 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride; 4,4'-oxydiphthalic dianhydride; 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic dianhydride; 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane; dianhydride bisphenol A.
• the aromatic diamine may correspond to a product of general formula (V)
• ⁇ 3 ⁇ 4 is a divalent organic group containing at least one aromatic ring and preferably having at most 25 carbon atoms.
• ⁇ 3 ⁇ 4 can be chosen for example from the following list:
• the aromatic diamine may be chosen from the following compounds: 3,4'-oxydianiline; 1,3-bis (4-aminophenoxy) benzene; 4,4'-oxydianiline; 1,4-diaminobenzene; 1,3-diaminobenzene; 2,2'-bis (trifluoromethyl) benzidene; 4,4'-diaminobiphenyl; 4,4'-diaminodiphenyl sulfide; 9,9'-bis (4-amino) fluorite.
• the polycondensation reaction leading to the polyimide consists of reacting the anhydride groups present on the aromatic dianhydride of formula (IV) and the amino groups present on the aromatic diamine of formula (V).
• the reaction may be incomplete so that some of the anhydride groups open without forming the imide functions, which then leads to a polymer comprising the units of general formula (VI):
• R 5 is a tetravalent organic group containing at least one aromatic nucleus and preferably having at most 25 carbon atoms;
• Each carboxylic group -COOH present on R 5 is attached to a carbon atom of R 5 adjacent to another carbon atom of R 5 to which the amide group is attached;
• ⁇ R 6 is a divalent organic group containing at least one aromatic nucleus and preferably having at most 25 carbon atoms;
• the amino group -NH- is attached to a carbon atom of the aromatic group of R6.
• polyamic acid a polymer commonly referred to as polyamic acid according to the following reaction:
• This incomplete reaction has the advantage that the resulting polymer can be more easily dissolved in an organic solvent than a polyimide which would result from the complete reaction.
• the polymer of formula (VI) therefore constitutes a polyimide precursor.
• the polyimide precursor can then be converted chemically to polyimide by an imidization reaction.
• the imide functions of the polyimide are formed.
• This conversion generally takes place by applying a heating of the precursor polymer at a temperature generally of between 90 ° C. and 500 ° C.
• a catalyst such as, for example, benzoic acid may be advantageously added to promote the imidization reaction.
• Application EP 0984030 describes examples of preparation of polyimide precursor and conversion of the precursor to polyimide.
• the polymer can also be crosslinkable. It is for example an ethylene-vinyl acetate copolymer (EVA) to which a crosslinking agent, for example of the radical initiator type, has been added.
• EVA ethylene-vinyl acetate copolymer
• the invention also relates to the use of a suspension according to the invention for dispersing the particles of cerium oxide, of cerium hydrated oxide or of a mixed cerium oxide and at least one other element.
• E selected from La, Pr, Nd, Sr, Y, Al, Ti or Zr in at least one polymer, especially a polyimide precursor or a polyimide.
• the polymer may be in the form of a film, in particular a transparent film.
• the particles being of small size, they make it possible to obtain protection of the film without degrading the optical properties of the film.
• the film may have an average thickness of at most 800 ⁇ . This thickness can be between 25 ⁇ and 800 ⁇ , particularly between 100 ⁇ 500 ⁇ . The average thickness is measured at 25 ° C on the film using a micrometer from 20 measurements taken at random over the entire surface of the film.
• the invention also relates to a dispersion process in which the suspension according to the invention is brought into contact with stirring with at least one polymer (Pi) and optionally at least one organic solvent (S p0 i) of the polymer in order to disperse the particles of cerium oxide in the polymer (Pi), then totally or partially DMSO, the compound Si and optionally S p0 i are eliminated, and the polymer (Pi) is chemically modified to be converted into polymer (P2) . Removal of volatile compounds and chemical modification can be accomplished in two separate steps. It is also possible to envisage that they be carried out at the same time.
• Pi may be a polymer of formula (VI) and P 2 is a polyimide.
• Pi may also be an uncrosslinked EVA which has been mixed with a crosslinking agent and P 2 is a crosslinked EVA.
• the d 5 o was determined using a Zetasizer Nano ZS from the company Malvern following the manufacturer's recommendations. In a quartz cell, a small amount of the suspension is taken from the micropipette and diluted in the same liquid medium as that of the suspension. For the automated calculation of d 5 o, the optical index for the cerium oxide retained is equal to 2.1. The optical index and the viscosity of the liquid medium are also introduced into the software of the apparatus. dlVlET, d [3ET and dXR were determined using the previously described methods.
• RhodiaSolv Polarclean which is an Si compound of formula MeOOC-ArCONMe2 in which Ai denotes a mixture of the two alkylene groups-CHMe-CH 2 CH 2 - and -CH 2 CH 2 -CHMe-.
• the suspension SA1 was prepared by reacting cerium nitrate and ammonia according to the process described in Example 1 of EP 208580.
• the suspension SA2 was prepared by the method described in WO 2008/043703. Table I
• Rhodafac ASI 100 0.19 g of 10% by weight Rhodafac ASI 100 is added to a suspension of 2% by weight of cerium oxide water and then stirred for 15 minutes. The particles of cerium oxide decant. The mixture is dried in an oven maintained at 100 ° C. for 1 h 30 in order to obtain a dry powder.
• Rhodasurf 40/70 dry in an oven at 100 ° C, 0.16 g of Rhodasurf 40/70 (10% by weight) for 30 min. 0.016 g of a powder which is dissolved in 31.0 g of a mixture of the two solvents is recovered. 1.55 g of the aqueous suspension of cerium oxide SA1 (proportion by weight of cerium oxide 20.7%, ie 0.32 g of cerium dioxide) are added. After magnetic stirring (300 rpm for 15 min), the mixture has a homogeneous appearance and no settling is observed.
• the mixture is then heated under vacuum at 100 ° C for 120 min (in the flask, 22-33 ° C at the top of the column, vacuum of 50 mbar) to remove water by vacuum distillation.
• a suspension according to the invention is then recovered at 1% by weight of cerium oxide.
• Table II summarizes the various tests carried out in the presence of the two suspensions SA1 and SA2. It can be seen that it is possible to obtain a suspension according to the invention from these two aqueous suspensions according to one of the two processes described above. On the other hand, in the presence of another polar solvent, PGMEA or propylene glycol monomethyl acetate ether of formula j j
• Figures 1 and 2 show the volume distribution curves of the particle size of cerium oxide obtained using the Zetasizer (abscissa: size in nm, ordinate%) suspended in water or in a polar mixture . These figures show that the transfer of particles from water to the mixture leads to similar distributions, which is a sign that there is no agglomeration.

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• 2017
  • 2017-12-01 CN CN201780084359.3A patent/CN110214126A/zh active Pending
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