EP1157071A1 - Organische sol und feststoff auf basis von ceriumoxyd und einem amphiphilem stoff und verfahren zur herstellung - Google Patents
Organische sol und feststoff auf basis von ceriumoxyd und einem amphiphilem stoff und verfahren zur herstellungInfo
- Publication number
- EP1157071A1 EP1157071A1 EP00903784A EP00903784A EP1157071A1 EP 1157071 A1 EP1157071 A1 EP 1157071A1 EP 00903784 A EP00903784 A EP 00903784A EP 00903784 A EP00903784 A EP 00903784A EP 1157071 A1 EP1157071 A1 EP 1157071A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cerium oxide
- mixture
- liquid phase
- amphiphilic compound
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/41—Particular ingredients further characterized by their size
- A61K2800/413—Nanosized, i.e. having sizes below 100 nm
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
- C10L1/1233—Inorganic compounds oxygen containing compounds, e.g. oxides, hydroxides, acids and salts thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
- C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
- C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
- C10L1/1985—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid polyethers, e.g. di- polygylcols and derivatives; ethers - esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/20—Organic compounds containing halogen
- C10L1/201—Organic compounds containing halogen aliphatic bond
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/22—Organic compounds containing nitrogen
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
- C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
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- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/26—Organic compounds containing phosphorus
- C10L1/2666—Organic compounds containing phosphorus macromolecular compounds
- C10L1/2683—Organic compounds containing phosphorus macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon to carbon bonds
Definitions
- the present invention relates to an organic soil and a solid compound based on cerium oxide and on an amphiphilic compound and their methods of preparation
- Colloidal soils or dispersions of cerium oxide in organic media are known
- the soils prepared by these processes are essentially soils in a non-polar organic medium.
- the processes of the prior art generally go through the preparation of an aqueous soil in a first step and, in a second step, by bringing this aqueous soil into contact with an organic phase to effect the transfer of the oxide of cerium in the organic phase.
- Such a way of operating is not suitable for the preparation of soils in polar phases miscible with water.
- cerium oxide soils can be used in multiple applications such as catalysis, anti-corrosion coatings, paints. This variety of applications therefore leads to a need for soils with varied characteristics and types different from those already known and also a need for processes suitable for their preparation.
- An object of the present invention is to provide such organic soils
- Another object of the invention is a method allowing access to a wide range of organic soils and in particular to soils in polar solvents.
- the organic soil of the invention is caracté ⁇ sé in that it comprises particles of cé ⁇ um oxide; an organic liquid phase and at least one amphiphilic compound chosen from polyoxyethylenated alkyl ethers of carboxylic acids, polyoxyethylenated alkyl ethers phosphates, dialkyl sulfosuc nates and quaternary ammonium compounds.
- the invention also relates to a process for the preparation of such a sol which, according to a first variant, is characterized in that the above-mentioned amphiphilic compound and the organic liquid phase are mixed, then the cerium oxide particles are dispersed in the mixture obtained.
- the method is characterized in that a mixture of cerium oxide and at least one aforementioned amphiphilic compound is formed, then said mixture is dispersed in the organic liquid phase.
- sol or colloidal dispersion of cerium oxide designates any system consisting of fine solid particles of colloidal dimensions based on cerium oxide and / or hydrated oxide (hydroxide) of cerium suspended in a liquid phase, said species possibly also containing, optionally, residual quantities of bound or adsorbed ions such as, for example, nitrates, acetates, citrates or ammoniums. It will be noted that in such dispersions, the cerium can be found either completely in the form of colloids, or simultaneously in the form of ions and in the form of colloids.
- the cerium oxide particles generally have an average diameter of at most 100 nm, more particularly at most 50 nm and even more particularly at most 20 nm. For example, this diameter can be between 5 and 10 nm. It is specified HERE that the mean diameter of the particles or colloids must be understood as designating the mean hydrodynamic diameter of the latter, and as determined by quasi-elastic light scattering according to the method determined by Michael L. Me CONNELL in the journal Analytical Chemistry 53, No. 8, 1007 A, (1981).
- cerium is generally present in the form of cerium IV.
- Cerium can also be present in the form of a mixture of cerium III and cerium IV in any respective proportions.
- the organic liquid phase of the soil of the invention can be based on a liquid or a mixture of organic liquids of very varied nature
- the organic solvent or liquid can be an inert aliphatic, cycloaliphatic hydrocarbon, or a mixture thereof, such as for example mineral or petroleum spirits which may also contain aromatic components. Mention may be made, by way of indication, of hexane, heptane, octane, nonane, decane, cyclohexane, cyclopentane, cycloheptane and liquid naphthenes.
- Aromatic solvents such as benzene, toluene, ethylbenzene and xylenes are also suitable as well as petroleum fractions of the ISOPAR or SOLVESSO type (trademarks registered by the company EXXON), in particular SOLVESSO 100 which essentially contains a mixture of methylethyl and t ⁇ methylbenzene, and SOLVESSO 150 which contains a mixture of alkyl benzenes, in particular dimethylethylbenzene and tetramethylbenzene
- chlorinated hydrocarbons such as chloro or dichiorobenzene, chlorotoluene, as well as aliphatic and cycloaliphatic ethers such as dusopropyl ether, dibutyie ether and aliphatic and cycloaliphatic ketones such as methylisobutyletone , diisobutyleetone, mesityl oxide.
- ketones such as acetone, aldehydes, nitrogen solvents such as acetonitrile, alcohols, acids and phenols.
- Esters can also be envisaged. Mention may be made, as esters which can be used, in particular those resulting from the reaction of acids with C1 to C8 alcohols and in particular the secondary alcohol palmitates such as isopropanol.
- the acids from which these esters can be aliphatic carboxylic acids, aliphatic sulfonic acids, aliphatic phosphonic acids, alkylarylsulfonic acids, and alkylarylphosphonic acids having about 10 to about 40 carbon atoms, whether natural or synthetic.
- tall oil fatty acids coconut oil, soybean, tallow, linseed oil, oleic acid, linoleic acid, stearic acid and its isomers , pelargonic acid, cap ⁇ que acid, lau ⁇ que acid, my ⁇ stic acid, dodecylbenzenesulfonic acid, 2-ethylhexanoic acid, naphtenic acid, hexoic acid, toluenesulfonic acid , toluene-phosphonic acid, lauryl-sulfonic acid, lauryl-phosphonic acid, palmityl-sulfonic acid, and palmityl-phosphonic acid
- the organic liquid phase is based on a polar solvent or on a mixture of polar solvents.
- polar solvent is meant those having a dielectric constant ⁇ r greater than 5, such that defined in particular in the book “Solvents and Solvent Effects m Organic Chemistry", C Reichardt, VCH, 1988.
- This polar solvent can be chosen from halogenated solvents such as dichloromethane, esters of the ethyl acetate type, isopropyl palmitate , methoxy-propyl acetate, alcohols such as ethanol, butanol or isopropanol, polyols such as propane diol, butane diol or diethylene glycol; ketones such as cyclohexanone or 1-methylpyrrol ⁇ d ⁇ n-2-one
- the soil also comprises an amphiphilic compound Without wishing to be bound by an explanation, it may be thought that this amphiphilic compound is adsorbed on or in electrostatic interaction with or complex with cerium oxide particles
- This compound can be chosen first of all from polyoxyethylenated alkyl ethers of carboxylic acids.
- R ⁇ is a linear or branched alkyl radical which may especially comprise 4 to 20 carbon atoms
- n is an integer which may range from example up to 12
- R 2 is a residue of carboxylic acid such as for example -CH 2 COOH
- amphiphilic compound can also be chosen from alkyl ethers polyoxyethylenated phosphates.
- ICI means polyoxyethylenated alkyl phosphates of formula Ra-O ⁇ CHz-CHz-Oî n -P-tOM, ⁇
- R 3 , R, R 5 which are identical or different, represent a linear or branched alkyl radical, in particular from 2 to 20 carbon atoms, a phenyl radical; an alkylaryl radical, more particularly an alkylphenyl radical, in particular with an alkyl chain of 8 to 12 carbon atoms; an arylalkyl radical, more particularly a phenylaryl radical; n the number of ethylene oxide which can vary from 2 to 12 for example; M., represents a hydrogen, sodium or potassium atom
- the radical R 3 can in particular be a hexyl, octyl, decyl, dodecyl, oleyl, nonylphenyl radical
- Rhodafac® PA 17 poly-oxy-ethylene nonyl (branched) ether phosphate Rhodafac® RE 610
- the amphiphilic soil compound of the invention can also be chosen from dialkyl sulfosuccinates, and in particular alkaline dialkyl sulfosuccinates such as sodium dialkyl sulfosuccinates, that is to say the compounds of formula R 6 -0-C (0) - CH 2 - CH (S0 3 M 2 ) -C (O) -0-R 7 in which R and R 7 , which are identical or different, represent an alkyl radical from C 4 to C 4 for example and M 2 is an alkali metal or hydrogen.
- dialkyl sulfosuccinates and in particular alkaline dialkyl sulfosuccinates such as sodium dialkyl sulfosuccinates, that is to say the compounds of formula R 6 -0-C (0) - CH 2 - CH (S0 3 M 2 ) -C (O) -0-R 7 in which R and R 7 , which are identical or different, represent an alkyl radical
- amphiphilic compounds which are suitable for the present invention, mention may also be made of quaternary ammonium compounds. Mention may more particularly be made of mono, di or tri alkyl ammonium compounds, one of the radicals attached to the nitrogen atom which can be an alkyl radical comprising from 1 to 3 carbon atoms, including these alkyl radicals from 1 to 3 carbon atoms carrying inert substituents for example halogen, acetate, methylsulfate, etc. one of the other radicals which may be an alkyl radical of C 4 to C 20.
- the choice of the amphiphilic compound is made according to the nature of the organic liquid phase.
- this choice is made by adapting the hydrophilic / lipophilic balance of the amphiphilic compound with the lipophilic hydrophilic nature of the organic phase.
- the more polar the solvent entering into the constitution of the organic phase the more hydrophilic the amphiphilic compound will be.
- the proportion of amphiphilic compound relative to cerium oxide is adjusted so as to obtain a stable dispersion, it is generally between 2 and 10 molecules per nm 2 of surface of cerium oxide, assuming a surface per complexing head cation cé ⁇ um compnse between 10 and 80 ⁇ 2
- the soils according to the invention have a concentration of compound of ce ⁇ um which can be at least 10% exp ⁇ mée by weight of Ce0 2 relative to the total weight of the dispersion
- the organic soils thus produced have excellent stability. No settling is observed after several months.
- the water content of the soils of the invention can be at most equal to 1%, advantageously 1000 ppm, preferably 100 ppm.
- the present invention also relates to a solid compound which is characterized in that it comprises a mixture of particles of cerium oxide and of at least one amphiphilic compound chosen from those which have been found above.
- This solid compound is present either in the form of a paste or in the form of a powder.
- Ce ⁇ um oxide is present in this solid compound in the form of unaggregated elementary c ⁇ stallites of average size of approximately 5nm or aggregated in medium-sized aggregates which can range from 200nm to 10nm approximately, these aggregates being able to form agglomerates which can be disaggregable .
- the solid compound has the property of being redispersible, that is to say of being able to give a sol according to the invention and as described above when it is suspended in an organic liquid phase. What was stated above for the nature of the soil particles also applies HERE for the solid compound
- cerium oxide capable of being able to give a sol when it is dispersed in a liquid phase is used as starting material and in particular any cerium oxide capable of being in the form which has been described above with regard to the solid compound
- cerium oxide prepared by thermohydrolysis mention may be made of cerium oxide prepared by thermohydrolysis.
- Thermohydrolysis is, essentially, a process in which an aqueous solution is prepared containing a soluble cé ⁇ um compound, this aqueous solution is reacted with a base; the medium obtained is then heated, the reaction product is recovered and finally, optionally, the recovered product is dried.
- a process is described in patent application EP-A-208580, the teaching of which is incorporated here.
- Mention may more particularly be made, as compounds soluble in the water of the cerum, of the cerum (IV) salts such as nitrates or cerium ammonium nitrates for example, which are particularly suitable here or also the organic cerum (IV) salts.
- cé ⁇ que nitrate is used.
- the base added to the solution can be a solution of ammonia or alternatively alkali hydroxides (sodium, potassium). The reaction with the base makes it possible to obtain a dispersion containing ions and colloids of a cé ⁇ um compound.
- neutralization rate is meant the following ratio:
- ni represents the total number of moles of Ce IV present in the solution after neutralization
- n2 represents the number of moles of OH ions "effectively necessary to neutralize the initial free acidity provided by (an aqueous solution of cerium salt IV
- n3 represents the total number of moles of OH ions" provided by the addition of the base.
- the precipitation of the cerium dioxide is carried out by a heat treatment of the dispersion obtained after the reaction with the base.
- the temperature at which this heat treatment is carried out can be comp ⁇ se between 80 ° C. and the critical temperature of the medium. reaction, in particular between 80 ⁇ C and 350 ⁇ C, preferably between 90 ° C and 160 ° C.
- This treatment can be carried out, depending on the temperature conditions adopted, either under normal atmospheric pressure or under pressure such as for example the saturated vapor pressure corresponding substantially to the temperature of the heat treatment.
- the treatment temperature is chosen to be higher than the reflux temperature (under ordinary pressure) of the reaction mixture (that is to say generally greater than 100 ° C.), for example chosen between 120 ° C., more often between 150 ° C. C and 350 ° C.
- the operation is then carried out in a closed enclosure which is more particularly a closed reactor more commonly called an autoclave.
- the aqueous mixture containing the abovementioned species is introduced into this enclosure, the necessary pressure results only from the heating of the reaction medium (autogenous pressure).
- the pressure in the closed reactor varies between a value greater than 1 Bar (10 5 Pa) and 200 Bar (20.10 7 Pa), preferably between 5 Bar (5.10 5 Pa) and 150 Bar (1.5.10 7 Pa) It is of course also possible to exert an external pressure which is then added to that subsequent to heating.
- the heating can be carried out either under an atmosphere of air, exits under an atmosphere of inert gas, preferably nitrogen.
- the duration of the treatment is not critical, and can thus vary within wide limits, for example between 1 and 48 hours, preferably between 2 and 24 hours.
- the temperature rise takes place at a speed which does not is not critical, and the fixed reaction temperature can be reached by heating the medium for example between 30 minutes and 4 hours, these values being given for information only
- thermohydrolysis At the end of the thermohydrolysis, a solid precipitate is recovered which can be separated from its medium by any conventional technique of solid-liquid separation such as for example, elut ⁇ ation, filtration, decantation, spinning or cent ⁇ fugabon
- thermohydrolysis thermohydrolysis
- the precipitate is then optionally dried.
- This precipitate constitutes a starting product which is subsequently used in the processes for preparing the soil of the invention which will be described later.
- This process comprises the following stages - a solution or suspension is prepared comprising at least one acetate or a chloride of this t ⁇ valent ce ⁇ um,
- the solution is brought into contact with a basic medium and the reaction mixture thus formed is kept at a basic pH
- basic medium any medium having a pH greater than 7.
- the basic medium will usually be an aqueous solution containing a base.
- Products of the hydroxide type may in particular be used as base.
- Alkali hydroxides or alkaline earth metal Secondary, tertiary or quaternary amines can also be used However, amines and ammonia may be preferred insofar as they reduce the risks of pollution by alkaline or alkaline earth cations.
- the abovementioned mixture and the basic medium are brought into contact under conditions such that the pH of the reaction mixture which is thus formed remains basic.
- this pH value will be at least 9 It may more particularly be at most 11 More particularly still, this value may be comp ⁇ se between 9.5 and 1 1
- the abovementioned mixture and the basic medium can be brought into contact by introducing the mixture into the basic medium. It is also possible to carry out the placing in continuous contact, the pH condition being achieved by adjusting the respective flow rates of the mixture and basic medium
- the contacting is usually done at room temperature.
- a precipitate or a suspension is obtained which can be separated, if necessary, from the reaction mixture by any known means.
- the separated product can be washed.
- the precipitate is then optionally dried.
- the soil preparation process of the invention can be implemented according to a first variant.
- the above-mentioned amphiphilic compound and the organic liquid phase are mixed, then the cerium oxide particles are dispersed in the mixture obtained. It should be noted that one can either introduce the solid particles into the mixture of amphiphilic compound / organic phase or pour this mixture onto the cerium oxide particles. Once the particles, the amphiphilic compound and the organic phase have been brought into contact, the mixture is stirred until a stable colloidal dispersion is obtained.
- a third variant will now be described which is more particularly suitable for the preparation of a soil in the polar organic phase.
- This variant for the preparation of a soil according to the invention in an organic liquid phase (a) comprises a first step in which a dispersion is formed comprising particles of cerium oxide and at least one amphiphilic compound of the aforementioned type in an organic liquid phase (b) based on a solvent of lower polarity than that of the solvent in the organic liquid phase (a)
- a dispersion comprising particles of cerium oxide and at least one amphiphilic compound of the aforementioned type in an organic liquid phase (b) based on a solvent of lower polarity than that of the solvent in the organic liquid phase (a)
- the solid phase is separated from the dispersion of the liquid phase (b) thereof.
- This separation can be done by any suitable technique. On can thus effect the separation by flocculation with a third solvent or also by distillation.
- a solid phase is collected which can be dried and which occurs according to the level of drying achieved and the nature of the amphiphilic compound, either in the form of powder either in the form of a paste and which constitutes a solid compound according to the invention
- the phase or the solid compound thus obtained is redispersed in the organic phase (a) to thereby obtain the desired soil
- the soils obtained can undergo a post-treatment of dehydration by passing over a solid desiccating agent for example.
- the soils of the invention can be used in numerous applications. Mention may be made of lubrication, ceramics They can be used also as siccatives in the paint and varnish industry with a view to accelerating the drying of unsaturated oils, on a substrate as an anticorrosion agent or also in the preparation of cosmetic compositions in particular in the preparation of anti-UV creams.
- interesting use is that as a combustion adjuvant in fuels or liquid fuels of energy generators such as internal combustion engines, oil burners, or jet propellers
- the soils of the invention are more particularly suitable as an adjuvant for diesel oils for a diesel engine.
- Nonlimiting examples will now be given.
- This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in xylene medium.
- a colloidal dispersion of Ce ⁇ 2 in xylene medium In a beaker, 22.4 g of an amphiphilic compound of the polyoxyethylene phosphate ester type Rhodafac RS 410, marketed by Rhodia, and 100 g of Isopar solvent are introduced at room temperature.
- Rhodia polyoxyethylene phosphate ester type
- the mixture is left under stirring until a stable colloidal dispersion is obtained.
- the small volume of aqueous phase obtained by separation is separated and the dispersion thus obtained is fioculated by addition of acetone.
- the precipitate obtained is collected by centrifugation and allowed to dry at temperature. ambient
- This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in CH2Cl2 medium.
- 30.5 g of an amphiphilic compound of the polyoxyethylenated alkyl ether type AKIPO LF4 alkyl ether, marketed by Kao Chemicals Gmbh are introduced at ambient temperature.
- 100g of CH2CI2- 40g of cerium oxide hydrated at 65.7% in Ce0 2 is gradually added like that described in Example 1 and the mixture is made up to 200g in total with CH2CI2- The whole is stirred at room temperature until a stable colloidal dispersion is obtained.
- the dispersion thus obtained is evaporated at room temperature.
- a paste is obtained containing the nanoparticles of cé ⁇ que oxide and the amphiphilic compound. 4g of this product thus obtained are dispersed in 16g of CH2Cl2.
- a colloidal dispersion is obtained. By quasi elastic light scattering, a hydrodynamic diameter of the colloids comp ⁇ s is determined between 5 to 10 nm
- Example 3 This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in ethyl acetate medium.
- the dispersion thus obtained is evaporated at room temperature.
- a paste is obtained containing the nanoparticles of cé ⁇ que oxide and the amphiphilic agent.
- This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in ethyl acetate medium.
- 30.5 g of an amphiphilic AKIPO LF4 compound are added and the mixture is completed with 100 g of CH2Cl2.
- 40 g of the oxide of ce ⁇ um from Example 1 is gradually added at room temperature and the mixture is made up to 200 g in total. through
- the dispersion thus obtained is evaporated at room temperature.
- a paste is obtained containing the nanoparticles of cé ⁇ que oxide and the amphiphilic agent. 4 g of this product thus obtained are put to disperse in 16 g of ethyl acetate.
- a colloidal dispersion is obtained. By quasi elastic light scattering, a hydrodynamic diameter of the colloids comp ⁇ s is determined between 5 to 10 nm.
- Example 5 This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in a methoxypropylacetate medium
- the dispersion thus obtained is evaporated at room temperature
- a paste is obtained containing the ce ⁇ que oxide nanoparticles and the amphiphilic agent 4g of this product thus obtained are put to disperse in 16g of methoxypropylacetate.
- a colloidal dispersion is obtained. By quasi-elastic light scattering, a hydrodynamic diameter of the colloids between 10 and 20 nm is determined.
- the percentage of water in the dispersion is equal to 0.9%
- This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in ethanol medium
- This example illustrates the preparation of a colloidal dispersion of Ce ⁇ 2 in ethanol medium.
- 30.5 g of an amphiphilic AKIPO LF4 compound and 100 g of CH2Cl2 are introduced into a beaker at ambient temperature.
- 40g of the cerium oxide of Example 1 is gradually added and the mixture is made up to 200g in total with CH2Cl2.
- the whole is stirred and at room temperature until a stable colloidal dispersion is obtained.
- the dispersion thus obtained is evaporated at room temperature.
- a paste is obtained containing the ceric oxide nanoparticles and the amphiphilic agent.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9901939A FR2789601B1 (fr) | 1999-02-17 | 1999-02-17 | Sol organique et compose solide a base d'oxyde de cerium et d'un compose amphiphile et procedes de preparation |
FR9901939 | 1999-02-17 | ||
PCT/FR2000/000330 WO2000049098A1 (fr) | 1999-02-17 | 2000-02-10 | Sol organique et compose solide a base d'oxyde de cerium et d'un compose amphiphile et procede de preparation |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1157071A1 true EP1157071A1 (de) | 2001-11-28 |
Family
ID=9542148
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP00903784A Withdrawn EP1157071A1 (de) | 1999-02-17 | 2000-02-10 | Organische sol und feststoff auf basis von ceriumoxyd und einem amphiphilem stoff und verfahren zur herstellung |
Country Status (9)
Country | Link |
---|---|
US (1) | US6649156B1 (de) |
EP (1) | EP1157071A1 (de) |
JP (1) | JP2002537308A (de) |
CN (1) | CN1144851C (de) |
BR (1) | BR0008339A (de) |
CA (1) | CA2360820A1 (de) |
FR (1) | FR2789601B1 (de) |
NO (1) | NO20014029L (de) |
WO (1) | WO2000049098A1 (de) |
Families Citing this family (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2789602B1 (fr) * | 1999-02-17 | 2001-05-11 | Rhodia Chimie Sa | Sol organique et compose solide a base d'oxyde de titane et d'un compose amphiphile et procedes de preparation |
FR2797199B1 (fr) * | 1999-08-04 | 2001-10-05 | Rhodia Terres Rares | Dispersion colloidale organique de particules essentiellement monocristallines d'au moins un compose a base d'au moins une terre rare, son procede de preparation et son utilisation |
AU2001267700B2 (en) | 2000-06-29 | 2006-07-27 | Neuftec Limited | A fuel additive |
FR2833862B1 (fr) * | 2001-12-21 | 2004-10-15 | Rhodia Elect & Catalysis | Dispersion colloidale organique de particules de fer, son procede de preparation et son utilisation comme adjuvant de carburant pour moteurs a combustion interne |
WO2003060019A1 (en) | 2002-01-04 | 2003-07-24 | University Of Dayton | Non-toxic corrosion protection pigments based on cobalt |
FR2836479B1 (fr) * | 2002-02-27 | 2005-09-09 | Rhodia Elect & Catalysis | Utilisation d'un sol organique de cerium dans les peintures, notamment les lasures ou les vernis |
FR2840313B1 (fr) * | 2002-05-28 | 2004-08-27 | Rhodia Elect & Catalysis | Composition a base d'une peinture aqueuse, notamment d'une lasure ou d'un vernis, et d'une dispersion colloidale aqueuse de cerium |
GB0301599D0 (en) * | 2003-01-23 | 2003-02-26 | Oxonica Ltd | Cerium oxide nanoparticles as fuel additives |
FR2853261B1 (fr) | 2003-04-04 | 2006-06-30 | Rhodia Elect & Catalysis | Dispersion colloidale d'un compose d'une terre rare comprenant un agent anti-oxydant et son utilisation comme adjuvant de gazole pour moteurs a combustion interne |
ES2670344T3 (es) | 2003-09-05 | 2018-05-30 | Infineum International Limited | Composiciones de aditivo para combustible diésel estabilizado |
EP1512736B1 (de) * | 2003-09-05 | 2018-05-02 | Infineum International Limited | Stabilisierte Additivzusammensetzungen für Dieselkraftstoffe |
FR2860443B1 (fr) * | 2003-10-03 | 2006-06-16 | Rhodia Elect & Catalysis | Dispersion colloidale organique de cerium et d'un element choisi parmi le rhodium et le palladium et son utilisation comme adjuvant de gazoles pour moteurs a combustion interne |
US7458384B1 (en) * | 2004-07-15 | 2008-12-02 | University Of Central Florida Research Foundation, Inc. | Surfactant incorporated nanostructure for pressure drop reduction in oil and gas lines |
FR2885367B1 (fr) * | 2005-05-03 | 2007-07-27 | Rhodia Chimie Sa | Organosol stabilise par des polymeres sequences amphiphiles |
FR2885308B1 (fr) * | 2005-05-04 | 2007-07-06 | Eastman Kodak Co | Procede pour maintenir l'etat de dispersion d'une solution colloidale de particules d'oxyde metallique |
KR101356870B1 (ko) * | 2005-10-08 | 2014-01-29 | 재단법인서울대학교산학협력재단 | 세륨 산화물 나노 입자 제조 방법 |
WO2007068809A1 (fr) * | 2005-12-13 | 2007-06-21 | Rhodia Operations | Poudre pouvant etre redispersee de dispersions de particules minerales stabilisees avec un polymere |
US8883865B2 (en) * | 2006-09-05 | 2014-11-11 | Cerion Technology, Inc. | Cerium-containing nanoparticles |
US10435639B2 (en) | 2006-09-05 | 2019-10-08 | Cerion, Llc | Fuel additive containing lattice engineered cerium dioxide nanoparticles |
WO2008030805A1 (en) * | 2006-09-05 | 2008-03-13 | Cerion Technology, Inc. | Cerium dioxide nanoparticle-containing fuel additive |
US8679344B2 (en) * | 2008-12-17 | 2014-03-25 | Cerion Technology, Inc. | Process for solvent shifting a nanoparticle dispersion |
EP2379221A4 (de) * | 2008-12-17 | 2013-05-15 | Cerion Technology Inc | Brennstoffadditiv, enthaltend nanopartikel aus gittertechnisch verändertem cerdioxid |
EP2809437B1 (de) * | 2012-01-30 | 2018-03-28 | Cerion LLC | Verbessertes verfahren zur herstellung von stabilen organischen kolloiden aus ceroxid |
US20130192122A1 (en) * | 2012-01-30 | 2013-08-01 | Cerion Technology, Inc. | Rapid method for production of cerium-containing oxide organic colloids |
WO2015058037A1 (en) | 2013-10-17 | 2015-04-23 | Cerion, Llc | Malic acid stabilized nanoceria particles |
EP3080849B1 (de) * | 2013-12-12 | 2018-09-05 | Avantama AG | Elektronikvorrichtungen mit in lösung verarbeitbaren metalloxid-pufferschichten |
EP3352895B8 (de) * | 2015-09-23 | 2020-11-04 | Rhodia Operations | Hydrophobisch modifizierte ceriumoxidpartikel umfassende zusammensetzung |
CN108431129B (zh) | 2015-12-25 | 2021-10-08 | 株式会社可乐丽 | 水性乳液和使用其得到的粘接剂 |
US11060051B2 (en) * | 2018-10-12 | 2021-07-13 | Fujimi Incorporated | Composition for rinsing or cleaning a surface with ceria particles adhered |
KR102342903B1 (ko) * | 2019-02-28 | 2021-12-24 | 코스맥스 주식회사 | 세륨옥사이드를 포함하는 광차단용 화장료 조성물 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
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FR2583761B1 (fr) * | 1985-06-20 | 1987-08-14 | Rhone Poulenc Spec Chim | Procede de preparation d'une dispersion colloidale d'un compose de cation metallique en milieu organique et les sols obtenus |
JP2509826B2 (ja) * | 1991-03-28 | 1996-06-26 | 多木化学株式会社 | 酸化第二セリウムゾル |
FR2677544B1 (fr) * | 1991-06-14 | 1993-09-24 | Oreal | Composition cosmetique contenant un melange de nanopigments d'oxydes metalliques et de pigments melaniques. |
FR2680684B1 (fr) * | 1991-08-29 | 1993-11-12 | Oreal | Composition cosmetique filtrante comprenant un nanopigment d'oxyde metallique et un polymere filtre. |
DE69516569T2 (de) * | 1994-02-18 | 2001-01-04 | Rhodia Chimie, Courbevoie | Organische Sole von vierwertigen Metalloxid und deren Verwendung in Kohlenwasserstoffzusammensetzungen |
FR2719502B1 (fr) * | 1994-05-09 | 1996-06-07 | Rhone Poulenc Chimie | Dispersion colloïdale à base d'oxyde de cérium et d'oxyde de titane son procédé de préparation, son application au revêtement de substrats et substrats ainsi revêtus. |
FR2721615A1 (fr) * | 1994-06-24 | 1995-12-29 | Rhone Poulenc Chimie | Procédé de préparation de particules d'oxyde métallique organophiles. |
US6210451B1 (en) * | 1995-02-21 | 2001-04-03 | Rhone-Poulenc Chimie | Colloidal organic sols comprising tetravalent metal oxide/organic acid complexes |
FR2741281B1 (fr) * | 1995-11-22 | 1998-02-13 | Rhone Poulenc Chimie | Sol organique comportant au moins un compose oxygene de terre(s) rare(s), procede de synthese du dit sol et utilisation du dit sol pour la catalyse |
FR2780879B1 (fr) * | 1998-07-09 | 2002-09-20 | Oreal | Composition cosmetique photoprotectrice contenant un tensio-actif anionique, un compose filtrant le rayonnement ultraviolet et un compose cationique ou zwitterionique amphiphile et son utilisation |
-
1999
- 1999-02-17 FR FR9901939A patent/FR2789601B1/fr not_active Expired - Fee Related
-
2000
- 2000-02-10 CA CA002360820A patent/CA2360820A1/fr not_active Abandoned
- 2000-02-10 EP EP00903784A patent/EP1157071A1/de not_active Withdrawn
- 2000-02-10 JP JP2000599831A patent/JP2002537308A/ja not_active Abandoned
- 2000-02-10 CN CNB008059802A patent/CN1144851C/zh not_active Expired - Fee Related
- 2000-02-10 WO PCT/FR2000/000330 patent/WO2000049098A1/fr not_active Application Discontinuation
- 2000-02-10 BR BR0008339-9A patent/BR0008339A/pt not_active IP Right Cessation
- 2000-02-10 US US09/913,709 patent/US6649156B1/en not_active Expired - Fee Related
-
2001
- 2001-08-17 NO NO20014029A patent/NO20014029L/no not_active Application Discontinuation
Non-Patent Citations (1)
Title |
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See references of WO0049098A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2789601A1 (fr) | 2000-08-18 |
CA2360820A1 (fr) | 2000-08-24 |
NO20014029L (no) | 2001-10-17 |
CN1144851C (zh) | 2004-04-07 |
US6649156B1 (en) | 2003-11-18 |
NO20014029D0 (no) | 2001-08-17 |
WO2000049098A1 (fr) | 2000-08-24 |
BR0008339A (pt) | 2002-01-29 |
FR2789601B1 (fr) | 2001-05-11 |
JP2002537308A (ja) | 2002-11-05 |
CN1346391A (zh) | 2002-04-24 |
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