Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/017—Mixtures of compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/017—Mixtures of compounds
  • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
  • C09K23/16—Amines or polyamines

Definitions

• the subject of the present invention is a method for preparing an emulsion by diluting an emulsifiable concentrate comprising a copolymer comprising at least one hydrophilic segment and at least one hydrophobic segment.
• emulsions are very widely developed, whether in phytosanitary fields, metal treatment, in the paper industry, paints, treatment of textile fibers (in particular textile sizing), cosmetics , etc.
• the emulsions comprise two phases, one of which is dispersed in the other, the whole being kept stable by the use of suitable surfactants.
• the emulsions include non-negligible contents of surfactants.
• the presence of surfactants in these amounts can have negative consequences limiting the use of these emulsions or making their use more complex.
• the use of large amounts of surfactants in the emulsions leads to the appearance of a phenomenon of foam which in most cases is not desired. It is therefore often necessary to incorporate an anti-foaming agent into the formulation.
• Another difficulty with the use of emulsions lies in the fact that in certain applications, we are confronted with the use of active materials reactive with respect to water.
• emulsifiable concentrates represent a very interesting alternative. They are in fact advantageous in the sense that being free of water, they provide a solution to the problem of stability of the emulsions as well as to that of the use of hydrolysable compounds. Furthermore, they are self-emulsifying formulations, which means that when they are brought into contact with the required quantity of aqueous phase, they give a direct emulsion.
• the difficulty is that in order to obtain an emulsion with suitable drop size characteristics, for example, it is necessary to use relatively high levels of surfactants. Consequently, it is not uncommon for emulsions obtained from emulsifiable concentrates also to include high levels of surfactants.
• the present invention therefore aims to remedy the drawbacks mentioned above.
• a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant is diluted in an aqueous phase, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exclusion of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co- surfactant and optionally at least one neutralizing agent; • the total content of amphiphilic compounds representing 1 to 40% by weight of the emulsifiable concentrate;
• Another subject of the invention consists of a clear emulsifiable concentrate comprising an oil phase, optionally water, and amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and propylene oxide, optionally at least one co-surfactant and optionally at least one neutralizing agent;
• the present invention therefore relates to emulsifiable concentrates which, while having lower levels of surfactants, make it possible to obtain by dilution, emulsions whose droplet size characteristics are of the same order of magnitude as those reached by diluting emulsifiable concentrates including higher levels of usual surfactants.
• the process according to the invention makes it possible, thanks to the use of the above-mentioned amphiphilic copolymer, to substantially reduce, or even more than 10 points in certain embodiments, the content of surfactant necessary to obtain emulsion sizes. after diluting the concentrate as fine as those obtained with conventional surfactant contents, ie 10 points higher.
• the method according to the invention makes it possible to reduce the drawback associated with the appearance of foam during the dilution of the emulsifiable concentrate.
• the invention provides greater stability, over time and / or in temperature, of the emulsion obtained by diluting the emulsifiable concentrate.
• stability over time is intended to mean the period during which no phenomenon of coalescence, creaming or demixing is observed, at a given temperature. No temperature stability, we mean the temperature below which these phenomena are not observed, at a given time. It is thus possible to obtain increased stability by using as much or less surfactant, and / or equal stability by using less surfactant.
• the stability required often depends on the field of use of the emulsifiable compound.
• a stability of a few hours, at temperatures of up to about 40 ° C, is useful.
• the method according to the invention also makes it possible to be able to have formulations comprising compounds sensitive to hydrolysis without having to previously prepare derivatives of these compounds for which the reactive function with respect to water will have been masked. This is particularly the case for compositions intended for example for the preparation of formulations for paints.
• the fact of obtaining emulsions with less surfactant has the advantage of limiting the migration phenomena of surfactants often observed in films, especially paintings.
• the fact that there is less surfactant in the emulsions obtained from emulsifiable concentrates provides an additional advantage as regards the recycling of such emulsions.
• other characteristics and advantages of the present invention will appear more clearly on reading the description and the examples which follow.
• the average droplet size of the emulsion obtained from the emulsifiable concentrate corresponds to the volume median diameter (d50), that is to say the droplet diameter equal to 50% of the cumulative distribution.
• the size of the droplets is measured using a Horiba type particle size analyzer. These particle size measurements are carried out by adding the emulsifiable concentrate in water at 20 ° C. and at the desired concentration; the addition operation being carried out with stirring for 5 minutes at 200 rpm using a pale frame.
• the emulsifiable concentrate comprises an oil and optionally water.
• the emulsifiable concentrate is in the form of a single-phase composition.
• the oil is more particularly chosen from compounds whose solubility in water does not exceed 10% by weight at 20 ° C. ,
• the oil is more particularly in a liquid form at the temperature of use of the emulsion obtained from the emulsifiable concentrate.
• the operating temperature range is close to ambient temperature, that is to say approximately between 15 and 40 ° C., although higher temperatures are not excluded; the latter, however, preferably remaining below 100 ° C.
• the oil can consist of a mixture of several compounds, one of which may not be liquid at use temperature, as soon as the assembly is liquid in this temperature range.
• organic oils of animal origin mention may be made, among others, of sperm whale oil, whale oil, seal oil, sardine oil, herring oil, shark, cod liver oil. Beeswax, pork or mutton fats may also be suitable.
• organic oils of vegetable origin there may be mentioned, among others, rapeseed oil, sunflower oil, peanut oil, olive oil, oil nuts, corn oil, soybean oil, linseed oil, hemp oil, grape seed oil, coconut oil, palm oil, oil cottonseed, babassu oil, jojoba oil, sesame oil, castor oil, carnauba wax.
• mineral oils With regard to mineral oils, mention may be made, inter alia, of oils obtained from petroleum fractions such as, for example, naphthenic, paraffinic oils (petroleum jelly), hexadecane, as well as paraffin waxes.
• the products derived from the alcoholysis of the abovementioned oils can also be used. It would not be departing from the scope of the present invention to use at least one fatty acid, saturated or not, at least one fatty acid ester, saturated or not, at least one fatty alcohol, saturated or not, or mixtures thereof.
• said acids, esters or alcohols comprise at least one hydrocarbon radical having from 10 to 40 carbon atoms, more particularly 18 to 40 carbon atoms, and can comprise one or more carbon-carbon double bonds, conjugated or not. Furthermore, the acids, esters or alcohols can comprise one or more hydroxyl groups.
• saturated fatty acids mention may be made of palmitic, stearic, isostearic and behenic acids.
• unsaturated fatty acids there may be mentioned myristoleic, palmitoleic, oleic, erucic, linoleic, linolenic, arachidonic, ricinoleic acids, as well as their mixtures.
• fatty acid esters there may be mentioned the esters of the acids previously listed, for which the part deriving from the alcohol comprises 1 to 6 carbon atoms, such as the methyl, ethyl, propyl and isopropyl esters. , etc.
• esters of the abovementioned acids and of polyols such as for example glycerol, polyglycerol (such as for example polyglycerol polyricinoleate), glycol, propylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, neopentylglycol (such as
• Neopentylglycol pentaerythritol, dipentaerythritol, trimethylolpropane, sorbitol, mannitol, xylitol, mesoerythritol.
• the oil can likewise be chosen from alkyd resins (such as, for example, Coporob 3115 DE resins, sold by the company Novance), epoxy resins, masked (or advantageously unmasked) poly (isocyanates) as soon as the emulsifiable concentrate is free of water.
• the oil can also be chosen from essential oils, mono-, di- and tri-glycerides.
• the silicones can likewise be used in the emulsifiable concentrates according to the invention.
• - a is an integer from 0 to 3;
• radicals R are identical or different and represent: - a saturated or unsaturated aliphatic hydrocarbon group containing from 1 to 10 carbon atoms;
• radicals R ′ are identical or different and represent:
• silicones can optionally comprise, preferably less than 5 mol%, units of formulas T and / or Q: RSiO 32 (unit T) and / or SiO 2 (unit Q) formula in which R has the definition given above .
• alkyl preferably C ⁇ C 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
• aryls preferably C 6 -C 13 , such as phenyl.
• polar organic groups R of: - hydroxyfunctional groups such as alkyl groups substituted by one or more hydroxy or di (hydroxyalkyl) amino groups and optionally interrupted by one or more divalent hydroxyalkylamino groups.
• alkyl is meant a hydrocarbon chain preferably C ⁇ C, more preferably C ⁇ Ce; examples of these groups are - (CH 2 ) 3 -OH; - (CH 2 ) N (CH 2 CH 2 OH) 2 ; - (CH 2 ) 3 -N (CH 2 CH 2 OH) -CH 2 -CH 2 -N (CH 2 CH 2 OH) 2 :
• radicals R ′ there may be mentioned the groups:
• - alkyl preferably CC 10 optionally halogenated alkyl, such as methyl, ethyl, octyl, trifluoropropyl;
• aryls preferably C 6 -C 13 , such as phenyl
• alkyl or aryl substituted by amino alkyl preferably being CC 6 and aryl denoting a cyclic aromatic hydrocarbon group preferably C 6 -C 13 such as phenyl; examples are ethylamino, phenylamino;
• alkylcarbonylamino where alkyl is preferably CC 6 ; examples are methylacetamido.
• T units As concrete examples of "T units”, mention may be made of: CH 3 SiO 32 ;
• silicones contain reactive and / or polar radicals R (such as
• the latter generally do not represent more than 5% by weight of the silicone, and preferably not more than 1% by weight of the silicone.
• volatile oils such as hexamethyldisiloxane, octamethyldisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylhexa siloxane; the heptaméthyl-
• non-volatile silicones such as polydimethylsiloxane oils and gums and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxanes as well as polydimethylsiloxanes, polyphenylmethylsiloxane and ⁇ , ⁇ -bis (hydroxy) poly dimethylsiloxanes gums.
• ⁇ , ⁇ -bis (trimethyl) polydimethyl siloxane oils More particularly preferred are the ⁇ , ⁇ -bis (trimethyl) polydimethyl siloxane oils, the ⁇ , ⁇ -bis (hydroxy) polydimethyl siloxane oils, and very particularly the silicones of polydimethylsiloxane (dimethicone) and diphenyldimethicone type.
• the oil may optionally include an active ingredient, unless it is itself considered as an active ingredient.
• the active ingredient if it is different from the oil, is in a form miscible with oil or even dissolved in an organic solvent miscible with oil.
• the active ingredient is chosen from compounds whose solubility in water does not exceed 10% by weight, at 20 ° C.
• silicone oils belonging for example to the family of dimethicones
• lipophilic vitamins such as vitamin A and its derivatives, in particular its esters such as acetate, palmitate, propionate, vitamin B2, pantothenic acid, vitamin D and vitamin E.
• the phytosanitary active materials can be chosen from the family of ⁇ -cyano-phenoxybenzyl carboxylates or ⁇ -cyano-halogenophenoxy-carboxylates, the family of N-methylcarbonates comprising aromatic substituents, the active materials such as AIdrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butriflorazin, Metollorin , Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.
• AIdrin Azinphos-methyl
• Benfluralin Benfluralin
• Bifenthrin Chlorpho
• Said active ingredients mentioned above can optionally be in a form dissolved in a suitable solvent, for example xylene, Solvesso®.
• the active ingredient is usually an oil, an oil derivative or a fatty acid ester.
• the active material can also be chosen from organic solvents or mixtures of such solvents which are not or only slightly miscible in water, such as in particular those used for cleaning or pickling, such as petroleum cuts.
• aromatic, terpene compounds such as D- or L-limonenes, as well as solvents such as Solvesso®.
• solvents such as Solvesso®.
• aliphatic esters such as methyl esters of a mixture of acetic, succinic and glutaric acids (mixture of acids by-product of the synthesis of Nylon), hydrocarbon oils such as petroleum jelly, and chlorinated solvents.
• an active ingredient other than the oil is present, its content is usually less than or equal to 50% by weight of oil, preferably between 10 and 50% by weight of oil.
• the total oil content in the emulsifiable concentrate including, where appropriate, the active material, advantageously represents from 60 to 95% by weight of the emulsifiable concentrate.
• the emulsifiable concentrate comprises water
• its content is such that the emulsifiable concentrate remains clear in the sense indicated above.
• the content varies according to the various constituent elements of the emulsifiable concentrate and remains easily determinable by a person skilled in the art.
• the water content in the emulsifiable concentrate if it is present, is less than or equal to 10% by weight of the concentrate.
• the emulsifiable concentrate further comprises amphiphilic compounds consisting of at least one surfactant, at least one copolymer having at least one hydrophilic segment and at least one hydrophobic segment, optionally at least one co-surfactant and optionally at least one neutralizing agent.
• the assembly comprising the surfactant, optionally the co-surfactant and optionally the neutralizing agent is soluble in oil, at ambient temperature (approximately 20 ° C.).
• the surfactant (s) are chosen from surfactants soluble in oil at the concentrations used in the invention.
• the surfactants are chosen from nonionic or anionic surfactants.
• the surfactant (s) are chosen from nonionic surfactants.
• alkoxylated fatty alcohols more particularly comprising from 6 to 22 carbon atoms; alkoxylated mono-, di- and tri-glycerides; - alkoxylated fatty acids, more particularly comprising from 6 to 22 carbon atoms; alkoxylated sorbitan esters (cyclized fatty acid sorbitol esters having 10 to 20 carbon atoms); alkoxylated fatty amines, more particularly comprising from 6 to 22 carbon atoms;
• Alkoxylated alkylphenols more particularly comprising one or two alkyl groups, linear or branched, having 4 to 12 carbon atoms; - alkylpolyglucosides; polyoxyalkylenated surfactants, such as for example the compounds sold under the Pluronic or Poloxamer range by the company BASF;
• the surfactant (s) are chosen from anionic surfactants in acid form or associated (s) with a multivalent counter ion.
• the multivalent counterion is preferably an alkaline earth metal such as magnesium, calcium, alone or in combination.
• alkyl esters sulfonates for example of formula R-CH (SO 3 M) -CH2COOR ', where R represents a C 8 -C 20 , preferably C 10 -C 16 hydrocarbon radical, optionally carrying one or more unsaturations, R 'a C1-C6 alkyl radical, preferably in CC 3 and M a hydrogen atom or an alkaline-earth cation. Mention may very particularly be made of methyl ester sulfonates whose radical R is C 14 -C 16 ;
• alkyl esters sulfates for example of formula R-CH (OSO 3 M) -CH2COOR ', where R represents a C 8 -C 2 o, preferably C 10 -C 16 hydrocarbon radical, optionally bearing one or several unsaturations, R ′ an alkyl radical in C C ⁇ , preferably in C ⁇ Cs and M a hydrogen atom or an alkaline earth cation; alkylbenzenesulfonates, more particularly C 9 -C 20 , primary or secondary alkylsulfonates, especially C ⁇ -C 22 , alkylglycerol sulfonates; alkyl sulphates, for example of formula ROSO 3 M, in which R represents a C 10 -C 24 , preferably C 12 -C 20 , alkyl or hydroxyalkyl radical; M a hydrogen atom or a cation of the same definition as above; alkyl ether sulfates for example of formula RO (AO)
• RCONHR'OSO 3 M where R represents a C 2 -C 22 , preferably C 6 -C 20 , alkyl radical, R 'a radical C 2 -C 3 alkyl, M representing a hydrogen atom or a cation of the same definition as above, as well as their polyalkoxylated derivatives (ethoxylated and / or propoxylated); the salts of saturated or unsaturated fatty acids, for example such as those in C 8 - C 24 , preferably in C 14 -C 20 and of an alkaline-earth cation, N-acyl N-alkyltau rates, alkylisethionates, alkylsuccinamates and alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, polyethoxycarboxylates; and the mono and di phosphat
• amphiphilic compounds present in the emulsifiable concentrate there are copolymers having at least one hydrophilic segment and at least one hydrophobic segment, with the exception of copolymers comprising only segments obtained from ethylene oxide and oxide propylene.
• amphiphilic compound is chosen so that all of the amphiphilic compounds are soluble in oil, if necessary, in the presence of a small amount of water.
• said amphiphilic compound is chosen from compounds soluble in oil.
• hydrophobic segment of the copolymer this can be obtained from one or more of the following monomers: the esters of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation, and optionally carrying a hydroxyl group; ⁇ -ethylenically unsaturated nitriles, vinyl ethers, vinyl esters, vinyl aromatic monomers, vinyl or vinylidene halides, linear or branched hydrocarbon monomers, aromatic or not, comprising at least one ethylenic unsaturation, oxide of propylene, butylene oxide, alone or in mixtures, as well as the macromonomers derived from such monomers.
• hydrophobic monomers capable of entering into the preparation of the hydrophobic segment (s) of the amphiphilic segmented copolymer mention may be made of:
• the preferred monomers are the esters of acrylic acid with linear or branched C1-C4 alcohols such as methyl, ethyl, propyl and butyl acrylate, vinyl esters such as vinyl acetate, styrene, ⁇ -methylstyrene.
• the hydrophilic segment of the amphiphilic copolymer the latter can be obtained from one or more monomers having an anionic or anionizable function.
• the functions of the anionic segment or segments of the copolymer are in an at least partially ionized (dissociated) form. More particularly, at least 10 mol% of the functions of the segment or segments are in ionized form.
• the determination of this value poses no problem to those skilled in the art; it is in particular a function of the pKa of the ionizable functions of the units of the copolymer and of the number of these functions (ie of the number of moles of monomer carrying ionizable functions used during the preparation of the copolymer).
• More particularly comprising at least one carboxylic, sulfonic, sulfuric, phosphonic, phosphoric, sulfosuccinic function, their salts, as well as the corresponding macromonomers.
• the anionic or anionizable monomer (s) can be chosen from the following: linear, branched, cyclic or aromatic mono- or polycarboxylic acids, N-substituted derivatives of such acids; monoesters of polycarboxylic acids, comprising at least one ethylenic unsaturation; linear, branched, cyclic or aromatic vinyl carboxylic acids; amino acids comprising one or more ethylenic unsaturations; alone or as mixtures, their precursors, their sulfonic or phosphonic counterparts, their salts, as well as the macromonomers derived from such monomers or from their salts.
• anionic / anionizable monomers there may be mentioned without intending to be limited thereto: acrylic acid, methacrylic acid, fumaric acid, itaconic acid, citraconic acid, acid maleic, acrylamido glycolic acid, 2-propene 1-sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, ⁇ -acrylamido methylpropane sulfonic acid, 2-sulfoethylene methacylate, sulfopropyl acrylic acid , bis-sulfopropyl acrylic acid, bis-sulfopropyl methacrylic acid, sulfatoethyl methacrylic acid, hydroxyethyl methacrylic acid phosphate ester, as well as alkali metal salts, such as sodium, potassium, or ammonium; vinyl sulfonic acid, vinylbenzene sulfonic acid, vinyl phosphonic acid, vinylidene phosphonic acid
• monomers which are precursors of those which have just been mentioned.
• these monomers have units which, once incorporated in the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the above-mentioned anionic / anionizable species.
• the fully or partially esterified monomers of the aforementioned monomers can be used to be, subsequently, completely or partially hydrolyzed.
• the hydrophilic segment or segments can be obtained from one or more monomers having a cationic or cationizable function.
• aminoalkyl (meth) acrylates aminoalkyl (meth) acrylamides; monomers comprising at least one secondary, tertiary or quaternary amine function, or a heterocyclic group containing a nitrogen atom, vinylamine, ethylene;
• the - diallyldialkyl ammonium salts alone or in mixtures, or the corresponding salts; as well as the macromonomers derived from such monomers. If they are in the form of salts, the latter are preferably chosen such that the counterion is a halide such as, for example, a chloride, or a sulfate, a hydrosulfate, an alkylsulfate, a phosphate, a citrate, a formate, an acetate.
• the ammonium function comprises at least one alkyl or aryl radical optionally carrying one or more alkyl radicals, having from 1 to 6 carbon atoms, preferably methyl, ethyl.
• Suitable cationic monomers include the following monomers: - dimethyl amino ethyl (meth) acrylate, dimethyl amino propyl (meth) acrylate ditertiobutyl aminoethyl (meth) acrylate, dimethyl amino methyl (meth) acrylamide, dimethyl amino propyl (meth) acrylamide; ethylene imine, vinylamine, 2-vinylpyridine, 4-vinylpyridine; - trimethylammonium ethyl (meth) acrylate chloride, trimethylammonium ethyl acrylate methyl sulfate, benzyl dimethylammonium ethyl (meth) acrylate chloride, 4-benzoylbenzyl dimethyl ammonium ethyl acrylate chloride, trimethyl ammonium ethyl (meth) chloride acrylamido, trimethyl ammonium chloride, vinylbenzyl; diallyldimethyl ammonium chloride; alone or
• hydrophilic segment or segments of the amphiphilic copolymer can be obtained from nonionic hydrophilic monomer (s).
• amphiphilic copolymers can be block polymers and comprise at least two blocks, one being hydrophilic, the other hydrophobic. Recall that such copolymers are linear.
• the copolymers used are diblock or triblock copolymers.
• a copolymer is used, the backbone of which is hydrophilic and the pendant groups are hydrophobic, or vice versa.
• non-ionic hydrophilic monomers mention may be made of ethylene oxide; amides of mono- or polycarboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives; hydrophilic esters derived from (meth) acrylic acid; vinyl esters making it possible to obtain polyvinyl alcohol blocks after hydrolysis; vinypyrrolidone; sugar type monomers such as (meth) acrylates oligosaccharides or oligoholosides, as well as the macromonomers derived from these monomers.
• nonionic hydrophilic monomers mention may be made very particularly of (meth) acrylamide, N-methyloI (meth) acrylamide, 2-hydroxyethyl (meth) acrylate, vinyl esters making it possible to obtain blocks polyvinyl alcohol after hydrolysis, such as vinyl acetate, vinyl Versatate®, vinyl propionate.
• hydrophobic segment of the copolymer can comprise one or more hydrophilic units, likewise the hydrophilic segment can comprise one or more hydrophobic units.
• the distribution of the latter within the segment may be statistical, block or according to a concentration gradient.
• the copolymers which can be used in the context of the invention can be prepared by carrying out polymerizations by the anionic route, by the cationic route, by the so-called living or controlled radical route. It is likewise possible to carry out, depending on the monomers used, a group transfer polymerization (called “group transfer”) or else a cycle opening polymerization (in particular case of polymerization from the N-carboxy anhydride cycle) , or also by a polymerization involving a transesterification of terminal groups.
• group transfer group transfer polymerization
• cycle opening polymerization in particular case of polymerization from the N-carboxy anhydride cycle
• the polymers are obtained by implementing at least one step of living radical polymerization.
• living or controlled polymerization processes reference may in particular be made to: radical polymerization controlled by xanthates according to the teaching of application WO 98/58974, radical polymerization controlled by dithioesters according to teaching of the application WO 98/01478,
• polymers bearing grafts they can in particular be obtained by various methods, such as for example a copolymerization of a monomer with a macromonomer. More particularly, this method firstly implements the grafting at the end of the segment of a radical polymerizable function. This grafting can be carried out by usual methods of organic chemistry. Then, in a second step, the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
• Comb polymers can also be obtained by polymerization of a monomer followed by grafting onto the skeleton thus obtained.
• the grafting of the lateral polymer segments onto a skeleton polymer segment can be carried out according to conventional techniques familiar to those skilled in the art (European Polymer Journal 4, 343 (1968) for example). Among these conventional techniques, mention may be made in particular of those known as direct grafting.
• segment copolymers comprising repeating units having one or more silicon atoms
• copolymers used in the composition of the emulsifiable concentrate more particularly have a molar mass by weight of at most 50,000 g / mol, preferably at most 20,000 g / mol.
• the weight-average molar mass of the copolymer is advantageously at least 2500 g / mol, preferably at least 5000 g / mol.
• the content of copolymer is such that when this copolymer is added to a mixture comprising the oil, the surfactant (s), optionally the co-surfactant, optionally the neutralizing agent, there is a clear solution in the sense indicated above, possibly by adding water, in the case where the oil and the active agent which it possibly contains, are not sensitive to hydrolysis.
• the content of amphiphilic copolymer represents from 0.1 to 25% by weight of said amphiphilic compounds as defined above.
• the proportion by weight of copolymer relative to the surfactant is preferably between 0.5 and 10% by weight.
• the emulsifiable concentrate used in the process according to the invention can optionally comprise at least one co-surfactant.
• a co-surfactant or a mixture of co-surfactants soluble in oil is chosen.
• this is chosen from primary alcohols comprising at least one aliphatic radical, linear or branched, saturated or not, comprising from 4 to 22 carbon atoms, or at least one aromatic radical, preferably comprising 6 carbon atoms , optionally carrying one or more alkyl substituents comprising 1 to 10 carbon atoms.
• alcohols capable of entering into the composition of the emulsifiable concentrates is suitable in particular isopropanol, ethylhexanol, dodecanol, hexadecanol, benzyl alcohol, alone or in mixtures.
• the weight ratio of co-surfactant / surfactant is preferably between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
• the emulsifiable concentrate can also optionally comprise at least one neutralizing agent.
• a neutralizing agent is used which is soluble in the emulsifiable concentrate between 15 and 40 ° C. or a compound which, once heated beyond its melting point in the presence of oil, then cooled, remains soluble in oil.
• the neutralizing agent is chosen from compounds soluble in the oil phase and carrying at least one amine or carboxylic function.
• amines comprising one to three radicals, identical or not, comprising 1 to 10 carbon atoms, optionally carrying a hydroxyl radical, are suitable for this purpose.
• ethylenediamine triethylamine, dimethylbutylamine, diimethylisopropylamine, dimethylcyclohexylamine, tripropylamine, monoethanolamine, diethanolamine, aminoethylethanolamine, Paminomethylpropanolamine can be used as neutralizing agent.
• surfactant comprises a compound which can be ionized under the pH conditions of the final emulsion.
• the neutralizing agent is used in an amount such that the proportion by weight of neutralizing agent / surfactant is between 0 excluded and 50% by weight, preferably between 5 and 40% by weight.
• the emulsifiable concentrate can comprise a co-surfactant and / or a neutralizing agent.
• the emulsifiable concentrate comprises either a co-surfactant or a neutralizing agent.
• the total content of amphiphilic compounds in the emulsifiable concentrate represents from 1 to 40% by weight of the emulsifiable concentrate.
• the total content of amphiphilic compounds is between 5 and 30% by weight of the emulsifiable concentrate.
• the emulsifiable concentrate is obtained by a simple mixture of the various constituent elements which have just been detailed.
• the temperature at which this mixing is carried out is generally such that all of the compounds are in liquid form.
• this temperature is above the melting point of each of the compounds.
• the emulsion is obtained by diluting the emulsifiable concentrate in an aqueous phase.
• This emulsion is a direct emulsion, that is to say for which the continuous phase is an aqueous phase.
• the aqueous phase with which the emulsifiable concentrate is diluted is in itself a formulation usable in a particular field.
• said aqueous phase comprises the usual additives in the field of use.
• the dilution of the emulsifiable concentrate leads to the production of an emulsion for which at least 75% by volume of the droplets has an average size (ds) less than or equal to 1 ⁇ m.
• the average size of the droplets of the emulsion thus obtained is less than that of an emulsion obtained by dilution of an emulsifiable concentrate devoid of the copolymer detailed previously; the total concentration of amphiphilic compounds being the same in both cases.
• the average size of the droplets of the emulsion obtained according to the method according to the invention is therefore less than or equal to 1 ⁇ m, more particularly between 0.2 and 1 ⁇ m.
• the dilution of the emulsifiable concentrate is preferably carried out by adding the emulsifiable concentrate to the aqueous phase.
• the content of emulsifiable concentrate in the final formulation is very variable depending on the field of use of the concentrate.
• the content of emulsifiable concentrate represents 0.1 to 40% by weight of the final aqueous formulation, preferably 0.1 to 30% by weight of the final aqueous formulation.
• the dilution operation conventionally takes place with slight agitation, in particular by means of a pale frame.
• the emulsion thus obtained can be used in many fields, depending on the nature of the oil, if any, of the active ingredient present, forming part of the composition of the emulsifiable concentrate.
• the emulsifiable concentrate can be used in the field of phytosanitary formulations.
• the preparation of the emulsion is made by the user before applying it to the plants or fields to be treated.
• the emulsions can likewise be used in the field of cosmetics.
• the emulsions can likewise be used in the field of paints, varnishes, adhesives.
• They can also be used in metal transformation and deformation processes, and in particular as a cutting fluid.
• the emulsions obtained according to the invention can also be used in the field of the paper industry where emulsions of relatively fine size are sought.
• Step 1 Synthesis of the monoblock p (ABu) 10 o 0 Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• Ethanol, butyl acrylate, azo-bis-isobutyronitrile (AIBN) and S-ethylpropionyl O-ethyldithiocarbonate are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer.
• the reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
• Polymer samples are taken regularly to check the conversion.
• the solid content is 30.2% at the end of the reaction.
• Step 2 Synthesis of the diblock p (ABu -b-pfAA nn Composition of the reaction mixture:
• AIBN Azo-bis-isobutyronitrile
• the above ingredients are loaded into a dry container under a dry nitrogen atmosphere for 20 minutes, then transferred to the polymerization reactor, comprising the polymer from the previous step, using a syringe with two tips. .
• reaction mixture is then heated to 60 ° C. and kept at this temperature for 20 hours.
• Polymer samples are taken from time to time to check the conversion.
• the solid content is 30% at the end of the reaction.
• reaction mixture is allowed to cool and the solvents are removed using a rotary evaporator.
• the solid content is 30% at the end of the reaction.
• the number-average molar mass of the copolymer is 5000 g / mol (theoretical value).
• AIBN Azo-bis-isobutyronitrile 0.44 g
• the above-mentioned ingredients are introduced into a 100 ml flask fitted with a condenser and a magnetic stirrer.
• the reaction medium is brought to 70 ° C. and is maintained at this temperature for 3 hours.
• a sample is then taken and analyzed by steric exclusion chromatography and the molar mass in number is of the order of 3100 g / mol.
• Step 2 Synthesis of the diblock p (ABu) 3ooo-bp (VP) 6 ooo Composition of the reaction mixture:
• Ethanol, N-vinyl pyrrolidone and AIBN are introduced. The reaction is maintained for 6 hours from the time when the reagents are introduced.
• composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
• the emulsifiable concentrate is prepared by mixing the required quantities of hexadecane (AIdrich), Synperonic® L7 (ICI) and dodecanol (Prolabo) previously heated to 50 ° C in a shaking flask, as well as the polymer P1.
• the copolymer P1 is introduced from a 16% aqueous solution at neutral pH.
• the emulsification is carried out by rapidly introducing the emulsifiable concentrate into the purified water with gentle mechanical stirring with a pale frame at 200 rpm and stirring for 5 minutes.
• the water content of the emulsion is 90%.
• the size distribution of the oil droplets is determined by laser diffraction (Horiba LA-910).
• composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
• the amphiphilic / oil ratio is the same as in Example 3.
• composition of the emulsifiable concentrate is a composition of the emulsifiable concentrate:
• the copolymer is introduced from a 16% aqueous solution.
• composition of emulsifiable concentrates Composition of emulsifiable concentrates:
• Géronol FF4 and FF6 products marketed by Rhodia, mixtures of ethoxylated tristyrylphenol and calcium dodecyl benzene sulfonate in isobutanol ** :
• P3 is a diblock copolymer polystyrene - poly acrylic acid with a molecular weight by weight of 3800 - 1200 g / mol (p (St) 38 oo-bp (AA) 12 oo).
• the emulsifiable concentrates are prepared at 20 ° C. by mixing the required quantities of xylene (Prolabo), Geronol FF4 and FF6, as well as the polymer P3, in a shaking flask.
• the copolymer P3 is introduced in dry form.
• the emulsification is carried out by introducing into a cylindrical test tube 9.5 mL city water then 0.5 mL of emulsifiable concentrate, and then making 20 turns.

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• Organic Chemistry (AREA)
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• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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