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
  • C09D9/00—Chemical paint or ink removers
  • C09D9/04—Chemical paint or ink removers with surface-active agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2093—Esters; Carbonates

Definitions

• the invention relates to carboxylic acid diester formulations and their use for the treatment of materials, and more particularly to the treatment of textiles for the removal of, in particular, paint stains.
• diesters of dicarboxylic acids also called “dibasic esters”, “Dibasic Esters” in English ”
• the acid of which is linear, in particular the mixture of succinate, glutarate, and dimethyl adipate.
• US Pat. No. 4,780,235 for example describes the combination of at least one C 1 -C 4 dialkyl ester of an aliphatic dibasic acid with 1 to 80% of n-methyl pyrrolidone (NMP), a thickener and a molecule.
• NMP n-methyl pyrrolidone
• Activator such as acetic acid, for removing paint from surfaces of rigid objects (stripping).
• US Pat. No. 5,613,984 discloses a method of cleaning garments soiled with different kinds of paints, comprising the steps of exposing the soiled garment to a dibasic ester, washing the garment with a detergent comprising a surfactant and a solvent, and then dry it.
• the dibasic ester is in particular a dibasic ester whose acid is linear, such as the mixture of succinate, glutarate, and dimethyl adipate.
• US Pat. No. 4,673,524 describes a cleaning composition for removing hard-to-remove materials from the surface of the hands, for example paints or printing inks.
• This composition comprises a mixture of succinate, glutarate, and dimethyl adipate, combined with an aliphatic hydrocarbon solvent, and an ethoxylated nonylphenol surfactant, or combined with octophenoxypolyethoxyethanol.
• WO 96/30453 discloses cleaning or stripping compositions for removing hard-to-remove materials, for example rigid surface paints. These compositions comprise a mixture of succinate, glutarate, and dimethyl adipate, combined with an ether such as anisole, optionally with an aliphatic hydrocarbon solvent, and optionally with an ethoxylated nonylphenol surfactant.
• EP 743 358 discloses compositions for cleaning textiles comprising a mixture of succinate, glutarate, and dimethyl adipate, and an ethoxylated fatty alcohol surfactant.
• the present invention responds to this need by proposing a liquid formulation, intended to be used in particular for the treatment of materials, characterized in that it comprises:
• At least one dicarboxylic acid diester corresponding to formula (I): R'-OOC-A-COO-R 2 (I) where
• R 1 and R 2 which are identical or different, represent a linear or branched, cyclic or non-cyclic alkyl, aryl, alkylaryl or arylalkyl group, in C 1 -C 20 ,
• the group A represents a linear or branched divalent alkylene group; and at least one polyalkoxylated terpene nonionic surfactant.
• said polyalkoxylated terpene nonionic surfactant is a polyethoxylated and / or polypropoxylated terpene, preferably polyethoxylated and polypropoxylated, the ethoxy and propoxy units being distributed in random form or in sequential form.
• said nonionic surfactant is a polyalkoxylated terpene corresponding to the following formula (III):
• X represents -CH 2 -C (R 3 ) (R 4 ) -O- or -O-CH (R ' 3 ) -C (R' 4 ) -O- in which: R, R, R 'and R 1 , which are identical or different, represent hydrogen or a saturated or unsaturated, linear, branched or cyclic, C 1 -C 22 > preferably C 4 -C 6 hydrocarbon-based radical;
• R7 represents hydrogen, a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, aromatic or non-aromatic, C1-C22, optionally substituted (for example with an OH group); n, p, q and are integers or not, greater than or equal to 0, n + p + q> 1, preferably from 2 to 200, preferably from 5 to 50.
• n, p and q are chosen so that:
• - n is an integer or not, between 2 and 10 inclusive; p is an integer or not between 3 and 20 inclusive;
• q is an integer or not between 0 and 30 inclusive.
• Rhodoclean® MSC Such a polyalkoxylated terpene nonionic surfactant is for example marketed by Rhodia under the name Rhodoclean® MSC.
• the groups R 1 and R 2 which may be identical or different, may especially be chosen from methyl, ethyl, n-propyl, isopropyl, benzyl, phenyl, n-butyl, isobutyl, cyclohexyl, hexyl, n-hexyl and isooctyl groups. -éthylhexyle. They correspond to the alcohols of formulas R 1 -OH and R 2 -OH, which are identical or different.
• the dicarboxylic acid diester is in the form of a mixture of different dicarboxylic acid diesters of formula (I).
• a particular diester may designate a single diester of formula (I) or a mixture or combination of two or more particular diesters having the formula ( I).
• Group A is a divalent alkylene group.
• the corresponding acid is the compound of formula HOOC-A-COOH.
• A is a linear divalent alkylene group of formula (CH 2) r , where r is an average number of between 2 and 4 inclusive.
• the diester used in the present invention is chosen from
• dimethyl adipate for example from 9 to 17% by weight, by gas phase chromatography
• dimethyl glutarate for example from 59 to 67% by weight
• dimethyl succinate for example from 20 to 28% by weight
• diisobutyl adipate for example from 9 to 17% by weight, by gas chromatography
• diisobutyl glutarate for example from 59 to 67% by weight
• diisobutyl succinate for example from 20 to 28% by weight
• % by weight for example marketed by Rhodia under the name Rhodiasolv® DIB.
• a diester of a dicarboxylic acid of formula (I) is used, the group A of which is a branched C 3 -C 10 divalent alkylene group.
• this diester of a dicarboxylic acid may be referred to as "diester connected”.
• the group A can in particular be a C 3, C 4 , C 5 , C 6 , C 7 , C 8 or C 9 group , or a mixture. It is preferably a C 4 group .
• Group A is preferably chosen from the following groups:
• the branched diester is dimethyl of 2-methylglutaric acid, corresponding to the following formula:
• the particular diester is in the form of a mixture comprising the dicarboxylic acid diesters of formulas (T), (T ') and optionally (II) as follows:
• MG is a group of formula -CH (CH 3 ) -CH 2 -CH 2 - ,
• a ES is a group of formula -CH (C 2 Hs) -CHi-.
• the groups R 1 and R 2 can in particular be methyl, ethyl or isobutyl groups.
• the mixture of diesters comprises: from 70 to 95% by weight of the dicarboxylic acid diester of formula (I 1 ), preferably methyl diester,
• the diester used in the invention can be obtained by any known method leading to diesters, in particular by reaction of an alcohol corresponding to the groups R 1 and R 2 with a dicarboxylic acid corresponding to group A or a di (acyl chloride ) of formula ClOC-A-COCl or a corresponding dinitrile of formula NC-A-CN.
• a dicarboxylic acid corresponding to group A or a di (acyl chloride ) of formula ClOC-A-COCl or a corresponding dinitrile of formula NC-A-CN a dicarboxylic acid diesters
• the same type of reaction can be carried out from a mixture corresponding dicarboxylic acids or acyl chlorides or dinitriles.
• the diester (s) connected in a mixture can in particular be obtained from a mixture of dinitrile compounds, in particular produced and recovered in the process for the manufacture of adiponitrile by double hydrocyanation of butadiene.
• This process is widely used in industry to produce the vast majority of adiponitrile consumed in the world is described in many patents and books.
• the reaction of the hydrocyanation of butadiene mainly leads to the formation of linear dinitriles but also to the formation of branched dinitriles, the two main ones being methylglutaronitrile and ethylsuccinonitrile.
• the branched dinitrile compounds are separated by distillation and recovered, for example, as a top fraction in a distillation column.
• the mixture of branched dinitrile compounds is converted into diesters to thereby obtain a new solvent.
• the diesters used in the invention can also be obtained by a reaction between the dinitrile compounds, water and an alcohol in the gas phase and in the presence of a solid catalyst.
• the reaction temperature is advantageously greater than the condensation temperature of the diesters formed.
• an acidic solid catalyst such as, for example, a silica gel, a silica-alumina mixture or boric or phosphoric acids which are supported.
• macroporous aluminas such as those described in European Patent EP 0 805 801.
• the reaction temperature is between 200 and 450 ° C., preferably between 230 and 350 ° C.
• the reaction can be carried out under any pressure, advantageously between 0.1 and 20 bar. At the outlet of the reactor, the vapors are rapidly cooled to a temperature of less than or equal to 150 ° C. From the mixture obtained, ammonia is distilled off, followed by excess water and alcohol.
• the diesters of the invention may also be obtained by reaction between the dinitrile compounds and a mineral base to obtain acid salts, and then neutralization of these salts with an acid followed by esterification with an alcohol. Finally, the diesters can be purified according to the purification methods conventionally used in the technical field of the preparation of organic compounds and in particular by distillation in one or more columns.
• the mixture may comprise other compounds than the diester of the invention. It may in particular comprise by-products of an esterification reaction, and / or products derived from by-products of a prior reaction.
• the particular diester is associated, in the liquid formulation, with at least one polyalkoxylated terpene nonionic surfactant, preferably corresponding to the formula (III) defined above.
• a first type of compound is defined by the formula (III) wherein X is equal to
• the radical Z is chosen from the radicals of formulas c) to g). It should be noted that the radical Z is more particularly attached to the rest of the chain via any one of the carbon atoms 1 to 6, the carbon atoms 1, 5 and 6 being preferred. Moreover, the radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals.
• the carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.
• One of the preferred compounds used in the present invention therefore consists of a compound whose radical Z corresponds to one of those appearing in FIG. C) to g), and more preferably, the radicals d) and e ); the radical Z being substituted by two methyl radicals, located on carbon 7.
• the radical Z corresponds to formulas d) or e), attached to the rest of the chain by carbon 5 or 1, and bearing two methyl substituents on carbon 7.
• R.3, R4, which may be identical or different, represent a hydrogen or a methyl radical.
• R.3, R4 7 represent a hydrogen atom.
• radicals R 5 and R 6 which may be identical or different, represent hydrogen or a hydrocarbon radical, saturated or non-saturated, linear, branched or cyclic, with 1 to 22 carbon atoms, with the proviso that at least 1 one of the radicals R 5 OR R 6 is different from hydrogen.
• said radicals represent hydrogen or a C 1 -C 6 alkyl radical, preferably the methyl radical or the ethyl radical, with the proviso that at least one of these two radicals is different from hydrogen.
• one of the radicals represents hydrogen and the other a methyl radical.
• R7 represents hydrogen, a hydrocarbon radical, saturated or unsaturated, linear, branched or cyclic, aromatic or otherwise, optionally substituted for example by an OH group, Ci-C22.
• R 1 is a hydrocarbon radical
• the latter is more particularly a C 1 -C 6 alkyl radical, or an alkylphenyl radical, optionally substituted by a halogen (such as chlorine for example).
• R is a hydrogen atom.
• n is
• p is more particularly between 6.2 and 7, inclusive.
• p is between 6.3 and 7, inclusive.
• n is between 4 and 5, inclusive.
• the value of p is preferably between 7 inclusive and 10 excluded, preferably between 8 inclusive and 10 excluded.
• q is equal to 0. If q is other than 0, then q is preferably between 5 and 25 inclusive.
• a second type of compounds is defined by the formula (III) wherein X. represent
• the radical Z corresponds to radical c), the bicyclic compound having no double bond.
• radical Z is more particularly attached to the rest of the chain via any of the carbon 1 to 6.
• the carbon atoms 1, 3, 4 or 6 are more particularly retained .
• the radical Z may be substituted on at least one of its carbon atoms by two C 1 -C 6 alkyl radicals, preferably two methyl radicals. More particularly, the carbon 7 is substituted by these two alkyl radicals, more precisely two methyls.
• radical Z bears on one of the carbon atoms 2 or 5, an alkyl substituent at -CO-C, preferably a methyl radical.
• radicals R'3 and R'4 which are identical or different, represent hydrogen or a hydrocarbon radical, saturated or non-saturated, linear, branched or cyclic, in C 1 -C 22, with the proviso that that one of them is different from hydrogen.
• said radicals represent hydrogen or a C1-C6 alkyl radical, preferably the methyl radical.
• the compounds of formula (III) can be prepared by reacting: for obtaining compounds (HIa), a reagent of formula (IVa)
• Radicals Z, R3, R4 ; R5 R6 e t have been defined previously.
• the reaction may further be carried out in the presence of a catalyst.
• Suitable catalysts include strong bases such as alkali metal, alkaline-earth or quaternary ammonium hydroxides of N (R) 4+ type, in which R, which may be identical or different, represent hydrogen or a radical.
• R which may be identical or different, represent hydrogen or a radical.
• C1-C6 alkyl preferably methyl, ethyl.
• the hydroxides of sodium, potassium and tetramethylammonium are suitable for carrying out this reaction. It is likewise possible to use catalysts chosen from alkali metal or alkaline earth metal alkoxides, for example sodium or potassium methylate, ethylate or tertiobutylate.
• the amount is more particularly between 0.5 and 40 mg, based on the weight of the final product.
• the amount of acid catalyst varies more particularly between 0.1 and 10 mmol per mole of reagent (IVa) or (IVb).
• the contacting is carried out at a temperature sufficient to allow the completion of the reaction.
• the temperature is greater than 100 0 C, more particularly between 120 and 250 0 C, and preferably between 150 and 200 0 C.
• the reaction is carried out under an inert atmosphere under the reaction conditions, such as nitrogen, or a rare gas such as argon or carbon monoxide. Nitrogen is preferred.
• the reaction can be carried out under atmospheric pressure, under reduced pressure or slight suppression. Usually, it is preferred to work under a pressure of between 1 and 4 bar.
• the amounts of the compounds (Vop) and (Voe) are calculated according to the characteristics of the formula (III), more particularly the desired values of n and p.
• the reaction mixture is preferably neutralized in order to obtain a pH of between 5 and 8, preferably 6 and 7.
• the neutralization is done using acetic acid, or sodium hydroxide, carbonate or bicarbonate, depending on the nature of the catalyst involved in the reaction.
• the compound (III) is such that the radical R7 is hydrogen. It is quite possible to implement a step of functionalizing said radical, that is to say a step for converting the terminal hydrogen into one of the other radicals R7 as defined previously. Thus, it is possible to carry out an etherification or esterification operation of the terminal hydrogen atom; this step is well known in itself; it is preferably carried out after the neutralization.
• the surfactant of formula (III) may be used diluted by adding up to 50% water or organic solvent, such as polyethylene glycol.
• the amount of polyalkoxylated terpene nonionic surfactant is advantageously between 0.1% and 10%, preferably between 0.1% and 5%, preferentially between 0.5% and 4%, and more preferably still between 0.5 and 3%, preferably between 0.5% and 2% or even between
• the formulation of the invention is surprisingly effective even at low levels of surfactant.
• the formulation is substantially free of other nonionic surfactants, preferably other surfactants in general.
• the formulation according to the invention may also comprise: a. water, b. an additional co-solvent, c. an additional surfactant, for example an anionic, nonionic (non-terpene), amphoteric, zwitterionic and / or cationic surfactant, d. an antioxidant, e. a corrosion inhibitor, f. a thickening agent, g. a dye, h. a perfume, i. a stabilizer, or j. any combination of the above items.
• an additional surfactant for example an anionic, nonionic (non-terpene), amphoteric, zwitterionic and / or cationic surfactant
• an antioxidant e. a corrosion inhibitor
• f. a thickening agent g. a dye, h. a perfume, i. a stabilizer, or j. any combination of the above items.
• the formulation according to the invention does not comprise a hydrocarbon solvent.
• the formulation according to the invention does not include non-polyalkoxylated terpene, such as limonene or pine oil.
• the additional surfactants may be chosen from the usual surfactants.
• Known surfactants are given in McCutcheon's Emulsifiers & Detergents, North American & International Edition, 2004 Annuals.
• the formulation according to the invention does not comprise polyalkoxylated fatty alcohols, such as polyethoxylated and / or polypropoxylated fatty alcohols.
• the formulation according to the invention does not comprise polyalkoxylated alkylphenols such as polyethoxylated and / or polypropoxylated nonyl or octyl phenols and, where appropriate, terminated with an ethyl or methyl unit.
• the present invention also relates to the use, for the treatment of materials, of a liquid formulation, in particular a formulation as described above, comprising at least one dicarboxylic acid diester having the formula (I) as defined above and at least one polyalkoxylated terpene nonionic surfactant.
• said polyalkoxylated terpene nonionic surfactant corresponds to formula (III) as defined above.
• said material to be treated is chosen from the group comprising textiles, for example polyester fiber textiles, metals and plastics.
• said material treatment may comprise a cleaning for removing a soil, a coating, or a manufacturing aid agent such as a lubricant or an anti-adhesion agent (sizing, lubricants), on said material, and more particularly on a textile.
• a manufacturing aid agent such as a lubricant or an anti-adhesion agent (sizing, lubricants)
• said stain is a paint stain, one-component or two-component, water-based or solvent-based, resin, vegetable or mineral-based lubricant, products derived from bitumens and petroleum. , sludge, grease, feed residues, etc., especially on a polyester fiber fabric.
• the soil may be fresh or older.
• the formulation according to the invention is effective regardless of the type of paint to be cleaned, such as epoxy paints, polyurethanes, acrylics, alkyds, glycerophthalic, etc.
• the liquid formulation may be applied to the material to be treated by any suitable means.
• said textile is immersed in the liquid formulation for the time required, for example 1 hour, at room temperature or in a formulation heated to a temperature between 30 ° C. and
• the textile is rinsed once or several times in tap water and then dried in ambient air or in an oven.
• the textile may undergo, after the washing step in the formulation of the present invention, a second wash
• the liquid formulation of the present invention may be applied by any appropriate means: using a cloth, pressure sprinkling, dipping, or any other suitable method for the surface to be cleaned.
• the formulation can also be implemented in the context of substrate cleaning operations during the manufacture of semiconductors, including integrated circuits or during the manufacture of printed circuit boards.
• the M mixture of dinitrile compounds is composed of:
• the 100% complement corresponds to the impurities present in this mixture, which are generally not dinitrile compounds.
• the reaction medium is heated to reflux and maintained at this temperature for 3 hours.
• the reaction mass is heterogeneous and fluid.
• the reaction medium is maintained at 65 ° C. for 2 hours.
• reaction medium becomes biphasic.
• the two phases are decanted and analyzed.
• the recovered organic phase is washed with a saturated aqueous solution of sodium chloride with addition of ammonia to obtain a pH in the region of 7.
• a second wash is performed with a saturated aqueous solution of sodium chloride.
• Painted polyester coveralls have been stained with paint for about a month.
• the stains correspond to the different types of applied paint layers, namely an adhesion primer, a "basecoat” (paint and metallic pigments), and a “clearcoat” (resin without transparent pigment, acting as a protective layer) .
• the evaluation of the performances of the formulations is carried out using a tergotometer: it is the miniature reproduction of the washing machines of the USA, consisting of 6 stainless steel pots on which pulsed stirrers are fitted with variable stirring. The pots are placed in a thermostatically controlled tank of water.
• the washing conditions are as follows:
• an alkaline lye concentration at 0.36% of an alkaline lye of 45% +/- 2% of active ingredient comprising 1/3 of NaOH or KOH in pellet, 1/3 of metasilicate or silicate of Na and 1 / 3 Tetrapotassium diphosphate + 3% polyalkoxylated terpene surfactant
• active ingredient comprising 1/3 of NaOH or KOH in pellet, 1/3 of metasilicate or silicate of Na and 1 / 3 Tetrapotassium diphosphate + 3% polyalkoxylated terpene surfactant

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Health & Medical Sciences (AREA)
• Emergency Medicine (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2007
  • 2007-07-20 FR FR0756631A patent/FR2918994B1/fr not_active Expired - Fee Related
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