WO2009092795A1 - Utilisation d'esteramides, nouveaux esteramides et procédés de préparation d'esteramides - Google Patents
Utilisation d'esteramides, nouveaux esteramides et procédés de préparation d'esteramides Download PDFInfo
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- WO2009092795A1 WO2009092795A1 PCT/EP2009/050780 EP2009050780W WO2009092795A1 WO 2009092795 A1 WO2009092795 A1 WO 2009092795A1 EP 2009050780 W EP2009050780 W EP 2009050780W WO 2009092795 A1 WO2009092795 A1 WO 2009092795A1
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- 0 *OC(*C(Cl)=O)=O Chemical compound *OC(*C(Cl)=O)=O 0.000 description 1
- WNQMEELXVMZQDN-UHFFFAOYSA-N CCN(CC)C(CCC(C)C(OC1CCCCC1)=O)=O Chemical compound CCN(CC)C(CCC(C)C(OC1CCCCC1)=O)=O WNQMEELXVMZQDN-UHFFFAOYSA-N 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
- C07C235/74—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- 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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- 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
- C09D9/005—Chemical paint or ink removers containing organic solvents
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- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/32—Amides; Substituted amides
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- 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
- C11D3/43—Solvents
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- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/32—Organic compounds containing nitrogen
- C11D7/3263—Amides or imides
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
- C11D7/5004—Organic solvents
- C11D7/5013—Organic solvents containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to the use as solvents of esteramide compounds. It also relates to particularly practical processes for the preparation of esteramides. It also relates to new esteramides, which can in particular be used as solvents, for example in phytosanitary formulations.
- solvents for example to prepare chemicals and materials, to formulate chemical compounds, or to treat surfaces.
- solvents are used for the formulation of phytosanitary active agents, especially in the form of concentrates.
- Emulsifiable (Emulsifiable Concentrate "EC") intended to be diluted in water by the farmer, before application to a field.
- R-CONME 2 or R is a hydrocarbon group such as an alkyl, typically C 6 -C 30 .
- Such products are in particular marketed under the name Genagen® by the company Clariant. These solvents find applications particularly in the phytosanitary field.
- Dicarboxylic acid diesters are also known as solvents,
- MeOOC-CHEt-CH 2 -CONMe 2 has been identified by CAS Registry Number® 368212-04-8, with reference to WO 01/79167 relating to a remote domain, and whose relevance is doubtful.
- MeOOC-CH 2 -CH (CH 3 ) -CH 2 -CONMe 2 has been identified by CAS Registry Number® 70367-41-8, with reference to a document relating to the implementation of lithium enolates.
- Example 9 the compound designated by DMGME, of formula O: MeOOC-CH 2 -CH 2 -CH 2 -CONMe 2 .
- This compound is prepared by reacting dimethyl glutarate with dimethylamine and then isolating the DMGME by distillation from the resulting complex mixture (it is actually a by-product).
- DMGME is said to have a melting point of 7.5 ° C.
- MeOOC-CH 2 -CH 2 -CONMe 2 has been identified by the CAS Registry Number® 30891-34-0, with reference to documents relating to remote domains, whose relevance is questionable.
- DE 1040234 describes the following compounds and their use as plasticisers:
- the invention fulfills at least one of the abovementioned needs by proposing the use as a solvent or coalescing agent of an esteramide compound of formula (I) below: R 1 OOC-A-CONR 2 R 3 O) or:
- - R 1 is a group selected from hydrocarbon groups comprising an average number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, - R 2 and R 3 , identical or different , are groups chosen from hydrocarbon groups comprising an average number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, optionally substituted, R 2 and R 3 possibly forming together a ring, optionally substituted and / or optionally comprising a heteroatom, and
- A is a linear or branched divalent alkyl group comprising an average number of carbon atoms ranging from 2 to 12, preferably from 2 to 4.
- R 1 may be a different group than a menthyl group.
- the subject of the invention is also a method of solvation, co-solvation, plasticization, coalescence and / or crystallization inhibition by addition of the compound of the invention.
- the invention also relates to formulations comprising the compound of the invention.
- the formulations may in particular be phytosanitary formulations.
- the esteramide compound is used in a phytosanitary composition, a composition of cleaning, degreasing or stripping.
- A is branched, then the esteramide compound is used in a phytosanitary composition, a cleaning composition, degreasing or pickling.
- esteramide compound is used in a phytosanitary composition, a cleaning, degreasing or pickling composition.
- the invention also relates to at least one process for preparing the esteramide compound.
- the invention also relates to novel esteramide compounds which may be particularly suitable for the uses mentioned above.
- the invention also relates to an esteramide compound of formula (I) below:
- R 1 OOC-A-CONR 2 R 3 (I) in which: R 1 is a group chosen from hydrocarbon groups comprising an average number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, possibly aromatic,
- R 2 and R 3 which are identical or different, are groups chosen from hydrocarbon groups comprising an average number of carbon atoms ranging from 1 to 36, saturated or unsaturated, linear or branched, optionally cyclic, optionally aromatic, optionally substituted, R 2 and R 3 may optionally together form a ring, optionally substituted and / or optionally comprising a heteroatom, and
- A is a linear or branched divalent alkyl group comprising an average number of carbon atoms ranging from 2 to 12, preferably from 2 to 4, with the exception of the following compounds or mixtures:
- solvent is understood in a broad sense, covering in particular the co-solvent functions, crystallization inhibitor, stripper.
- solvent can in particular designate a liquid product at the use temperature, preferably having a melting point less than or equal to 20 ° C., preferably at 5 ° C., preferably at 0 ° C., which can contribute to making a liquid solid material, or to prevent or retard the solidification or crystallization of material in a liquid medium.
- a “compound of the invention” refers to any compound of the general formula (I). It is mentioned that the term “compound” also covers mixtures of several molecules corresponding to the general formula (I). It can therefore be a molecule of formula (I) or a mixture of several molecules of formula (I). Such a compound may especially be a “compound of the new invention” excluding the following compounds or mixtures (the latter may be designated as “compounds of the ancient invention”): - MeOOC-CHEt-CH 2 -CONMe 2
- composition of matter means a composition, more or less complex, comprising several chemical compounds. It can typically be an unpurified or modestly purified reaction product.
- the compound of the invention may in particular be isolated and / or marketed and / or used in the form of a composition of matter comprising it. If the compound of the invention is a mixture of several compounds of formula (I) then it is also a composition of matter.
- the compound of the invention in the form of a pure molecule or in the form of a mixture corresponding to formula (I), may be included in a composition of matter.
- the compound of the invention may represent at least 10% by weight. Preferably, it is the main compound of the composition of matter.
- the term "main compound” as used herein means the compound whose content is the highest, even if its content is less than 50% by weight (for example in a mixture of 40% A, 30% B, and 30% of C, product A is the main compound). Even more preferably, the compound of the invention is at least 50% by weight of the composition of matter, for example 70 to 95% by weight, and even 75 to 90% by weight.
- the composition of matter may be a reaction product.
- the compound of the invention is a compound of general formula (I) given above.
- the groups R 1 , R 2 and R 3 which may be identical or different, may in particular be groups chosen from alkyl, aryl, alkaryl, arylC 1 -C 2 alkyl or phenyl group.
- the groups R 2 and R 3 may optionally be substituted, in particular with hydroxyl groups.
- the group R 1 may especially be chosen from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, isoamyl, n-hexyl, cyclohexyl, 2-ethylbutyl, n-octyl, isooctyl, 2 -ethylhexyl, tridecyl.
- the groups R 2 and R 3 which may be identical or different, may especially be chosen from methyl, ethyl, propyl (n-propyl), isopropyl, n-butyl, isobutyl, n-pentyl, amyl, isoamyl, hexyl and cyclohexyl groups. hydroxyethyl.
- A comprises a group of formula --CH 2 -CH 2 - and / or of formula -CH 2 -CH 2 -CH 2 -CH 2 - and / or of formula - (CH 2 ) 8 - linear then it is a mixture of groups A.
- A is linear, then it is a mixture of groups A, for example a mixture of two or three of -CH 2 -CH 2 - (ethylene) groups; -CH 2 -CH 2 -CH 2 - (n-propylene); and -CH 2 -CH 2 - CH 2 -CH 2 - (n-butylene).
- the group A is a divalent linear alkyl group chosen from the following groups of formulas:
- the compound of the invention is chosen from the following compounds: MeOOC-CH 2 -CH 2 -CONMe 2
- the group A is a divalent branched alkylene group of one of the formulas (IIa), (Nb), (IIc), (NIa), and (NIb) below, or mixture of at least two groups selected from groups of formulas (IIa), (Nb), and (Nc) or from groups of formulas (INa) and (INb), or a mixture of at least two groups selected for one of the groups of formulas (IIa), (Nb), and (Nc) and for the other of the groups of formulas (INa) and (NIb):
- x is an integer greater than
- y is an average integer greater than or equal to
- z is an average integer greater than or equal to 0,
- R 6 which is identical or different, is a C 1 -C 6 alkyl group, preferably C 1 -C 4 , and
- R 7 is a hydrogen atom or a C 1 -C 6 alkyl group, preferably dC 4 .
- the compound of the invention is chosen from the following compounds, and mixtures thereof:
- MG represents a group MG a of formula -CH (CH 3 ) -CH 2 -CH 2 -, or MG b of formula -CH 2 -CH 2 -CH (CH 3 ) - or a mixture of groups MG a and MG b -
- a E s represents an ES 3 group of formula -CH (C 2 H 5 ) -CH 2 -, or ES b of formula -CH 2 -CH (C 2 H 5 ) - or a mixture of ES 3 groups and ES b
- Pe represents a pentyl group, preferably isopentyl or isoamyl
- Cyclo represents a cyclohexyl group
- - Eh represents a 2-ethylhexyl group
- - Bu represents a butyl group, preferably n-butyl or tert-butyl
- EtBu represents an ethylbultyl group
- n-He represents an n-hexyl group.
- the compound of the invention is a compound different from the following compounds:
- the compound of the invention is a novel compound of the invention, different from the following compounds or mixtures, if the latter, individually, are not used in admixture with other compounds of formula (I):
- the compound of the invention is a novel compound of the invention, different from the following compounds or mixtures, if the latter, individually, are not used in admixture with other compounds of formula (I):
- the esteramide has a melting point of less than or equal to 20 ° C., preferably at 5 ° C., preferably at 0 ° C.
- the compound of the invention may be prepared by any suitable method.
- the anhydride may be prepared in a prior step a) of cyclizing a diacid of formula HOOC-A-COOH, preferably by reaction of the diacid with acetic anhydride. In particular, reflux can be carried out in an excess of acetic anhydride. Then the product of formula (I 1 ) can be condensed.
- Step 1 c) transforming the compound of formula (I ") into a compound of formula (I) with the aid of an amine of formula HNR 2 R 3 , Sequence 2):
- Step 2b) the anhydride of formula (I 1 ) is reacted with an amine of formula HNR 2 R 3 so as to obtain an amide-acid compound of formula (N ")
- Step 2c) the compound of formula (N ") is converted into a compound of formula (I) with the aid of an alcohol of formula R 1 -OH.
- Step 1b) is preferably carried out using at least 1 molar equivalent of alcohol, relative to the anhydride. It is possible to use a large excess of alcohol, for example from 2 to 20 equivalents, in particular from 5 to 15. It is possible in particular to use the alcohol as the solvent for the reaction.
- step 1c) comprises the following steps (which may be simultaneous or subsequent, preferably subsequent): 1c1) the compound of formula (I ") is converted into an acyl chloride of formula (T") below, preferably by reaction with thionyl chloride,
- Step 1c2) is accompanied by the formation of hydrochloric acid.
- a base can be used to trap it, for example triethanolamine or triethylamine (TEA).
- TAA triethylamine
- This step can be carried out with at least 0.8 molar equivalent of amine, preferably with at least one equivalent. In particular, an excess of from 1.05 to 1, 4 molar equivalents may be used.
- reaction step 3 of a diester of formula R 1 OOC-A-COOR 1 with an amine of formula HNR 2 R 3 is carried out , then optionally a step reaction with an alcohol of formula R 1 -OH, where R 1 is a group selected from the groups R 1 mentioned above, but different from the group R 1 of the diester.
- R 1 is a group selected from the groups R 1 mentioned above, but different from the group R 1 of the diester.
- reaction sequence 3 can be used: Sequence 3
- Step 3b) optionally, reacting with an alcohol of formula R 1 -OH so as to obtain a product comprising an esteramide of formula R 1 OOC-A-CONR 2 R 3 , preferably R 1 OOC-A MG -CONR 2 R 3 OR R 1 OOC-A ES -CONR 2 R 3 .
- R 1 is a group selected from the groups R 1 mentioned above, but different from the group R 1 of the diester.
- step 3b is generally unnecessary. Otherwise we will typically implement this step.
- the diester having the desired R 1 group is started.
- step 3a from 0.7 to 1.5, for example 0.8 to 1.2 moles, preferably from 0.9 to 1.1 moles, preferably about 1 mole, is preferably used.
- amine per mole of diester It is advantageous to operate with a slight excess such as an excess of at least 1.05 moles of amine per mole of diester, for example from 1.05 to 1.1 moles of amine per mole of diester.
- Step 3a) can be carried out in solution, for example in aqueous solution, or in solution in a solvent such as toluene or an alcohol. It is preferred to operate in non-aqueous solution, avoiding any presence of water. During this step it is possible to gradually eliminate the methanol formed in order to promote the reaction. The removal may be accompanied by removal of the solvent, for example an azeotrope. After separation of the methanol, the removed solvent can be reintroduced into the process.
- Step 3a) is preferably carried out in the presence of a catalyst, in particular a basic type catalyst. It is possible, for example, to use methylates such as MeONa, carbonates such as K 2 CO 3 and Na 2 CO 3 , and titanates.
- Step 3b) is a trans-esterification step. It may in particular be catalyzed by acids or bases, for example by K 2 CO 3 or Na 2 CO 3
- the reaction may be followed by filtration and / or purification steps, for example by distillation.
- the diacids where appropriate in the form of mixtures, can in particular be obtained from a mixture of dinitrile compounds, where appropriate in the form of mixtures.
- the dinitriles may in particular be dinitriles produced and recovered in the process for the manufacture of adiponitrile by double hydrocyanation of butadiene.
- the hydrocyanation reaction 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 distilled off and recovered, for example, as overhead in a distillation column.
- Useful diacids can 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.
- Useful diacids can also be obtained by acid hydrolysis of the dinitrile compounds.
- Diesters of formula R 1 OOC-A-COOR 1 useful for the implementation of the sequence 3 are commercially available, in particular from Invista under the DBE references, or from Rhodia under the name Rhodiasolv® RPDE.
- the compound of the invention and / or a composition of matter comprising it described above may in particular be used as a solvent, co-solvent and / or crystallization inhibitor or as a coalescing agent.
- co-solvent is meant that other solvents may be associated with it.
- the use as a solvent or co-solvent includes the use to dissolve a compound in a formulation, in a reaction medium, the use to solubilize totally or partially a product to be removed (degreasing, stripping), and / or or to facilitate take-off of material films.
- the compound of the invention and / or a composition of matter comprising it described above may in particular be used, for the functions indicated above or for others, in a phytosanitary formulation, in a cleaning formulation, in a a stripping formulation, in a degreasing formulation, in a lubricant or textile formulation, in a coating formulation, for example in a paint formulation, in a pigment or ink formulation.
- the compound may for example be used as a coalescing agent in an aqueous paint formulation.
- the compound may especially be used as a degreasing agent on metal surfaces, for example surfaces of tools, manufactured articles, sheets, molds, in particular steel or aluminum or alloys of these metals.
- the compound can especially be used as a cleaning solvent on hard surfaces or textile surfaces.
- the compound can in particular be used as a solvent for stripping paint or resins, on tool surfaces, for example foundry molds, on surfaces of industrial sites (floors, partitions, etc.).
- the cleaning and / or degreasing formulations may especially be formulations for household care, operated in the homes or in the fields public (hotels, offices, factories .7) - These can be formulations for the cleaning of hard surfaces such as floors, furnishing surfaces and equipment of kitchens and bathrooms, dishes. These formulations can also be used in the industrial sphere to degrease manufactured products and / or cleaned.
- the compound of the invention and / or a composition of matter comprising it described above can in particular be used in phytosanitary formulations comprising a solid active product. More details are given below, where the word
- solvent may refer to the compound of the invention or a composition of matter comprising it, described above.
- the phytosanitary formulation is generally a concentrated phytosanitary formulation comprising an active compound.
- Agriculture uses many active ingredients such as fertilizers or pesticides, for example insecticides, herbicides or fungicides.
- active plant protection products or active ingredient.
- Active plant protection products are usually produced in pure or highly concentrated form. They must be used on farms at low concentrations. For this purpose, they are usually formulated with other ingredients to allow easy weight dilution by the farmer.
- We speak of phytosanitary formulations. The dilution carried out by the farmer is generally carried out by mixing the phytosanitary formulation with water.
- the phytosanitary formulations must allow easy weight dilution by the farmer, in order to obtain a product in which the phytosanitary product is correctly dispersed, for example in the form of a solution, emulsion, suspension, or suspension. emulsion.
- the phytosanitary formulations thus allow the transport of a phytosanitary product in relatively concentrated form, easy packaging and / or easy handling for the end user.
- Different types of phytosanitary formulations can be used depending on the different plant protection products. Examples include emulsifiable concentrates (Emulsifiable Concentrates "EC"), concentrated emulsions (Emulsion in water "W”), microemulsions ("ME”), wettable powders (WP), water dispersible granules (“WDG”).
- the formulations that can be used depend on the physical form of the phytosanitary product (for example solid or liquid), and its physico-chemical properties in the presence of other compounds such as water or solvents.
- the phytosanitary product may be in various physical forms: solution, dispersion of solid particles, dispersion of droplets of the product, droplets of solvent in which the product is dissolved ...
- Phytosanitary formulations generally include compounds to obtain these physical forms. It may for example be surfactants, solvents, mineral carriers, and / or dispersants. Often these compounds do not have an active character, but a character of intermediary for formulation aid.
- the phytosanitary formulations may in particular be in liquid form, or in solid form. In order to prepare phytosanitary formulations of solid active plant protection products, it is known to solubilize the product in a solvent.
- the phytosanitary formulation thus comprises a solution of the product in the solvent.
- the formulation may be in solid form, for example in the form of a wettable powder (WP) in which the solution soaks an inorganic support, for example kaolin and / or silica.
- WP wettable powder
- the formulation may alternatively be in liquid form, for example in the form of an emulsifiable concentrate (EC) having a single clear liquid phase comprising the solvent and the product in solution, capable of forming an emulsion by adding water, without stirring or with a weak agitation. It can also be or in the form of a concentrated emulsion (EW), cloudy, whose phase dispersed in water comprises the solvent and the product in solution in the solvent. It can also be a clear microemulsion (ME) whose dispersed phase in water comprises the solvent and the product in solution in the solvent.
- EW concentrated emulsion
- ME clear microemulsion
- tebuconazole is a particularly effective and widely used fungicide for soybean cultivation in particular.
- Crystals can have negative effects, including clogging filters devices used to spread the diluted composition, clog the spray devices, decrease the overall activity of the formulation, create unnecessary problems of waste streams to eliminate the crystals, and / or cause a poor distribution of the active product on the agricultural field .
- the formulations comprising the solvent have in particular:
- the phytosanitary formulation may also be a concentrated phytosanitary formulation comprising: a) an active plant protection product, b) the solvent (esteramide compound) c) optionally at least one emulsifying agent, preferably a surfactant, and d) optionally water.
- Active plant protection products especially non-water soluble and solid products are known to those skilled in the art.
- the active plant protection product may in particular be a herbicide, an insecticide, an acaricide, a fungicide, or a rodent killing agent ("rodenticide" in English) for example a rat poison.
- suitable active ingredients mention may be made, inter alia, of Amtretryne, Diuron, Linuron, Chlortoluron, Isoproturon, Nicosulfuron, Metamitron, Diazinon, Aclonifen and Atrazine.
- Chlorothalonil Bromoxynil, Bromoxynil heptanoate, Bromoxynil octanoate, Mancozeb, Maneb, Zineb, Phenmedipham, Propanyl, phenoxyphenoxy series, heteroaryloxyphenoxy series, CMPP, MCPA, 2,4 -D, Simazine, the active products of the imidazolinones series, the organophosphorus family, with in particular Azinphos-ethyl, Azinphos-methyl, Alachlor, Chlorpyriphos, Diclofop-methyl, Fenoxaprop-p Methyl Chlorine, Methoxychlor, Cypermethrin, Fenoxycarb, Cymoxanil, Chlorothalonyl, neonicotinoid insecticides, triazole fungicide family such as azaconazole, bromuconazole, cyproconazole, difenoconazole, dini
- the phytosanitary formulation may comprise an emulsifying agent, typically and preferably a surfactant.
- the emulsifying agents are agents intended to facilitate the emulsification or dispersion after placing the formulation in contact with water, and / or to stabilize (in time and / or in temperature) the emulsion or the dispersion. for example by avoiding sedimentation.
- Surfactants are known compounds, which have a generally relatively low molar mass, for example less than 1000 g / mol.
- the surfactant can be an anionic surfactant in salified or acidic form, preferably polyalkoxylated nonionic, cationic, amphoteric (term also including zwitterionic surfactants). It may be a mixture or combination of these surfactants.
- anionic surfactants mention may be made, without intending to be limited thereto:
- alkylsulphonic acids arylsulphonic acids, optionally substituted with one or more hydrocarbon groups, and whose acid function is partially or totally salified, such as C 8 -C 50 alkylsulphonic acids, more in particular C 8 -C 30 , preferably C 10 -C 22 , benzenesulphonic acids, naphthalenesulphonic acids, substituted with one to three alkyl groups d-C30, preferably C 4 -C 6 , and / or alkenyls C 2 -C 30 , preferably C 4 -C 6 .
- alkylsulfosuccinic acids of which the linear or branched alkyl part, optionally substituted with one or more hydroxylated and / or alkoxylated, linear or branched C 2 -C 4 (preferably ethoxylated, propoxylated, ethopropoxylated) groups; ).
- the phosphate esters chosen more particularly from those comprising at least one saturated, unsaturated or aromatic hydrocarbon group, linear or branched, comprising 8 to 40 carbon atoms, preferably 10 to 30, optionally substituted by at least one alkoxylated (ethoxylated) group, propoxylated, ethopropoxylated).
- they comprise at least one phosphate ester group, mono- or diesterified so that one or two free acid groups or partially or totally salified.
- the preferred phosphate esters are of the mono- and diester type of phosphoric acid and of alkoxylated (ethoxylated and / or propoxylated) mono-, di- or tristyrylphenol, or of alkoxylated (ethoxylated) mono-, di- or trialkylphenol and / or propoxylated), optionally substituted with one to four alkyl groups; phosphoric acid and a C 8 -C 30 alcohol, preferably C 10 -C 22 alkoxylated (ethoxylated or ethopropoxylated); phosphoric acid and a C 8 -C 22 alcohol, preferably C 10 -C 22 , non-alkoxylated.
- sulphate esters obtained from saturated or aromatic alcohols, optionally substituted with one or more alkoxylated groups (ethoxylated, propoxylated, ethopropoxylated), and for which the sulphate functional groups are in the free acid form, or partially or completely neutralized .
- sulfate esters obtained more particularly from saturated or unsaturated C 8 -C 20 alcohols, which may comprise 1 to 8 alkoxylated units (ethoxylated, propoxylated, ethopropoxylated); sulphate esters obtained from polyalkoxylated phenol, substituted with 1 to 3 saturated or unsaturated C 2 -C 30 hydroxycarbon groups, and in which the number of alkoxylated units is between 2 and 40; sulfate esters obtained from polyalkoxylated mono-, di- or tristyrylphenol in which the number of alkoxylated units ranges from 2 to 40.
- the anionic surfactants can be in acid form (they are potentially anionic), or in partially or totally salified form, with a counterion.
- the counterion may be an alkali metal, such as sodium or potassium, an alkaline earth metal, such as calcium, or an ammonium ion of formula N (R) 4 + in which R, which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted by an oxygen atom.
- R which may be identical or different, represent a hydrogen atom or a C 1 -C 4 alkyl radical optionally substituted by an oxygen atom.
- alkoxylated ethoxylated, propoxylated, ethopropoxylated substituted by at least one alkyl radical C 4 -C 2 O, preferably C 4 -C 2, or substituted by at least one alkylaryl radical in which the alkyl part is Ci -C ⁇ . More particularly, the total number of alkoxylated units is between 2 and 100.
- ethoxylated and / or propoxylated, sulphated and / or phosphated di- or tristyrylphenols mention may be made of ethoxylated di- (1-phenylethyl) phenol, containing 10 oxyethylenated units, ethoxylated di (1-phenylethyl) phenol.
- alcohols or fatty acids C 6 -C 22 which are polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated).
- the number of alkoxylated units is between 1 and 60.
- ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by esterification of a fatty acid with a polyethylene glycol. .
- polyalkoxylated triglycerides ethoxylated, propoxylated, ethopropoxylated
- triglycerides from lard, tallow, peanut oil, butter oil, cottonseed oil, linseed oil, olive oil, are suitable.
- the term ethoxylated triglyceride is intended both for the products obtained by ethoxylation of a triglyceride by ethylene oxide and those obtained by ethoxylation of a triglyceride with ethylene oxide. by trans-esterification of a triglyceride with a polyethylene glycol.
- the optionally polyalkoxylated (ethoxylated, propoxylated, ethopropoxylated) esters of sorbitan more particularly the cyclized sorbitol esters of C 10 -C 20 fatty acids such as lauric acid, stearic acid or oleic acid, and comprising a total number of alkoxylated units of between 2 and 50.
- Useful emulsifiers include the following products, all marketed by Rhodia: - Soprophor® TSP / 724: surfactant based on ethopropoxylated tristyrylphonol
- Soprophor® 796/0 surfactant based on ethopropoxylated tristyrylphonol
- Soprophor® BSU surfactant based on ethoxylated tristyrylphonol - Alkamuls® RC: surfactant based on ethoxylated castor oil
- the formulation advantageously comprises at least 4%, preferably at least 5%, preferably at least 8%, by weight of dry matter, of at least one surfactant c).
- the solvent may be combined with an aromatic and / or nonaromatic surfactant.
- the phytosanitary formulation preferably does not include significant amounts of water.
- the water content is less than 50% by weight, preferably less than 25% by weight. It will generally be less than 10% by weight.
- the formulation is preferably a liquid formulation, for example in the form of an emulsifiable concentrate (EC), a concentrated emulsion (EW) or a micoremulsion (ME). In this case, it preferably comprises less than 500 g / l of water, more preferably less than 250 g / l. It will generally be less than 100 g / L.
- the formulations may advantageously comprise: a) from 4 to 60%, preferably from 10 to 50%, of the phytosanitary product, by weight of active ingredient, b) from 10 to 92%, preferably from 20 to 80%, of the solvent by weight, c) from 4 to 60%, preferably from 5 to 50%, preferably from 8 to 25%, by weight of dry matter, of an emulsifier, preferably of a surfactant, d) of 0 at 10% by weight of water.
- solid formulations for example formulations in which a liquid comprising the phytosanitary product solubilized in the solvent, is supported by a mineral and / or dispersed in a solid matrix.
- the formulation can of course include other ingredients (or "other additives") than the active plant protection product, the solvent (s), the emulsifying agent (s) optional (s) and optional water. It may especially comprise viscosity modifiers, defoamers, especially silicone antifoams, anti-rebound agents, anti-leaching agents, inert fillers, in particular mineral fillers, anti-freeze agents, etc.
- the formulations may comprise additives, known as other additives, that do not fall within the definition of products a), b), or c), such as: other solvents, generally in small amounts, for example in an amount less than amount of compound of formula (I).
- solvents of the family of phosphates, phosphonates or phosphine oxides such as TEBP, TBP, TEPO, DBBP.
- alkyldimethyleamides in which the alkyl is C ⁇ -C-1, in particular those sold under the trademark Genagen.
- Ester lactates, especially those marketed under the trademark Purasolv are also mentioned.
- Diacid diesters (“DiBasic Esters”) are also mentioned, in particular those marketed by Rhodia under the trade names Rhodiasolv RPDE and Rhodiasolv DIB.
- hydrocarbon cuts such as NMP, lactones.
- cyclic amides such as NMP, lactones.
- the bis (dialkylamides) described in WO 2008 // 074837 are also mentioned.
- crystallization inhibitors It can be solvents mentioned above. It may also be fatty acids or non-polyalkoxylated fatty alcohols. For example, mention is made of the product Alkamuls® OL700 marketed by Rhodia.
- the concentrated phytosanitary formulation is intended to be spread over a cultivated field or to be cultivated, for example a soybean field, most often after dilution in water, to obtain a diluted composition.
- Dilution is generally carried out by the farmer, directly in a tank ("tank-mix"), for example in the tank of a device for spreading the composition. It is not excluded that the operator adds other phytosanitary products, for example fungicides, herbicides, pesticides, insecticides, fertilizers.
- the formulation can be used to prepare a composition diluted in the water of the active plant protection product, by mixing at least one part by weight of concentrated formulation with at least 10 parts of water, preferably less than 1000 parts. Dilution rates and amounts to be applied in the field usually depend on the crop product and the desired dose to treat the field; this can be determined by the farmer.
- the ester / acid and the thionyl chloride are mixed at room temperature.
- the reaction mixture can be refluxed to complete the reaction.
- the volatile species are removed by distillation under reduced pressure to obtain the crude product which is typically used without further purification.
- Toluene and trimethylamine are mixed under an inert atmosphere and cooled to -20 ° C.
- the dimethylamine (DMA) is then added.
- the ester / acid chloride is slowly added to maintain the temperature below 0 ° C.
- the mixture is then stirred at room temperature overnight and then filtered to remove the precipitate.
- the filtrate is evaporated under vacuum to obtain the crude product.
- the final product is obtained by distillation under reduced pressure of the crude reaction.
- the acidic amide and the alcohol are mixed at room temperature and thionyl chloride is added slowly to maintain the temperature below 30 ° C.
- the hydrochloric acid formed during the reaction can be trapped by a concentrated solution of welded.
- the reaction mixture is stirred at ambient temperature until the feedstocks have been consumed.
- the reaction can be followed by GC.
- the volatile species are evaporated under vacuum to obtain the crude product. In some cases the crude is dissolved in methanol and the pH adjusted to around 6-7 before evaporation of the solvent. The final product is then obtained after distillation under reduced pressure.
- the synthetic route is as follows:
- Step 1
- the acid ester is obtained by Procedure A.
- the acid ester is obtained by Procedure A.
- the anhydride is obtained by Procedure F.
- the acid ester is obtained by Procedure A.
- the anhydride is obtained by Procedure F.
- a crude "MGN” mixture comprising 2-methylglutaroinitrile (2-MGN), predominantly ethylsuccinonitrile (ESN) and adiponitrile (DNA) is hydrolyzed to give a mixture called MGA: 2-methyl-glutaric acid (86 mol%), ethylsuccinic acid (11 mol%) and adipic acid (3 mol%)
- the dimethyl amide ester is obtained according to Procedure E.
- Gross product 300 g
- MGN ethylsuccinonitrile
- DNA adiponitrile
- the dimethyl amide ester is obtained according to Procedure E except that the acidic amide is dissolved in dichloromethane before the reaction.
- MGN ethylsuccinonitrile
- DNA adiponitrile
- the dimethyl amide ester is obtained according to Procedure E except that the acidic amide is dissolved in dichloromethane before the reaction.
- MGN ethylsuccinonitrile
- DNA adiponitrile
- the diethyl amide ester is obtained according to Procedure E except that the acidic amide is dissolved in dichloromethane before the reaction.
- MGN ethylsuccinonitrile
- DNA adiponitrile
- the diethyl amide ester is obtained according to Procedure E except that the acidic amide is dissolved in dichloromethane before the reaction.
- MGN ethylsuccinonitrile
- DNA adiponitrile
- the diethyl amide ester is obtained according to Procedure E except that the acidic amide is dissolved in dichloromethane before the reaction.
- a transamidification reaction is carried out on a mixture of methyl diesters, comprising dimethyl 2-methylglutarate (85% by weight), ethylsuccinate (12% by weight) and adipate (3% by weight).
- the excess dimethylamine is then distilled off to a temperature of 25 +/- 5 ° C and a vacuum of 200 mb causing methanol.
- the condensed mixture of dimethylamine dissolved in methanol is recycled to the next batch.
- Catalytic sodium methylate is neutralized with concentrated sulfuric acid or with ion exchange resins (Amberlist or Amberlit type sulfonic resins). The sodium sulphate or the resin is removed from the medium by filtration and rinsed with fresh methanol.
- the methanol is then removed by distillation under vacuum (up to 120 0 C and 10 mb) resulting in the unreacted methyl diesters (representing 1% yield); the mixture of methanol and methyl diesters is recycled in the production of methyl diesters.
- the product is then distilled at a maximum temperature in the boiler of 140 ° C. and a vacuum of 5 mb; 4050 kg are recovered, representing a yield of 92.3%.
- the distillation residue still contains 280 kg of product (yield of 6.3%); it is recycled in the distillation of the next operation.
- the typical analysis of the distilled product is as follows: Appearance: clear, colorless to light yellow liquid.
- a crude "MGN” mixture comprising 2-methylglutaroinitrile (2-MGN), predominantly ethylsuccinonitrile (ESN) and adiponitrile (DNA) is hydrolyzed to give a mixture called MGA: 2-methyl-glutaric acid (86 mol%), ethylsuccinic acid (11 mol%) and adipic acid (3 mol%)
- the acid amide is mixed with dichloromethane and then cooled to about 4 ° C.
- Thionyl chloride is slowly charged in about 1.5 hours while controlling the temperature below 25 ° C.
- the reaction mixture is stirred at ambient temperature for 10 hours.
- the volatile species are removed to obtain the crude product.
- Gross product 687g (dark liquid).
- the dichloromethane is mixed with tert-butanol and cooled to 4 ° C.
- the crude product of step 2 diluted in dichloromethane, is then slowly added for approximately 1.5 h while controlling the temperature below 100 ° C.
- the volatiles are removed at the rotoevaporator.
- the crude reaction is treated with 1500 g of sodium hydrogencarbonate and filtered.
- the cake is washed with 150OmL of dichloromethane and the filtrate is dried over sodium sulfate. After evaporation of the solvent, the crude product is obtained. This is purified by distillation (120 ° C / 250Pa).
- Gross product 301 g
- Final product 150g CG (surface) analysis> 98% (8/92 isomers)
- Example 1.13 Preparation of Et-butyl-OOC-AM ⁇ -CONME?
- a crude "MGN” mixture comprising 2-methylglutaroinitrile (2-MGN), predominantly ethylsuccinonitrile (ESN) and adiponitrile (DNA) is hydrolyzed to give a mixture called MGA: 2-methyl-glutaric acid (86 mol%), ethylsuccinic acid (11 mol%) and adipic acid (3 mol%)
- the formulations include:
- the active ingredient in quantity by weight (of active ingredient) indicated in the table below,
- Example 2.1.1 is a comparative example in which the product Rhodiasolv® ADMA10, Rhodia (Asia Pacific zone) is used as solvent: alkyl dimethylamide solvent.
- a crystal of the active ingredient is introduced into the formulation having spent 7 days at 0 ° C. for nucleation, and the formulation is again placed for 7 days at 0 ° C. appearance of the formulation and the presence of crystals is optionally identified.
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Abstract
Description
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Priority Applications (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18198337.0A EP3520613A1 (fr) | 2008-01-25 | 2009-01-23 | Utilisation d'esteramides comme solvants, nouveaux esteramides et procede de preparation d'esteramides |
AU2009207634A AU2009207634B2 (en) | 2008-01-25 | 2009-01-23 | Use of ester amides as solvents, ester amides as such, and method for preparing ester amides |
PL09704290.7T PL2252144T3 (pl) | 2008-01-25 | 2009-01-23 | Zastosowanie amidów estrowych, nowe amidy estrowe i sposób wytwarzania amidów estrowych |
EP09704290.7A EP2252144B1 (fr) | 2008-01-25 | 2009-01-23 | Utilisation d'esteramides, nouveaux esteramides et procédé de préparation d'esteramides |
US12/864,119 US8735324B2 (en) | 2008-01-25 | 2009-01-23 | Esteramide solvents/coalescing agents in phytosanitary, cleaning, degreasing, stripping, lubricating, coating, and pigment/ink compositions |
JP2010543508A JP5606925B2 (ja) | 2008-01-25 | 2009-01-23 | エステルアミドの溶剤としての使用、新規のエステルアミド及びエステルアミドの製造方法 |
ES09704290T ES2960114T3 (es) | 2008-01-25 | 2009-01-23 | Uso de esteramidas, nuevas esteramidas y procedimiento para preparar esteramidas |
CN200980105066.4A CN101945575B (zh) | 2008-01-25 | 2009-01-23 | 酯酰胺的用途、新的酯酰胺以及酯酰胺的制备方法 |
BRPI0905784-6A BRPI0905784A2 (pt) | 2008-01-25 | 2009-01-23 | Uso de um composto esteramida, processos de preparação de um composto esteramida e composto esteramida |
CA2712318A CA2712318C (fr) | 2008-01-25 | 2009-01-23 | Utilisation d'esteramides a titre de solvants, esteramides en tant que tels et procede de preparation d'esteramides |
US14/249,021 US9392785B2 (en) | 2008-01-25 | 2014-04-09 | Use of esteramides as solvents, novel esteramides and process for preparing esteramides |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR08/00393 | 2008-01-25 | ||
FR0800393A FR2926699B1 (fr) | 2008-01-25 | 2008-01-25 | Utilisation d'esteramides, nouveaux esteramides et procede de preparation d'esteramides |
FR08/05133 | 2008-09-18 | ||
FR0805133 | 2008-09-18 |
Related Child Applications (3)
Application Number | Title | Priority Date | Filing Date |
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EP18198337.0A Previously-Filed-Application EP3520613A1 (fr) | 2008-01-25 | 2009-01-23 | Utilisation d'esteramides comme solvants, nouveaux esteramides et procede de preparation d'esteramides |
US12/864,119 A-371-Of-International US8735324B2 (en) | 2008-01-25 | 2009-01-23 | Esteramide solvents/coalescing agents in phytosanitary, cleaning, degreasing, stripping, lubricating, coating, and pigment/ink compositions |
US14/249,021 Continuation US9392785B2 (en) | 2008-01-25 | 2014-04-09 | Use of esteramides as solvents, novel esteramides and process for preparing esteramides |
Publications (1)
Publication Number | Publication Date |
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WO2009092795A1 true WO2009092795A1 (fr) | 2009-07-30 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/EP2009/050780 WO2009092795A1 (fr) | 2008-01-25 | 2009-01-23 | Utilisation d'esteramides, nouveaux esteramides et procédés de préparation d'esteramides |
Country Status (12)
Country | Link |
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US (2) | US8735324B2 (fr) |
EP (3) | EP2347652A1 (fr) |
JP (2) | JP5606925B2 (fr) |
CN (1) | CN101945575B (fr) |
AU (1) | AU2009207634B2 (fr) |
BR (1) | BRPI0905784A2 (fr) |
CA (1) | CA2712318C (fr) |
ES (1) | ES2960114T3 (fr) |
HU (1) | HUE063816T2 (fr) |
PL (1) | PL2252144T3 (fr) |
TW (1) | TW200936045A (fr) |
WO (1) | WO2009092795A1 (fr) |
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Also Published As
Publication number | Publication date |
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CA2712318A1 (fr) | 2009-07-30 |
TW200936045A (en) | 2009-09-01 |
AU2009207634B2 (en) | 2012-12-20 |
CN101945575A (zh) | 2011-01-12 |
AU2009207634A1 (en) | 2009-07-30 |
JP2014208653A (ja) | 2014-11-06 |
JP2011510046A (ja) | 2011-03-31 |
EP2347652A1 (fr) | 2011-07-27 |
US20140221211A1 (en) | 2014-08-07 |
ES2960114T3 (es) | 2024-02-29 |
CN104336010A (zh) | 2015-02-11 |
EP3520613A1 (fr) | 2019-08-07 |
HUE063816T2 (hu) | 2024-02-28 |
CN101945575B (zh) | 2014-11-19 |
PL2252144T3 (pl) | 2024-04-08 |
JP5908942B2 (ja) | 2016-04-26 |
US20110166025A1 (en) | 2011-07-07 |
BRPI0905784A2 (pt) | 2015-07-14 |
EP2252144A1 (fr) | 2010-11-24 |
US9392785B2 (en) | 2016-07-19 |
JP5606925B2 (ja) | 2014-10-15 |
CA2712318C (fr) | 2015-12-08 |
US8735324B2 (en) | 2014-05-27 |
EP2252144B1 (fr) | 2023-08-02 |
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