MXPA01009368A - Use of copolymers derived from polyamides as gelling agents for compounds with low polarity - Google Patents

Abstract

The invention concerns the use of copolymers comprising at least polyoxyalkylene polyamide functions, as gelling agents for compounds with low polarity or ionic surfactants. Said sequence copolymers comprise the following units:-X-(R1)m-(OA)n-X- (I), and -[NH-R2-NHCO-R'2-CO]r (IIa), and/or -[NH-R3-CO]s- (IIb), and -OC-R4-CO- (III) units wherein R1, R'1, R2, R'2, R3 and R4 represent a hydrocarbon radical;X corresponds to the terminal function of said unit after reaction with an amine function or carboxylic acid;OA, an oxyethylene, oxypropylene and/or oxybutylene radical;m is equal to 0 or 1;n is an integer ranging between 4 and 800;r and s are such that the number of amide bonds ranges between 1 and 15, for each unit (I);the mol ratio of the number of units (III)/number of units (I) ranges between 0.5/1 and 1.4/1 and the molar mass in number of the copolymer is less than 10000 g/mol.

Description

USE OF POLYAMIDE-DERIVED COPOLYMERS AS GELIFICATION AGENTS FOR LOW POLARITY COMPOUNDS The present invention relates to the use of copolymers, which comprise at least polyoxyalkylenated polyamide functions, as gelling agents, for relatively non-polar compounds or for surfactants, which are preferably non-ionic. Although there are many possibilities for preparing aqueous gels, gels obtained from relatively non-polar compounds or surfactants have not been developed particularly, although many fields may be interested in the production of said gels. This is the case especially for the field of cosmetics (for example sun creams); the industrial field of cleaning / separation of paints (treatment of vertical surfaces); the field of plant protection (maintenance in suspension of active materials, sensitive to hydrolysis, for example); the field of printing inks; the detergency field; the field of public works and construction; the papermaking field (for example the foaming back formulation for the manufacture of paper pulp); the field of explosives (for example, the gelation of ergoles or propellants for military and civil applications) or the field of hydraulic fluids. The object of the present invention is to propose a simple and efficient means for gelling relatively non-polar media or means of surfactants. Thus, an object of the invention is to use as a gelling agent, a relatively non-polar compound or a non-ionic surfactant, of at least one block copolymer, comprising the following units: -X- (R1) m- ( 0A) nX- (I) and - [NH-R2-NHCO-R '-CO] x- (Ha) and / or - [NH-R3-CO] s- (IIb), and -OC-R4-CO - (III) in said units: QX corresponds to the terminal function of said unit, after the reaction with an amine or carboxylic acid function; Q the R1, which may be identical or different, represent an alkyl radical, linear or branched, comprising from 2 to 4 carbon atoms; Q OA, which may be identical or different, represent an oxyethylenated, oxypropylenated or oxybutylenated radical, or mixtures thereof; Q R2, R'2, R3 and R4, which may be identical or different, represent: 1 an alkyl radical, linear or branched, comprising from 2 to 18 carbon atoms, "an aryl radical, comprising one or more nuclei aromatics, optionally substituted, O m is equal to 0 or 1, Q n is an integer between 4 and 800, O r is such that the number of amide bonds is between 1 and 15 per unit (I), Q s is such that the number of amide bonds is between 1 and 15 per unit (I), ü the molar ratio of the number of units (III) to the number of units (I) is between 0.5 / 1 and 1.4 / 1; units are linked together at least by amide bonds, or the number of the average molar mass in copolymer number is less than 100 000 g / mol.However, other characteristics will be clearer from the reading of the description and the Examples that follow Before describing the copolymer used in the invention in more precise detail, the nature of the compound being It can gelify, according to the invention, it will be supplied. Thus, the term "relatively non-polar compound" means any constituent that is liquid at a temperature to prepare and / or use the formulation from which one of the constituent elements is formed. Also, this liquid, which is in Hansen's solubility space (Handbook of solubility parameters and other cohesion parameters - Alian FM Barton, CRC Press Inc., 1983-) more particularly has the following parameters: "dP of the Keeson interactions of less than or equal to 16. 5 (J / cm3) "dH of hydrogen bonds less than or equal to 10.5 (J / cm3)" dD of the interactions of London, greater than or equal s 15 (J / cm3) More particularly, the coefficient dP is between 2 and 16.5 (J / cm3) - Preferably, the coefficient dP is between 2 and . 5 (J / cm3) 'It should be noted that the coefficient dD is usually between 15 and 23.

As non-limiting examples of relatively non-polar compounds, mention may be made of: "saturated and unsaturated fatty acid triglycerides, containing at least 12 carbon atoms and preferably from 14 to 20 carbon atoms, they may be synthetic or, preferably, natural triglycerides, for example plant oils, such as rape seed oil, soybean oil, peanut oil, butter oil, cottonseed oil, linseed oil, coconut oil, olive oil , palm oil, grapeseed oil, fish oil, castor oil or copra oil; "methyl esters of saturated or unsaturated fatty acids, containing at least 12 carbon atoms and preferably from 14 to 20 carbon atoms; carbon, for example methyl oleate; "C8-C8 aliphatic or cyclic alkyl esters of saturated monocarboxylic acids, for example methyl acetate, ethyl acetate or cyclohexyl acetate;" terpene compounds (D-limonene, L-limonene, etc.); C 1 -C 4 alkyl diesters of at least one C 4 -C 6 aliphatic diacid Mixtures of diacid esters which are the esters derived essentially from adipic acid, glutaric acid and succinic acid, are more particularly used, the alkyl groups of the ester moiety being selected especially from the methyl and ethyl groups, but may also be propyl, isopropyl, butyl, n-butyl and isobutyl; 1 anisole; "n-methylpyrrolidone; "dimethyl sulfoxide;" ketones, for example cyclopentanone or methyl isobutyl ketone; m polyalkylene glycols, for example polyethylene glycol 400 or polypropylene glycol 400.

The present invention can be used to gel a relatively non-polar compound or a mixture of several such compounds. The surfactants and, more particularly, the nonionic surfactants, can similarly be gelled according to the process of the present invention. More particularly, the surfactant is in the form of a liquid at the temperature of the preparation and / or use of the formulation, of which they form one of the constituent elements.

In addition, the surfactant is preferably free of polar solvents, pro, if said solvent is present, the content of the solvent in this surfactant remains such that it does not prevent the subsequent gelation of said surfactant. In the form of the nonionic surfactant, which is most suitable particularly for the invention, mention may be made, however, without being limited to: "polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols in which the alkyl substituent is C6- C 2 and contains from 5 to 25 oxyalkylene units, examples which may be mentioned are Triton X-45, X-114, X-100 or X-102, sold by Rohm &Haas Co., and the Igepal NP2 to NP17 from Rhodia Chimie; "polyoxyalkylenated C8-C22 aliphatic alcohols, containing from 1 to 25 oxyalkylene units (oxyethylene or oxypropylene); examples that may be mentioned are the Tergitol 15-S-9 and 24-L-6 NM products, sold by Union Carbide Corp., Neodol 45-9, 23-65, 45-7 and 45-4 sold by Shell Chemical Co ., Kyrol EOB, sold by Procter & Gamble Co., Synperonic A3 to A9 from ICI and Rhodasurf IT, DB and B from Rhodia Chimie; "products resulting from the condensation of ethylene oxide and / or propylene oxide with propylene glycol or ethylene glycol, with a weight average molecular weight of about 2,000 to 10,000, such as Pluronic products sold by BASF; "alkoxylated amide amines, containing from 1 to 50, preferably from 1 to 25 and more particularly from 2 to units of oxyalkylene (preferably oxyethylene); "alkoxylated terpene hydrocarbons, such as ethoxylated and / or propoxylated α- or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units; in particular those described in the international application WO 96/01245, to which reference can be made in particular; "the alkyl polyglycosides, which can be obtained by the condensation (for example by acid catalysis) of the glucose with primary fatty alcohols (US-A-3 598 865, US 4 565 647, EP 132 046, etc.), which contain a C4-C20 alkyl group and preferably C8-C? 8 and also an average number of glucose units of about 0.5 to 3 and preferably about 1.1 to 1.8 per mol of alkyl polyglycoside (APG); in particular, of those containing a C 8 -C 4 alkyl group and an average of 1.5 glucose units per mole, a C 2 -C 4 alkyl group and an average of 1.4 glucose units per mole, a C 8 -C alkyl group and an average of 1.5 units of glucose per mole, a C 8 -C 0 alkyl group and on average 1.6 units of glucose per mole, sold, respectively, under the names of Glucopon 600 EC®, 600 CSUP®, 650 EC® and 225 CSUP® by Henkel The present invention makes it possible to gel one of the surfactants mentioned before and also their mixtures. The copolymer will now be described. As mentioned before, the copolymer comprises the units (I) to (III), which are more particularly randomly distributed. The copolymer comprises amide bonds, ether bonds arising from unit (I) and, depending on the nature of the reactive functions of unit (I), possibly ester or urethane linkages. Also, the final functions of this copolymer are the amines, more particularly the primary amines, carboxylic acids and, optionally, the alcohols. The copolymer comprises at least one unit (I) of the following formula: -X-. { R1) m-. { OA) n-X-, in which: Q X corresponds to the final function of said unit, after the reaction with an amine or carboxylic acid function; Q the R1, which may be the same or different, represent an alkyl radical, linear or branched, comprising from 2 to 4 carbon atoms; Q OA, which may be identical or different, represent an oxyethylenated, oxypropylenated or oxybutylenated radical, or mixtures thereof; Q m is equal to 0 or 1; Q n is an integer between 4 and 800. According to a more particular embodiment of the invention, the unit (I) of the copolymer comprises a sequence of oxyethylenated, oxypropylenated or oxybutylenated radicals, or a combination of two or three of these units, the sum of the units being equal to n. It should be noted that the copolymers forming the object of the use according to the invention can, depending on their subsequent use, have their structure adapted, especially by means of the nature and number of oxyalkylenated units. Thus, for example, the compatibility of the copolymer with a polar compound very scarcely can be increased by reducing the number of oxyethylenated radicals and / or increasing the number of oxypropylenated or even oxybutylenated radicals. Preferably, the number of the OA units is between 4 and 300. X corresponds to the final function of said unit, after the reaction with an amine or carboxylic acid function. To be more precise, X is obtained from the reaction of the monomers or prepolymers, which are, for the copolymer forming the material of the invention, the source of the unit (I) with an amine or carboxylic acid function . It should be noted that it is advantageous to use the prepolymers corresponding to unit (I), which are obtained extemporaneously and which contain final functions capable of reacting with the functions of amine or carboxylic acid. Among these suitable terminal functions, mention may be made more particularly to alcohols, amines, carboxylic acids, epoxides and isocyanates. Thus, when X is obtained from the reaction of a final function of amine, with a carboxylic acid, that is to say an amine function, X corresponds to the following function: -NH-. When X is obtained from the reaction of a final function of alcohol with a carboxylic acid, ie an ester function, X corresponds to the following function: -0-; etc . According to a first preferred embodiment of the invention, unit (1) contains a group X, which results from the reaction of an amine function with a carboxylic acid, in which case m is 1. According to this particular embodiment, when the radical OA is an oxyethylenated radical, the radical R1 may contain from 2 to 4 carbon atoms. When the OA radical is an oxypropylenated or oxybutylenated radical, the radical R1 comprises, more particularly, 3 or 4 carbon atoms, respectively. Said units (I) are derived from the polyoxyalkylenated diamines. These compounds are well known to those skilled in the art and are sold, in particular, under the trade name Jeffamine® (Texaco-Huntsmann). According to a second preferred embodiment of the invention, the unit (I) contains a group X resulting from the reaction of an alcohol with a carboxylic acid, in which case m is preferably 0. The units (I), corresponding to this variant is obtained from block or random copolymers of polyalkylene glycols or polyalkylene glycol.

Compounds that can be used in the present invention are sold, in particular, under the trade name of Pluronic PE® (BASF). When the unit (I) contains a group X, which results from the reaction of an epoxide or an isocyanate with an amine or a carboxylic acid, then m is preferably equal to 0. The copolymer, according to the invention, can comprise only a type of unit (I) or a combination of several of said units, if these units are differentiated by the nature of their units X and / or their units OA. The second type of units of the copolymers used in the invention have the following formulas: - [NH-R2-NHCO-R2-CO] x (Ha) and / or - [NH-R3-CO] s (Hb), in said formulas: Q R2, R'2, R3 and R4, which may be identical or different, represent: "an alkyl radical, linear or branched, comprising 2 to 18 carbon atoms," an aryl radical, comprising one or more aromatic nuclei, optionally substituted, Q r is such that the number of amide bonds is between 1 and 15 per unit (I), Q s is such that the number of amide bonds is between 1 and 15 per unit (I ). More particularly, the radicals R2, R'2 and R3, which may be the same or different, represent straight or branched radicals, comprising from 2 to 12 carbon atoms and preferably methylene radicals, optionally bearing one or more radicals of methyl. According to a preferred embodiment, said radicals, which may be the same or different, are chosen in particular from divalent radicals of ethyl, 1-methylethyl, propyl, 1-methylpropyl, butyl, hexyl, heptyl, octyl, decyl, undecyl and lauryl. . Another possibility consists of radials R2, R'2 and R3, which may be the same or different, representing aryl radicals, comprising one or more aromatic nuclei, optionally substituted. When the aforementioned radicals comprise only one aromatic nucleus, preferably they contain 6 carbon atoms, the reactive functions (carboxylic acids and / or amines) are in the ortho, meta or para position.

It should be noted that when the aforementioned radicals comprise several aromatic nuclei, preferably two aromatic nuclei, said nuclei may be peri-fused or linked by means of inert groups, such as single valence bonds or an alkyl radical comprising 1 to 4 carbon atoms. Among the radicals comprising two aromatic nuclei, mention may be made more particularly of divalent naphthyl radicals, attached to reactive functions (carboxylic acids and / or amines) by means of the carbon atoms I 2, I 4, I 5, I 6 and I 6. , 1 and 7 or 2 and 7. The values of r and s are, more particularly, between 5 and 10 per unit (I). The units (Ha) are obtained by reacting a diamine with a diacid and the units (Hb) are obtained by reacting the amino acids or lactams. Said units can be obtained in itself, during the preparation of the copolymer used in the invention, or alternatively, they can be prepared extemporaneously; These units are produced according to a conventional polyamidation process, which will be described in detail below. Thus, according to a preferred variant of the invention, the units used as units (Ha) or (Hb) are polyamides, such as polyamide 6, polyamide 10, polyamide 11, polyamide 12 or polyamide 6,6 or a random copolymer of at least two of said polyamides, in all proportions, preferably 50/50. It should be noted that the use of the units (Ha) and (Ilb) which have just been described has the additional advantage that it is possible to obtain a copolymer whose melting point is not very high, thus facilitating the preparation of the gel, during which the polymer melts. With respect to the units (III), its formula is as follows: -OC-R4-CO, in which the R4, which may be the same or different, have the same meaning as the one given for the radicals R2 to R3, mentioned before. You can refer to them. The units (III) are obtained from the corresponding diacid. The molar ratio of the number of units (III) to the sum of the number of units (I) is between 0.5 / 1 and 1.4 / 1. According to the preferred embodiment of the invention, the number of units (III) is such that it is close to the stoichiometry between the functions of the number of amines, carboxylic acid and, optionally, alcohol, isocyanate and epoxy.

The copolymers, or the mixture of copolymers used in the invention, also have the advantage of having a relatively low melting point, ie a melting point of less than about 190 ° C, more particularly between 70 and 190 ° C and preferably between 100 and 190 ° C. The copolymers, which have been justly described, can be prepared by the reaction of dicarboxylic acids, polyoxyalkylenated compounds, containing terminal functions capable of reacting with the functions of amine or carboxylic acid (in the form of monomers or prepolymers), amino acids or lactams, or alternatively polyamides. The process is carried out by placing the various reagents in contact, preferably in the absence of the solvent. The first stage is generally carried out without heating. However, when no or more of the reactants is in a solid form, the operation is carried out at a temperature at least equal to the highest melting point. The various reagents are used in amounts that are suitable for obtaining a copolymer, as defined above. Once the reagents have been placed in contact, the actual polymerization reaction is executed. To do this, the temperature rises to a value generally between 100 and 300 ° C. During this step, the reaction water is removed by evaporation. The pressure conditions during the polymerization reaction can easily be determined by a person skilled in the art. A catalyst can optionally be used to promote the polyamidation reaction, such as, for example, hypophosphorous acid, phenylphosphinic acid, phenylphosphonic acid or tris (nonylphenyl) phosphite. A catalyst that promotes polyesterification may also be used, if necessary. Among the catalysts that can be used, mention is made of catalysts based on zirconium and titanium, among others, such as, for example, tetrabutyl titanium orthotitanate and tetrabutyl orthocytosate. The catalyst may represent from 0 to 1% by weight relative to the total weight of the various monomers, more particularly up to 0.5% and preferably from a few tens to a few hundred parts per million. As previously mentioned, the copolymers used in the invention have a number average molar mass of less than or equal to 100 000 g / mol and more particularly between 10,000 and 50,000 g / mol.

It should be noted that the molar masses, averaged in number, of the copolymers are evaluated by steric exclusion chromatography, using polystyrene as the standard. The copolymers are used more particularly in a proportion of 0.1 to 15% by weight, relative to the relatively non-polar compound or the surfactant. Advantageously, the content of the copolymer is between 0.5 and 10% by weight with respect to the same reference. In the case of a gelation of a relatively non-polar compound, it should be noted that the copolymer used in the present invention can be combined with at least one nonionic or anionic surfactant, in order to make said compound relatively non-polar, auto -emulsifier. In such a case, the surfactant is preferably free of the polar solvent or, in any case, the content of the solvent in this surfactant, if present, should be such that it does not prevent the subsequent gelation of the copolymer / surfactant / mixture. relatively non-polar compound. Among the nonionic surfactants which are suitable, mention may be made of: "polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols, wherein the alkyl substituent is C6-C1 and contains from 5 to 25 oxyalkylene units; they can mention are the Triton X-45, X-114, X-100 or X-102, sold by Rohm &Haas Co., and the Igepal NP2 to N017, of Rhodia Chimie; "polyoxyalkylenated C8-C2 aliphatic alcohols containing from 1 to 25 units of oxyalkylene (oxyethylene or oxypropylene); examples that can be mentioned are the Tergitol 15-S-9 and 24-L-6 NMW products, sold by Union Carbide Corp., Neodol 45-9, 23-65, 45-7 and 45-4, sold by Shell Chemical Co., Kyro EOB, sold by -Protecter & Gamble Co., Synperonic A3 to A9, from ICI and Rhodasurf IT, DB and B from Rhodia Chimie; "Ethoxylated or ethoxylated propoxylated triglycerides of vegetable or animal origin, such as, for example, shortening, tallow, peanut oil, butter oil, cottonseed oil, linseed oil, olive oil, palm oil, grapeseed oil, fish oil, soybean oil, castor oil, rape seed oil, copra oil or coconut oil; "the products resulting from the condensation of ethylene oxide and / or oxide of propylene with propylene glycol or ethylene glycol, with a weight-average molecular weight of about 2,000 to 10,000, such as the Pluronic products (BASF); "products resulting from the condensation of ethylene oxide and / or propylene oxide with ethylenediamine, such as Tetronic products (BASF);" ethoxylated and / or propoxylated C8-C18 fatty acids, containing from 5 to 25 units ethoxylated and / or propoxylated; "C8-C20 fatty acid amides containing from 5 to 30 ethoxylated units;" ethoxylated amines containing from 5 to 30 ethoxylated units; ethoxylated amide amines, containing from 1 to 50, preferably from 1 to 25, and more particularly from 2 to 20 oxyalkylene units (preferably oxyethylene units); "amine oxides, such as alkyl dimethylamine oxides ( C? 0-C? 8) and the oxides of (C8-C22 alkoxy) ethyldihydroxyethylamine; "alkoxylated terpene hydrocarbons, such as the ethoxylated and / or propoxylated a- or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units, for example those described in WO 96/01245; "alkyl polyglycosides, which can be obtained by the condensation (for example by acid catalysis) of the glucose with primary fatty alcohols (US-A-3 598 865, US 4 565 647, EP 132 043, EP 132 046, etc.) , which contain a C4-C20 alkyl group and preferably C8-Cis and also an average number of glucose units of about 0.5 to 3 and preferably about 1.1 to 1.8 per mol of alkyl polyglycoside (APG); particular, of those in particular containing a C 8 -C 4 alkyl group and an average of 1.4 glucose units per mole, a C 2 -C 4 alkyl group and an average of 1.4 glucose units per mole; alkyl C8_C? 4 and on average 1.5 glucose units per mol, a C8-C? 0 alkyl group and on average 1.6 glucose units per mol, sold, respectively, under the names of Glucopon 600 EC®, 600 C CSUP ®, 650 EC® and 225 CSUP® from Henkel With regard to anionic surfactants, more use is made of icularly of surfactants which are in liquid form or in a form which is soluble in the relatively non-polar compound. Examples which may be mentioned are: "alkyl ester sulfonates of the formula R-CH (S03M) -COOR ', wherein R represents a C8-C20 alkyl radical and preferably C? 0-C? 6, R' represents a C.sub.1 -C.sub.6 alkyl radical and preferably C.sub.1 -C.sub.3 and M represents a cation chosen from an alkali metal or an alkaline earth metal (sodium, potassium, lithium or calcium), an ammonium residue, substituted or unsubstituted (methyl-, dimethyl- , trimethyl- or tetramethylammonium, dimethyl-piperidinium, etc.) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.); "alkyl sulfates of the formula ROS03M, where R represents a C5-C24 alkyl and preferably C? 0-C18 or a hydroxyalkyl radical, M represents a hydrogen atom or a cation as defined above, and also its ethoxylated (EO) and / or propoxylated (PO) derivatives, which contain an average of 0.5 to 30 and preferably 0.5. to 10 units of EO and / or PO; • alkylamide sulfates of the formula RCONHR 'OS03M, in which R represents an alkyl radical V2-C22 and preferably C6-C2o, R1 represents a C2-C3 alkyl radical, M represents a hydrogen atom or a cation of the same definition as before, and also its ethoxylated (EO) and / or propoxylated (PO) derivatives, which contain an average of 0.5 to 60 units of EO and / or PO; "the alkoxylated phosphate esters (ethoxylated and / or propoxylated) derived from aliphatic alcohols, alkylphenols or alkylarylphenols; "the salts of saturated or unsaturated fatty acids, C8-C2 and preferably C4-C20, C9.20 alkylbenzenesulfonates, C8-C22 alkylsulfonates / primary or secondary, alkylglyceryl sulfonates, the sulfonated polycarboxylic acids, described in GB-A- 1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkyl phosphates, isothionates, alkyl succinamates, alkyl sulfosuccinates, sulfosuccinate monoesters or diesters, N-acyl sarcosinates, alkylglycoside sulfates and polyethoxy carboxylates; "sophorolipids, such as those in the form of acid or lactone, derivatives of 17-hydroxyoctadeceneic acid;" the associated cation has the same definition as that given for M, or is a hydrogen atom. When a surfactant is present, the amount used is more particularly between 5 and 20% by weight, relative to the relatively non-polar compound. The advantage of introducing a surfactant into the mixture of the copolymer & relatively non-polar compound is that it makes the resulting gel self-emulsifier. The copolymer, according to the invention, can be similarly used with a filler, such as, for example, a lamellar structure filler. In the form of illustration, smectites (montmorilonite, beidelite, nontronite, hectorite, saponite, etc.) can be used. The content of the filling varies within a wide range. Advantageously, and when present, its content may represent up to 20% by weight of the copolymer. This filler can be used in several ways. The first is to use it during the preparation of the copolymer. This possibility has the surprising advantage of reducing the melting point of the copolymer, thus obtained. This may prove to be advantageous when the copolymer is used to prepare the gel. The second is to add the filling when the copolymer is used. Said operation makes it possible to increase the hardness of the resulting gel. It goes without saying that it will not constitute a deviation from the context of the present invention to combine these two variants. One of the fields of application of the mixture comprising the copolymer and the relatively non-polar compound or the surfactant refers to the formulations intended to clean or separate the paints and varnishes on various surfaces, for example metals.

The advantage of this mixture, according to the invention, is that it makes it possible to obtain a highly viscous composition, which makes the cleaning / separation operation more efficient by means of a better "fixation" of the active composition to the leaving support. to treat. The mixtures, according to the invention, can be used, for example, for the cleaning / separation of vertical surfaces. Another field of application of the mixture, according to the invention, refers to that of industrial detergency, to make it possible to provide a means for gelling solutions, comprising, for example, compounds of the type such as limonenes. Similarly, it makes it possible to gel liquid additives for the formulations of solid detergents. The mixture, according to the invention, can also be used in the field of plant protection. It can be advantageous to have available gelled mixtures, comprising one or more active materials that are liquid, dissolved or retained in suspension, in a suitable solvent, since these mixtures show solubility parameters within the ranges indicated above. Specifically, said mixtures are stable at temperatures up to at least about 50 ° C.

The mixture, according to the invention, also finds an application in the field of printing inks, with the gelation of mineral oils or of plants, among others. Said mixtures, according to the invention, are obtained by placing the copolymer in contact with the relatively non-polar compound or the surfactant and, when appropriate, the aforementioned additives. This contacting preferably takes place with heating in a period that is sufficient to dissolve or disperse the (co) polymer. For example, a temperature of at least 90 ° C is suitable for carrying out the invention. Advantageously, the solution or dispersion can be carried out at a temperature at which the copolymer is in molten form. In the case of the gelation of relatively non-polar compounds, it may be that the melting point of the copolymers, previously described, is greater than the flash point of said relatively non-polar compounds. Consequently, the operation of placing in contact may preferably take place under a stream of nitrogen. The time for which the compounds are contacted is more particularly such that the copolymer dissolves.

Once the dissolution has been achieved, the mixture is cooled without stirring, to facilitate gel formation. Concrete, but not limiting, examples of the invention will now be provided.

EXAMPLE 1 1) Preparation of the copolymer The following reagents were placed in a glass reactor: (*) Jeffamine ED 2003 (Huntsmann); Mn = 2276 g / ml; Molar ratio of ethylene oxide (EO) / propylene oxide (PO) = 37.5 / 5.5. The reactor was then purged (vacuum / nitrogen) and the temperature raised to 230 ° C, under nitrogen. After holding at this temperature for one hour, a vacuum of 1 mbar, about half an hour, was gradually applied at 230 ° C. These conditions were maintained for 10 minutes.

A block copolymer, comprising on average 4 amide bonds per polyamide block (determined by NMR spectroscopy) was obtained.

In addition, the number average molar mass is about 46 400 g / mol (determined by steric exclusion chromatography, polystyrene standard). 2) Preparation of a gel The copolymer, previously obtained, dissolved while hot (above the melting point of the copolymer), under a stream of nitrogen, in Rhodiasol RPDE, sold by Rhodia Chimie (mixture of short-chain adipic acid, glutaric acid and succinic acid esters). The copolymer is present in 1% by weight, relative to Rhodiasolv RPDE. Once the dissolution has been achieved, the mixture was cooled without stirring, to facilitate gel formation. The gel is stable up to 50 ° C.

EXAMPLE 2 1) Preparation of the copolymer The process was carried out as in Example 1, except that the composition used is as follows: (*) Jeffamine D 2000 (Texaco); Mn = 2202 g / mol; propylene oxide A block copolymer, comprising on average 5 amide bonds per polyamide block (determined by NMR) was obtained. In addition, the average number-average molar mass is about 17 200 g / mol (determined by steric exclusion chromatography, polystyrene standard). 2) Preparation of a gel The copolymer, previously obtained, was dissolved while it was hot, under a stream of nitrogen, in methyl oleate of Phytrorob 926-67, sold by Novance This copolymer is present in 1% by weight relative to methyl oleate. Once the dissolution was achieved, the mixture was cooled without agitation. The gel is stable up to 50 ° C.

EXAMPLE 3 1) Preparation of the copolymer with a mineral filler The process was carried out as in Example 1, except that the composition used is as follows: (*) Jeffamine D 2000 (Texaco); Mn = 2002 g / mol; polypropylene oxide (**) Montmorilonite SCPX 1789 from Laporte, untreated. X represents 0, 5 or 20% by weight relative to the weight of the copolymer. A block copolymer, comprising on average 5.5 amide bonds per polyamide block (determined by NMR) was obtained. 2) Measurement of Melting Points Montmorillonite Point Content Melting 0 127 ° C 5% 116 ° C 20% 111 ° C EXAMPLE 4 The copolymer obtained in Example 1, dissolved while hot (above the melting point of the copolymer) under a stream of nitrogen, in PPG 400 (polypropylene glycol with a weight average molar mass of 400 - sold by Dow). The copolymer is present at 5% by weight relative to PPG 400. Once the dissolution was achieved, the mixture was cooled without stirring, to facilitate the formation of the gel. The gel is stable up to 50 ° C. A similar result was obtained using the PEG 400 (polyethylene glycol with a weight average molar mass of 400 - sold by Dow) with 2% of the copolymer. EXAMPLE 5 The copolymer obtained in Example 1 was dissolved while hot, in Synperonic A7 (C 2 -C 4 fatty alcohol, comprising 7 oxyethylenated units sold by ICI). The copolymer is present in 2% by weight relative to Synperonic A7. A gel was obtained once the solution was achieved, and the mixture was cooled without agitation, to facilitate gel formation. EXAMPLE 6 The copolymer obtained in Example 1, was dissolved while hot, in nonylphenol EO (Igepal NIO - Rhodia Chimie). The copolymer is present in 5% by weight relative to nonylphenol. A gel was obtained once the solution was achieved, and the mixture was cooled without agitation, to facilitate gel formation. EXAMPLE 7 The copolymer obtained in Example 1, was dissolved while hot, in an alkyl polyglycoside, comprising an alkyl unit Ci2-Cie (plantar 1200). The copolymer is present in 5% by weight in relation to Plantaren. A gel was obtained once the solution was achieved, and the mixture was cooled without agitation, to facilitate gel formation. EXAMPLE 8 The copolymer obtained in Example 1 was dissolved while hot, in a nopol, containing 3 units of propylene oxide (PO) and 6.5 units of ethylene oxide (EO). This product was obtained by carrying out the teachings of the international application WO 96/01245. A gel was obtained once the solution was achieved, and the mixture was cooled without agitation, to facilitate gel formation.

Claims (23)

1. CLAIMS 1. The use, as a gelling agent, of a relatively non-polar compound, or a non-ionic surfactant, of at least one block copolymer, which comprises the following units: -X- (R1) m- (OA) nX- (I) and - [NH-R2-NHCO-R, 2-CO] x- (Ha) and / or - [NH-R3-CO] s- (Ilb), and -OC-R4 -CO- (III) in said units: ü X corresponds to the terminal function of said unit, after the reaction with an amine or carboxylic acid function; Q the R1, which may be identical or different, represent an alkyl radical, linear or branched, comprising from 2 to 4 carbon atoms; Q OA, which may be identical or different, represent an oxyethylenated, oxypropylenated or oxybutylenated radical, or mixtures thereof; Q R2, R'2, R3 and R4, which may be identical or different, represent: "an alkyl radical, linear or branched, comprising from 2 to 18 carbon atoms," an aryl radical, comprising one or more nuclei aromatics, optionally substituted, Q m is equal to O or 1, O n is an integer between 4 and 800, O r is such that the number of amide bonds is between 1 and 15 per unit (I), Q s is such that the number of amide bonds is between 1 and 15 per unit (I), Q the molar ratio of the number of units (III) to the number of units (I) is between 0.5 / 1 and 1.4 / 1; Q the various units are linked together at least by means of amide bonds; ü The number of the average molar mass in the copolymer number is less than 100 000 g / mol.
2. 2. The use, as claimed in the preceding claim, characterized in that the units (I) of the copolymer comprise a sequence of oxyethylenated, oxypropylenated or oxyethylenated and oxypropylenated radicals, the sum of the units being equal to n.
3. 3. The use, as claimed in any of the preceding claims, characterized in that the radicals R2, R'2, R3 and R4, which may be the same or different, represent radicals, linear or branched, comprising from 2 to 12 carbon atoms , and preferably methylene radicals, which optionally carry one or more methyl radicals.
4. 4. The use, as claimed in the preceding claim, characterized in that the radicals R2, R'2, R3 and R4, which may be the same or different, are chosen from: ü ethyl, 1-methylethyl, propyl, 1-methylpropyl radicals, butyl, hexyl, heptyl, octyl, decyl, undecyl and lauryl.
5. 5. The use, as claimed in any of the preceding claims, characterized in that the radicals R2, R'2, R3 and R4, which may be the same or different, represent aryl radicals comprising one or more aromatic nuclei, optionally substituted.
6. 6. The use, as claimed in the preceding claim, characterized in that the radicals R2, R'2, R3 and R4, which may be the same or different, comprise: "an aromatic nucleus, the reactive functions (amines or carboxylic acids) being in the ortho, meta or para position, "two aromatic nuclei, linked by means of inert groups, or peri-molten, for example divalent naphthyl radicals, the reactive functions (amines or carboxylic acids) being at the carbon atoms 1 and 2 , and 4, 1 and 5, 1 and 6, 1 and 7 or 2 and 7.
7. 7. The use, as claimed in any of the preceding claims, characterized in that the units (Ha) or (Hb) are chosen from polyamide 6, polyamide 10, polyamide 11, polyamide 12, polyamide 6,6 or a random copolymer of minus two of said polyamides, in all proportions, preferably 50/50.
8. 8. The use, as claimed in any of the preceding claims, characterized in that r and s, which may be identical or different, are such that the number of amide bonds is between 5 and 10 per unit (I).
9. 9. The use, as claimed in any of the preceding claims, characterized in that the number average molecular mass of the copolymer is between 10,000 and 50,000 g / mol.
10. 10. The use, as claimed in any of the preceding claims, characterized in that the relatively non-polar compound is in Hansen's solubility space and has the following parameters: "dP of Keeson interactions less than or equal to 16.5 (J / cm3)" dH of hydrogen bonds less than or equal to 10.5 (J / cm3) * "dD of London's interactions, greater than or equal to 15 (J / cm3)
11. 11. The use, as claimed in any of the preceding claims, characterized in that the nonionic surfactant is chosen from: "polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated alkylphenols, in which the alkyl substituent is C5-C? 2 and contains to 25 units of oxyalkylene; "polyoxyalkylenated C8-C22 aliphatic alcohols, containing from 1 to 25 units of oxyalkylene (oxyethylene or oxypropylene;" products resulting from the condensation of ethylene oxide and / or propylene oxide, with propylene glycol or ethylene glycol; ethoxylated and / or propoxylated C8-C8 fatty acids, containing from 5 to 25 ethoxylated and / or propoxylated units; "alkoxylated amido amines, containing from 1 to 50 oxyalkylenated units; "alkoxylated terpene hydrocarbons, such as the α- or β-pinenes, ethoxylated and / or propoxylated, containing from 1 to 30 oxyethylene and / or oxypropylene units; "alkyl polyglycosides, which can be obtained by the condensation of glucose with primary fatty alcohols, containing a C -C0 alkyl group and also an average number of glucose units of about 0.5 to 3 per mole of alkyl polyglucoside.
12. 12. The use, as claimed in any of the preceding claims, characterized in that the amount of the copolymer, relative to the relatively non-polar compound or the nonionic surfactant, is between 0.1 to 15% by weight and preferably between 0.5 and 15% by weight. 10% by weight.
13. 13. The use, as claimed in any of the preceding claims, characterized in that, in the case of the gelation of a relatively non-polar compound, the copolymer is combined with a nonionic or anionic surfactant.
14. 14. The use, as claimed in the preceding claim, characterized in that the amount of the nonionic or anionic surfactant, relative to the relatively non-polar compound, is between 5 and 20% by weight.
15. 15. The use, as claimed in any of the preceding claims, characterized in that the copolymer is combined with a filler of laminar structure.
16. 16. The use, as claimed in the preceding claim, characterized in that the amount of the filler represents up to 20% by weight of the copolymer.
17. 17. The use, as claimed in any of claims 15 and 16, characterized in that the filling is introduced during the preparation of the copolymer and / or during the use of said copolymer.
18. 18. The use as claimed in any of the preceding claims, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant are part of the composition of the formulations intended to clean metals.
19. 19. The use, as claimed in any of claims 1 to 17, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant, form part of the composition of detergent formulations, which can be used in the industrial field.
20. 20. The use as claimed in any of claims 1 to 17, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant are part of the composition of formulations intended to separate paints and varnishes.
21. 21. The use as claimed in any of claims 15 to 17, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant form part of the composition of formulations intended to clean and separate paints and varnishes from vertical surfaces .
22. 22. The use as claimed in any of claims 1 to 17, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant are part of the composition of formulations intended for the treatment of plants.
23. 23. The use as claimed in any of claims 1 to 17, characterized in that the copolymer and the relatively non-polar compound or the nonionic surfactant are part of the composition of formulations used in the field of printing inks.