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    • 专利摘要:
    The present invention relates to a surfactant composition based on the glycine amide salt of betaine, as well as to the process for its preparation. It also relates to its use as a wetting agent, dispersing of particles and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances, as well as in the manufacture of various products intended for the treatment and / or cleaning of the body, plants or hard surfaces, the treatment of water or the extraction of petroleum. It further relates to a product comprising the above composition.
    公开号:FR3082522A1
    申请号:FR1855359
    申请日:2018-06-19
    公开日:2019-12-20
    发明作者:Freddy PESSEL；Francis Galle；Pierre-Yves Divet；Xavier Roussel
    申请人:Surfactgreen SAS；
    IPC主号:
    专利说明:

    Surfactant composition based on amide salts of glycine betaine, process for its preparation and its uses
    OBJECT OF THE INVENTION
    The present invention relates to a surfactant composition based on glycine betaine amide salts, as well as a process for its preparation. It also relates to its use as a wetting agent, dispersing of particles and / or corrosion inhibitor and / or for improving the disinfecting power of antimicrobial substances, as well as in the manufacture of various products intended for the treatment and / or cleaning of the body, hard plants or surfaces, water treatment or petroleum extraction. It further relates to a product comprising the above composition.
    BACKGROUND OF THE INVENTION
    Surfactants are essential raw materials for the manufacture of a variety of products. Among these, cationic surfactants certainly represent a less extensive market than that of anionic or nonionic surfactants, but they nevertheless have an interest in multiple applications, in particular in the manufacture of detergents and cosmetic products, as well as in water treatment.
    Due to their toxicity, certain surfactants such as dimethyldialkylammonium salts, present in most fabric softeners, see their use limited, even abandoned, in certain European countries such as Germany and the Netherlands. Under ecological pressure, producers of surfactants must not only offer products that are less polluting, more biodegradable and have the lowest possible ecotoxicity. In addition to environmental constraints, consumers want to have the most natural products possible.
    In this context, glycine betaine, an inexpensive natural substance, constitutes a raw material of choice for the preparation of surfactants. Derived from the sugar beet molasses, obtained after sucrose extraction, it currently remains a by-product of the sugar industry. The grafting on glycine betaine of fatty alcohols and amines makes it possible to access cationic amphiphilic molecules without the conventional stage of quaternization of a tertiary amine using generally toxic methylating agents.
    It has thus been proposed in US Pat. No. 7,829,521 amides of betaine glycine obtained by reacting betaine glycine with a sulfonic acid, such as methanesulfonic acid, and an alcohol, such as n-butanol, to produce an ester. glycine betaine which is then subjected to an aminolysis reaction using a fatty amine of vegetable origin comprising at least 18 carbon atoms. The cationic surfactants thus obtained have a surface tension of at least 36 mN / m and are more particularly intended for cosmetic application. Other similar shorter chain surfactants are presented in the publication by F. Goursaud et al in Green Chem., 2008, 10, 310-320, namely glycine laurylamide betaine, the surface tension of which is, again very high (50 mN / m). This surfactant is also described in patent application WO 2013/188508. In this document, it is demonstrated (Table 5) that the crude reaction mixture has a lower surface tension (25mN / m) than the pure glycine betaine amide (38 mN / m), making it possible to envisage its use in household detergents. This reaction mixture contains precisely 68% of laurylamide, 29% of ammonium salts of laurylamine and 3% of residual glycine betaine.
    By modifying the operating conditions described in WO 2013/188508 the inventors were able to obtain a surfactant composition enriched in glycine amide betaine and depleted in alkylammonium salts, which has been found to have a lower surface tension than the surfactant compositions described in this document and therefore suitable for many other applications.
    A similar composition, based on a mixture of laurylamide of glycine betaine and myristylamide of lauryl betaine was mentioned in document WO 2017/034793. However, the very general process presented in this document does not make it possible to obtain this composition, a fortiori in a reproducible manner, for lack of indication of the precise operating parameters used.
    The synthesis process used according to the invention is simple, effective, respectful of the environment, without solvent or polluting discharge, and easily transposable on an industrial scale to obtain in a reproducible manner a particularly effective surfactant composition.
    SUMMARY OF THE INVENTION
    The subject of the invention is a surfactant composition comprising:
    (a) from 70 to 85% by weight of one or more betaine glycine amide salt (s) of formula (1): X n [(CH3) 3N + -CH2-CONH-R] n where R is a linear saturated or unsaturated alkyl group comprising from 8 to 18 carbon atoms, it being understood that 40 to 100% by weight of the salts of formula (I) consist of the laurylamide salt of glycine betaine;
    (b) from 5 to 20% by weight of alkylammonium salt of formula (2): X n '[NH3 + R] n where R is a linear saturated or unsaturated alkyl group comprising from 8 to 18 carbon atoms, being understood that at least 40% by weight of the alkylammonium salts of formula (2) consist of laurylammonium salt;
    (c) from 5 to 10% by weight salt of betaine glycine ester of formula (3): X n [(CH3) 3 N + -CH 2 COOR '] n where R' is n-butyl, isobutyl or sec-butyl; and (d) from 0 to 5% by weight of glycine betaine of formula (4): (CH3) 3N + -CH2-COO '; or :
    X is an organic or inorganic anion and n is 1 or 2.
    It also relates to a process for the preparation of this surfactant composition, comprising the successive stages consisting in:
    (1) reacting betaine glycine or one of its salts with butanol, in the presence of an organic or inorganic acid, at a temperature of 100 to 160 ° C and under reduced pressure;
    (2) cooling the reaction medium to a temperature of 20 to 80 ° C;
    (3) adding one or more alkylamines containing from 8 to 18 carbon atoms, of which at least 40% by weight of laurylamine;
    (4) removing the residual butanol; and (5) recovering the surfactant composition thus obtained, characterized in that:
    - or step (1) is carried out under conditions making it possible to achieve a conversion rate of betaine glycine to betaine glycine ester salt of at least 95%, as measured by 1 H NMR and defined by the following equation:
    ^ XOGBOBu / / 2 η = Ί ---— i ----- T 'XOGB / -p ^ XOGBOBU / ^ XOGBOBu ΙχΟΰΒ + ^ XOGBOBU where:
    q is the conversion rate • L is the integration value of the signal characteristic of the compound i [(4.23 ppm, t, 2 H) for XOGBOBu, (4.28 ppm, s, 2 H) for XOGB when X = mesylate] • XOGBOBu denotes the salt of the glycine ester betaine formed • XOGB denotes the glycine salt betaine formed,
    - either the salt of the betaine glycine ester formed in step (1) is separated from the reaction medium between steps (2) and (3) and reacted with the alkylamine (s) in step (4).
    Another subject of the invention is the use of the above-mentioned surfactant composition as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances. It also relates to the use of this composition for the manufacture of plastics or of products intended:
    - the treatment and / or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle wash products, household products, industrial cleaning products, fiber sizing products and pesticides ;
    - water treatment;
    - oil extraction.
    It further relates to a product comprising the above-mentioned composition and at least one constituent chosen from: (a) anionic surfactants, nonionic surfactants and their mixtures and / or (b) antimicrobial agents.
    In addition to its low surface tension, the surfactant composition according to the invention has the advantage of being biodegradable (according to OECD standard 310), slightly toxic for the environment (according to OECD standards 201 and 202) and for humans , soluble in cold, stable whatever the pH and to present a good foaming power.
    DETAILED DESCRIPTION
    Surfactant composition
    The surfactant composition according to the invention comprises:
    (a) from 70 to 85% by weight of one or more betaine glycine amide salt (s) of formula (1): X n [(CH3) 3N + -CH2-CONH-R] n where R is a linear saturated or unsaturated alkyl group comprising from 8 to 18 carbon atoms, it being understood that 40 to 100% by weight of the salts of formula (I) consist of the laurylamide salt of glycine betaine;
    (b) from 5 to 20% by weight of alkylammonium salt of formula (2): X n [NH3 + R] n where R is a saturated or unsaturated linear alkyl group comprising from 8 to 18 carbon atoms, it being understood that at least 40% by weight of the alkylammonium salts of formula (2) consist of laurylammonium salt;
    (c) from 5 to 10% by weight of betaine glycine ester salt of formula (3): X n '[(CH3) 3N + -CH2COOR'] n where R 'is an n-butyl, isobutyl or sec-butyl; and (d) from 0 to 5% by weight of glycine betaine of formula (4): (CH3) 3N + -CH2-COO ';
    or :
    X is an organic or inorganic anion and n is 1 or 2.
    The group X can in particular be chosen from anions derived from organic or inorganic acids. It may in particular be a chloride, a sulfate, a perchlorate, an alkylsulfate ion, in particular decylsulfate or laurylsulfate, an arylsulfonate ion, especially benzene sulfonate, paratoluene sulfonate, camphosulfonate, an alkylsulfonate ion, in particular triflate, methanesulfonate, decylsulfonate, laurylsulfonate, of a sulfosuccinate ion, and mixtures thereof. It is preferred according to the invention that X is chosen from alkylsulfonates and arylsulfonates, in particular from methanesulfonate, triflate, paratoluenesulfonate and camphosulfonate ions. It is advantageously the methanesulfonate ion.
    It is moreover preferred that R 'denotes the n-butyl radical.
    Advantageously, the compounds of formula (1), (2), (3) and (4) represent in total from 90 to 100%, and preferably from 95 to 100% of the weight of the composition. Better still, the composition according to the invention exclusively comprises the compounds of formulas (1), (2), (3) and (4).
    Process
    The surfactant composition according to the invention can be prepared according to a process as described above.
    The first step in this process consists of an esterification reaction of betaine glycine, or trimethylglycine. The glycine betaine can be of vegetable or synthetic origin. It can optionally be in the form of a salt, for example an inorganic salt. It is generally necessary to protonate it beforehand using an organic or inorganic acid, insofar as it is in zwitterionic form (presence of a carboxylate function), except in the case where a glycine salt is used betaine. The acid can in particular be chosen from inorganic acids such as hydrochloric acid, sulfuric acid, perhalohydric acids, such as perchloric acid, and mixtures thereof. Alternatively, it can be chosen from organic acids, such as alkyl sulfuric acids, for example decyl or lauryl sulfuric acid; arylsulfonic acids, such as benzene sulfonic acid, paratoluene sulfonic acid, camphosulfonic acid; alkylsulfonic acids, such as triflic acid, methanesulfonic acid, decylsulfonic acid, laurylsulfonic acid; sulfosuccinic acid; and their mixtures. Lewis acids can also be used. Preferably, it is an alkylsulfonic acid and in particular methanesulfonic acid.
    During the actual esterification, the acid of betaine reacts with butanol in the presence of the acid, to lead to a glycine ester betaine in the form of salt. By butanol is meant in this description as well n-butanol, isobutanol and sec-butanol. Butanol is preferred for use in this invention. This reaction is generally carried out in the absence of any solvent, the butanol used constituting both the reagent and the medium. The water produced during the reaction also contributes to the solubilization of the glycine betaine in the reaction mixture.
    For the implementation of this step, it is possible to use from 1.1 to 20 equivalents, for example from 2 to 4 equivalents, of butanol and from 1.0 to 1.5 equivalents of sulfonic acid, for example from 1, 0 to 1.2 equivalent and preferably 1.1 equivalent of sulfonic acid, for 1 equivalent of glycine betaine. The esterification can be carried out at a temperature of 100 to 160 ° C, preferably from 120 to 150 ° C under atmospheric pressure or under reduced pressure. During this reaction, the equilibrium is shifted towards the formation of the reaction product by distillation of the water-butanol azeotrope, typically using a Dean-Starck arrangement.
    In a first variant of the invention, the conditions of the esterification are adjusted to reach a conversion rate of at least 95%. To do this, the reaction medium is placed under reduced pressure if it was not already. The distillation can for example be started after 2 to 4 hours of reaction time and continued for 2 to 4 hours before lowering the pressure, for example to a value of 500 to 900 mbar, in particular from 600 to 800 mbar. Unlike the methods for synthesizing glycine betaine amides, the rate of conversion of betaine glycine to the sulfonate salt of betaine glycine ester is followed by 1 H NMR and the reaction is continued until it reaches a value of at least 95%, that is to say for a duration ranging for example from 5 to 48 hours and preferably from 12 to 24 hours.
    Once this step is complete, and unlike the methods of the prior art, it is not useful to add to the reaction medium a strong and congested organic base, such as dibutylamine.
    The reaction medium is then cooled to a temperature of 20 to 80 ° C, preferably 40 to 80 ° C in the first variant described above.
    In a second variant of the process according to the invention, it is not necessary for the glycine betaine conversion rate to be at least 95% and it can be from 75 to 90% only, for example around 80 %, before the above-mentioned cooling step, which in this case will preferably be carried out up to a value of 20 to 40 ° C. In this second variant, the product of the esterification reaction is however treated so as to separate the salt of the glycine ester betaine formed from the reaction medium. To do this, it is possible, for example, to carry out a filtration of the reaction medium, which makes it possible to separate the abovementioned salified ester, soluble in butanol, from the other constituents which are not soluble.
    Then added either to the reaction medium (first variant), or to the isolated ester (second variant) one or more C8-C16 alkylamine (s) including at least 40% by weight of laurylamine. To do this, either laurylamine alone or a mixture of laurylamine with other alkylamines, obtained for example from coconut oil, can be used. Such a mixture typically contains from 40 to 60% by weight of laurylamine, from 15 to 22% by weight of myristylamine, from 5 to 12% by weight of palmitylamine, from 2 to 12% by weight of stearylamine, from 4 to 7% by weight of caprylamine and from 3 to 7% by weight of caprylylamine. The addition of alkylamine (s) is preferably carried out after removing part of the residual butanol and the traces of residual water by distillation under reduced pressure. In this step, the alkylamine is advantageously used in the molten form. The amount of alkylamine (s) added may for example represent from 0.9 to 1.5 equivalent and preferably from 1.0 to 1.2 equivalent per 1 equivalent of glycine betaine initially used. This aminolysis reaction is typically carried out at a temperature of 50 to 180 ° C and preferably from 120 to 140 ° C, under reduced pressure, for example under a pressure of 1 to 30 mbar.
    In parallel with the aminolysis reaction, the butanol is removed by distillation under reduced pressure. The aminolysis reaction and the distillation are carried out for a period of 1 to 7 hours, in particular from 3 to 5 hours.
    The surfactant composition thus obtained is then recovered.
    uses
    The surfactant composition according to the invention has a surface tension value less than 24 mN / m, or even less than 22 mN / m and generally more than 20 mN / m, measured according to standard NF EN 14370.
    It is thus possible to envisage its use in a variety of applications as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power of antimicrobial substances. It can in particular be used for the manufacture of plastics or of various products intended in particular:
    - treatment and / or cleaning of the body, plants, textiles or hard surfaces, in particular cosmetic products, such as shampoos, liquid soaps, bubble baths and shower gels; vehicle wash products such as cars, trucks, trains, buses or planes; household products such as detergents for windows, wall surfaces, floors or dishes; detergents or fabric softeners; industrial cleaning products; fiber sizing products; phytosanitary products; pigmented products such as paints or varnishes;
    - water treatment;
    - oil extraction.
    In the case where it is used in the cleaning of hard surfaces, such as windows or body surfaces, or even of textiles, it has in particular been observed that the composition according to the invention accelerates the subsequent drying of the surface without leave traces of lime on drying. In addition, when the surface is a vehicle, it has been observed that the cleaning of fine brake particles on the wheels is improved compared to conventional cationic surfactants. Finally, the effectiveness of the composition according to the invention in an alkaline medium makes it possible to avoid the drawbacks linked to the use of acid compositions, in particular their corrosive effect.
    In the case of water treatment, the composition according to the invention makes it possible to take off the biofilm without destroying the effectiveness of ion exchange resins, unlike conventional cationic surfactants which, moreover, have a non-negligible environmental impact taking into account their lack of biodegradability, or their slower biodegradability. This ability to take off biofilms can also be used in oil extraction processes.
    In cosmetic applications, the composition according to the invention is compatible with conventional anionic surfactants and makes it possible to improve the creamy character of the foam which they generate. It also protects iron aerosol devices against corrosion.
    In the manufacture of plastics, the composition according to the invention makes it possible to impart electrostatic properties to the surface of the plastic, without affecting its recycling capacities taking into account its bio-based nature.
    When used in the manufacture of phytosanitary products, the composition according to the invention makes it possible to improve the persistence of the active materials and the water resistance of the products such as herbicides, pesticides or agents modifying the growth of plants, which can be used in smaller quantities. This composition can thus be added, in diluted form to 25% in water, at a rate of 0.4% by weight, in a product containing a neutral or alkaline medium, for example.
    The composition according to the invention can also be used in a process for extracting, storing, storing or refining petroleum to limit corrosion of the equipment. In this application, it can be added to petroleum up to 500 to 1000 ppm, for example.
    A subject of the invention is also a product, for example chosen from those described above, comprising a composition according to the invention and at least one compound chosen from: anionic surfactants, nonionic surfactants, antimicrobial agents and their mixtures. Examples of anionic surfactants are: the sulfate salts of ethoxylated fatty alcohols, the sulfosuccinates, the sarcosinates, the alkyl- and dialkylphosphates, the fatty acid soaps and their mixtures. The nonionic surfactants can for example be chosen from: esters of fatty acids and of polyols such as esters of fatty acids and of glycerol optionally polyethoxylated, esters of fatty acids and of sorbitan optionally polyethoxylated, esters of fatty acids and polyoxyethylene, esters of fatty acids and sucrose such as sucrose stearate; fatty alcohol and polyoxyethylene ethers, fatty alcohol and sugar ethers, in particular alkylpolyglucosides (APG), polyether modified polysiloxanes, and mixtures thereof. The antimicrobial agents can be chosen from quaternary ammoniums, aldehydes (such as glutaraldehyde and formaldehyde), ethanol, halogenated derivatives, oxidants, phenolic compounds, parabens, isothiazolones (or isothiazolinones), benzoates, imidazoline, hydantoin, guanidine, organic acids such as lactic acid, and mixtures thereof.
    This product is advantageously in the form of an aqueous solution or an aqueous gel. Alternatively, it may be in the form of an oil-in-water or water-in-oil emulsion or even a paste. In any event, the aqueous phase contained in this product advantageously has a pH ranging from 1 to 12, in particular from 8 to 12 and preferably from 9 to 11. This product can be packaged in any device suitable for the intended use and in particular in a pump bottle, tube, jar, aerosol device or wipe.
    It advantageously contains from 0.1 to 25% by weight, for example from 1 to 10% by weight, of surfactant composition according to the invention.
    The product according to the invention can also comprise, in addition to the abovementioned antimicrobial agents and surfactants, and depending on the application envisaged, at least one ingredient chosen from: phytosanitary or cosmetic active agents, enzymes, chelating agents, thickeners , fatty substances (oils, waxes and / or pasty), fillers, preservatives, pigments and dyes, antioxidants, optical brighteners, and mixtures thereof.
    EXAMPLES
    The invention will be better understood in the light of the following examples, which are given purely by way of illustration and are not intended to limit the scope of the invention, defined by the appended claims.
    Example 1: Synthesis of a surfactant composition according to the invention (first variant)
    The glycine betaine (1.0 eq), the butanol (3.0 eq) and the 70% methanesulfonic acid solution (1.1 eq) are introduced into a reactor topped with a condenser. The mixture is heated to 140 ° C under atmospheric pressure. After 3 hours of reaction, a Dean-Stark filled with butanol is mounted on the reactor. The mixture is left under atmospheric pressure because the distillation of the water-butanol azeotrope is initially sufficiently large. After an additional 3 h of reaction, when the distillation speed of the water-butanol azeotrope decreases, the pressure is reduced to 700 mbar in order to accelerate the elimination of the water and allow the balance to shift towards butyl ester of glycine betaine. The conversion rate is followed by 1 H NMR analyzes.
    • The NMR method consists in performing an H spectrum of the sample dissolved in a CDCI3 / CD3OD mixture (1/1, v / v) using the methanol signal as a reference at 3.31 ppm. The characteristic signals of the various compounds are then integrated: MsOGBOBu (4.23 ppm, t, 2 H), MsOGB (4.28 ppm, s, 2 H), butanol (3.53 ppm, t, 2 H), methanesulfonate (2.74 ppm, s, 3 H), dibutyl ether (3.40 ppm, t, 4 H), where XOGBOBu denotes the sulfonate salt of the glycine ester betaine formed and XOGB denotes the glycine sulfonate betaine formed . The characteristic signal of methanesulfonate takes into account both the methanesulfonic acid present in the medium, but also methanesulfonate which is the counter ion of glycine betaine and butyl betainate mesylate (MsOGBOBu).
    The conversion rate of the reaction is obtained thanks to the integration values by the following calculation:
    'MsOGBOBuj η = -, ------- j— --- 1 MsOGB_ | _' MSOGBOBu / ^ ^ MsOGBOBu
    IMsOGB + / MsOGBOBU
    OR :
    • rj is the conversion rate • L is the integration value of the characteristic signal of compound i.
    Once the conversion rate of the esterification reaction reaches 98%, the reaction mixture is allowed to cool to 60 ° C. During this cooling phase, the Dean-Stark assembly is replaced by a distillation assembly and the reactor is placed under reduced pressure in order to remove part of the butanol and the traces of water remaining in the reaction mixture. Once the mixture at 60 ° C, laurylamine (1.1 eq) previously melted is added. The reaction mixture is then heated to 130 ° C under reduced pressure. The pressure is gradually reduced to 10 mbar. After the total distillation of the butanol (approximately 4 hours), the reaction mixture is recovered and constitutes the surfactant composition.
    The latter has the following mass composition:
    Component Molar mass(G / mol) % in weight Betainylaminododecane mesylate 380.588 77% Dodecylammonium mesylate 281.455 15% Butyl betainate mesylate 269.356 7% Wisteria betaine 117.148 1% butanol 74.120 0%
    The surface tension of this surfactant composition was measured at CMC, after adjusting the pH to 10 using sodium hydroxide.
    The surface tension measurement was carried out according to standard NF EN 14370, using a Krüss tensiometer with a platinum ring suspended horizontally. Before each measurement, the ring is thoroughly cleaned and flame dried. The sample cup is a conical PTFE container placed in a temperature-controlled enclosure at 25 ° C. The sample is prepared with Milli-Q water and continuously stirred with a magnetic bar before each measurement.
    The surface tension thus measured was 22 mN / m.
    Example 2: Synthesis of a surfactant composition according to the invention (second variant)
    The glycine betaine (1.0 eq) and the butanol (3.0 eq) are introduced into a reactor surmounted by a Dean-Starck filled with butanol. The mixture is heated to 140 ° C under a reduced pressure of 700 mbar. Once the temperature and pressure setpoints are reached, the 70% methanesulfonic acid solution is added to the mixture. The conversion rate is followed by 1 H NMR analyzes. Once the conversion rate of the esterification reaction reaches approximately 80%, the reaction mixture is allowed to return to ambient temperature and atmospheric pressure. The mixture is then filtered in order to separate the solid betaine glycine mesylate from the butyl betainate mesylate which is dissolved in butanol. The filtrate is introduced into a reactor surmounted by a distillation assembly. The laurylamine (0.9-1.5 eq) previously melted is added. The reaction mixture is then heated to 130 ° C under reduced pressure. The pressure is gradually reduced to 10 mbar. After the total distillation of the butanol (approximately 4 hours), the reaction mixture is recovered and constitutes the surfactant composition according to the invention.
    Example 3 Synthesis of a Comparative Surfactant Composition
    A surfactant composition was prepared in a similar manner to the method described in Example 1, except that the esterification conditions were adjusted so as to obtain a conversion rate of only 91%.
    To do this, glycine betaine (1.0 eq), butanol (3.0 eq) and the 70% methanesulfonic acid solution (1.1 eq) are introduced into a reactor topped with a filled Dean-Stark butanol. The mixture is heated to 140 ° C under atmospheric pressure. Despite an extended reaction time, the conversion rate does not exceed 91%.
    The reaction mixture is allowed to cool to 60 ° C. Once the mixture at 60 ° C, laurylamine (1.1 eq) previously melted is added. The reaction mixture is then heated to 130 ° C under reduced pressure. The pressure is gradually reduced to 10 mbar. After the total distillation of the butanol (approximately 4 hours), the reaction mixture is recovered and constitutes the surfactant composition.
    The mass composition of the surfactant thus obtained is as follows:
    Component Molar mass (g / mol) % in weight Betainylaminododecane mesylate 380.588 68% Dodecylammonium mesylate 281.455 23% Butyl betainate mesylate 269.356 6% Wisteria betaine 147,148 3% butanol 74.120 0%
    This composition therefore contains less laurylamide of glycine betaine and more laurylammonium salt than the composition according to the invention. This difference has a direct impact on the surface tension of this composition, which turns out to be higher than that of the surfactant composition according to the invention (25 mN / m at CMC).
    Example 4: Formulations
    Several types of products can be prepared using the surfactant composition according to the invention, hereinafter designated by GBA C12.
    Household detergentLactic acid 80%GBA C12 2.00%0.40% Hydroxyethyl cellulosechelating 0.30%0.20% Perfume 0.20% Dye 0.01% Deionized water qs 100.00%
    This product can be used for cleaning hard surfaces.
    Body shampoo
    GBA C12 3-5% Ethoxylated alcohol 0-5% Chelating agent * 5-10% Welded 0.5-2% Water qs 100%
    * Dissolvine® GL from AKZO NOBEL or Trilon® M from BASF
    This product can be applied to a vehicle and then, after an exposure time of 5 minutes, be rinsed under high pressure.
    Water treatment
    MEA (monoethanol amine) 5-10%
    GBA C12 20-25%
    Anti-deposition polymer 10-25%
    Water qs 100%
    权利要求:
    Claims (9)
    [1" id="c-fr-0001]
    1. Surfactant composition comprising:
    (a) from 70 to 85% by weight of one or more betaine glycine amide salt (s) of formula (1): X n '[(CH3) 3N + -CH2-CONH-R] n where R is a linear saturated or unsaturated alkyl group comprising from 8 to 18 carbon atoms, it being understood that 40 to 100% by weight of the salts of formula (I) consist of laurylamide salt of glycine betaine;
    (b) from 5 to 20% by weight of alkylammonium salt of formula (2): X n '[NH3 + R] n where R is a linear saturated or unsaturated alkyl group comprising from 8 to 18 carbon atoms, being understood that at least 40% by weight of the alkylammonium salts of formula (2) consist of laurylammonium salt;
    (c) from 5 to 10% by weight of betaine glycine ester salt of formula (3): X n '[(CH3) 3 N + -CHsCOOR'] n where R 'is an n-butyl, isobutyl radical or sec-butyl; and (d) from 0 to 5% by weight of glycine betaine of formula (4): (CH3) 3N + -CH2-COO ';
    or :
    X is an organic or inorganic anion and n is 1 or 2.
    2. Composition according to Claim 1, characterized in that the group X is chosen from anions obtained from organic or inorganic acids, consisting of a chloride, a sulfate, a perchlorate, an alkyl sulfate ion, in particular decylsulfate or laurylsulfate, of an arylsulfonate ion, in particular benzene sulfonate, paratoluene sulfonate, camphosulfonate, of an alkylsulfonate ion, in particular triflate, methanesulfonate, decylsulfonate, laurylsulfonate, of a sulfosuccinate ion, and their mixtures, preferably X chosen from alkylsulfonates and arylsulfonates, in particular from methanesulfonate, triflate, paratoluenesulfonate and camphosulfonate ions, more preferably X is the methanesulfonate ion.
    3. Composition according to claim 1 or 2, characterized in that the compounds of formula (1), (2), (3) and (4) represent in total from 90 to 100%, preferably from 95 to 100% of the weight of the composition, better, the composition comprises exclusively the compounds of formulas (1), (2), (3) and (4).
    4. Method for preparing the composition according to any one of claims 1 to 3, comprising the successive steps consisting in:
    1) reacting betaine glycine or one of its salts with butanol, in the presence of an organic or inorganic acid, at a temperature of 100 to 160 ° C and under reduced pressure;
    [2" id="c-fr-0002]
    (2) cooling the reaction medium to a temperature of 20 to 80 ° C;
    [3" id="c-fr-0003]
    3) add one or more alkylamines containing 8 to 18 carbon atoms, at least 40% by weight of laurylamine;
    [4" id="c-fr-0004]
    4) removing the residual butanol; and
    [5" id="c-fr-0005]
    5) recover the surfactant composition thus obtained, characterized in that:
    - or step (1) is carried out under conditions making it possible to achieve a conversion rate of betaine glycine to betaine glycine ester salt of at least 95%, as measured by 1 H NMR and defined by the following equation:
    ^ XOGBOBuI η = ------------—--- IxOGB4- IxOGBOBuj ^ XOGBOBu
    IxOGB + IxOGBOBU where:
    y is the conversion rate • L is the integration value of the signal characteristic of the compound i [(4.23 ppm, t, 2 H) for XOGBOBu, (4.28 ppm, s, 2 H) for XOGB when X = mesylate] • XOGBOBu denotes the salt of the betaine glycine ester formed • XOGB denotes the salt of betaine glycine ester formed,
    - either the salt of the betaine glycine ester formed in step (1) is separated from the reaction medium between steps (2) and (3) and reacted with the alkylamine (s) in step (4).
    5. Method according to claim 4, characterized in that the butanol is chosen from nbutanol, isobutanol and sec-butanol, preferably n-butanol.
    [0006]
    6. Method according to claim 4 or 5, characterized in that 1.1 to 20 equivalents of butanol are used, from 1.0 to 1.5 equivalents of sulfonic acid and from 0.9 to 1.5 equivalents of alkylamine, for 1 equivalent of glycine betaine.
    [0007]
    7. Use of the composition according to any one of claims 1 to 3 as a wetting agent, particle dispersant and / or corrosion inhibitor and / or for improving the disinfecting power and / or the persistence of the disinfecting effect of antimicrobial substances .
    [0008]
    8. Use of the composition according to any one of claims 1 to 3 for the manufacture of plastics or of products intended:
    - the treatment and / or cleaning of the body, plants or hard surfaces, in particular cosmetic products, vehicle washing products, household products, cleaning products
    10 industrial cleaning of fiber sizing products and phytosanitary products;
    - water treatment;
    - oil extraction.
    [0009]
    9. Product comprising the composition according to any one of claims 1 to 3 and at least one compound chosen from: anionic surfactants, nonionic surfactants, antimicrobial agents and mixtures thereof.
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3584303A1|2019-12-25|
    US20190380333A1|2019-12-19|
    BR102019012423A2|2019-12-17|
    JP2019218544A|2019-12-26|
    CA3045341A1|2019-12-19|
    US11224220B2|2022-01-18|
    FR3082522B1|2020-09-18|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    WO2005121291A1|2004-05-04|2005-12-22|Eiffage Travaux Publics|Surfactant composition method for production thereof and cosmetic comprising said composition|
    US20130338227A1|2012-06-13|2013-12-19|Marie-Esther Saint Victor|Green Glycine Betaine Derivative Compounds And Compositions Containing Same|
    US10604724B2|2015-08-27|2020-03-31|S. C. Johnson & Son, Inc.|Cleaning gel with glycine betaine amide/nonionic surfactant mixture|CN111663143A|2020-07-02|2020-09-15|重庆电力高等专科学校|Acid-washing compound corrosion inhibitor for thermal equipment and preparation method thereof|
    FR3112688A1|2020-07-22|2022-01-28|Surfactgreen|Use of a glycine betaine derivative as a pediculicidal agent|
    FR3112946A1|2020-07-31|2022-02-04|Surfactgreen|Use of a cosmetic composition containing a glycine betaine derivative for protecting the skin against external aggressions|
    法律状态:
    2019-06-18| PLFP| Fee payment|Year of fee payment: 2 |
    2019-12-20| PLSC| Publication of the preliminary search report|Effective date: 20191220 |
    2020-06-08| PLFP| Fee payment|Year of fee payment: 3 |
    2021-06-18| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1855359A|FR3082522B1|2018-06-19|2018-06-19|SURFACTORY COMPOSITION BASED ON BETAINE GLYCINE AMIDE SALT, ITS PREPARATION PROCESS AND ITS USES|
    FR1855359|2018-06-19|FR1855359A| FR3082522B1|2018-06-19|2018-06-19|SURFACTORY COMPOSITION BASED ON BETAINE GLYCINE AMIDE SALT, ITS PREPARATION PROCESS AND ITS USES|
    CA3045341A| CA3045341A1|2018-06-19|2019-06-05|Tensioactive composition based on glycine betaine amide salts, its preparation process and use|
    EP19179511.1A| EP3584303A1|2018-06-19|2019-06-11|Surfactant composition made of amide salts of glycine betaine, method for preparing same and uses thereof|
    BR102019012423A| BR102019012423A2|2018-06-19|2019-06-17|surfactant composition based on betaine glycine amide salts, preparation process and uses thereof|
    JP2019112829A| JP2019218544A|2018-06-19|2019-06-18|Surfactant composition based on glycine betaine amide salts, process for preparing the same and uses thereof|
    US16/445,441| US11224220B2|2018-06-19|2019-06-19|Surfactant composition based on glycine betaine amide salts, process for preparing same and uses thereof|
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