Process for producing ester amines and salts thereof using orthoesters as catalysts

Abstract

Methods for producing ester amines and salts thereof using orthoesters as catalysts, ester amines, salts thereof, uses and compositions thereof, in particular cleaning compositions comprising such ester amines and / or salts thereof.

Description

[0001] The use of ortho esters in the synthesis of amino acid esters is described in the literature; however, in all the literature, the ortho ester is used in stoichiometric amounts relative to the amino acid. Additionally, in all those literature, the alkyl residue in the formed amino acid ester is the same as the alkyl residue in the used ortho ester.

[0002] For example, US 7205433 / WO 2004018407 (priority date 23.08.2002) describes alanine methyl or ethyl ester as alkyl sulfonate, which is obtained from alanine, methanol or ethanol, an alkyl sulfonic acid and a stoichiometric amount of trimethyl or triethyl ortho ester.

[0003] WO 2005 / 110986 uses a stoichiometric amount of trimethyl orthoformate to obtain allyl glycine methyl ester from allyl glycine and methanol and hydrochloric acid.

[0004] The present invention relates to a process for the synthesis of amino acid esters and their acid salts using at least one ortho ester in sub-stoichiometric amounts, preferably catalytic amounts. The present invention further relates to the amino acid esters and their salts obtainable by such process.

[0005] The ester amines and their salts obtainable or obtained by the process according to the present invention can be used in specific compositions, such as detergents, cleaning and / or fabric and home care compositions / formulations.

[0006] When used for example in cleaning compositions, the ester amines and their salts obtainable or obtained by the process according to the present invention show good biodegradable properties.

[0007] Due to climate change, one of the most important goals of the detergent and cleaning (D&C) industry nowadays is to significantly reduce the CO2 emissions per wash by improving for example cold water conditions (by improving the cleaning efficiency at low temperatures below 40, 30 or 20 or even lower) thus reducing the amount of chemicals used per wash, increasing the weight efficiency of the cleaning technology, introducing biologically derived components, etc. Therefore, one important goal of the D&C industry is the demand for biodegradable ingredients to improve the sustainability of cleaning formulations (and especially laundry and dish wash formulations) and to avoid the accumulation of non-degradable compounds in the ecosystem. Therefore, there is a need to provide compounds which are biodegradable and still have at least the same performance as known but non-biodegradable compounds, such as biodegradation measured under prescribed conditions within 28 days is required by many users, especially in the detergent field, and is a future requirement by applicable legislation in several countries and regions of the world.

[0008] The reduction of such CO2 emissions or the improvement of the "footprint" of any product, either in its origin like from natural or renewable resources, or in its production efficiency and thus reduced energy use, its use efficiency such as reduced amount for the same performance or increased performance for the same use level, its persistence in the natural environment when and / or after its use, such as biodegradability, is of high and even further rising interest in industry as well as for consumers.

[0009] Furthermore, there is a need to improve the process of producing such ester amines and salts thereof with an improved process using less starting materials and reducing the need for purification steps to reduce the overall use of compounds and energy and thus also the carbon footprint of such a process.

[0010] As a result of these trends, there is a need for an improved process to produce ester amines and salts thereof, as detailed in the present invention, providing at least comparable clean properties and reduction of the CO2 footprint, not only by the properties of the produced compounds, but also by the products of producing such compounds.

[0011] This goal is achieved by the present invention as described hereinafter and as reflected in the claims.

[0012] definition

[0013] Throughout this specification and the annexed claims, unless the context requires otherwise, the word "comprise," and variations such as "comprises" and "comprising," will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The term "comprising" as used herein can be replaced by the term "containing" or "including" or sometimes by the term "having" when used herein.

[0014] "Consisting of" when used in the context of the present invention excludes any element, step, or ingredient not specified in the claim. "Consisting essentially of" when used in the context of the present invention does not exclude materials or steps not specified in the claim which do not materially affect the basic and novel characteristics of the claimed invention.

[0015] In each case herein, any of the terms "comprising", "consisting essentially of and "consisting of can be replaced by any of the other two terms. In preferred embodiments, "comprising" can be replaced by "consisting essentially of and in even more preferred embodiments, both can be replaced by "consisting of.

[0016] The compositions of the present disclosure can "comprise" the components of the present disclosure (i.e. contain other ingredients), "consist essentially of the components of the present disclosure (contain primarily or almost exclusively the recited ingredients and only very small amounts of other ingredients as impurities), or "consist of the components of the present disclosure (i.e. contain only the recited ingredients and can contain only impurities which are unavoidable in the technical environment, preferably only these ingredients).

[0017] Similarly, the term "substantially free of or "substantially free from" or "substantially not (containing / comprising)" can be used herein; this means that the indicated material is present in very small amounts which are not intentionally added to the composition to form part thereof, or, preferably, not at analytically detectable levels. It is meant to include compositions in which the indicated material is present only as an impurity in one of the other materials which is intentionally included. If at all, the indicated material can be present at a level of less than 1% by weight of the composition, or even less than 0.1%, or even far less than 0.01%, or even 0%.

[0018] In particular, the term "water-free" means that the composition contains no more than 5 wt.-% of water based on the total amount of solvent, in another embodiment no more than 1 wt.-% of water based on the total amount of solvent, in a further embodiment the solvent contains no water at all.

[0019] Generally, as used herein, the term "available through..." means that the corresponding product is not necessarily produced (i.e., obtained) by the corresponding method or process described in the corresponding particular context, but includes a product exhibiting all the characteristics of a product produced (obtained) by said corresponding method or process, wherein said product is not actually produced (obtained) by such method or process. However, the term "available through..." also includes the more restrictive term "obtained through...", namely, a product actually produced (obtained) by the method or process described in the corresponding particular context.

[0020] When used herein in any definition requiring a compound or its substituents to consist of “at least a plurality of carbon atoms,” the number of carbon atoms refers to the total number of carbon atoms in the compound or its substituents. For example, for a substituent disclosed as “an alkyl ether having at least eight carbon atoms comprising an alkylene oxide group,” the total number of at least eight carbon atoms needs to be the sum of the number of carbon atoms in the alkyl moiety and the number of carbon atoms in the alkylene oxide moiety.

[0021] All such terms that are not specifically defined have their general meaning as known in the field of organic chemistry.

[0022] The term "containing one hydroxyl group" means that only one -OH group is present. Any functionalized group derived from the hydroxyl group, such as an ether group, is not considered a -OH group.

[0023] The term "containing at least two hydroxyl groups" means the presence of two or more -OH groups. The term "hydroxyl group" is equivalent to the term "hydroxyl group" or "-OH group". Therefore, alcohols / compounds having only one hydroxyl group (such as methanol or ethanol) do not fall within the definition of an alcohol containing at least two hydroxyl groups according to compound (A) of the present invention. Any functionalized group derived from a hydroxyl group, such as an ether group, is not considered a -OH group.

[0024] As used herein, when used in the claims or embodiments, the articles “a” and “an” should be understood to mean one or more of the claimed or described. As used herein, the terms “include” and “including” are non-limiting and therefore cover more than the specific entries mentioned after these words.

[0025] The term "about" as used herein encompasses the recited exact value "X", e.g. "about X%", etc., as well as small variations of X, including deviations of -5% to +5% from X (for this calculation X is set to 100%), preferably -2% to +2%, more preferably -1% to +1%, even more preferably -0,5% to +0,5% and smaller variations. Of course, if the given value X is "100%" itself already (as for purity, etc.), the term "about" obviously can and thus only means a deviation of less than "100".

[0026] All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. All measurements herein are made at 20 °C and at atmospheric pressure, unless otherwise specified. In all examples of the present disclosure, all percentages are by weight of the total composition, unless specifically stated otherwise. All ratios are weight ratios, unless specifically stated otherwise.

[0027] The phrase "fabric care composition" means to include compositions and formulations designed for treating fabrics. Such compositions include, but are not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment, ironing aids, unit dose formulations, delayed delivery formulations, porous substrates or nonwoven sheets containing or impregnated with a detergent, and other suitable forms as can be apparent to those skilled in the art in view of the teachings herein and detailed below in describing the compositions. Such compositions can be used as a prewash treatment, postwash treatment, or can be added during the rinse or wash cycle of a laundering operation, and are further detailed below in describing the present invention and the use and application of compositions containing such ester amines and salts thereof.

[0028] "Sulfonate" in the present invention is an anion derived from a sulfonic acid, preferably an alkane sulfonic acid and / or an aryl sulfonic acid, more preferably an alkane sulfonic acid, most preferably methanesulfonic acid; such acid is used to at least partially protonate the ester amine, thereby forming a sulfonate salt of the ester amine.

[0029] Throughout the present specification, the term "inventive compound" can be used instead of "inventive esteramine(s) and / or their salt(s)" and "esteramine(s) and / or their salt(s) of this (present) invention", meaning that these compounds are as defined herein as disclosed by the present invention, by their structure and / or by their method of production or obtainable by the methods defined herein. DETAILED DESCRIPTION

[0030] The definitions given before in the "definitions" - section and preferences thereof are included as part of the present invention as described herein below.

[0031] The present invention encompasses the specific embodiments as described throughout the present disclosure as part of the present invention; the various further options are disclosed in the present specification as "optional", "preferred", "more preferred", "even more preferred" or "most preferred" (or "preferably" and the like), the options of the specific embodiments can be selected individually and independently (unless such independent selection is not possible due to the nature of the feature or if such independent selection is explicitly excluded) and then combined with any other embodiment (wherein also the other such options and preferences can be selected individually and independently, unless such independent selection is not possible due to the nature of the feature or if such independent selection is explicitly excluded), wherein each and any and all such possible combinations are included as part of the present invention as a separate embodiment.

[0032] Methods for producing ester amines and their salts

[0033] It was surprisingly found that the esterification of amino acids can be improved by using sub-stoichiometric and even catalytic amounts of ortho esters.

[0034] Additionally and surprisingly, esteramines can be produced, wherein the ester is derived from another alcohol than the alcohol present in the ortho ester used as catalyst.

[0035] Thus, the present invention relates to an improved method for the production of amino acid esters and salts thereof using sub-stoichiometric or even catalytic amounts of ortho esters.

[0036] Thus, the present invention relates to a method for the production of esteramines or salts thereof using catalytic amounts of at least one ortho ester, the method comprising the steps of

[0037] a) reacting

[0038] i) at least one amino acid selected from the group consisting of a-, b-, g-, d-, e-, etc. amino acids, such as alanine, glycine, leucine, isoleucine, valine, proline, phenylalanine, arginine, asparagine, aspartic acid, aspartate, glutamine, glutamic acid, histidine, lysine, threonine, tryptophan, tyrosine, cysteine, methionine; a- amino acids having a secondary or tertiary amino group, such as sarcosine, N,N- dimethylglycine; other amino acids, such as 6-aminohexanoic acid, 4-aminobutyric acid, 3- aminopropanoic acid, 12-aminododecanoic acid, 11-aminoundecanoic acid; amino acids formally derived from the hydrolysis of a- lactams (three ring atoms), b- lactams (four ring atoms), g- lactams (five ring atoms), etc.; such lactams are preferably b-propiolactam, g-butyrolactam, d-valerolactam, g-valerolactam, e-caprolactam, d-decalactam, g-decalactam, e-decalactam; preferably alanine, valine, b-alanine, 6-aminohexanoic acid;

[0039] with

[0040] ii) at least one alcohol with at least one hydroxyl group selected from the group consisting of mono-, di- and polyols, all of which can optionally be alkoxylated, wherein the alkoxylating of the at least one hydroxyl group takes place in a step prior to step a), wherein the alcohol is alkoxylated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles of alkylene oxide per hydroxyl group;

[0041] in the presence of

[0042] iii) at least one acid (C) selected from the group consisting of inorganic acids and organic acids, wherein the organic or inorganic acid preferably has a pKa value in the range of -3 and up to +5, more preferably -2,5 to 1,5, preferably at least one organic acid (such as a sulfonic acid), more preferably an alkane sulfonic acid and / or an aryl sulfonic acid, more preferably an alkane sulfonic acid, most preferably methanesulfonic acid;

[0043] and

[0044] iv) in the presence of at least one ortho ester, such as triethyl orthoformate, trimethyl orthoformate, triethyl orthoacetate, trimethyl orthoacetate, etc.;

[0045] wherein the ortho ester is used in substoichiometric amounts, preferably catalytic amounts (relative to the amount of amino acid)

[0046] and

[0047] wherein the alcohol used for esterification is different from the alcohol residue in the ortho ester;

[0048] to produce an amino acid ester salt;

[0049] b) optionally removing water and / or excess alcohol during and / or after the reaction to obtain a purified amino ester salt;

[0050] c) optionally neutralizing the obtained amino acid ester salt with at least one base to obtain a free amino acid ester.

[0051] Further method steps can be included in the method of the present application:

[0052] The reaction mixture can be inertized before and / or during the reaction, preferably before the addition of acid C.

[0053] Inertization can be achieved by a steam of a gas, such as nitrogen or argon and / or by adding an oxygen scavenging compound.

[0054] Such oxygen scavenging compounds are known. It is advantageous to use small amounts of inorganic salts with reducing properties towards oxygen, such as hypophosphorous compounds, such as hypophosphorous acid or any salt thereof, especially any alkali metal or ammonium or alkaline earth metal salt, more preferably the acid, which can be added to the reaction mixture before the addition of sulfuric acid.

[0055] As one of the effects, this addition of an oxygen scavenging compound leads to an improved color of the resulting product, i.e. meaning a reduced coloration, when compared to omitting such an addition.

[0056] The reaction is carried out under the following conditions

[0057] - at a temperature from 50 °C to 200 °C, preferably 70 °C - 180 °C, more preferably 80 °C - 160 °C, most preferably 120 °C - 150 °C, such as 60 °C, 65 °C, 75 °C, 85 °C, 90 °C, 95 °C, 100 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 155 °C, 165 °C, 170 °C, 190 °C;

[0058] - for a period of time from 1 to 30, preferably from 2, more preferably from 3 hours, even more preferably at least 5 hours, and preferably up to 48, more preferably up to 20, even more preferably up to 15 hours, such as preferably 3 to 24, more preferably 5 to 24, most preferably 10 - 24 hours; and

[0059] - at a pressure from 0,001 to 10 bar, such as from 0,001, more preferably from 0,005, even more preferably from 0,1, and preferably up to 8, more preferably up to 5, even more preferably up to 4 bar, such as 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 bar, or such as 1 to 1000 mbar, more preferably 100 to 500 mbar.

[0060] Preferably, the temperature, duration, and pressure are defined individually as previously, preferably a preferred range for all three parameters is selected, more preferably a more preferred range for all three parameters is selected, etc.

[0061] In one embodiment of the invention, the temperature remains constant throughout the duration of the reaction. In another embodiment, the temperature varies within a temperature range during the duration of the reaction.

[0062] In one embodiment of the invention, the reaction with acid C is carried out at atmospheric pressure. In another embodiment, the reaction with acid C is carried out in a closed container at a pressure from 0.001 to 1 bar. In yet another embodiment, the reaction with acid C is carried out in a closed container at a pressure greater than 1 to 10 bar.

[0063] In one embodiment, a protective atmosphere of an inert gas such as nitrogen or argon is used to carry out the reaction.

[0064] In another embodiment, inertization is carried out by adding an oxygen scavenger, preferably a small amount of an inorganic salt with reducing properties to oxygen, such as hypophosphoric acid, such as hypophosphoric acid or any salt thereof, especially any alkali metal or ammonium or alkaline earth metal salt, more preferably a hypophosphoric acid compound, more preferably hypophosphoric acid.

[0065] In another embodiment, inertization is performed by adding an oxygen scavenger as previously defined and using a protective atmosphere of an inert gas as previously defined.

[0066] Clearly, temperature, pressure, and duration can be selected and combined with each other independently of the disclosed values ​​and ranges. Similarly, inertization can be implemented in a manner that combines it with the selected temperature, duration, and pressure, all as previously defined.

[0067] During or after the reaction, preferably at least during the reaction, water and / or excess alcohol can be removed. The removal of water and alcohol can be carried out by all techniques known in the art, such as by applying a gas stream and / or applying a distillation method, preferably distillation, more preferably distillation under reduced pressure and / or at elevated temperatures, preferably both, with the preferred method being the use of equipment such as a Dean-Stark-trap.

[0068] In another embodiment, a gas stream is used to remove water and / or alcohol, such as using an inert gas like nitrogen or argon, preferably nitrogen, or steam made from water, preferably an inert gas, more preferably nitrogen.

[0069] In a more preferred embodiment, water and / or alcohol are removed by applying a vacuum and / or increasing the temperature, most preferably using a device such as a Dean-Stark water separator.

[0070] Optionally, water and / or excess alcohol can be removed, more preferably by applying a vacuum in the range of 0.1 mbar to 800 mbar, preferably 1 mbar to 500 mbar, and more preferably 10 mbar to 100 mbar, and using an elevated temperature.

[0071] In a preferred embodiment, during the reaction, vapors of an inert gas (such as nitrogen or argon, preferably nitrogen) are passed through the reaction mixture. This helps to keep the reaction mixture inert and also supports the removal of water formed during the chemical reaction, and thus controls the amount of water present.

[0072] The molar ratio of the amino acid to the hydroxyl group of the (optionally alkoxylated) alcohol is

[0073] (0.8 * n): 1 to (1 * n): 1.5, wherein the number of hydroxyl groups of the (optionally alkoxylated) alcohol is n.

[0074] In one embodiment, the method is carried out with a molar ratio of acid C to amino acid ranging from 0.8:1 to 1.2:1.

[0075] Suitable solvents for the reaction can be toluene, xylene, heptanol, cyclohexene, etc., and preferably, the reaction is carried out in the absence of a solvent.

[0076] In a preferred embodiment, the reaction is carried out at the beginning and for most of the reaction, more preferably from the beginning to substantially the completion of the reaction, in the presence of the least possible amount of water, preferably substantially no water, and most preferably no water.

[0077] Obviously, such amino acids are known and can generally be prepared from natural sources. Others can be produced from natural sources by modifying them to obtain amino acids as starting materials for this invention. If such modification does result in the addition of carbon atoms, for example by a chemical addition reaction, and if such an addition reaction uses non-fossil carbon atoms, then the amino acid contains only non-fossil carbon. Therefore, it is preferred that only naturally occurring amino acids and / or naturally derived amino acids are used in this invention (not prepared by adding non-fossil carbon to structural units to obtain such naturally derived amino acids). Even more preferably, only naturally occurring amino acids are used.

[0078] The same applies to lactams: whenever lactams are available from natural sources, such natural or naturally derived lactams are preferred; naturally occurring lactams are even more preferred to increase the total content of non-fossil carbon.

[0079] at least one alcohol with at least one hydroxyl group selected from mono-, di- and polyhydric alcohols, all of which can optionally be alkoxylated, wherein the alkoxylating of the at least one hydroxyl group occurs in a step prior to step a), wherein the alcohol is alkoxylated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles of alkylene oxide per hydroxyl group, and in one embodiment, even more preferably up to 20, such as up to 15 or even up to 10 moles of alkylene oxide per hydroxyl group;

[0080] Alcohols containing one hydroxyl group are well known in the art. Similarly, alcohols containing at least two hydroxyl groups according to compound (A) are known to the person skilled in the art. As mentioned above, the respective alcohol can contain one, two, three, four, five or even more hydroxyl groups within the respective molecule / compound. The respective alcohol can contain linear, branched and / or cyclic alkyl fragments. In addition thereto, the respective alcohol can also contain aromatic fragments as well as combinations of alkyl and aromatic fragments (“aralkyl” fragments). Furthermore, the respective alcohol can also contain alkyl ether fragments. Examples of alcohols according to compound (A) are glycerol, pentaerythritol, sorbitol, 1,1,1-trimethylolpropane (TMP), erythritol or alkoxylated alcohols such as polyethylene glycol.

[0081] Many alcohols according to compound (A) of the present application are commercially available, for example from BASF SE under the trade name “Pluronic(s)” or “Pluriol” (for example as polyethylene glycol block (co)polymers).

[0082] The alcohol (A) for the esteramine of the present application and the process of the present application as described herein is selected from

[0083] (Aa) monoalcohols such as Ci- to C36-alkanols selected from the group of non-alkoxylated linear C2- to C36-alcohols, such as mixtures of C6- to C22-fatty alcohols, preferably C8- to C22-fatty alcohols, more preferably C12- and C14-fatty alcohols, most preferably C16- and C18-fatty alcohols; non-alkoxylated branched C3- to C36-alcohols, such as 2-ethylhexanol, 2-propylheptanol, isotridecanol, isononyl alcohol, C9-C17 oxoalcohols;

[0084] alkoxylated linear C2- to C36-alcohols, such as alkoxylated mixtures of C6- to C22-fatty alcohols, preferably alkoxylated mixtures of C8- to C22-fatty alcohols, more preferably alkoxylated mixtures of C12- and C14-fatty alcohols, most preferably alkoxylated mixtures of C16- and C18-fatty alcohols;

[0085] alkoxylated branched C3- to C36-alcohols, such as alkoxylated 2-ethylhexanol, alkoxylated 2-propylheptanol, alkoxylated isotridecanol, alkoxylated isononyl alcohol, alkoxylated C9-C17 carbonyl synthesis alcohol;

[0086] (Ab) diols such as alkane diols, polyalkoxylated C2-C6-alkanediols with at least two hydroxyl groups,

[0087] (Ac) oligomeric alcohols with at least three hydroxyl groups, such as sugar alcohols, polyalkoxylated sugar alcohols, C3-C6-alkanetriols, polyalkoxylated C3-C6-alkanetriols,

[0088] (Ad) polyols, such as C5-C6-alkane polyols, polyalkoxylated C5-C6-alkane polyols, polyether alcohols such as polyglycerol or di- or tri-pentaerythritol, alkoxylated polyether alcohols such as alkoxylated polyglycerol, alkoxylated di- or tri-pentaerythritol,

[0089] (Ae) phenoxyalkanols, such as phenoxyethanol;

[0090] wherein the one or more alcohols selected from the group of monoalcohols and alkoxylated diols, oligomeric alcohols and alkoxylated polyols are preferred, and alcohols selected from the group of monoalcohols and alkoxylated diols are even more preferred.

[0091] In one embodiment of the present application, at least one linear or branched C2- to C 36 -alcohol containing at least one hydroxyl group is used.

[0092] In a preferred embodiment thereof, at least one C8- to C 22 -fatty alcohol containing at least one hydroxyl group is used.

[0093] In a more preferred embodiment thereof, a mixture of C 16 - and C 18 -fatty alcohols each containing at least one hydroxyl group is used.

[0094] In another more preferred embodiment thereof, a mixture of C 18 - and C 22 -fatty alcohols each containing at least one hydroxyl group is used.

[0095] In another more preferred embodiment thereof, at least one branched C9 to C 17 -alcohol is used.

[0096] In a further more preferred embodiment thereof, a linear or branched C8- to C 10 -monoalcohol containing at least one hydroxyl group is used.

[0097] In a further even more preferred embodiment thereof, 2-propylheptanol or 2- ethylhexanol is used.

[0098] In a further even more preferred embodiment thereof, 2-propylheptanol or 2- ethylhexanol is used.

[0099] In a further preferred embodiment of the present application, at least one phenoxyalkanol is used. In a further more preferred embodiment, phenoxyethanol is used.

[0100] It is apparent that such alcohols are known, many of which are from natural sources. Others can be produced starting from natural sources by modifying them. If such modification does indeed result in the addition of carbon atoms, for example by chemical addition reactions. And if such addition reactions use non-fossil carbon atoms, the alcohol contains only non-fossil based carbon. It is therefore preferred that only naturally occurring and / or naturally derived alcohols (not prepared by adding non-fossil carbon in the structural unit to obtain such naturally derived alcohols) are employed in the present application. Even more preferably, only naturally occurring alcohols are employed.

[0101] In a more preferred embodiment, the ester amine used in the present application and the alcohol (A) of the process of the present application is an alkoxylated alcohol. Such alkoxylated alcohols are typically and thus preferably obtained by alkoxylating at least one hydroxyl group of an alcohol as defined herein before with one or more alkylene oxides to yield an alkyleneoxy chain comprising one or more moieties derived from an alkylene oxide selected from C2 to C22-alkylene oxides, preferably C2-C4-alkylene oxides, wherein the moieties derived from the one or more alkylene oxides can be arranged in a random, block or multi-block sequence or a combination thereof, preferably as a block.

[0102] In one embodiment of the present application, alkyl alcohols alkoxylated with only a single alkylene oxide are used. In a further embodiment, alkyl alcohols alkoxylated with a first alkylene oxide, followed by an alkoxylating with a second alkylene oxide, thereby forming a block structure of different alkylene oxide blocks are used.

[0103] It is also preferred in the context of the present application that in case the compound (A) comprises an alkoxylated alcohol comprising an alkoxylated segment based on at least one C2-C22alkylene oxide, preferably C2-C4-alkylene oxide, more preferably ethylene oxide and / or propylene oxide, most preferably the respective alcohol comprises at least one block based on ethylene oxide and / or propylene oxide, and even more preferably contains only one block consisting of ethylene oxide or consists of two blocks, wherein the first block - preferably the "inner block" directly connected to the hydroxyl group of the alcohol - consists of ethylene oxide and the second block - preferably the "outer block" connected to the ethylene oxide block - consists of propylene oxide.

[0104] More preferably, the EO-block comprises 3 to 10 EO-derived moieties and the PO-block comprises 1 to 10 PO-derived moieties.

[0105] Most preferably, only ethylene oxide is employed.

[0106] The alkoxylation of the alcohol can be achieved by an alkoxylation reaction with only one alkylene oxide or with more than one alkylene oxide. If more than one alkylene oxide is used, the resulting alkyl ether alcohol comprises a random distribution of alkylene oxide units, or a block of one alkylene oxide followed by a block of another alkylene oxide, or a block of one alkylene oxide followed by another block comprising two or more alkylene oxides arranged in a random order, or a block comprising two or more alkylene oxides followed by another block comprising two or more alkylene oxides, wherein each such block differs in its relative amount of alkylene oxides, its arrangement of alkylene oxides, and / or the identity of the alkylene oxides, such that the two blocks connected to each other differ in their chemical composition and / or arrangement; any combination of such arrangements is in principle possible and thus encompassed by the present invention.

[0107] In one embodiment of the present invention, an alkyl alcohol is used that is alkoxylated with only a single alkylene oxide. In a further embodiment, an alkyl alcohol is used that is alkoxylated with a first alkylene oxide followed by an alkoxylization with a second alkylene oxide, thereby forming an alkyl alcohol of a block structure of different alkylene oxide blocks.

[0108] It is clear that when switching from one block to the next block there can be - depending on how the alkoxylation reaction proceeds - a relatively small "zone" between the blocks, which zone is identical on each molecule of the alkoxylated monoalkanol between the blocks does not have a clear "boundary", such that there can be some "dirty" structures, which means that some very small amount (like a single or possibly two or three) of the first type of alkylene oxide employed can have been inserted only after one or more of the second alkylene oxides have reacted; this depends mainly on the conversion achieved by the first alkylation reaction at the point in time when the second alkylene oxide is added, i.e. whether there is still some unreacted amount of the first alkylene oxide at that time when the second alkylene oxide is added.

[0109] Similarly, it is clear that due to the statistical nature of the alkoxylation polymerization, the block length can vary slightly from one compound to the next, and thus the "alkoxylated monoalkanol" is in fact a mixture of compounds with slightly different chain lengths and block lengths.

[0110] The alkoxylation reaction can generally be carried out in the presence of a catalyst at a reaction temperature of from about 70 °C to about 200 °C, in a further embodiment from about 80 °C to about 160 °C. The reaction can be carried out at a pressure of up to about 10 bar, in a further embodiment at a pressure of up to about 8 bar.

[0111] Examples of suitable catalysts include basic catalysts such as alkali and earth alkali hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular C1-C4-alkoxides of sodium and potassium such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali and earth alkali hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. In one embodiment, an alkali hydroxide is used. In another embodiment, potassium hydroxide and sodium hydroxide are used. Based on the alcohol and C2- to C4-alkylene oxide, the typical amount of base used is 0.01 to 10 % by weight, in particular 0.05 to 2 % by weight. 22 The typical amount of base used is 0.01 to 10 % by weight, in particular 0.05 to 2 % by weight, based on the total amount of alkylene oxide, preferably C2-C4-alkylene oxide.

[0112] It is noted that the alkylene oxides used for the preparation of one or more alkoxylated alcohols can be derived from fossil or non-fossil carbon sources or even mixtures thereof. Preferably, the amount of non-fossil carbon atoms in the alkylene oxides employed is at least 10 %, at least 20 %, at least 40 %, at least 70 %, at least 95 % and most preferably up to 100 % based on the non-fossil derived carbon atoms; this equally applies to the compounds of the present invention as such. The skilled person is well aware of commercial alkylene oxide products made from non-fossil carbon sources which are frequently sold as “sustainable”, “renewable” or “bio-based”. For example, Croda International, Snaith, UK, sells ethylene oxide as well as related products based on bio-ethanol as the “ECO” series. Additionally, processes for the preparation of bio-based propylene oxide are known (see Abraham, D. S., “Production of propylene oxide from propylene glycol” Master’s Thesis University of Missouri-Columbia (2007) (75 pages)).

[0113] The acid (C) used in the esteramines and salts thereof of the present invention and the process of the present invention is selected from

[0114] i) sulfonic acids, such as alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, camphorsulfonic acid; alkylarylsulfonic acids, and in particular alkylbenzenesulfonic acids, such as toluenesulfonic acid (including mixtures of isomers thereof), p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, xylene sulfonic acid (mixture of isomers), 2,6-xylenesulfonic acid, 2,5-xylenesulfonic acid, 2,4-xylenesulfonic acid, 4-dodecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, ethylbenzenesulfonic acid and naphthalenesulfonic acid,

[0115] and

[0116] ii) inorganic acids, such as hydrochloric acid, hydrobromic acid, phosphoric acid.

[0117] The acid employed for the concentration is preferably chosen such that the amount of water introduced into the reaction is minimized or employed as a solid. Likewise, a gas such as hydrogen chloride can also be employed, as this can be introduced as a gas.

[0118] In one embodiment of the esteramine for use in the present application and the process of the present application, the acid is preferably selected from group i), more preferably p-toluenesulfonic acid and / or methanesulfonic acid, most preferably methanesulfonic acid.

[0119] In case an amount of water is introduced into the reaction via the acid introduction, the water can be removed using known means such as distillation procedures and equipment (such as Dean-Stark traps etc.) prior to the introduction of the orthoester.

[0120] The esteramine is obtained as a salt of at least partial protonation in cationic form.

[0121] In a preferred embodiment, methanesulfonic acid is employed as concentrated methanesulfonic acid. In another preferred embodiment, methanesulfonic acid is used as a methanesulfonic acid solution in water of about 70 wt.-% or as a "pure" acid, e.g. typically close to 100 wt.% purity (equal to "about 100 wt.%"); however, any concentration in between can also be employed. In a further preferred embodiment, methanesulfonic acid is used as a methanesulfonic acid solution in water of about 70 wt.-%. However, in the most preferred embodiment, the sulfonic acid such as methanesulfonic acid is introduced as a solid, even more preferably as a dry solid (to reduce the amount of water introduced into the reaction).

[0122] In one embodiment of the present application, the total amount of acid (C) is added at the beginning of the reaction. In another embodiment, the acid is added dropwise over a certain period of time, provided that the acid (C) is always present during the reaction.

[0123] The present application can also provide the amino acid ester of the present application and salts thereof starting from natural amino acids and / or natural alcohols and thus enable the provision of products with a high content of biologically derived materials. Since the alkylene oxide(s) can also be derived from non-fossil sources, the compounds of the present application can only contain carbon atoms from non-fossil sources. Such products are highly sought after by consumers and the industry.

[0124] use

[0125] Another subject of the present application is the use of the above-mentioned esteramine and salts thereof (as disclosed via its structure or via the production process) in cleaning compositions.

[0126] The esteramine and salts thereof can be added to a cleaning composition.

[0127] The esteramine and / or salts thereof are present in the formulation in a concentration of 0.1 to 5 wt.-%, preferably in a concentration of 0.5 to 2 wt.-%.

[0128] The esteramine and salts thereof of the present application can also be added to a cleaning composition comprising from about 1% to about 70% by weight of a surfactant system. The esteramine and / or salts thereof of the present application can be present in the cleaning composition in a concentration of from about 0.1% to about 5% by weight of the composition, or in a concentration of from about 0.5% to about 2% by weight of the composition.

[0129] Therefore, another subject matter of the present application is the use of the esteramine and salts thereof of the present application and / or obtained or obtainable by the process of the present application and / or as previously detailed for improved oily and fatty stain removal, removal of solid soils such as clay, prevention of graying of fabric surfaces, and / or anti-soil agents in fabric and home care products, in particular cleaning compositions, wherein the cleaning composition is preferably a laundry detergent formulation and / or a dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid manual dishwashing detergent formulation.

[0130] Therefore, another subject matter of the present application is also a cleaning composition, fabric and home care product, industrial and institutional cleaning product, preferably in laundry detergents, in cleaning compositions, and / or in fabric and home care products, each comprising at least one esteramine or salt thereof as defined above or obtained or obtainable by the process of the present application and / or as detailed herein.

[0131] A further subject matter of the present application is a fabric and home care product, cleaning composition, industrial and institutional cleaning product, preferably a laundry detergent, cleaning composition, and / or fabric and home care product, each containing at least one esteramine or salt thereof of the present application and / or as described above.

[0132] In a preferred embodiment, it is a cleaning composition and / or fabric and home care product and / or industrial and institutional cleaning product, comprising at least one esteramine or salt thereof as defined above. In particular, it is a cleaning composition, preferably a laundry detergent formulation and / or a manual dishwashing detergent formulation, more preferably a liquid laundry detergent formulation and / or a liquid manual dishwashing detergent formulation, for improved cleaning performance, in particular improved primary wash.

[0133] In a preferred embodiment, the cleaning composition of the present application is a liquid or solid laundry detergent composition, preferably a liquid laundry detergent composition.

[0134] In another preferred embodiment, the cleaning composition of the present application is a liquid or solid (e.g. powder or tablet / single dose) detergent composition for manual or automatic dishwashing, preferably a liquid manual dishwashing detergent composition. Such compositions are known to the person skilled in the art.

[0135] In another embodiment, the cleaning composition of the present application is a hard surface cleaning composition which can be used for cleaning various surfaces such as hardwood, tile, ceramic, plastic, leather, metal, glass.

[0136] In one embodiment of the present application, the esteramine or salt thereof of the present application is a component of a cleaning composition or fabric and home care product, preferably a component of a laundry cleaning composition, laundry care product or laundry treatment product or laundry washing product, preferably a component of a liquid laundry detergent formulation or liquid laundry detergent product, each additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0137] In one embodiment, it is also preferred in the present application that the cleaning composition additionally comprises (in addition to at least one esteramine or salt thereof as described above) at least one enzyme, preferably selected from one or more lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase, pectatelyase, cutinase, deoxyribonuclease, xylanase, oxicoreductase, dispersin, mannanase and peroxidase, and combinations of at least two of the aforementioned types, preferably at least one enzyme is selected from lipase.

[0138] Even more preferably, the cleaning compositions of the present application comprising at least one esteramine or salt of the present application and optionally further comprising at least one surfactant or surfactant system - as detailed previously - are those for improved cleaning performance in laundry and manual dishwash applications, even more specifically for improved cleaning performance (as such effects are detailed previously) on fabrics and dishware, and can additionally comprise at least one enzyme selected from the list consisting of: optionally further comprising at least one enzyme, preferably selected from one or more lipase, hydrolase, amylase, protease, cellulase, hemicellulase, phospholipase, esterase, pectinase, lactase, pectatelyase, cutinase, deoxyribonuclease, xylanase, oxidoreductase, dispersase, mannanase, and peroxidase, and combinations of at least two of the foregoing types, preferably selected from one or more lipase, hydrolase, amylase, protease, cellulase, and combinations of at least two of the foregoing types, more preferably at least one enzyme is selected from lipase.

[0139] In one embodiment, the esteramine or salt thereof of the present application can be used in a cleaning composition comprising a surfactant system comprising C10-C15 alkyl benzene sulfonate (LAS) as the primary surfactant and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0140] In a further embodiment, the esteramine or salt thereof of the present application can be used in a cleaning composition or fabric and home care product, preferably a laundry cleaning composition, laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising as the primary surfactant a C12-C18 alkyl ethoxylate surfactant having 5-10 ethoxy units and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other nonionic surfactants, or mixtures thereof.

[0141] In a further embodiment, the esteramine or salt thereof of the present application can be used in a cleaning composition or fabric and home care product, preferably a laundry cleaning composition, laundry care product or laundry treatment product or laundry washing product, preferably a liquid laundry detergent formulation or liquid laundry detergent product, comprising as the primary surfactant a C8-C18 linear or branched alkyl ether sulfate having 1-5 ethoxy units and one or more additional surfactants selected from nonionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

[0142] In one embodiment of the present application, the esteramine or salt thereof is a component of a cleaning composition, such as preferably a laundry or dishwashing formulation, more preferably a liquid laundry or manual dishwashing formulation, each additionally comprising at least one surfactant, preferably at least one anionic surfactant.

[0143] In a further embodiment, the present application also encompasses a composition comprising at least one esteramine or salt thereof as described herein before, further comprising an antimicrobial agent as disclosed hereinafter (preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1% to 2% phenoxyethanol.

[0144] In a further embodiment, the present application also encompasses a composition, preferably a cleaning composition, more preferably a liquid laundry detergent composition or a liquid manual dish composition, even more preferably a liquid laundry detergent composition, or a liquid softener composition for use in laundry, such composition comprising an esteramine or salt thereof as described herein before in the amounts detailed before, such composition further comprising 4,4'-dichloro 2-hydroxydiphenyl ether in a concentration of from 0.001% to 3%, preferably from 0.002% to 1%, more preferably from 0.01% to 0.6% each by weight of the composition.

[0145] In a further embodiment, the present application also encompasses a composition, especially a cleaning composition, more preferably a cleaning composition in the form of a liquid, solid or semi-solid, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid hand dishwash detergent formulation or a solid automatic dishwashing formulation, more preferably a laundry detergent formulation, comprising an esteramine or salt thereof as described herein before and in the amounts detailed before, preferably a detergent composition, such composition further comprising an antimicrobial agent as disclosed hereinafter (the antimicrobial agent preferably selected from the group consisting of 2-phenoxyethanol), more preferably comprising said antimicrobial agent in an amount ranging from 2 ppm to 5% by weight of the composition; even more preferably comprising 0.1% to 2% phenoxyethanol.

[0146] In further embodiments, the present application also encompasses a method of preserving an aqueous composition, especially a cleaning composition, more preferably a cleaning composition in liquid, solid or semi-solid form, preferably a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid hand dishwash detergent formulation or a solid automatic dishwash formulation, more preferably a laundry detergent formulation, comprising an esteramine or salt thereof as herein before described and in an amount as herein before detailed, preferably a detergent composition, against microbial contamination or growth, comprising adding at least one antimicrobial agent selected from the disclosed antimicrobial agents disclosed below, preferably the antimicrobial agent is 2-phenoxyethanol.

[0147] In further embodiments, the present application also encompasses a method of washing fabrics or cleaning hard surfaces, the method comprising treating a fabric or hard surface with a cleaning composition, more preferably a liquid laundry detergent composition or a liquid hand dishwash composition, even more preferably a liquid laundry detergent composition or a liquid fabric softener composition for use in laundry, the composition comprising an esteramine or salt thereof in an amount as herein before detailed, the composition further comprising 4,4'-dichloro 2-hydroxy diphenyl ether.

[0148] As used herein, the phrase "cleaning composition" as used in connection with the compositions and products of the present application includes compositions and formulations designed for cleaning soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewash, laundry pretreat, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatment, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms as can be apparent to those skilled in the art in light of the teachings herein. Such compositions can be used as a pre-wash treatment, a post-wash treatment, or can be added during the rinse or wash cycle of a washing operation. The cleaning composition can have a form selected from the group consisting of a liquid, a powder, a single or multi-phase unit dose, a pouch, a tablet, a gel, a paste, a bar, or a flake.

[0149] The cleaning compositions of the present application comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of a surfactant system, by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of a surfactant system, by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of a surfactant system, by weight of the composition. The surfactant system can comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. One of ordinary skill in the art will appreciate that detersive surfactants encompass any surfactant or mixture of surfactants that provide a cleaning, stain removal, or washing benefit to soiled material.

[0150] Even more preferably, the compositions or products of the present application as detailed previously herein, comprising at least one estamine of the present application and / or salts thereof, obtained or obtainable from the process of the present application as detailed herein and in the amounts specified in the previous paragraphs, optionally further comprising at least one surfactant or surfactant system in an amount of from about 1% to about 70% by weight of the composition or product, preferably those useful for primary cleaning (i.e. stain removal) and more preferably within laundry applications, and can additionally comprise at least one enzyme selected from the group consisting of lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersase, pectinase, oxidoreductase, cutinase, lactase, and peroxidase, more preferably at least two of the foregoing types.

[0151] The phrase "cleaning composition" as used herein includes compositions and formulations and products designed for cleaning soiled material. Such compositions, formulations, and products include those designed for cleaning any kind of soiled material or soiled surface.

[0152] Compositions for "industrial and institutional cleaning" include such cleaning compositions designed for use in industrial and institutional cleaning, such as cleaning compositions for cleaning any kind of soiled material or surface, such as hard surface cleaners for any kind of surface, including tile, carpet, PVC-surfaces, wooden surfaces, metal surfaces, painted surfaces.

[0153] "Compositions for fabric and home care" include cleaning compositions, including but not limited to laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric freshening compositions, laundry pre-washes, laundry pre-treats, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, wash additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, single dose formulations, delayed delivery formulations, detergents contained on or in porous substrates or nonwoven sheets, and other suitable forms that can be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used as a pre-wash treatment, a post-wash treatment, or can be added during the rinse or wash cycle of a washing operation, preferably during the wash cycle of a laundry or dishwashing operation.

[0154] Cleaning compositions, such as fabric and home care products and formulations for industrial and institutional cleaning, more specifically laundry detergents and hand dishwashing detergents, are known to the person skilled in the art. Any composition etc. known to the person skilled in the art (in conjunction with the respective use) can be used in the context of the present application by comprising at least one compound of the present application, preferably at least one such compound of the present application, in an amount suitable for exhibiting a certain property within such composition, especially when such composition is used in its field of use.

[0155] The cleaning compositions of the present application can be in any form, i.e. in the form of a liquid; a solid, such as a powder, a granulate, an agglomerate, a paste, a tablet, a pouch, a stick, a gel; an emulsion; of the type delivered in a dual- or multi-compartment container; a single- or multi-phase unit dose; a spray or foam detergent; a pre-moistened wipe (i.e. a cleaning composition in combination with a nonwoven material, such as the cleaning compositions discussed in US 6,121,165, Mackey et al.); a dry wipe (i.e. a cleaning composition in combination with a nonwoven material, such as the cleaning compositions discussed in US 5,980,931, Fowler et al.) which is activated with water by the user or consumer; and other homogeneous, heterogeneous or single- or multi-phase cleaning product forms.

[0156] The liquid cleaning compositions of the present application preferably have a viscosity of 50 to 10000 mPa*s; liquid hand dish cleaning compositions (also liquid hand "dishwashing compositions") have a viscosity of preferably 100 to 10000 mPa*s, more preferably 200 to 5000 mPa*s and most preferably 500 to 3000 mPa*s at 20 1 / s and 20°C; liquid laundry cleaning compositions have a viscosity of preferably 50 to 3000 mPa*s, more preferably 100 to 1500 mPa*s and most preferably 200 to 1000 mPa*s at 20 1 / s and 20°C.

[0157] The cleaning compositions and formulations of the present application can, and preferably do, contain adjunct cleaning additives (also abbreviated herein as "adjuncts"), such adjuncts being preferably in addition to the surfactant system as defined previously.

[0158] Suitable adjunct cleaning additives include builders, co-builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil removal agents, dispersants such as polymeric dispersants, polymeric grease cleaning agents, solubilizing agents, chelating agents, enzymes, enzyme stabilizers, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibitors, chelating agents, sudsing agents, suds inhibitors (antifoams), color speckle, silver care, anti-tarnish and / or anti-corrosion agents, alkalinity sources, pH adjusting agents, pH buffering agents, hydrotropes, detersive particles, antibacterial agents, antioxidants, softening agents, carriers, processing aids, pro-perfumes and perfumes. All such adjuncts are known in principle and are further detailed and exemplified below.

[0159] The liquid cleaning compositions can additionally, and preferably do, contain at least one of a rheology control agent / modifier, emollients, humectants, skin- brightening actives and solvents.

[0160] The solid compositions can additionally, and preferably do, contain at least one of fillers, bleaching agents, bleach activators and catalytic materials.

[0161] Suitable examples of such cleaning adjuncts and levels of use are found in WO 99 / 05242, U.S. Patent Nos. 5,576,282, 6,306,812 Bl and 6,326,348 Bl.

[0162] The liquid cleaning compositions of the present application can have any suitable pH. Preferably, the pH of the composition is adjusted to between 4 and 14. More preferably, the composition has a pH of 6 to 13, even more preferably 6 to 10, most preferably 7 to 9. The pH of the composition can be adjusted using pH modifying ingredients known in the art and measured at 10% product concentration in demineralized water at 25°C. For example, NaOH can be used and the actual wt% of NaOH can be varied and adjusted to the desired pH, such as pH 8.0. In one embodiment of the present application, the pH is adjusted to > 7 by using amines, preferably alkanolamines, more preferably triethanolamine.

[0163] It will be understood by one of ordinary skill in the art that detersive surfactant encompasses any surfactant or mixture of surfactants that provides a cleaning, stain removal, or washing benefit to a soiled material.

[0164] Accordingly, the cleaning compositions of the present application, such as fabric and home care products, as well as formulations for industrial and institutional cleaning, more specifically laundry detergents and hand dishwashing detergents, preferably additionally comprise a surfactant system, and more preferably further comprise additional adjuncts, such as the adjuncts described in more detail above and below.

[0165] The surfactant system can consist of one surfactant or of a combination of surfactants selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof. It will be understood by one of ordinary skill in the art that surfactant system for a detergent encompasses any surfactant or mixture of surfactants that provides a cleaning, stain removal, or washing benefit to a soiled material.

[0166] The cleaning compositions of the present application preferably comprise a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% of a surfactant system, by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% of a surfactant system, by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% of a surfactant system, by weight of the composition. The surfactant system can comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, and mixtures thereof.

[0167] In addition to all other mentioned ingredients, the liquid formulation of the present application can and preferably does comprise 0% to 2%, preferably about 1% of 2-phenoxyethanol.

[0168] In addition to all other mentioned ingredients, the liquid formulation can and preferably does comprise 0% - 0,2%, preferably about 0,15% of 4,4'-dichloro-2-hydroxydiphenyl ether. In addition to all other mentioned ingredients, the solid laundry composition without bleach can comprise 0% - 0,2%, preferably about 0,15% of 4,4'-dichloro-2-hydroxydiphenyl ether.

[0169] The formulations of the present application can and preferably do comprise one or more enzymes selected from those disclosed hereinbefore, more preferably proteases and / or amylases, wherein even more preferably the protease is a protease having at least 90% sequence identity to SEQ ID NO: 22 of EP 1921147 B1 and having the amino acid substitution R101E (numbering according to BPN), and wherein the amylase is an amylase having at least 90% sequence identity to SEQ ID NO: 54 of WO 2021032881 A1, such enzymes preferably being present in the formulations at a level of from about 0.00001% to about 5%, preferably from about 0.00001% to about 2%, more preferably from about 0.0001% to about 1%, or even more preferably from about 0.001% to about 0.5%, enzyme protein by weight of the composition.

[0170] It is preferred that the at least one esteramine and / or salt thereof as described in the present application is present in the respective laundry detergent, cleaning composition and / or fabric and home care product at a concentration of from about 0.1% to about 20%, preferably from about 0.2% to 5%, more preferably from about 0.5% to about 5%, relative to the total weight of such composition or product, relative to the total weight of such composition or product.

[0171] All such cleaning compositions, their ingredients (including (auxiliary) cleaning additives), their general compositions and more specific compositions are known, as for example shown in WO 2022 / 136409 and WO 2022 / 136408, wherein in either of the aforementioned prior art documents, the general compositions disclosed in the aforementioned publications and also the esteramines and their salts within each individualized specific cleaning composition can be partially or completely replaced by the esteramines and / or salts thereof of the present application. In those aforementioned documents, various types of formulations for cleaning compositions are also disclosed; all such composition types - general compositions and also each individualized specific cleaning composition - can likewise be applied to those cleaning compositions envisaged herein.

[0172] Therefore, in addition to or as an alternative to any of the prior art compositions already existing containing an esteramine or esteramine salt or any such compound which can be replaced by such an esteramine or salt of the present invention - such alternatives being known to the person skilled in the art - the present invention also encompasses any and all such compositions disclosed in any and all of the prior art disclosures mentioned before, preferably those in the previous paragraph, but further comprising at least one of the esteramines and / or salts thereof of the present invention, wherein the content of the esteramine or salt thereof of the present invention is present in the formulation in a concentration of typically 0,05 wt.% to 20 wt.%, preferably up to 10 wt.%, more preferably 0.1 wt.% to 5 wt.%, even more preferably in a concentration of 0.5 wt.% to 2 wt.%, all relative to the total weight of such composition or product and all numbers in between and including all ranges resulting from combining any of the lower limit values mentioned and further including 0.2, 0.3, 0.4, 1, 1,5, 2, 2.5, 3, 3.5 and 4 with any of the upper limit values mentioned and further including 19, 18, 17, 16, 14, 13, 12, 11, 9, 8, 7 and 6.

[0173] The present invention encompasses the specific embodiments as described throughout the present disclosure as part of the present invention; the various further options disclosed in the present specification as “optional”, “preferred”, “more preferred”, “even more preferred” or “most preferred” options of specific embodiments can be selected individually and independently (unless such independent selection is not possible due to the nature of the feature or if such independent selection is explicitly excluded) and then combined within any other embodiment (wherein other such options and preferences can also be selected individually and independently), wherein each and any and all such possible combinations are included as part of the present invention as separate embodiments.

[0174] Experimental Section

[0175] Method

[0176] 1 H NMR was measured in MeOD with a Bruker Avance 400 MHz spectrometer.

[0177] pH was measured in a 10% aqueous solution.

[0178] Hydroxyl number was measured according to DIN 53240-1.

[0179] The molecular weight of a polyalkylene oxide (e.g. polyethylene glycol) is calculated from the measured hydroxyl number by the following formula:

[0180] Molecular weight [g / mol] = 1000 / (hydroxyl value [mgKOH / g] / 56.11) × per hydroxyl molecule

[0181] (E = Example of the present invention; CE = Comparative example)

[0182]

[0183] 2-EH: 2-Ethylhexanol

[0184] 2-PH: 2-Propylheptanol

[0185] Lutensol XP30: 2-propylheptanol with an average of 3 EO / OH ethoxylated.

[0186] Example 1: L-valine-2-propylheptyl ether ester as a methanesulfonate catalyzed by 0.02 equivalents of triethyl orthoformate.

[0187] In a four-necked container equipped with a thermometer, a Dean-Stark water separator with a reflux condenser, a nitrogen inlet, a dropping funnel, and a stirrer, 237.5 g of 2-propylheptanol, 0.9 g of hypophosphite (50% in water), 117.1 g of L-valine, and 2.9 g of triethyl orthoformate were placed. 99.0 g of methanesulfonic acid was added over 15 minutes. During the addition, the temperature was increased from room temperature to 47°C. The reaction mixture was heated to a bath temperature of 135°C under a constant nitrogen flow through the reaction mixture via bubbling. Water was distilled off the reaction mixture using a Dean-Stark water separator. The mixture was stirred for 3.5 hours, and the sample was analyzed by 1H-NMR in MeOD (results shown in the table). The mixture was stirred for another 5 hours, and a sample was taken for 1H-NMR in MeOD (results shown in the table). For the esterified CH2-OH group, the conversion to ester was inferred by the multivariate integral from 4.1 to 4.2 ppm in 1H-NMR in MeOD.

[0188] Other instances were synthesized in a similar manner using the ingredients and conditions listed in the previous table, with the results also given in that table.

Claims

1. A process for the production of an ester amine or a salt thereof using a catalytic amount of at least one orthoester, which process comprises the steps of a) a reaction of i) at least one amino acid selected from the group of a-, b-, g-, d-, e-amino acids, such as alanine, glycine, leucine, isoleucine, valine, proline, phenylalanine, arginine, asparagine, aspartic acid, aspartate, glutamine, glutamic acid, histidine, lysine, threonine, tryptophan, tyrosine, cysteine, methionine, serine; a-amino acids with secondary or tertiary amino groups, such as sarcosine, N,N-dimethylglycine; other amino acids, such as 6-aminohexanoic acid, 4-aminobutyric acid, 3-aminopropanoic acid, 12-aminododecanoic acid, 11-aminoundecanoic acid; amino acids formally derived from the hydrolysis of a-lactams (three ring atoms), b-lactams (four ring atoms), g-lactams (five ring atoms), etc.; such lactams are preferably b-propiolactam, g-butyrolactam, d-valerolactam, g-valerolactam, e-caprolactam, d-decanolactam, g-decanolactam, e-decanolactam; preferably alanine, valine, b-alanine, 6-aminohexanoic acid; with ii) at least one alcohol (A) carrying at least one hydroxyl group selected from the group of mono-, di- and polyols, all of which can optionally be alkoxylated, wherein the alkoxylating of the at least one hydroxyl group takes place in a step prior to step a), wherein the alcohol is alkoxylated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles of alkylene oxide per hydroxyl group; in the presence of iii) at least one acid (C) selected from the group of mineral and organic acids, wherein the organic or mineral acid preferably has a pKa value in the range of -3 and up to +5, more preferably -2,5 to 1,5, preferably at least one organic acid, such as sulfonic acid, more preferably alkane sulfonic acid and / or aryl sulfonic acid; and iv) in the presence of at least one orthoester, such as triethylorthoformate, trimethylorthoformate, triethylorthoacetate, trimethylorthoacetate, etc.; the orthoester is used in substoichiometric amounts, preferably in catalytic amounts (relative to the amino acid); and wherein the alcohol used for esterification is different from the alcohol residue in the orthoester; to produce an amino acid ester salt; b) optionally neutralizing the obtained amino acid ester salt with at least one base to obtain the free amino acid ester. The alcohol (A) is selected from (Aa) mono alcohols such as Ci- to C36-alkanols selected from the group of non-alkoxylated straight-chain C2- to C36-alcohols, such as mixtures of such alcohols selected from C6- to C22-fatty alcohols, preferably C8- to C22-fatty alcohols, more preferably C12- and C14-fatty alcohols, most preferably C16- and C18-fatty alcohols; non-alkoxylated branched-chain C3- to C36-alcohols, such as 2-ethylhexanol, 2-propylheptanol, isotridecanol, isononyl alcohol, C9-C17 carbonyl synthesis alcohols; ​ ​ ​ ​ ​ ​ wherein ​ ​ ​ ​ ​ 2. The method of claim 1, wherein, ​ ​ alkoxylated linear C2- to C36-alcohols, such as alkoxylated mixtures of C6- to C22-fatty alcohols, preferably of C8- to C22-fatty alcohols, more preferably of C12- and C14-fatty alcohols, most preferably of C16- and C18-fatty alcohols; alkoxylated branched C3- to C36-alcohols, such as alkoxylated 2-ethylhexanol, alkoxylated 2-propylheptanol, alkoxylated isotridecanol, alkoxylated isononyl alcohol, alkoxylated C9-C17 carbonyl synthesis alcohol; (Ab) diols such as alkane diols, polyalkoxylated C2-C6-alkanediols with at least two hydroxyl groups, (Ac) oligomeric alcohols with at least three hydroxyl groups, such as polyalkoxylated C3-C6-alkanetriols, (Ad) polyols, such as sugar alcohols, polyalkoxylated C5-C6-alkane polyols, glycerol such as diglycerol, triglycerol, polyglycerol, di- and tri-pentaerythritol; and / or (Ae) phenoxy alcohols, such as phenoxyethanol; wherein the one or more alcohols selected from the group of mono- and alkoxylated diols, oligomeric alcohols and alkoxylated polyols are preferred, and the alcohols selected from the group of mono- and alkoxylated diols are even more preferred.

3. The method according to any of the preceding claims, wherein, The alcohol (A) employed is an alkoxylated alcohol, which is obtained by alkoxylating at least one hydroxyl group of the alcohol according to claim 2 with one or more alkylene oxides to yield alkyleneoxy chains, which comprise one or more moieties derived from alkylene oxides selected from C2 to C22-alkylene oxides, preferably C2-C4-alkylene oxides, wherein the moieties derived from the one or more alkylene oxides can be arranged in a random, block or multi-block sequence or a combination thereof, preferably as a block, more preferably containing only one block consisting of ethylene oxide or consisting of two blocks, wherein the first block - preferably the "inner block” directly connected to the hydroxyl group of the alcohol - consists of ethylene oxide and the second block - preferably the "outer block” connected to the ethylene oxide block - consists of propylene oxide, such a di-block even more preferably consisting of 3 to 10 EO-derived moieties and the PO-block consisting of 1 to 10 PO-derived moieties.

4. The method according to any of the preceding claims, wherein, The acid (C) is selected from i) alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, camphorsulfonic acid; alkylarylsulfonic acids, and in particular alkylbenzenesulfonic acids, such as toluenesulfonic acid (including mixtures of isomers thereof), p-toluenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, xylene sulfonic acid (mixture of isomers), 2,6-dimethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 2,4-dimethylbenzenesulfonic acid, 4-dodecylbenzenesulfonic acid, isopropylbenzenesulfonic acid, ethylbenzenesulfonic acid and naphthalenesulfonic acid, preferably p-toluenesulfonic acid and methanesulfonic acid, more preferably methanesulfonic acid; ii) inorganic acids, such as hydrochloric acid, hydrobromic acid, phosphoric acid; preferably selected from group i).

5. The method according to any one of the preceding claims, wherein, The acid (C) is chosen such that the esteramine is obtained as a salt in cationic form, preferably the acid chosen is methanesulfonic acid and the esteramine obtained is a salt in cationic form.

6. The method according to any one of the preceding claims, wherein, The molar ratio of amino acid to hydroxyl group of the (optionally alkoxylated) alcohol is (0.8 * n) : 1 to (1 * n) :

1. 1.5, wherein the number of hydroxyl groups of the (optionally alkoxylated) alcohol is n.

7. The method according to any one of the preceding claims, wherein, The process is carried out with a molar ratio of the acid (C) to the amino acid in the range of 0.8 : 1 to 1 : 1.

2.

8. The method of any of the preceding claims, wherein, In the process, the reaction is carried out - at a temperature of from 50 °C to 200 °C, preferably 70 °C - 180 °C, more preferably 80 °C - 160 °C, most preferably 120 °C - 150 °C, such as 60 °C, 65 °C, 75 °C, 85 °C, 90 °C, 95 °C, 100 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 155 °C, 165 °C, 170 °C, 190 °C; - for a period of from 1 to 30, preferably from 2, more preferably from 3 hours, even more preferably at least 5 hours, and preferably up to 48, more preferably up to 20, even more preferably up to 15 hours, such as preferably 3 to 24, more preferably 5 to 24, most preferably 10 - 24 hours; and - at a pressure of from 0,001 to 10 bar, such as from 0,001, more preferably from 0,005, even more preferably from 0,1, and preferably up to 8, more preferably up to 5, even more preferably up to 4 bar, such as 1 to 10, more preferably 1 to 5, even more preferably 1 to 4 bar, or such as 1 to 1000 mbar, more preferably 100 to 500 mbar.

9. The method of any of the preceding claims, wherein, In the process, the solvent used for the reaction is selected from water, toluene, xylene, heptanol, cyclohexene and the like, preferably only water.

10. The method of any of the preceding claims, wherein, During or after the reaction, preferably at least during the reaction, water and / or excess alcohol is removed, such removal is preferably carried out by applying a gas stream, such as using a gas, such as an inert gas, such as nitrogen or argon, preferably nitrogen, or steam made from water, preferably using an inert gas, more preferably nitrogen, and / or applying a distillation process, preferably distillation, more preferably a distillation process under reduced pressure and / or at elevated temperature, preferably both, the more preferred process is using a device, such as a Dean-Stark apparatus, most preferably using a Dean-Stark apparatus, such removal is more preferably carried out by applying a vacuum in the range of 0.1 mbar to 800 mbar, preferably 1 mbar to 500 mbar and more preferably 10 mbar to 100 mbar and using an elevated temperature.

11. The method of any of the preceding claims, wherein, The amount of orthoester in the resulting product is 10% relative to the esteramine salt obtained by such process.

12. Use of an esteramine or a salt thereof obtained or obtainable by the process according to any one of claims 1 to 11 in a composition, which composition is a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product, preferably in liquid or semi-liquid form, more preferably in liquid form.

13. Use according to claim 12, wherein, The composition comprises at least one esteramine and / or at least one salt thereof in a concentration of from about 0.1 % to about 5 % by weight, relative to the total weight of such composition or product, Preferably, the composition further fulfils at least one of the following requirements: a. comprises at least one enzyme, b. comprises from about 1 % to about 70% by weight of a surfactant system, c. comprises an effective amount of at least one further cleaning adjuvant, and d. exhibits improved wash performance, preferably in primary cleaning.

14. A composition, which is a cleaning composition or a fabric and home care product, preferably a cleaning composition, more preferably a laundry detergent or a dishwashing detergent, containing at least one esteramine and / or a salt thereof obtained or obtainable by the method according to any one of claims 1 to 11, the composition comprising the at least one esteramine and / or at least one salt thereof in a concentration preferably from about 0.1 % to about 5% by weight relative to the total weight of such composition or product, and optionally further comprising at least one of a) to c) a. at least one enzyme, preferably selected from one or more of lipase, hydrolase, amylase, protease, cellulase, mannanase, hemicellulase, phospholipase, esterase, xylanase, deoxyribonuclease, dispersase, pectinase, oxidoreductase, cutinase, lactase and peroxidase, more preferably at least two of the foregoing types, b. from about 1 % to about 70% by weight of a surfactant system, c. an effective amount of at least one further cleaning adjuvant, and optionally exhibits improved wash performance in primary cleaning, preferably in liquid or semi-liquid form, more preferably is a concentrated liquid detergent formulation, a single single-dose laundry detergent formulation, a liquid manual dishwashing detergent formulation, even more preferably a liquid laundry detergent formulation or a liquid manual dishwashing detergent formulation, optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2 ppm to 5%, more preferably from 0.1 % to 2%, by weight of the composition, and optionally comprising 4,4’-dichloro2-hydroxydiphenyl ether in a concentration of from 0.001 % to 3%, preferably from 0.002% to 1 %, more preferably from 0.01 % to 0.6%, each by weight of the composition.

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