EP-4735416-A1 - PROCESS TO PRODUCE ESTERAMINES AND THEIR SALTS USING ORTHOESTER AS CATALYST

Abstract

Process to produce Esteramines and their Salts using Orthoester as Catalyst, the esteramine, its salts, its uses, and compositions, specifically cleaning compositions, comprising such Esteramines and/or their Salts.

Inventors

• EBERT, SOPHIA
• DEL REGNO, ANNALAURA

Assignees

• BASF SE

Dates

Publication Date

20260506

Application Date

20240627

Claims (1)

1. Claims Claim 1 Process to produce an esteramine or salt thereof using catalytic amounts of at least one orthoester, the process comprising the steps of a) reaction of I) at least one aminoacid selected from alpha-, beta-, gamma-, delta-, epsilon- etc. amino acids,, such as alanine, glycine, leucine, isoleucine, valine, proline, phenylalanine, arginine, asparagine, aspartic acid, aspartate, glutamine, glutamate, histidine, lysine, threonine, tryptophan, tyrosine, cysteine, methionine, serine; alpha-amino acids with secondary or tertiary amino groups such as sarcosine, N, N-dimethylgly- cine; other amino acids such as 6-amino hexane acid, 4-amino butanoic acid, 3-amino propanoic acid, 12-amino dodecanoic acid, 11-aminoundecanoic acid; aminoacids formally derived from the hydrolysis of a-lactame (three ring atoms), p-lactame (four ring atoms), y-lactame (five ring atoms) and so on; such lactames preferably being p-propiolactame, g-butyrolactame, 5-valerolactame, g-valerolactame, e-capro- lactame, d-decalactame, g-decalactame, e-decalactame; preferably alanine, valine, beta-alanine, 6- amino hexane acid; with ii) at least one alcohol (A) bearing at least one hydroxy group, being selected from mono-, di- and polyols, all of which may be optionally alkoxylated, wherein the alkoxylation of the at least one hydroxy group takes place in a step before step a), with the alcohol being alkoy lated with at least one alkylene oxide, preferably at least 1 and up to 200, preferably 1 to 100, more preferably up to 50 moles alkylene oxide per hydroxy group; in presence of ill) at least one acid (C), being selected from inorganic and organic acids, wherein said organic or inorganic acid has preferably a pKa value in the range of from -3 and up to +5, more preferably from -2,5 to 1 ,5, preferably at least one organic acid, such as sulfonic acids, more preferably alkane sulfonic acid and/or aryl sulfonic acid; and iv) in the presence of at least one ortho ester, such as triethyl orthoformiate, trimethyl orthoformiate, triethyl orthoacetate, trimethyl orthoacetate, and the like; whereas the ortho ester is used in sub-stoichiometric amounts, preferably catalytic amounts (referred to the amino acid) and whereas the alcohol used for the esterification is different from the alcohol-residual in the ortho ester; to produce an amino acid ester salt; b) optional neutralization of the obtained amino acid ester salt with at least one base to obtain the free amino acid ester. Claim 2 Process according to Claim 1, wherein the alcohol (A) is selected from (Aa) mono-alcohols such as C1- to C36-alkanols, selected from the groups non-alkoxylated linear C2- to C36-alco- hols, such as mixture 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 C3- to C36-alcohols such as 2-ethylhexanol, 2-propylheptanol, isotridecanol, isonona- nol, C9-C17 oxoalcohols; alkoxy I ated linear C2- to C36-alcohols such as alkoxy lated mixture 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; alkoxylated branched C3- to C36-alcohols such as alkoxylated 2-ethylhexanol, alkoxylated 2-propylheptanol, alkoxylated isotridecanol, alkoxylated isononanol, alkoxylated C9-C17 oxoalcohols; (Ab) di-alcohols such als alkane diols, polyalkoxylated C2-C6-alkandiols bearing at least two hydroxy groups, (Ac) oligo-alcohols such as polyalkoxylated C3-C6-alkantriols, bearing at least three hydroxy groups, (Ad) polyols such as sugar alcohols, polyalkoxylated C5-C6-alkane polyols, glycerols such as diglycerol, triglycerol polyglycerol, dipentaerythritol, tripentaerythritol; and/or (Ae) phenoxyalkanols such as phenoxyethanol; with the alcohol(s) selected from the groups of mono-alcohols and alkoxylated di-, oligo-alcohols and alkoxylated polyols being preferred, and the alcohols selected from the group(s) mono-alcohols and alkoxylated di-alcohols being even more preferred. Claim 3 Process according to any of the previous claims, wherein the alcohol (A) employed is an alkoxylated alcohol which is obtained by alkoxylating at least one hydroxy group of the alcohol according to Claim 2 with one or more alkylene oxides to produce alkylene oxy-chains comprising one or more moieties stemming from alkylene oxides selected from C2 to C22-alkylene oxides, preferably C2-C4-alkylene oxides, whereas the moieties stemming from the alkylene oxide(s) may be arranged in random, block or multiblock-order or combinations thereof, preferably as block, more preferably contains only one block consisting of ethylene oxide or consisting of two blocks with the first block - preferably the "inner block” directly linked to the hydroxy-group of the alcohol - consisting of ethylene oxide and a second block - preferably being the "outer block linked to the ethylene oxide-block - consisting of propylene oxide, such diblock even more preferably consisting of 3 to 10 EO-derived moieties and the PO-block consisting of 1 to 10 PO-de- rived moieties. Claim 4 Process according to any of the previous claims, wherein the acid (C) is selected from i) alkyl sulfonic acids, such as methane sulfonic acid, ethylsulfonic acid, propylsulfonic acid, camphorsulfonic acid; alkylaryl sulfonic acids and specifically alkylbenzene sulfonic acids, such as toluene sulfonic acid (including the mixture of isomers thereof), p-toluene sulfonic acid, o-toluene sulfonic acid, m-toluene sulfonic acid, xylene sulfonic acid (mixture of isomers), 2, 6-dimethylbenzene sulfonic acid, 2, 5-dimethylbenzene sulfonic acid, 2, 4-dimethylbenzene sulfonic acid, 4-dodecylbenzene sulfonic acid, iso-propyl benzene sulfonic acid, ethylbenzene sulfonic acid, and naphthalene sulfonic acid, preferably para-toluene sulfonic acid and methane sulfonic acid, more preferably methane sulfonic acid; ii) inorganic acids such as hydrochloric acid, hydrobromic acid, phosphoric acid; preferably selected from group i). Claim 5 Process according to any of the previous claims, wherein the acid (C) is chosen such that the esteramine is obtained as salt in cationic form, preferably the acid chosen is methane sulfonic acid and the esteramine obtained is a salt in cationic form. Claim 6 Process according to any of the previous 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 .5, with the number of hydroxy-groups of the (optionally alkoxylated) alcohol being n. Claim 7 Process according to any of the previous claims, wherein the process is carried out with the molar ratio of the acid ( C ) to the amino acid is in the range of from 0.8 : 1 to 1 : 1 .2. Claim 8 Process according to any of the previous claims, wherein in the process the reaction is performed at a temperature of from 50 to 200°C, preferably 70- 180°C, more preferably 80°C- 160°C, most preferably 120°C - 150°C, such as 60, 65, 75, 85, 90, 95, 100, 110, 115, 120, 125, 130, 135, 140, 145, 155, 165, 170, 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 hour(s); and at from 0,001 to 10 bar pressure, 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. Claim 9 Process according to any of the previous claims, wherein in the process the solvents for the reaction are selected from water, toluene, xylene, heptanol, cyclohexene, and the like, preferably only being water. Claim 10 Process according to any of the previous claims, wherein during or following the reaction, preferably at least during the reaction, water and/or excess alcohol are removed, such removal preferably being carried out by application of a stream of gas such as using gas such as inert gas as nitrogen or argon, preferably nitrogen, or steam made from water, preferably using inert gas, more preferably nitrogen, and/or applying a distillation method, preferably a distillation, more preferably a distillation method under reduced pressure and/or at elevated temperature, preferably both, a more preferred method being the use of an apparatus such as a Dean-Stark-trap, most preferably using a Dean- Stark-trap, such removal more preferably carried out applying a vacuum in the range of from 0.1 mbar to 800 mbar, preferably of from 1 mbar to 500 mbar and more preferably of from 10 mbar to 100 mbar, and using elevated temperatures. Claim 11 Process according to any of the previous claims, wherein the amount of orthoester in the resulting product is 10% relative to the esteramine salt obtained by such process. Claim 12 Use of an esteramine or a salt thereof obtained or obtainable by a process according to any of Claims 1 to 11 in a composition, that is a fabric and home care product, a cleaning composition, or an industrial and institutional cleaning product, preferably being in liquid or semi-liquid form, more preferably in liquid form. Claim 13 The use according to Claim 12, wherein the composition comprises at least one esteramine and/ or at least one salt thereof at a concentration of from about 0.1 % to about 5% in weight % in relation to the total weight of such composition or product, preferably the composition further fulfilling at least one of the following requirements: a. comprising at least one enzyme, b. comprising about 1 % to about 70% by weight of a surfactant system, c. comprising at least one further cleaning adjunct in effective amounts, and d. exhibiting an improved washing performance, preferably in primary cleaning. Claim 14 A composition being a cleaning composition or a fabric and home care product, preferably a cleaning composition, more preferably a laundry detergent or a dish wash detergent, containing at least one esteramine and/or a salt thereof obtained by or obtainable by the process according to any of Claims 1 to 11, comprising the at least one esteramine and/or the at least one salt thereof at a concentration of preferably from about 0.1% to about 5% in weight % in relation 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 lipases, hydrolases, amylases, proteases, cellulases, mannanases, hemicellulases, phospholipases, esterases, xylanases, DNases, dispersins, pectinases, oxidoreductases, cutinases, lactases and peroxidases, more preferably at least two of the aforementioned types, b. about 1 % to about 70% by weight of a surfactant system, c. at least one further cleaning adjunct in effective amounts, and optionally exhibiting an improved washing performance in primary cleaning, preferably being in liquid or semi-liquid form, more preferably being a concentrated liquid detergent formulation, single mono doses laundry detergent formulation, liquid hand dish washing detergent formulation, even more preferably a liquid laundry detergent formulation or a liquid hand dish wash detergent formulation, optionally further comprising at least one antimicrobial agent, preferably 2-phenoxyethanol, in an amount ranging from 2ppm to 5%, more preferably 0.1 to 2% by weight of the composition, and optionally comprising 4,4'-dichloro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, preferably 0.002 to 1%, more preferably 0.01 to 0.6%, each by weight of the composition.

Description

Process to produce Esteramines and their Salts using Orthoester as Catalyst Description The use of orthoesters in the synthesis of amino acid esters is described in the literature; however, in all documents, the ortho esters are used in stoichiometric amounts referred to the amino acid. Additionally, the alkyl residual in the formed amino acid ester is identical in all of those documents to the alkyl residual in the used ortho ester. For example, US7205433/WC2004018407 (priority date 23.08.2002) describes alanine methyl esters or ethyl esters as alkyl sulfonate salts, which are obtained from alanine, methanol or ethanol, alkylsulfonic acid and stoichiometric amounts of trimethyl or triethyl orthoesters. WO 2005/110986 uses stoichiometric amounts of trimethyl orthoformiate to obtain allylglycine methyl-ester from allylglycine and methanol and hydrochloric acid. The invention relates to a process for the synthesis of amino acid esters and its acid salts using at least one orthoester in sub-stoichiometric amounts, preferably in catalytic amounts. The invention also relates to amino acid esters and its salts obtainable by such process. The esteramines and their salts obtainable or obtained by a process according to the present invention may be used in specific compositions, such as detergent, cleaning and/or fabric and home care compositions/formulations. The esteramines and their salts obtainable or obtained by a process according to the present invention show good biodegradability properties when being employed, for example, within cleaning compositions. Due to the climate change, one of the most important targets of the detergent and cleaning (D&C) industry today is to significantly lower the CO2 emission per wash, by improving e.g. cold water conditions by improving the cleaning efficiency at low temperatures of below 40, 30 or 20 or even colder, to lower the amounts of chemicals employed per wash, increasing the weight-efficiency of the cleaning technologies, introducing bio-derived components etc. Hence, one important target of the D&C industry is the need for biodegradable ingredients, to improve the sustainability of the cleaning formulations (and especially the laundry and dish wash formulations) and to avoid the accumulation of non-degradable compounds in the ecosystem. Hence, there is a need to provide compounds being bio-degradable and still having at least the same performance as already known but not bio-degradable compounds, such biodegradation as measured under defined conditions within 28 days as to be required by many users especially in the field of detergents, and as being a future requirement by applicable legislation in several countries and regions of the world. Such reduction in CO2-emision or the desire to improve the "footprint” of any product is of high and even further rising interest in the industry and with the consumers, be it in terms of its origin like being from natural or renewable resources, or - all compared to previous products - its production in terms of production efficiency and thus reduced usage of energy, its efficiency in usage such as reduced amounts for the same performance or higher performance at the same amount levels used, its persistence in the natural environment upon and/or after its usage such as biodegradation. Also, there is a need to improve the process to produce such esteramines and their salts with an improved process using less starting material, and with a reduced need for purification steps, to reduce the overall usage of compounds and energy and thus reduce also the carbon footprint of such process. As a result of these trends, there is a need for an improved process to prepare esteramines and their salts such as detailed in this present invention, providing at least comparable cleaning properties and a reduction in the CO2-foot- print not only by the properties of the compounds produced by also by the produces to produce such compounds. This goal was achieved by the present invention as described herein below and as reflected in the claims. Definitions Throughout this specification and the claims which follow, 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 integer or step. When used herein the term "comprising” can be substituted with the term "containing” or "including” or sometimes when used herein with the term "having”. When used herein, "consisting of" excludes any element, step, or ingredient not specified in the claim element. When used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. In each instance herein any of the terms "comprising", "consisting essentially of" and "consisting of" may be replaced with eithe