WO2025252513A1

WO2025252513A1 - Biodegradable amine containing alkoxylates, their preparation, uses, and compositions comprising them

Info

Publication number: WO2025252513A1
Application number: PCT/EP2025/064452
Authority: WO
Inventors: Ivette Garcia Castro; Yannick MATT; Torsten Roth; Eva Maria BETTHAUSEN
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2024-06-04
Filing date: 2025-05-26
Publication date: 2025-12-11
Anticipated expiration: 2026-12-04

Abstract

This invention deals with biodegradable amine containing alkoxylates, their manufacture, their uses, particularly for use in cleaning compositions such as laundry detergent compositions, and specifically for improved clay removal and/or oily/fatty soil removal and/or body soil removal and/or whiteness maintenance in laundry care.

Description

Biodegradable amine containing alkoxy lates, their preparation, uses, and compositions comprising them

This invention deals with biodegradable amine containing alkoxylates (in this present invention abbreviated as "inventive compound”, or "inventive polymer”, "alkoxylated polymer” or "compound of the invention” whenever the inventive amine containing alkoxylates are meant), their manufacture, their uses, particularly for use in cleaning compositions such as laundry detergent compositions, and specifically for improved clay removal and/or oily/fatty soil removal and/or body soil removal and/or whiteness maintenance in laundry care.

Detergent formulators are continuously faced with the task of developing improved products to remove a broad spectrum of soils and stains from fabrics and hard surfaces. Chemically and physico-chemically, the varieties of soils and stains spectrum range from polar soils, such as proteinaceous, clay, and inorganic soils, to non-polar soils, such as soot, carbon-black, by-products of incomplete hydrocarbon combustion, and organic soils like sebum and body soils. The removal of greasy (i.e., oily/fatty) stains has been a particularly challenging problem. This challenge has been accentuated by the recent high interest and motivation to reduce the level of surfactants in cleaning detergents for environmental, sustainability and cost reasons. A reduction of the amount of surfactants added, especially a reduction of anionic surfactants, such as linear alkyl benzene sulfonate, LAS, has typically been found to lead to an erosion of oily/fatty stain removal. Additionally, the global trend of using washing conditions at lower temperature further diminishes grease cleaning capabilities of typical detergents, since the class of oily and fatty stains shows the greatest performance drop when the temperature is decreased. On the other hand, clay soil stains, although in some instances contacting the fabric fibers with less force, nevertheless provide a specific type of soil removal problem due to the high degree of charge associated with the clay itself. This high surface charge density may act to repel some laundry ingredients, thus surfactants alone cannot remove or carry away the clay into the laundry liquor.

Another global trend is the compaction of laundry detergents, in order to improve the sustainability in terms of water usage and/or transportation costs, as well as to improve the convenience for the end consumer (e.g., single mono dose products, tabs, pouches and the like), which leads to a high market demand for new raw materials that have a higher weight-efficiency and a significantly broader performance profile.

A further strongly emerging trend is the desire to improve the "footprint” of any product, be it in terms of its origin like being from natural or renewable resources, or 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 after its usage, especially its biodegradation, since recycling is technically very challenging and therewith economically not attractive. Hence, due to the climate change, one of the most important targets of the detergent and cleaner (D&C) industry today is to significantly lower the CO2 emission per wash, by improving cold water conditions, improving the cleaning efficiency at low temperatures of 30 °C and below, and to lower the amounts of chemicals employed per wash, and increasing the weight-efficiency of the cleaning technologies. Another important target of the D&C industry is the need for biodegradable polymers, to improve the sustainability of the detergent formulations and to avoid the potential accumulation of the polymers or their degradation products, resulting from incomplete biodegradation of the polymers in the ecosystem, thus lowering the persistence in nature after usage of the materials.

As a result of these trends, there is a strong need for new biodegradable cleaning polymers that provide both excellent primary (i.e., soil removal) and/or secondary (i.e., whiteness maintenance) cleaning benefits for both hydrophobic and hydrophilic stains, and an improved biodegradability. The materials should exhibit good soil removal for oily/fatty/sebum and particulate stains and/or should also lead to improved whiteness maintenance, minimizing the amount of suspended and emulsified oily/fatty/sebum and particulate soil from redepositing on the surfaces of the textiles or hard surfaces. Preferably, the new ingredients would also display a synergy with other cleaning technologies, such as other cleaning polymers, surfactants and/or enzymes, known for improving solely the oily/fatty/sebum or particulate stain removal and/or whiteness of fabrics and hard surfaces, leading to further improved detergent compositions.

For example, alkoxylated polyalkylene imine and alkoxylated polyamine polymers, especially the class of alkoxylated hyperbranched polyethylene imine (PEI) and alkoxylated linear polypropylene imine (PPI) homo- and copolymers, are known in the literature to be able to contribute to particulate or to oily/fatty soil removal, especially at low surfactant levels and at cold water conditions (30 °C and below). However, their biodegradation performance generally is poor, and thus not acceptable for current and future requirements. Ideally, the polymers are readily biodegradable, i.e., show equal to or more than 60% oxygen consumption after 28 days in the OECD 301 F test or they are considered moderately biodegradable then they show equal to or more than 40% after 28 days in the OECD 301 F test. Alternatively, the polymers are inherently biodegradable in the OECD 302 B test, i.e., show equal to or more than 70% dissolved organic carbon (DOC) levels. Hence, there is a need to find improved polymer architectures with a similar or superior performance profile, a feasible preparation process and an improved biodegradation behavior.

In the following, a summary of the most relevant publications in the field of the present invention, amine containing alkoxylates, is given.

WO2021254824 A discloses amine containing alkoxylates obtained by reacting diamines with cycloalkylene groups and polycarboxylic compounds having three to ten carboxyl groups and subsequent alkoxylation. The document is silent about the biodegradability of the disclosed compounds and solely shows wash performance. In contrast to WO2021254824 A the present invention is directed to polymers combining linear amines with free NH-groups and nitrogen comprising multi acids. This combination results in structurally different polymers than the ones of WO2021254824 A possessing a higher nitrogen density with increased wash performance and significant biodegradability.

Surprisingly, the present inventors found that amine containing alkoxylates synthesized according to the present invention demonstrate in parallel excellent wash performance and show a significant biodegradation. Experimentally generated data proved that the inventive compounds can be used in combination with established components to significantly improve wash performance. Further, the inventive compounds demonstrate significant biodegradation (at least around 40% according to OECD 301 F within 28 days), whereas such biodegradation rate can be observed for polymers having a molecular weight average weight (Mw) of up to 46.000 g/mol. Further, the inventive compounds also show good stability in cleaning composition, especially in liquid cleaning composition.

Therefore, the object of the present invention is to provide novel alkoxylated polymers obtainable by a process comprising the following steps:

(i) reaction of

(a) at least one first amine (A1) or pre-alkoxylated amine (pA);

(b) at least one aliphatic carboxylic acid or salts, esters or anhydrides thereof (B);

(c) at least one amino group containing polycarboxylic acid or salts, amino group containing esters or amino group containing anhydrides thereof (C); and

(d) optionally at least one alkanolamine (D), in order to obtain a first intermediate (11), and

(ii) reaction of

(a) the first intermediate (11) with

(b) first alkylene oxide (AO1), preferably selected from the group consisting of at least one of a first ethylene oxide (EO1), first propylene oxide (PO1), and first butylene oxide (BO1), in order to obtain the alkoxylated polymer.

In the following, any alkylene oxide is generically referred to as "AO”, ethylene oxide is sometimes referred to as "EO” and propylene oxide as “PO”. "PEO” is used sometimes herein to describe polyethylene oxide homopolymers or PEO-blocks within a larger polymer structure; likewise, "PPO” describes the polypropylene oxide homopolymers or polymer-blocks within a larger polymer structure.

A process to produce the inventive compounds is also part of this invention. The use of the compounds of this invention for all kinds of applications for which the previously described polyamines, polyethylene imines, polypropylene imines, and their alkoxylated derivates have been used is encompassed by this present invention as well.

Compositions comprising such amine containing alkoxylates of this invention similar to those compositions in which the previously known polyamines, polyethylene imines, polypropylene imines, and their alkoxylated derivates have been employed - either the inventive amine containing alkoxylates instead of such known compounds or in combinations with such known compounds - forms part of this invention as well.

The term "compound of the invention”, or "inventive compound”, or "inventive polymer”, as used herein, refers to amine containing alkoxylates prepared as described below and/or in the appended claims.

Thus, subjects of the present invention are the following Embodiments 1 to 28 as defined and further explained with further embodiments hereinafter and further exemplified in the experimental section:

Embodiment 1

An alkoxylated polymer obtainable by a process comprising the following steps:

(I) reaction of

(a) at least one first amine (A1) or pre-alkoxylated amine (pA);

(ii) reaction of

(a) the first intermediate (11) with

The compounds of the invention comprise side chains, alkylene oxide branches, which are attached to oxygen or nitrogen atoms derived from the -OH, -COOH and NH-functionalities of the first intermediate (11). The side chains are made up from alkylene oxides, preferably ethylene oxides and propylene oxides. Typically, a side chain possesses on average 25 to 75 total AO units (EO units + PO units). More detailed embodiments describing the different chain lengths are provided below. The side chains comprise, and preferably consist of ethylene oxides and propylene oxides. The side chains preferably end with an -OH group but may alternatively be capped, such as with a C1 to 020 alkyl group, preferably 01 to 06 alkyl group, more preferably 01 alkyl group.

It is noted that all such numbers are numbers "on average” meaning that such numbers refer to the average number for such unit for one -OH, -C00H or NH-functionality calculated based on all -OH, -C00H and NH-functionalities of the first intermediate (11).

It is to be emphasized that the reactions leading to the inventive compounds are statistical reactions, meaning there is never just one chemically exactly defined compound present, but an inventive amine containing alkoxylate always is a mixture of slightly deviating structures, all stemming from the same reaction within one reaction space; the difference of those structures clearly stemming from the facts that no reaction proceeds in exactly the same way and the same speed on all functional units, especially as the chemical reactivities of the functional units - here those of the -OH, -C00H and NH-functionalities, differs according to their environment, meaning that, for example, a primary alcohol group reacts differently than a secondary alcohol, and also the chemical environment of the groups may be different; this leads in an overall view to slightly deviating structures being present, and thus any compound of this invention being defined as in the various embodiments including the numbered Embodiments 1 to 28, and exemplified in the examples never is just one chemical compound, but always a mixture of slightly deviating compounds, having a statistical distribution. As the reactivities of those groups are not differing by a large extent, the deviation is relatively small. Hence, defining an amine containing alkoxylate of the invention by a prototypical member is a viable way of defining the structure. Also, defining the composition of the side chains by average numbers (including those variables defined in the present and following Embodiments based on the numbers of -OH, -C00H or NH-functionalities being present in the first intermediate (11) is a useful way of defining the overall composition of any mixture herein defined as "an amine containing alkoxylate of the invention”.

Therefore, unless otherwise indicated, the values, ranges and ratios given in the specification for the number of functional groups and the molecular weight (Mn) relate to the number average values in heterogenic mixture of the synthesized amine containing alkoxylate containing individual, slightly from each other deviating chemical structures that result from the preparation method of the present invention. As known in polymer science, the weight-average molecular weight (Mw) is then a measure for the (in)homogeneity within the mixture of different species in "the amine containing alkoxylate”.

In line with the above, it is preferred that all functional groups, namely -OH, -C00H or NH-functionalities, of the first intermediate (11) have been substituted with alkylene oxide branches and the alkylene oxide branches have slight variations in the amounts of the different alkoxy lations. Inventive compounds bearing the above-described modification are also called being “alkoxylated”, "ethoxylated and propoxylated” and/or "modified”.

The term "alkylene oxide branch”, as used herein, refers to a sub-structure of the inventive compounds comprising, essentially consisting of or consisting of a plurality of AO units, preferably EO units and PO units.

The terms "essentially having” or "having essentially”, as used interchangeably herein, with respect to the inventive compounds mean that said polymers may comprise impurities or other types of polymers in an amount not more than 40% w/w, not more than 30% w/w, not more than 20% w/w, not more than 10% w/w, not more than 7% w/w, not more than 5% w/w, not more than 3% w/w, not more than 2% w/w, not more than 1% w/w, not more than 0.5% w/w or not more than 0.1 % w/w.

In preferred embodiments, the weight average molecular weight (Mw) of the amine containing alkoxylates is in the range of from 4.000 to 60.000 g/mol, preferably in the range of from 8.000 to 55.000 g/mol, more preferably in the range of from 15000 g/mol-50.000 g/mol.

The person skilled in the art knows how to determine/measure the respective weight average molecular weight (Mw). This can be done, for example, by using size exclusion chromatography (such as GPC, e.g., in combination with light scattering), by mass spectrometry, by mass photometry or by calculation from the used molar ratio of starting materials. Preferably, Mw values are determined by the method as follows: OECD TG 118 (1996), which means in detail

OECD (1996), Test No. 118: Determination of the Number-Average Molecular Weight and the Molecular Weight Distribution of Polymers using Gel Permeation Chromatography, OECD Guidelines for the Testing of Chemicals, Section 1, OECD Publishing, Paris, also available on the internet, for example, under https://doi . orq/10.1787/9789264069848-en .

Molecular weights of the amine containing alkoxylates and intermediates may be determined by gel permeation chromatography (GPC).

In preferred embodiments, the weight average molecular weight (Mw) of the inventive polymers or intermediates is measured as follows: GPC measurements were performed in HFIP (hexafluoro-isopropanol) at ambient temperature by PSS Agilent 1260 Series. The nominal solvent flow rate was 1 mL/min. Two SEC columns with a pore size of 100 and 1000 for HFIP from PSS Polymer Standards were used for fractionation. The refractive index detector G1362A and UVA/is detector G1365D from Agilent Technologies were used for HFIP. The calibration was carried out with poly(methylmethacrylate). The results were evaluated using WinGPC UniChrom V 8.20 software from Polymer Standards Service GmbH resulting in different parameters including the weight average molecular weight (Mw).

"Mw” is the weight average molecular weight and "Mn” is number average molecular weight.

In preferred embodiments, the number average molecular weight (Mn) of the inventive polymers and intermediates is measured as described for the weight average molecular weight (Mw) with the exception that the WinGPC UniChrom V 8.20 software determines the number average molecular weight (Mn).

In preferred embodiments, the acid numbers of the inventive polymers and intermediates can be determined according to DIN EN ISO 2114.

In preferred embodiments, the hydroxyl numbers (OH numbers) of the inventive polymers and intermediates can be determined according to DIN EN ISO 4629-1.

In preferred embodiments, the amine numbers of the inventive polymers and intermediates can be determined according to DIN EN ISO 9702.

The term "at least one”, as used herein, is defined as one or more, namely 1, 2, 3, 4, 5, 6, 7, 8, 9 or more.

Embodiment 2

The alkoxylated polymer according to Embodiment 1, wherein

(I) the first amine (A1) comprises at least two primary amino groups and preferably the total amount of nitrogen atoms is at least three, more preferably at least four; or

(II) the pre-alkoxylated amine (pA) consists of I) a second amine (A2) and II) alkylene oxide chain comprising second alkylene oxide (AO2), preferably selected from the group consisting of at least one of a second ethylene oxide (EO2), second propylene oxide (PO2), and second butylene oxide (BO2).

In preferred embodiments, the first amine (A1) comprises two primary amino groups and has in total three, four or five amino groups.

In preferred embodiments, the first amine (A1) comprises two or three primary amino groups and additionally two, three or four secondary amino groups, more preferably the first amine (A1) comprises two amino and additionally two, three or four secondary amino groups. In even more preferred embodiments, the first amine (A1) comprises two primary amino groups and two or three secondary amino groups.

In other preferred embodiments, the second amine (A2) is defined as the first amine (A1) in the preferred embodiments above.

In preferred embodiments, the second alkylene oxide (AO2) is selected from the group consisting of a second ethylene oxide (EO2) and second propylene oxide (PO2).

Embodiment 3

The alkoxylated polymer according to Embodiment 1 or 2, wherein the first amine (A1) or the second amine (A2) are selected from the group consisting of N,N'-Bis-(3-aminopropyl)-ethylenediamine (N4 amine), arginine, lysine, N,N-Bis(3-aminopropyl)methylamine (BAPMA), spermidine, spermine, tetraethylenpentamine (TEPA), triethylentetramine (TETA), pentaethylenehexamine (PEHA), 3-(2-aminoethylamino)propylamine (N3 amine), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), hexamethylenediamine (HMDA), heptamethylenediamine, octamethylenediamine (OMDA), dipropylene-triamine (DPTA), tripropylene-tetramine (TPTA), 4,7,10-Trioxa-tridecane-1,13-diamine (TTD), 4,4'- Diaminodicyclohexylmethane (MCDA), isophorone diamine (IPDA) and 4,9-Dioxado-decane-1 ,12-diamine (DODA). In preferred embodiments, the first amine (A1) or the second amine (A2) are selected from the group consisting of N,N'-Bis-(3-aminopropyl)-ethylenediamine (N4 amine), tetraethylenpentamine (TEPA), pentaethylenehexamine (PEHA) and triethylentetramine (TETA).

In further preferred embodiments, the first amine (A1) or the second amine (A2) is essentially one amine compound. In alternatively preferred embodiments, the first amine (A1) or the second amine (A2) are a mixture of at least two amine compounds as described above, in even more preferred embodiments the first amine (A1) or the second amine (A2) are mixtures of two amine compounds as described above. The ratio weight per weight (w/w) between the two amines may be in the range 1 : 1 to 1 :10, preferably 1 : 1 to 1 :5.

Embodiment 4

The alkoxylated polymer according to Embodiments 2 or 3, wherein the second amine (A2) is reacted with 0.1 mol to 10.0 mol, preferably 0.15 mol to 7.0 mol and even more preferably 0.2 to 4mol, of the second alkylene oxide (AO2) per mol of NH-functionality of the second amine (A2).

Embodiment 5 The alkoxylated polymer according to any one of Embodiments 1 to 4, wherein the aliphatic carboxylic acid or salts, esters or anhydrides thereof (B) comprise at least two carboxyl, ester or anhydride groups, preferably the aliphatic carboxylic acid or salts, esters or anhydrides thereof (B) is a dicarboxylic acid, di-ester or compound containing two anhydride groups or is selected from the group consisting of succinic acid, malic acid, malonic acid, tartaric acid, citric acid, levulinic acid, sebacic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, heneicosanedioic acid, docosanedioic acid, triacontanedioic acid, iminodiacetic acid (IDA), itaconic acid, and alkali metal or ammonium salts, esters and anhydrides thereof.

In preferred embodiments, the aliphatic carboxylic acid (B) comprises two carboxyl groups. And in even more preferred embodiments, the aliphatic carboxylic acid (B) is sebacic acid.

The term "aliphatic”, as used herein, includes both saturated and unsaturated, straight chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups. As will be appreciated by one of ordinary skill in the art, "aliphatic” is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties. Thus, as used herein, the term "alkyl” includes straight and branched alkyl groups. An analogous convention applies to other generic terms such as "alkenyl”, "alkynyl” and the like. Furthermore, as used herein, the terms "alkyl”, "alkenyl”, "alkynyl” and the like encompass both substituted and unsubstituted groups. In certain embodiments, as used herein, "aliphatic carboxylic acid” is used to indicate those compounds having two carboxyl groups and a linear alkyl group of about 1-12 carbon atoms.

The term "salt”, as used herein, refers to the (partially) deprotonated variant of the aliphatic carboxylic acid forming an anion that is bound to a cation. The cation may be a nitrogen containing compound or a metal.

The term "ester”, as used herein in the context of the aliphatic carboxylic acid (B) refers to compounds herein at one and preferably all of the carboxylic groups of the aliphatic carboxylic acid (B) have been converted to ester

O

R1 - U - o - R2 groups according to the following formula , wherein R1 represents the part derived from the aliphatic carboxylic acid (B) and R2 a C1 to C6 (linear) alkyl group.

The term "anhydride”, as used herein in the context of the aliphatic carboxylic acid (B) refers to compounds herein at one and preferably all of the carboxylic groups of the aliphatic carboxylic acid (B) have been converted to anhydride groups according to the following formula , wherein R1 represents the part derived from the aliphatic carboxylic acid (B) (and may be identical to R2) and R2 a C1 to C6 (linear) alkyl group.

Embodiment 6

The alkoxylated polymer according to any one of Embodiments 1 to 5, wherein the aminopolycarboxylic acid or salts, esters or anhydrides thereof (C) comprise at least three carboxyl, ester or anhydride groups or are selected from the group consisting of methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), nitrilotriacetic acid (NTA), N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), N-(2hydroxyethyl)iminodiacetic acid (HEIDA), hydroxyethylenediaminetriacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), glutamic acid-diacetic acid (GLDA), Ethylenediamine-N,N'-bis (2-hydroxyphenylacetic acid) (EDDHA), iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N, N-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP), N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-sulfoethyl) aspartic acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2-sulfoethyl) glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), serine-N, N-diacetic acid (SEDA), isoserine-N, N-diacetic acid (ISDA), phenylalanine-N, N-diacetic acid (PHDA), anthranilic acid-N, N-diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA), sulfomethyl-N, N-diacetic acid (SMDA) and alkali metal or ammonium salts, esters and anhydrides thereof. In preferred embodiments, the aminopolycarboxylic acid (C) is methylglycinediacetic acid (MGDA), glutamic acid-diacetic acid (GLDA), ethylenediaminetetraacetic acid (EDTA) or ethylenediaminedisuccinic acid (EDDS).

In preferred embodiments, the aminopolycarboxylic acid (C) comprises three or four carboxyl groups and at least one, two or three tertiary amino groups. Preferably, the amino groups are at least one or two tertiary amino groups or at least two secondary amino groups.

In preferred embodiments, the intermediate (11) is a branched compound. Meaning that the carbon atoms of the intermediate (11) are not essentially centered around one line but split into several branches of carbon atoms.

The terms "salts”, "esters” and "anhydrides” in relation to the aminopolycarboxylic acid (C) are defined in a corresponding matter as described above for the aliphatic carboxylic acid (B). Embodiment 7

The alkoxylated polymer according to any one of Embodiments 1 to 6, wherein the alkanolamine (D)

(I) comprises at least two or three hydroxyl groups; or

(II) is methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, diethanolamine, triethanolamine or triisopropanolamine (TIPA).

In preferred embodiments, the alkanolamine (D) is used in combination with arginine as the first amine (A1) or with a pre-alkoxylated amine (pA) that comprises arginine as the second amine (A2).

Embodiment 8

The alkoxylated polymer according to any one of Embodiments 1 to 7, wherein in the second reaction

(I) 10 mol to 50 mol, preferably 20 mol to 40 mol of the first ethylene oxide (EO1 ) is employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11);

(II) 2 mol to 40 mol, preferably 3 mol to 30 mol of the first propylene oxide (PO1) is employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11); or

(ill) 5 mol to 50 mol, preferably 15 mol to 45 mol of the first ethylene oxide (EO1) and 2 mol to 40 mol, preferably 3 mol to 30 mol of the first propylene oxide (PO1) are employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11).

In preferred embodiments of the above processes, 25 mol to 35 mol, preferably 27 mol to 32 mol of the first ethylene oxide (EO1) is employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11) and (independently or in combination) 5 mol to 20 mol, preferably 7 mol to 15 mol of the first propylene oxide (PO1) is employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11).

In more preferred embodiments, the alkylene oxide branches possess a block structure consisting of a PC block and an EC block, wherein the EC block is reacted with the first intermediate (11). Alternatively, the alkylene oxide branches possess a block structure consisting of an EC block and a PC block, wherein the PC block is reacted with the first intermediate (11).

Within the context of the present invention, the term "NH-functionality” is defined as follows: a primary amino group (-NH2) has two NH-functionalities, a secondary amino group only one NH-functionality, and a tertiary amino group, by consequence, has no reactive NH-functionality. The skilled person will understand that the first intermediate (11) may also be alkoxylated with other AOs than ethylene oxide or propylene oxide. In this context, butylene oxide is mentioned. Further, the skilled person is also well-aware of helpful modifications of the alkoxy chain, such as modifications with lactones or hydroxy carbon acid as described in WO2021165468 A.

It is noted that the alkylene oxide used to prepare the inventive compounds may be derived from a fossil or nonfossil carbon source or even a mixture of the before mentioned. Preferably, the amount of non-fossil carbon atoms in the alkylene oxide branch is at least 10%, at least 20%, at least 40%, at least 70%, at least 95% or it solely comprises non-fossil derived carbon atoms. The skilled person is well-aware of commercial alkylene oxide products made of non-fossil carbon sources (these products are often sold as being sustainable, renewable or bio-based). For example, Croda International, Snaith, UK, sells ethylene oxide and related products based on bio-ethanol as ECO Range. Additionally, methods to prepare bio-based propylene oxide are also known (see Abraham, D. S., "Production of propylene oxide from propylene glycol" Master's Thesis University of Missouri-Columbia (2007) (75 pages)).

Alternatively, the alkylene oxide may comprise non-fossil carbon atoms due to a synthesis involving recycling processes. For example, waste plastics can be recycled in a process resulting in ethylene (see Royer, SJ et al., PLoS One. 2018; 13(8): e0200574 and Kim, SW et al., Science of The Total Environment, Volume 903, 10 December 2023, 166789). In a subsequent synthesis step the recycled and non-fossil ethylene can be converted into ethylene oxide (EC). Such conversion steps are well-known to the person skilled in the art (e.g. WO2021092313 A).

In further preferred embodiments, the skilled person will also partially or fully replace fossil educts, such as the first amine (A1), the second amine (A2), the aliphatic carboxylic acid or salts, esters or anhydrides thereof (B), the amino group containing polycarboxylic acid or salts, amino group containing esters or amino group containing anhydrides thereof (C) and the alkanolamine (D) with non-fossil forms of such educts. In preferred embodiments, at least one of the above-described educts comprises at least 10%, at least 20%, at least 40%, at least 70%, at least 95% of non-fossil derived carbon atoms. For example, the amino group containing polycarboxylic acid may be ethylenediaminedisuccinic acid (EDDS) and the skilled person is well-aware of fermentative processes to obtain EDDS, such as disclosed by Edenhart et al. (Edenhart et al., Metabolic Engineering, Volume 60, July 2020, Pages 148-156).

Embodiment 9 In preferred embodiments, the amine containing alkoxylates of the invention demonstrates at least 20%, at least 30%, at least 40%, preferably at least 50% or more preferably at least 60% biodegradability according to standard OECD 301 F within 56 days, preferably within 28 days.

For the purposes of this invention, aerobic biodegradation in wastewater according to OECD 301 F is expressed as a percentage of the theoretical oxygen demand (ThOD, which is measured by the elemental analysis of the compound of interest), which is needed to completely biodegrade the compound sample. Thus, the amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD. The obtained values are preferably measured in triplicate using the OECD 301 F manometric respirometry method. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Details for the tests performed are given in the experimental section below.

Embodiment 10

The amine containing alkoxylates according to any of Embodiments 1 to 9, wherein all alkylene oxide branches attached to the first intermediate (11) have the same structure, in that sense that the number of EO and/or PC units per alkylene oxide branch is identical or, alternatively, the alkylene oxide branch structures vary slightly.

Without wishing being bound by the following explanation, a rationale exists to explain the resulting structures of the amine containing alkoxylates: Due to the fact that the reactions in questions necessarily employed to prepare those structural orders of the side chains, and thus to prepare the specific inventive compounds, are reactions of quite reactive species which can lead under suitable conditions to almost complete and even "essentially complete” conversions of almost 100 % if not even 100%, the statistical deviation of the composition of the mixture of "amine containing alkoxylates” in question is not that high, which in turn means that the structural order of the side chains do not show much deviation. Thus, it is a reliable assumption which can in principle be proven by sophisticated and thus time-consuming and expensive analytical means - such as multi-dimensional NMR-analyses - that it is generally accepted that such deviation exists; hence, no "specific amine containing alkoxylates” will be "just one chemical compound of a clearly defined chemical structure”, but clearly will consist of a) a mixture of slightly differing compounds, such differences lying in b) slight deviations may already in the structure of "the (unmodified) first intermediate (11)” being employed for the further modification steps, and c) the slight deviations in the structural orders of the side chains may be attached by way of d) multi-step reactions due to e) variations in the chemical reactivities of the -NH, -COOH and -OH groups, and f) due to slight inhomogeneities occurring in a commercial scale process. All of those factors a) to f) - to just mention a few important ones - lead to a "specific amine containing alkoxylate” which is not one specific chemical compound but in fact a mixture of slightly differing compounds having an overall very similar chemical structure; thus, such structure is best described by average numbers for the variables and percentages for the amounts of the dominating structural order.

Embodiment 11

In another embodiment of the present invention, it is preferred that up to 100% of the nitrogen atoms present in the amine containing alkoxylates are quaternized, preferably the degree of quaternization of the nitrogen atoms present in the amine containing alkoxylates lies in the range of 10% to 95%, 20% to 90% or 50% to 85%.

Moreover, the polymers of the invention may be further sulfated. The skilled person is well-aware how the inventive polymers can be quaternized and/or sulfated. Comparative polymers that are multifunctional alkoxylated oligoamines and being further quaternized and sulfated are disclosed in the art, e.g., the ones described in WO2021239547A1, especially examples P.1-P.6, and/or in WO2023227332.

Embodiment 12

A process to prepare an alkoxylated polymer according to any one of Embodiments 1 to 11 comprising carrying out the process steps according to any one of claims 1 to 11 .

All of the terms within Embodiment 12 have already been defined and explained in detail herein before within the description of the Embodiments 1 to 11 , such terms, definitions and further specifications of course apply to this Embodiment 12.

The conversion rate of the two reaction steps may be monitored and in preferred embodiments the conversion rate for the first or second step is at least 95%, preferably at least 99%, and even more preferably at least 99,5 % or even more. All other structural orders of the side chains as defined above but also the undefined structures resulting from non-controllable parameters are performed in this defined manner, leading - on statistical average - to a defined structural order directly derived from the way such reaction is performed.

The conversion rate of the reaction can be determined according to methods known to the skilled person, such as NMR-spectroscopy, such as 13C-NMR-spectroscopy and/or 1 H NMR-spectroscopy.

For the reaction conditions such as catalysts, temperatures, duration, purification etc. of the reactions to produce the units of the side chains of the inventive amine containing alkoxylates, the respective information within the disclosures EP3298120 A, JP2022056680 A and US7468348 B is fully encompassed into this recent disclosure by way of reference. Within this preferred Embodiment, the first or second alkoxylation is carried out in the presence of at least one catalyst. Within this single step reaction of the alkoxylation step, the catalyst is preferably a basic catalyst. Examples of suitable catalysts are alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, in particular sodium and potassium Ci-C4-alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Preference is given to the alkali metal hydroxides and the alkali metal alkoxides, a particular preference being given to potassium hydroxide and sodium hydroxide. Typical use amounts for the base are from 0.05 to 10% by weight of final product, in particular from 0.05 to 2% by weight, based on the total amount of the first intermediate (11) and alkylene oxide.

Embodiment 13

Process according to Embodiment 12, wherein the amine containing alkoxylate is further submitted to the following process steps of a. purification using standard means such as steam distillation, thermal distillation, vacuum evaporation, including removal of all solvent, dialysis and/or b. drying using standard drying means such as spray-, drum, paddle-, vacuum-drying means including agglomeration methods such as fluidized-bed-drying, to obtain a purified solution, a purified liquid, a solid compound or a purified solid compound, respectively.

In case that after the reaction leading to the inventive compound residual educts (amines, carboxylic acids, amino group containing carboxylic acids, alkanolamines and/or alkylene oxide) are present to a non-desirable extent, the resulting product mixture containing the amine containing alkoxylates may be further purified by standard means to reduce the content of residual educts, but also to reduce the amount of possible by-products, reduce the amount(s) of the solvent(s) employed (i.e., to concentrate) or replace solvent(s) with other solvents. Such processes are known to a person of skill in this field.

Preferably, undesirable amounts of residual non-reacted educts are removed, preferably by means of distillative processes, more preferably by thermal distillative processes, which may additionally comprise the application of reduced pressure to increase the speed and/or the effectiveness of the removal.

In a preferred embodiment only the additional process step a) is employed.

Embodiment 14 A compound that is the first intermediate (11) according to the first reaction of Embodiment 1, namely obtained by the reaction of

(a) at least one first amine (A1) or pre-alkoxylated amine (pA);

(d) optionally at least one alkanolamine (D).

All of the terms within Embodiment 14 have already been defined and explained in detail herein before within the description of the Embodiments 1 to 1 1 , such terms, definitions and further specifications of course apply to this Embodiment 14.

Use of and compositions comprising the inventive alkoxylated polymer

Part of this invention is also the use of the inventive alkoxylated polymer for various fields of applications, where they can replace currently known similar structures, but bring in their enhanced rate of biodegradation compared to those previously known structures.

Embodiment 15

Use of at least one amine containing alkoxylate according to any one of Embodiments 1 to 11 in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, in formulations for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, in cementitious compositions, as dispersant for agrochemical formulations.

A subject matter of the present invention is the use of the above-mentioned alkoxylated polymer in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, in formulations for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, in cementitious compositions and/or as dispersant for agrochemical formulations, preferably in cleaning compositions and/or in fabric and home care products, in particular cleaning compositions for improved removal of bleachable stains or clay removal or oily and fatty stain removal, wherein the cleaning composition is preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation. The alkoxylated polymer can be added to cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, formulations for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, in cementitious compositions. However, the inventive compounds can also be added to (used in) washing or cleaning compositions.

Another subject-matter of the present invention is, therefore, a cleaning composition, fabric and home care product, industrial and institutional cleaning product, cosmetic formulation, crude oil emulsion breaker, pigment dispersion for ink jet inks, formulation for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, cementitious composition and/or dispersant for agrochemical formulations, comprising at least one alkoxylated polymer, as defined above.

Preferably, it is a cleaning composition and/or fabric and home care product, comprising at least one alkoxylated polymer, as defined above, preferably for improved clay removal or oily and fatty stain removal, or sebum and body soil removal, preferably a laundry detergent formulation and/or a manual dish wash detergent formulation, more preferably a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

In another preferred embodiment of the present invention, the cleaning composition may be used for soil removal of particulate stains and/or oily and fatty stains, and additionally for whiteness maintenance, preferably in laundry care.

In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition that may be used for cleaning various surfaces such as hard wood, tile, ceramic, plastic, leather, metal, glass.

In another embodiment, the cleaning composition of the present invention is a liquid or solid automatic dish wash detergent composition, preferably a solid automatic dish wash detergent composition, that may be used for cleaning dish ware, e.g., dish ware such as glasses, wherein the inventive alkoxylated polymer is improving the removal of stubborn soils.

In another embodiment, the cleaning composition is designed to be used in personal care and pet care compositions such as shampoo compositions, body wash formulations, liquid or solid soaps.

In this invention, a preferred area of application for the use of the alkoxylated polymer is the field of fabric and home care products and cleaning compositions, preferably cleaning compositions for industrial and institutional use and the use by consumers in their household.

Embodiment 16 The use according to Embodiment 17 in cleaning compositions and/or in fabric and home care products, preferably in liquid and solid detergent compositions, such detergent compositions preferably being a) manual and automatic dish wash detergent compositions, comprising at least one alkoxy lated polymer, and at least one chelating agent and/or at least one surfactant or - more preferably - a chelating agent in case of a liquid or solid automatic dish wash composition and a surfactant system in case of a liquid manual dish wash detergent composition, respectively; and/or b) laundry detergent compositions comprising at least one al koxy lated polymer, and at least one surfactant or - preferably - a surfactant system.

Within such preferred application areas of use, typical tasks have to be fulfilled, all of which are commonly encompassed by the term "cleaning”, but in fact comprise different tasks such as clay removal or removing oily and fatty residues, solid residues, amphiphilic residues and hydrophilic residues. Other tasks are the protection of the goods to be cleaned from deterioration, such as protecting glass from corroding, silverware from oxidation, colors from fading etc. Other tasks are improving the overall appearance of the to be cleaned goods, such as increasing or protecting and restoring the color, preventing the transfer of dyes, the whiteness, imparting or increasing a shine. For many such applications additional ingredients are typically added, for cleaning applications important ones are for example enzymes, which help to biologically degrade residues.

Embodiment 17

The use according to Embodiment 15 or 16 for

I. clay removal, and/or

II. improved removal of oily/fatty stains, and/or ill. soil removal of particulate stains, and/or iv. dispersion and/or emulsification of soils, and/or v. modification of treated surface to improve removal upon later re-soiling, and/or vi. whiteness improvement, and/or vii. bleachable stains, and/or viii. dye transfer inhibition, and/or lx. color care, and/or most preferably in cleaning compositions for i) clay removal and/or II) removal of oily/fatty stains, each of the before mentioned options I) to lx) preferably for use in a laundry detergent formulation and/or a manual dish wash detergent formulation and/or in a formulation suitable for (pre)-treatment of textiles and/or soap bars, more preferably in a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

Embodiment 18

The use according to any of Embodiments 15 to 17 in cleaning compositions and/or in fabric and home care products, preferably in cleaning compositions for fabric and home care, the cleaning composition preferably being a laundry detergent formulation or a dish wash detergent formulation, even more preferably being a liquid laundry detergent formulation or a liquid dish wash detergent formulation.

Such ingredients are typically formulated with other ingredients in formulations and compositions, which may be also called "products” (as they are provided from a supplier as a formulation to another customer who uses such formulation directly for cleaning purposes etc. or for producing another formulation, which in turn could be sold to consumers as a "product” to be used by the consumer).

Embodiment 19

A composition that is a fabric and home care product, cleaning composition, industrial and institutional cleaning product, cosmetic or personal care product, oil field-formulation such as crude oil emulsion breaker, pigment dispersion for inks such as ink-jet inks, electro plating product, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, cementitious composition, lacquer, paint, agrochemical formulation, preferably a laundry detergent, a dish wash composition, a cleaning composition and/or a fabric and home care product, each comprising at least one alkoxylated polymer according to any of the Embodiments 1 to 11.

Embodiment 20

A composition according to Embodiment 18 being a solid or liquid laundry detergent composition or a solid or liquid manual dish wash detergent composition, preferably a liquid laundry detergent or a liquid manual dish wash detergent composition, more preferably a liquid laundry detergent composition, comprising at least one alkoxylated polymer according to any one of Embodiments 1 to 11 ; optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, disperses, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from proteases, optionally containing at least one antimicrobial agent, wherein at least one alkoxylated polymer is present in an amount ranging from about 0.01 % to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product, and such product or composition further comprising from about 1 % to about 70% by weight of at least one surfactant, preferably an anionic surfactant, or even more preferably of a surfactant system comprising at least one anionic surfactant.

Embodiment 21

A composition according to Embodiment 19 being a solid or liquid automatic dish wash detergent composition, preferably a solid automatic dish wash detergent composition, comprising the at least one alkoxylated polymer according to any one of Embodiments 1 to 11 ; optionally further comprising at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases, pectate lyases, mannanases and peroxidases, and combinations of at least two of the foregoing types, preferably at least one enzyme being selected from proteases and amylases, optionally containing at least one antimicrobial agent, optionally containing at least one compound selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, optionally containing at least one zinc salt, wherein the at least one alkoxylated polymer is being present in a total amount ranging from about 0.001 % to about 10%, preferably from about 0.005% to 5%, more preferably from about 0.01 % to about 3%, and most preferably from about 0.1 % to about 2%, and such product or composition further comprising at least one chelating agent being present in a total amount from about 1 % to about 70%, preferably from 10% to about 60% and even more preferably from 30% to about 50%, and optionally further comprising at least one surfactant or more preferably a surfactant system in a total amount of from about 1 % to about 70% by weight, all weight percent in relation to the total weight of such composition.

Embodiment 22

A composition according to Embodiment 21, being a solid automatic dish wash detergent composition, comprising at least one alkoxylated polymer according to any one of Embodiments 1 to 11 and additionally comprising at least one chelating agent selected from methylglycinediaceticacid (MGDA), glutamic acid diacetate (GLDA), citric acid, iminodisuccinic acid, iminodiacetic acid and salts thereof, at least one enzyme selected from proteases and/or amylases, at least one bleaching agent selected from alkali metal percarbonate, alkali metal perborate and alkali metal persulfate, preferably alkali metal percarbonate, at least one non-ionic surfactant, optionally at least one disintegrant, preferably a super-disintegrant, more preferably PVPP, and optionally containing at least one zinc salt.

Super-disintegrants are known by a person of skill in the art, e.g. from EP1004661 , EP1263814 and EP1036839, and are discussed also in Pharmaceutical Technology, Volume 2006 Supplement, Issue 5, "A Comparative Study of Current Superdisintegrants”, October 1 , 2006.

Embodiment 23 Composition according to any of Embodiments 19 and 20 being a detergent composition, comprising as surfactant at least one anionic surfactant.

Embodiment 24

Composition according to any of Embodiments 19 and 20 being a liquid detergent composition, comprising as surfactant at least one non-ionic surfactant, and further comprising water.

Embodiment 25

Composition according to any one of Embodiments 19 to 24 further comprising an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydiphenylether; preferably comprising 2- phenoxyethanol in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol or preferably comprising 4,4'-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, more preferably 0.002 to 1 %, even more preferably 0.01 to 0.6%, each by weight of the composition.

Embodiment 26

Composition according to any one of Embodiments 19 to 25 further comprising at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from proteases.

Embodiment 27

Method of preserving an aqueous composition according to any one of Embodiments 19 to 26 against microbial contamination or growth, which method comprises addition of an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydiphenylether.

Embodiment 28

A cleaning method comprising contacting a cleaning composition according to Embodiments 19 to 27 with an object that requires cleaning, preferably a laundry or a hard surface household item. The term "cleaning”, as used herein, refers to performing or aiding in any soil removal, bleaching, microbial population reduction, or combination thereof. This includes to rinse a fabric with water or to wash the fabric with the inventive liquid cleaning composition by means of a washing machine, automatic dish washer or by hand. It is preferred that the cleaning is carried out at a temperature of 60 °C or less, more preferably at a temperature of 40 °C or less, most preferably at a temperature of 30 °C or less. In other preferred embodiments, the cleaning method is performed under water conserving conditions. This means that not more than 60%, not more than 70%, not more than 80%, not more than 90% or not more than 95% of the water generally recommended for a given cleaning procedure is used for the cleaning method of the present invention.

Further description

It is also preferred in the present invention that the cleaning composition comprises (besides at least one alkoxylated polymer as described above) additionally at least one enzyme, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from proteases.

Preferably, the inventive cleaning composition is a fabric and home care product or an industrial and institutional (l&l) cleaning product, preferably a fabric and home care product, more preferably a laundry detergent or manual dish washing detergent, comprising at least one inventive alkoxylated polymer, and optionally further comprising at least one surfactant or a surfactant system, providing improved removal, dispersion and/or emulsification of soils and I or modification of treated surfaces and I or whiteness maintenance of treated surfaces.

At least one inventive alkoxylated polymer as described herein (such alkoxylated polymer as defined before and especially in the Embodiments 1 to 11 are in this following section also termed "inventive compound”) is present in said inventive cleaning compositions at a concentration from about 0.01 % to about 20%, preferably from about 0.05% to 15%, more preferably from about 0.1 % to about 10%, and most preferably from about 0.5% to about 5%, in relation to the total weight of such composition or product; such cleaning composition may - and preferably does - further comprise from about 1 % to about 70% by weight of a surfactant system.

Even more preferably, the cleaning compositions of the present invention comprising at least one inventive compound, and optionally further comprising at least one surfactant or a surfactant system, are those for primary cleaning (i.e., removal of stains) within laundry and manual dish wash applications, even more specifically, for removal of clay or oily and fatty stains such as those on fabrics and dishware, and may additionally comprise at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, DNases, mannanases, xylanases, disperses, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types of enzymes, more preferably at least one enzyme being selected from proteases.

In one preferred embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition.

In another preferred embodiment, the cleaning composition of the present invention is a liquid or solid (e.g., powder or tab/unit dose) detergent composition for manual or automatic dish wash, preferably either a liquid manual dish wash detergent composition or a solid automatic dish wash composition.

In one embodiment, the inventive compounds of the present invention may be utilized in cleaning compositions comprising a surfactant system comprising C10-C15 alkyl benzene sulfonates (LAS) as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment, the inventive compounds may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising Cs-C linear or branched alkyl ether sulfates with 1-5 ethoxy-units as the primary surfactant and one or more additional surfactants selected from non-ionic, cationic, amphoteric, zwitterionic or other anionic surfactants, or mixtures thereof.

In a further embodiment the inventive compounds may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising C12-C18 alkyl ethoxylate surfactants with 5-10 ethoxy-units as the primary surfactant and one or more additional surfactants selected from anionic, cationic, amphoteric, zwitterionic or other non-ionic surfactants, or mixtures thereof.

In a further embodiment the inventive compounds may be utilized in cleaning compositions, such as laundry detergents of any kind, and the like, comprising bio-based surfactants like rhamnolipids and/or sophorolipids as the primary surfactant.

In one embodiment of the present invention, the inventive compound is a component of a cleaning composition, such as preferably a laundry or a dish wash formulation, more preferably a liquid laundry or manual dish wash formulation, that each additionally comprise at least one surfactant, preferably at least one anionic surfactant. The selection of the additional surfactants in these embodiments may be dependent upon the application and the desired benefit.

As used herein, the articles "a” and "an” when used in a claim or an embodiment, are understood to mean one or more of what is claimed or described. As used herein, the terms "include(s)” and "including” are meant to be nonlimiting, and thus encompass more than the specific item mentioned after those words.

The compositions of the present disclosure can "comprise” (i.e., contain other ingredients), "consist essentially of” (comprise mainly or almost only the mentioned ingredients and other ingredients in only very minor amounts, mainly only as impurities), or "consist of' (i.e., contain only the mentioned ingredients and in addition may contain only impurities not avoidable in a technical environment, preferably only the ingredients) the components of the present disclosure.

Similarly, the terms "substantially free of ...” or "substantially free from ...” or “(containing/comprising) essentially no ...” may be used herein; this means that the indicated material is at the very minimum not deliberately added to the composition to form part of it, or, preferably, is not present at analytically detectable levels. It is meant to include compositions whereby the indicated material is present only as an impurity in one of the other materials deliberately included. The indicated material may be present, if at all, at a level of less than 1%, or even less than 0.1%, or even more less than 0.01 %, or even 0%, by weight of the composition.

The term "about”, as used herein, encompasses the exact number "X” mentioned as e.g., "about X%” etc., and small variations of X, including from minus 5 to plus 5 % deviation from X (with X for this calculation set to 100%), preferably from minus 2 to plus 2 %, more preferably from minus 1 to plus 1 %, even more preferably from minus 0,5 to plus 0,5 % and smaller variations. Of course, if the value X given itself is already "100%” (such as for purity etc.) then the term "about” clearly can and thus does only mean deviations thereof which are smaller than "100”.

Unless otherwise noted, all component or composition levels are in reference to the active portion of that component or composition, and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

All temperatures herein are in degrees Celsius (°C) unless otherwise indicated. Unless otherwise specified, all measurements herein are conducted at 20°C and under atmospheric pressure. In all embodiments 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.

Description of cleaning compositions, formulations and their ingredients The publication IPCOM000274489D published on www.IP.com is regarded as Reference RF1 , which is incorporated herein by reference in its entirety. The publication Prior Art Disclosure; Issue 684; paragraphs [3000] to [3061]; ISSN: 2198-4786; published: February 12, 2024 will be regarded as Reference RF2, which is incorporated herein by reference in its entirety.

The phrase "cleaning composition", as used herein, includes compositions and formulations designed for cleaning soiled material. Such compositions and formulations include those designed for cleaning soiled material or surfaces of any kind, more preferably compositions for Fabric and Home Care. "Cleaning compositions” are defined in more detail in paragraphs [0001], [0002], [0004] and [0007] of Reference RF1.

"Compositions for Fabric and Home Care” include cleaning compositions and formulations including but not limited to laundry cleaning compositions and detergents and hard surface cleaning compositions including dish washing compositions, more preferably liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions. "Compositions for Fabric and Home Care” are defined in more detail in paragraph [0003] of Reference RF1.

The cleaning compositions of the invention including the inventive polymer(s) may - and preferably do - contain adjunct cleaning additives (also abbreviated herein as "adjuncts”), such adjuncts being preferably in addition to a surfactant system as defined before.

Suitable adjunct cleaning additives include further polymers, surfactants or surfactant systems, builders, cobuilders, enzymes, enzyme stabilizing systems, structurants or thickeners, clay soil removal/anti-redeposition agents, solubilizing agents, chelating agents, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, malodor control agents, pigments, dyes, opacifiers, hueing agents, dye transfer inhibiting agents, chelating agents, suds boosters, suds suppressors (antifoams), color speckles, silver care, anti-tarnish and/or anti-corrosion agents, alkalinity sources, pH adjusters, pH-buffer agents, hydrotropes, scrubbing particles, antibacterial agents, anti-oxidants, softeners, carriers, processing aids, pro-perfumes, dye fixation agent and perfumes.

In preferred embodiments, the cleaning compositions comprise the inventive polymer(s) and an additional polymer, preferably cleaning polymers and/or soil release polymers. "Cleaning polymers and soil release polymers” are defined in more detail in paragraphs [0032] to [0034] of Reference RF1. These polymers include polycarboxylates, alkoxylated polyalkylenamines, alkoxylated polyalkylenimines, polyether-based polymers, rheology-modifying polymers, dye inhibition polymers and soil release polymers as defined in more detail in paragraphs [3035] to [3044] of Reference RF2. The additional polymers may include, without limitation, "multifunctional alkoxylated polyethylene imines” (for example BASF's Sokalan® HP20), "multifunctional alkoxylated diamines” (for example BASF's Sokalan® HP96), BASF's Sokalan® SR400 A and also terephthalic acid-based polyesters like Clariant's TexCare®, such as TexCare® SRN 170, TexCare® SRN 172, TexCare® SRN 260, TexCare® SRN 260 SG Terra and TexCare® SRA 300 as well as distinct combinations of all of the before mentioned polymers. Also included are graft polymers comprising a polyalkylene oxide based backbone with grafted side chains of vinyl ester monomers and optionally N-vinylpyrrolidone monomers.

In preferred embodiments, the cleaning compositions comprise the inventive polymer(s) and a surfactant or surfactant system. "Surfactants” are anionic, non-ionic, cationic, amphoteric and zwitter-ionic surfactants defined in more detail in paragraphs [3008] to [3034] of Reference RF2. In addition, these surfactants are also described in more detail in paragraphs [0008] to [0013] of Reference RF1.

Anionic surfactants for inventive cleaning compositions include linear alkylbenzenesulfonates (LAS), alkyl sulfates (AS), alkyl alkoxy sulfates (AES), alkyl alkoxy carboxylates, modified alkylbenzene sulfonates (MLAS), methyl ester sulfonates (MES), alkyl sulfosuccinates, alpha-olefin sulfonates (AOS), alkyl polyglycosides (APG) and biosurfactants, such as rhamnolipids and sophorolipids. Non-ionic surfactants for inventive cleaning compositions include alkoxylates (such as PLURONIC® from BASF), alkoxylated alcohols, alkoxylated fatty acids and alkoxylated (poly-)saccharides. Cationic surfactants for inventive cleaning compositions include surfactants comprising a quaternary ammonium. Amphoteric surfactants for inventive cleaning compositions include amine oxides. Zwitter-ionic surfactants for inventive cleaning compositions include betaines.

In preferred embodiments, the cleaning compositions comprise the inventive polymer(s) and a builder. "Builders” are defined in more detail in paragraphs [0014] to [0018] of Reference RF1. These builders include non-phosphate based builders (NPB) and phosphonates (CoP) described in more detail in paragraphs [3001] to [3005] of Reference RF2.

Builders may include, without limitation, methylglycinediaceticacid (MGDA), ethylenediaminedisuccinic acid (EDDS), glutamic acid diacetate (GLDA), citric acid, iminodisuccinic acid, iminodiacetic acid and salts thereof.

In preferred embodiments, the cleaning compositions comprise the inventive polymer(s) and an enzyme. "Enzymes” are defined in more detail in paragraphs [0020] to [0027] of Reference RF1.

Enzymes may include hydrolases, such as proteases, amylases, lipases, DNases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases. In more preferred embodiments, the cleaning composition comprises, in addition to the inventive compound(s), a protease and a protease stabilizing system comprising a peptide aldehyde.

In preferred embodiments, the cleaning compositions comprise the inventive polymer(s) and a biocide. "Biocides” are defined in more detail in paragraphs [0035] and [0036] of Reference RF1. These biocides also include compounds as defined in more detail in paragraphs [3006] and [3007] of Reference RF2.

Biocides may include, without limitation, 2-phenoxyethanol and 4,4'-dichoro 2-hydroxydiphenylether.

Further adjunct cleaning additives are included and described in more detail in paragraphs [0005], [0006], [0019], [0028] to [0031] and [0037] to [0039] of Reference RF1.

Liquid laundry formulations, solid laundry compositions, liquid manual dish wash formulations, automatic dish wash (ADW) gels and automatic dish wash (ADW) solid compositions comprising inventive polymer(s) are defined in more detail in paragraph [0041] of Reference RF1.

Examples

Synthesis of reference polymers

Ref. 1 is a PEI ethoxylate, namely PEI-600 + 20 EO/NH as described in EP3039057 B1 , example CE 1 .

Ref. 2 is an amphiphilic alkoxylated PEI, namely PEI-600 + 24 EO/NH + 16 PO/NH as described in EP2209837 B1 , example 1 .

Ref. 3 (synthesized as described in WO2021254824 A1):

The core for Ref. 3 was synthesized as described in WO2021254824 A1 , Core (a.1): The core was synthesized from 1 .2 mol (332 g) triethylcitrate and 3.34 mol (431 g) of methylcyclohexane diamine ("MCDA") as a 4:1 mixture of

A 1-1 flask with dropping funnel, nitrogen inlet, distillation overhead and stirrer was charged with 332 g triethylcitrate. Under stirring at ambient temperature, 431 g of MCDA were added dropwise in two portions over 10 minutes each. A slightly exothermic reaction was observed. The resultant colourless liquid was degassed under reduced pressure and then heated to 141 °C over a period of 8/2 hours. The distillate, 155 g of ethanol, was collected. Then, the pressure was reduced to 410 mbar and stirring was continued while cooling the mixture to ambient temperature. As a result, 541 g of the core were isolated as a sticky solid red-black material.

GPC in hexafluoroisopropanol ("HFIP"): Mn 667 g/mol, Mw 4010 g/mol

Amine number: 402 mg KOH/g

Alkoxylation of polymer Ref. 3:

A) Ethoxylation

Ref. 3 was ethoxylated as described in WO2021254824 A1 , example A.1.1 :

A 2-1 autoclave was charged with 100.0 g of the above triethylcitrate/MCDA core and 10 g water and flushed with nitrogen. The autoclave was heated to 120 °C and 31 g ethylene oxide were dosed within 10 minutes and the mixture was stirred for 16 hours. Then, 4 g of an aqueous potassium hydroxide solution 10 (50% wt) were added and the water was removed by heating the autoclave to 120 °C under reduced pressure. Then, 28 g ethylene oxide were added to the reaction mixture within 10 minutes and another 572 g ethylene oxide were added within 16 hours. The reaction mixture was allowed to react for additional 6 hours. Then the autoclave was cooled to 100 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, 731 g of intermediate polymer were obtained.

B) Propoxylation

A 2-1 autoclave was charged with 567 g of the above intermediate polymer and flushed with N2. Then, 4.9 g of an aqueous potassium hydroxide solution (50% wt) were added, and the water was removed by heating the autoclave to 130°C under reduced temperature. Then 50 g of propylene oxide were added to the reaction mixture within 10 minutes and another 600 g propylene oxide were added within 10.5 hours. The reaction mixture was allowed to react for additional 6 hours. Then the autoclave was cooled to 100°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. As a result, 1216 grams of the polymer (Ref. 3) were obtained.

Acid number: 69 mg KOH/g, Amine number: 23 mg KOH/g

The resulting polymer Ref. 3 has a ratio in weight between core:EO:PO of 6.4:40.2:53.4.

Synthesis of inventive polymers

Inventive Example 1 is based on 2 reactions steps:

1 a = synthesis of the Core 1 a

1 b = ethoxylation of Core 1 a

1a) Core 1a:

N4-Amine + Sebacic acid + ETDA + PEG 600 (1 :0, 9:0,1 :0,2) A 10OO-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amine (234.7 g, 1.35 mol), sebacic acid (245.2 g, 1.21 mol), EDTA (39.4 g, 0.14 mol) and PEG 600 (80.8 g, 0.14 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 19.5 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an amber, viscous material.

1b) ethoxylation of Core 1a

A 2-I autoclave was charged with 100.0 g core (1 a) and 4.3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 36 g ethylene oxide were dosed within 10 minutes. Then 930 g of ethylene oxide were added to the reaction mixture within 15,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 1 b was obtained as a brown solid (1070 g).

Inventive Example 2 is based on 4 reactions steps:

2a = synthesis of the Core 2a

2b = ethoxylation of Core 2a

2c= ethoxylation of 2b

2d = propoxylation of 2c

2a) Core 2a

N4-Amine + Sebacic acid + EDDS (1,5:0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amine (331.9 g, 1.90 mol), sebacic acid (231.0 g, 1.14 mol) and EDDS (61.4 g, 0.13 mol, 60% in water). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 170 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 170 °C (inside temperature) was continued under nitrogen atmosphere for a total of 21 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a greenish, viscous material.

2b) ethoxylation of Core 2a

A 2-I autoclave was charged with 70.0 g core (2a) and 3,4 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 45 g ethylene oxide were dosed within 15 minutes. Then 750 g of ethylene oxide were added to the reaction mixture within 12,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 2b was obtained as a brown solid (868 g).

2c) ethoxylation of product 2b

A 2-I autoclave was charged with 200 g product 2b and was flushing with nitrogen. The autoclave was heated to 130 °C and 61 g ethylene oxide were dosed within 15 minutes. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 2c was obtained as a light brown solid (261 g).

2d) propoxylation of product 2c

A 2-I autoclave was charged with 100 g product 2c and 0,8 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 33 g propylene oxide were dosed within 15 minutes. Then, 60 g propylene oxide were added to the reaction mixture within 1 hour. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 2d was obtained as brown solid (194 g).

Inventive Example 3 is based on 2 reactions steps:

3a = synthesis of the Core 3a

3b = ethoxylation of Core 3a

3a) Core 3a:

Pentaethylenehexamine + Sebacic acid + EDDS (1 :0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with Pentaethylenhexamin (314.3 g, 1.35 mol), sebacic acid (246.2 g, 1.22 mol) and EDDS (65.7 g, 0.14 mol, 60% in water). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 120 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 120 °C (inside temperature) was continued under nitrogen atmosphere for a total of 8 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material. 3b) ethoxylation of Core 3a (A 2-1 autoclave was charged with 100.0 g core (3a) and 5 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 44 g ethylene oxide were dosed within 15 minutes. Then 1110 g of ethylene oxide were added to the reaction mixture within 18 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 3b was obtained as a brown solid (1259 g).

Inventive Example 4 is based on 2 reactions steps:

4a = synthesis of the Core 4a

4b = ethoxylation of Core 4a

4a) Core 4a:

Pentaethylenehexamine + Tetraethylenepentamine + Sebacic acid + EDDS (0,5:0, 5:0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with Pentaethylenehexamine (100.9 g, 0.53 mol), Tetraethylenepentamine (123.9 g, 0.53 mol), sebacic acid (194.1 g, 0.96 mol) and EDDS (52.0 g, 0.11 mol, 60% in water). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 12 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material.

4b) ethoxylation of Core 4a

A 2-I autoclave was charged with 100.0 g core (4a) and 4,2 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 56 g ethylene oxide were dosed within 15 minutes. Then 900 g of ethylene oxide were added to the reaction mixture within 15 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 4b was obtained as a brown solid (1060 g)

Inventive Example 5 is based on 1 reaction step:

5) propoxylation of product 4b

A 2-I autoclave was charged with 210 g product 4b and 0,82 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 51g propylene oxide were dosed within 15 minutes. Then, 150 g propylene oxide were added to the reaction mixture within 2,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 5 was obtained as high viscous product (412g)

Inventive Example 6 is based on 1 reaction step:

6) propoxylation of product 4b

A 2-I autoclave was charged with 180 g product 4b and 0,87 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 35g propylene oxide were dosed within 10 minutes. Then, 180 g propylene oxide were added to the reaction mixture within 3 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 6 was obtained as high viscous product (396 g).

Inventive Example 7 is based on 3 reactions steps:

7a = synthesis of the Core 7a

7b = ethoxylation of Core 7a

7c = propoxylation of 7b

7a) Core 7a

N4-Amin + Tetraethylenepentamine + Sebacic acid + EDDS (0,5:0, 5:0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amin (99.8 g, 0.57 mol), Tetraethylenepentamine (108.4 g, 0.57 mol), sebacic acid (208.4 g, 1.03 mol) and EDDS (55.8 g, 0.11 mol, 60% in water). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 12.5 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material.

7b) ethoxylation of Core 7a

A 2-I autoclave was charged with 80.0 g core (7a) and 4,3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 42 g ethylene oxide were dosed within 15 minutes. Then 960 g of ethylene oxide were added to the reaction mixture within 16 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 7b was obtained as a brown solid (1087 g).

7c) propoxylation of product 7b

A 2-I autoclave was charged with 280 g product 7b and 0,7 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 32 g propylene oxide were dosed within 10 minutes. Then, 150 g propylene oxide were added to the reaction mixture within 2,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 7c was obtained as brown solid (463 g).

Inventive Example 8 is based on 1 reaction step:

8) propoxylation of product 7b

A 2-I autoclave was charged with 220 g product 7b and 0,7 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 29 g propylene oxide were dosed within 10 minutes. Then, 150 g propylene oxide were added to the reaction mixture within 2,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 8 was obtained as brown solid (400 g).

Inventive Example 9 is based on 2 reactions steps:

9a = synthesis of the Core 9a

9b = ethoxylation of Core 9a

9a) Core 9a:

N4-Amine + Sebacic acid + EDTA (1,5:0, 8:0, 2)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amine (244.2 g, 1.40 mol), sebacic acid (151.2 g, 0.75 mol) and EDTA (54.6 g, 0.19 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 14 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an off-white, viscous material. 9b) ethoxylation of Core 9a

A 2-1 autoclave was charged with 80.0 g core (9a) and 4,4 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 54 g ethylene oxide were dosed within 15 minutes. Then 960 g of ethylene oxide were added to the reaction mixture within 16 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product of inventive example 9b was obtained as a brown solid (1098 g).

Inventive Example 10 is based on 1 reaction step:

10) Propoxylation of product 9b

A 2-I autoclave was charged with 300 g product 9b and 1 ,2 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 53 g propylene oxide were dosed within 15 minutes. Then, 240 g propylene oxide were added to the reaction mixture within 3 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 10 was obtained as brown liquid (594 g).

Inventive Example 10 is based on 1 reaction step:

11) Propoxylation of product 9b

A 2-I autoclave was charged with 220 g product 9b and 1 , 1 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 29 g propylene oxide were dosed within 10 minutes. Then, 240 g propylene oxide were added to the reaction mixture within 4 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 11 was obtained as brown liquid (488 g).

Inventive Example 12 is based on 2 reactions steps:

12a = synthesis of the Core 12a

12b = ethoxylation of Core 12a

12a) Core 12a:

N4-Amine + Sebacic acid + EDTA (1,5:0, 7:0, 3) A 10OO-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amine (239.2 g, 1.38 mol), sebacic acid (129.8 g, 0.64 mol) and EDTA (80.4 g, 0.28 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 14 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an off-white, viscous material.

12b) ethoxylation of Core 12a

A 2-I autoclave was charged with 80 g core (12a) and 4.5 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 48 g ethylene oxide were dosed within 10 minutes. Then 990 g of ethylene oxide were added to the reaction mixture within 16,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 12b was obtained as a brown solid (1117g).

Inventive Example 13 is based on 2 reactions steps:

13a = synthesis of the Core 13a

13b = ethoxylation of Core 13a

13a) Core 13a

N4-Amin + Triethylenetetramine + Sebacic acid + EDTA (0,75:0,75:0,9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amin (130.2 g, 0.75 mol), Triethylenetetramine (109.3 g, 0.75 mol), sebacic acid (181.4 g, 0.90 mol) and EDTA (29.1 g, 0.10 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 14 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material.

13b) ethoxylation of Core 13aA 2-I autoclave was charged with 80 g core (13a) and 4.3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 33 g ethylene oxide were dosed within 10 minutes. Then 960 g of ethylene oxide were added to the reaction mixture within 16 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 13b was obtained as a brown solid (1071g).

Inventive Example 14 is based on 2 reactions steps:

14a = synthesis of the Core 14a

14b = ethoxylation of Core 14a

14a) Core 14a

Pentaethylenehexamine + Triethylenetetramine + Sebacic acid + EDTA (0,5:0, 5:0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with Pentaethylenehexamine (130.5 g, 0.56 mol), Triethylenetetramine (82.1 g, 0.56 mol), sebacic acid (204.5 g, 1.01 mol) and EDTA (32.8 g, 0.11 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 120 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 120 °C (inside temperature) was continued under nitrogen atmosphere for a total of 3 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material.

14b) ethoxylation of Core 14a

A 2-I autoclave was charged with 80 g core (14a) and 4.3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 38 g ethylene oxide were dosed within 10 minutes. Then 960 g of ethylene oxide were added to the reaction mixture within 16 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 14b was obtained as a brown solid (1078 g).

Inventive Example 15 is based on 3 reactions steps:

15a = synthesis of the Core 15a

15b = ethoxylation of Core 15a 15c = propoxylation of 15b

15a) Core 15a

N4-Amine + succinic acid + EDTA (1 :0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with N4-Amine (253.2 g, 1.45 mol), succinic acid (154.4 g, 1.31 mol) and EDTA (42.5 g, 0.15 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 140 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 450 rpm as viscosity decreased with rising temperature. Strong foaming was observed. Water was distilled off and collected. Stirring at 140 °C (inside temperature) was continued under nitrogen atmosphere for a total of 3.5 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an off-white, viscous material.

15b) ethoxylation of Core 15a A 2-I autoclave was charged with 60.0 g core (15a) and 3,7 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 43 g ethylene oxide were dosed within 10 minutes. Then 840 g of ethylene oxide were added to the reaction mixture within 14 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 15b was obtained as a brown solid (944 g).

15c) propoxylation of product 15b

A 2-I autoclave was charged with 173 g product 15b and 1 ,38 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 51g propylene oxide were dosed within 15 minutes. Then, 120 g propylene oxide were added to the reaction mixture within 2 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 15c was obtained as brown solid (345 g).

Inventive Example 16 is based on 1 reaction step.

16) propoxylation of product 15b

A 2-I autoclave was charged with 120 g product 15b and 0,6 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 58 g propylene oxide were dosed within 15 minutes. Then, 90 g propylene oxide were added to the reaction mixture within 1 ,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 16 was obtained as brown solid (345 g).

Inventive Example 17 is based on 3 reactions steps:

17a = synthesis of the partially alkoxylated amine

17b = synthesis of the Core 17b

17c = ethoxylation of Core 17b 17a) Angasung (pre-alkoxylation) Amine 0,5 EO/NH (131)

A 2-liter steel autoclave was charged with 800 g N4-amine and 80 g water and was then heated to 100 °C. Then, 50 g of ethylene oxide were dosed into the autoclave within 15 minutes. The start of an exothermic reaction was observed. Subsequently, 557 g of ethylene oxide (“EO”) were dosed into the autoclave within 7 hours. The system was kept at 100 °C for further 6 hours. After that, the mixture is removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 1407 g of 17a was obtained as a high viscous product.

17b) Core 17 b:

N4-Amine*0,5EO/NH + Sebacic acid + EDTA (1 :0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with 17a (710.3 g, 2.32mol), sebacic acid (421.9 g, 2.09 mol) and EDTA (67.7 g, 0.23 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 130 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 260 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 130 °C (inside temperature) was continued under nitrogen atmosphere for a total of 24 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as a yellow, viscous material.

17c) ethoxylation of Core 17b

A 2-I autoclave was charged with 100 g core (17b) and 3,3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 37 g ethylene oxide were dosed within 10 minutes. Then 690 g of ethylene oxide were added to the reaction mixture within 11 ,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 17c was obtained as a brown solid (830 g).

Inventive Example 18 is based on 1 reaction step:

18) ethoxylation of product 17b

A 2-I autoclave was charged with 100 g core (17b) and 4,8 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 41 g ethylene oxide were dosed within 15 minutes. Then 1050 g of ethylene oxide were added to the reaction mixture within 17,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 18 was obtained as a brown solid (1194 g).

Inventive Example 19 is based on 1 reaction step:

19) propoxylation of product 18

A 2-I autoclave was charged with 200 g product 18 and 1 ,6 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 43 g propylene oxide were dosed within 10 minutes. Then, 150 g propylene oxide were added to the reaction mixture within 2,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 19 was obtained as brown liquid (395 g).

Inventive Example 20 is based on 2 reactions steps:

20 a = ethoxylation of Core 17b

20 b = propoxylation of 20a

20a) ethoxylation of Core 17b

A 2-I autoclave was charged with 100 g core 17b and 5,5 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 42 g ethylene oxide were dosed within 15 minutes. Then 1230 g of ethylene oxide were added to the reaction mixture within 20,5hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 20a was obtained as a brown solid (1376 g).

20b) propoxylation of product 20a

A 2-I autoclave was charged with 200 g product 20a and 1 ,5 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 48 g propylene oxide were dosed within 10 minutes. Then, 120 g propylene oxide were added to the reaction mixture within 2 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 20b was obtained as brown liquid (370 g).

Inventive Example 21 is based on 1 reaction step: 21) ethoxylation of Core 17b

A 2I autoclave was charged with 90 g core 17b and 5,7 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 48 g ethylene oxide were dosed within 15 minutes. Then 1280 g of ethylene oxide were added to the reaction mixture within 21 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 21 was obtained as a brown solid (1424 g).

Inventive Example 22 is based on 1 reaction step:

22) propoxylation of product 21

A 2-I autoclave was charged with 200 g product 21 and 1 ,4 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 29 g propylene oxide were dosed within 10 minutes. Then, 120 g propylene oxide were added to the reaction mixture within 2 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 19 was obtained as brown solid (350 g).

Inventive Example 23 is based on 1 reaction step:

23) propoxylation of product 21

A 2-I autoclave was charged with 180 g product 21 and 1 ,4 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 27 g propylene oxide were dosed within 10 minutes. Then, 150 g propylene oxide were added to the reaction mixture within 2,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 23 was obtained as brown solid (348 g).

Inventive Example 24 is based on 2 reactions steps:

24a = synthesis of the Core 24a (core 171)

24b = ethoxylation of Core 24a

24 a) Core 24a:

L-Arginine + Sebacic acid + EDTA + Triethanolamine (1 :1 : 0, 1 : 1 ) A 10OO-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with L-Arginine (182.1 g, 1.05 mol), sebacic acid (211.4 g, 1.05 mol), EDTA (30.6 g, 0.11 mol) and triethanolamine (155.9 g, 1.05 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 155 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 240 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 155 °C (inside temperature) was continued under nitrogen atmosphere for a total of 133 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an amber, viscous material.

24b) ethoxylation of product 24b

A 2I autoclave was charged with 214 g core 24a and 4,9 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 49 g ethylene oxide were dosed within 15 minutes. Then 960 g of ethylene oxide were added to the reaction mixture within 16 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 24b was obtained as a brown solid (1228 g).

Inventive Example 25 is based on 2 reactions steps:

25a = synthesis of the Core 25a

25b = ethoxylation of Core 25a

25 a) Core 25a:

N4-Amine*0,5EO/NH + Sebacic acid + EDDS (1 :0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with 17a (343.3 g, 1.12 mol), sebacic acid (203.9 g, 1.01 mol) and EDDS (51.1 g, 0.11 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 130 °C (inside temperature) over a period of 90 minutes. The stirring speed was adjusted to 230 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 130 °C (inside temperature) was continued under nitrogen atmosphere for a total of 16.5 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an amber, viscous material.

25b) ethoxylation of product 25a

A 2I autoclave was charged with 150 g core 25a and 6,2 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 39 g ethylene oxide were dosed within 10 minutes. Then 1350 g of ethylene oxide were added to the reaction mixture within 22,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, product 25b was obtained as a brown solid (1545 g).

Inventive Example 26 is based on 1 reaction step:

26) propoxylation of product 25b

A 2-I autoclave was charged with 300 g product 18 and 2,3 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 46 g propylene oxide were dosed within 15 minutes. Then, 240 g propylene oxide were added to the reaction mixture within 4 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 26 was obtained as brown liquid (588 g).

Inventive Example 27 is based on 1 reaction step:

27) propoxylation of product 25b

A 2-I autoclave was charged with 270 g product 25b and 2,2 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 51 g propylene oxide were dosed within 15 minutes. Then, 270 g propylene oxide were added to the reaction mixture within 4,5 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 27 was obtained as brown liquid (593 g).

Inventive Example 28 is based on 3 reactions steps:

28a = synthesis of the partially alkoxy lated amine

28b = synthesis of the Core 28b

28c = ethoxylation of Core 28b

28a) Angasung (pre-alkoxylation) Amine 4 EO

28a1 ) A 2-liter steel autoclave was charged with 200 g N4-amine and 20 g water and was then heated to 100 °C. Then, 33 g of ethylene oxide were dosed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 240 g of ethylene oxide ("EC”) were dosed into the autoclave within 4 hours. The system was kept at 100 °C for further 6 hours. After that, the mixture is removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 473 g of 28a.1 was obtained as a high viscous product. 28a.2). A 2-liter steel autoclave was charged with 350 g of 28a.1 and 4,2 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. Then, 36 g of ethylene oxide were dosed into the autoclave within 10 minutes. The start of an exothermic reaction was observed. Subsequently, 660 g of ethylene oxide (“EO”) were dosed into the autoclave within 11 hours. The system was kept at 130 °C for further 6 hours. After that, the mixture is removed from the autoclave and residual EO and water were stripped under reduced pressure (20 mbar) at 80 °C for two hours. 1050 g of 28a.2 was obtained as a high viscous product.

28b) Core 28b:

N4-Amine*4EO/NH + Sebacic acid + EDTA (1 :0, 9:0,1)

A 1000-ml flask equipped with stirrer, Dean-Stark apparatus, nitrogen inlet and inside thermometer was charged with 28a.2 (204.9 g, 0.17 mol), sebacic acid (30.3 g, 0.15 mol) and EDTA (4.90 g, 0.02 mol). The reaction mixture was stirred at 60 rpm under nitrogen atmosphere and heated to 130 °C (inside temperature) over a period of 60 minutes. The stirring speed was adjusted to 210 rpm as viscosity decreased with rising temperature. Mild foaming was observed. Water was distilled off and collected. Stirring at 130 °C (inside temperature) was continued under nitrogen atmosphere for a total of 0.5 hours. Then, the reaction mixture was slowly cooled down and the resulting sample was collected as an amber, viscous material.

28c) ethoxylation of Core 28b

A 2-I autoclave was charged with 180 g core (17b) and 4,4 g of an aqueous potassium hydroxide solution (50% wt) and the water was removed by heating the autoclave to 120 °C under reduced pressure and flushing with nitrogen. The autoclave was heated to 130 °C and 30 g ethylene oxide were dosed within 10 minutes. Then 900 g of ethylene oxide were added to the reaction mixture within 15 hours. The resultant reaction mixture was allowed to react for additional 6 hours at 130°C. Then the autoclave was cooled to 80 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, inventive example 17c was obtained as a brown solid (114 g).

Inventive Example 29: alkoxylation of Core 4a with 6.3% Core: 40.4% EO and 53.3% PO in weight

A) Ethoxylation

A 2-1 autoclave was charged with 100.0 g of the core 4a. Then 2.9 g of an aqueous potassium hydroxide solution 10 (50% wt) were added to the core, and the water was removed by heating the autoclave to 130 °C under reduced pressure. Then, 38 g ethylene oxide were added to the reaction mixture within 10 minutes and another 600 g ethylene oxide were added within 10 hours. The reaction mixture was allowed to react for additional 6 hours. Then the autoclave was cooled to 100 °C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80 °C. As a result, 741 g of intermediate polymer were obtained. B) Propoxylation

A 2-1 autoclave was charged with 400 g of the intermediate polymer described above and flushed with N2. Then, 1 .8 g of an aqueous potassium hydroxide solution (50% wt) were added, and the water was removed by heating the autoclave to 130°C under reduced temperature. Then 36 g of propylene oxide were added to the reaction mixture within 10 minutes and another 420 g propylene oxide were added within 7 hours. The reaction mixture was allowed to react for additional 6 hours. Then the autoclave was cooled to 100°C. The reaction mixture was stripped with nitrogen and volatile compounds were removed in vacuo at 80°C. As a result, 856 grams of the polymer IE29 were obtained. The amine number of this polymer is 39 mg KOH/g.

The resulting polymer IE29 has a ratio in weight between core:EO:PO of 6.3:40.4:53.3.

The table below shows cores of the inventive polymers with corresponding acid numbers

The below table summarizes the chemistry of the inventive examples and shows the corresponding OH and amine numbers

FG is the sum of all functional groups of the first intermediates (11), which can be alkoxylated, for example OH, COOH, NH- functionality = FG/g

FG x grams of Core x desired mol of EO x 44 (Mw of EO) = g of EO to be added into the reactor for alkoxylation. For the propoxylation the same approach is followed, but considering 58 g/mol instead of 44 g/mol in the Formula.

The below table shows inventive examples and corresponding weight average molecular weight (Mw) and number average molecular weight (Mn)

Weight average molecular weight (Mw) and number average molecular weight (Mn) have been determined as described above.

Inventive example IE29 has been selected to be compared with reference 3.

Polymer biodegradability

Biodegradation in wastewater was tested in triplicate using the OECD 301 F manometric respirometry method. OECD 301 F is an aerobic test that measures biodegradation of a sample by measuring the consumption of oxygen. To a measured volume of medium, 100 mg/L test substance, which is the nominal sole source of carbon is added along with the inoculum (30 mg/L, aerated sludge taken from Mannheim wastewater treatment plant). This is stirred in a closed flask at a constant temperature (20°C or 25°C) for 28 or 56 days, respectively. The consumption of oxygen is determined by measuring the change in pressure in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Evolved carbon dioxide is absorbed in a solution of sodium hydroxide. Nitrification inhibitors are added to the flask to prevent usage of oxygen due to nitrification. The amount of oxygen taken up by the microbial population during biodegradation of the test substance (corrected for uptake by blank inoculum, run in parallel) is expressed as a percentage of ThOD (Theoretical oxygen demand, which is measured by the elemental analysis of the compound). A positive control Glucose/Glucosamine is run along with the test samples for each cabinet.

The below table shows biodegradability data for inventive polymers and references 1 and 2

Tef. 1 is a PEI ethoxylate, namely PEI-600 + 20 EO/NH as described in EP3039057 B1 , example CE 1.

Wash tests

1. Particulate stains

Table 1 shows the base liquid laundry detergent without any polymer (LLD.1) that has been used to carry out the application tests to determine the impact of the inventive polymers on the primary cleaning performance.

Table 1. Composition of the base liquid laundry detergent.

*) All data are wt% active ingredient, independent of the respective product form. Primary cleaning performance

To determine the primary detergency, the cleaning performance on 4 different particulate stains on a polyester fabric (CFT, Vlaardingen, The Netherlands) was measured by determining the color difference (delta E) between the stains before and after wash using a reflectometer (Mach5 plus, a multi area color measurement instrument from ColourConsult). Each experiment containing the 4 different circular particulate stains (Clay ground soil, Standard clay, Red pottery clay, Tennis court clay; all 4 stains on one polyester fabric, 1 of those fabrics per wash) was repeated 6 times in total (2 repetitions per Launder-O-Meter, 3 separate Launder-O-Meter experiments), and the obtained data was used to calculate the average delta E value.

By using these delta E values, the so-called "standardized cleaning performance” (delta delta E) has been calculated for each individual stain. The "standardized cleaning performance” (delta delta E) is the difference of the performance of the laundry detergent including the inventive polymer, or the comparative polymer, respectively, vs. the laundry detergent without any alkoxylated polymer, or comparative polymer, respectively.

Table 2 shows the washing test conditions and Table 3 summarizes the obtained standardized cleaning performance on particulate stains. The standardized cleaning performance shown in Table 3 is the sum of the standardized cleaning performance of all 4 particulate stains. The bigger the sum of the delta delta E value, the bigger the positive contribution of the inventive polymers or the comparative polymer, respectively, vs. the laundry detergent without any inventive polymer or comparative polymer, respectively, on the cleaning performance.

Table 2. Washing conditions for evaluation of primary cleaning performance.

Washing conditions

Device Launder-O-Meter from SDL Atlas, Rock Hill, USA

Washing liquor 250 mL, 50 steel balls

Washing time 30 minutes

Washing temperature 30 °C

Detergent concentration 3.0 g/L

Water hardness (Ca:Mg:HCO₃) 2.5 mmol/L (4:1 :8) (14 °dH)

Fabric to liquor ratio ca. 1 : 10

Alkoxylated polymer or comparative 60 ppm of the polymer in wash liquor, 100% active ingredient polymer, respectively Test fabrics * 4 different circular particulate stains (P-H018, P-H115, P-H144, P-

H145) (CFT, Vlaardingen, The Netherlands) on one polyester fabric; 1 stained fabric per wash

Ballast fabric 2.5 g SBL 2004 (Soil Ballast Fabric 'Formula 2004' that simulates sebum grease stains; WFK Testgewebe GmbH, Brueggen, Germany);

4 different circular bleachable stains (KC-H245, KC-H130, KC-H044, KC-H005) (CFT, Vlaardingen, The Netherlands) on one knitted cotton fabric; 1 stained fabric per wash; cotton and polyester ballast to yield a ratio of ca. 1 : 0.5 of cotton: polyester fabric per experiment

*) After the washing experiment, the test fabrics were rinsed with tap water followed by drying at ambient room temperature overnight, prior to the measurement with the Mach5 plus.

Table 3. Results from washing tests (primary cleaning performance on particulate stains)

*) All data are referring to the active ingredient, independent of the respective product form. Ref. 1 is as defined above.

Test results:

A value >2 (sum delta delta E) means that the respective polymer exhibits a directional and visible contribution to the overall cleaning performance of the respective detergent formulation; any value >4 (sum delta delta E) means that the respective polymer exhibits even a significant contribution to the overall cleaning performance, i.e., the respective polymer leads to a significant improvement of the formulation.

The inventive materials exhibit significant biodegradation properties in the OECD 301 F test after 28 days. Therefore, the inventive materials show a good combination of cleaning performance and biodegradation. 2. Oily/fatty stains

To determine the primary detergency, the cleaning performance on 8 different oily/fatty stains on cotton and polycotton fabrics (CFT, Vlaardingen, The Netherlands) was measured by determining the color difference (delta E) between the stains before and after wash using a reflectometer (Mach5 plus, a multi area color measurement instrument from ColourConsult). Each experiment containing the 8 different oily/fatty stains (Butterfat, Lard, Soybean Oil, Cocoa, Lipstick, Surfactant-sensitive soil, Sebum Bey and Chocolate Mousse) was repeated 3 times, and the obtained data was used to calculate the average delta E value.

By using these delta E values, the so-called "standardized cleaning performance” (delta delta E) has been calculated for each individual stain. The "standardized cleaning performance” (delta delta E) is the difference of the performance of the laundry detergent including the inventive polymer, or the comparative polymer, respectively, vs. the laundry detergent without any inventive polymer, or comparative polymer, respectively.

Table 4 shows the washing test conditions and Table 5 summarizes the obtained standardized cleaning performance on oily/fatty stains. The application tests were carried out in the base liquid laundry detergent without any polymer (LLD.1) described in Table 1 to determine the impact of the inventive polymers on the primary cleaning performance. The standardized cleaning performance shown in Table 5 is the sum of the standardized cleaning performance of all 8 stains. The bigger the sum of the delta delta E value, the bigger the positive contribution of the inventive polymers or the comparative polymer, respectively, vs. the laundry detergent without any inventive polymer or comparative polymer, respectively, on the cleaning performance.

Table 4. Washing conditions for evaluation of primary cleaning performance on oily/fatty stains.

Washing conditions

Device Launder-O-Meter from SDL Atlas, Rock Hill, USA

Washing liquor 250 mL, 20 steel balls

Washing time 60 minutes

Washing temperature 40 °C

Detergent concentration 2.0 g/L

Water hardness (Ca:Mg:HCO₃) 2.5 mmol/L (4: 1 :8) (14 °dH)

Fabric to liquor ratio 1 :10

Alkoxylated polymer or comparative 3% by weight (vs. liquid laundry detergent), 100% active ingredient polymer, respectively Test fabrics * 8 different oily/fatty stains (CFT-C-S-10, CFT-C-S-62, CFT-C-S-78, SWI-E-112, SWI-E-141/1, SWI-E-125, WFK-W-20D, CFT-C-S-70) (CFT, Vlaardingen, The Netherlands)

Ballast fabric 1 wfk BW 283 (WFK Testgewebe GmbH, Brueggen, Germany)

Table 5. Results from washing tests (primary cleaning performance) on 8 different oily/fatty stains

*) All data are referring to the active ingredient, independent of the respective product form. Ref. 2 is as defined above.

As described above, inventive example IE29 and reference example Ref. 3 have an almost identical weight ratio between core: EG: PO (see Table above). As these weight ratios are comparable the cleaning performance depends on the core structure of the polymers. IE29 possesses a core according to the present invention, whereas Ref. 3 possesses a core according to WO2021254824 A1. The inventive examples IE27 and IE29 exhibit significantly better cleaning performance on the oily test fabric SWI-E-125 (CFT, Vlaardingen, The Netherlands) as shown in Table 6. The respective wash tests to the data reported in Table 6 were performed according to the method described above in Table 4.

Table 6. Results from washing tests (primary cleaning performance) on the oily test fabric SWI-E-125

*) All data are referring to the active ingredient, independent of the respective product form. Ref. 2 is as defined above. Ref. 3 is synthesized as described above according to WO2021254824 A1.

Claims

1 . An alkoxylated polymer obtainable by a process comprising the following steps:

(I) reaction of

(a) at least one first amine (A1) or pre-alkoxylated amine (pA);

(ii) reaction of

(a) the first intermediate (11) with

2. The alkoxylated polymer according to claim 1 , wherein

3. The alkoxylated polymer according to claim 1 or 2, wherein the first amine (A1) or the second amine (A2) are selected from the group consisting of N,N'-Bis-(3-aminopropyl)-ethylenediamine (N4 amine), arginine, lysine, N,N-Bis(3-aminopropyl)methylamine (BAPMA), spermidine, spermine, tetraethylenpentamine (TEPA), triethylentetramine (TETA), pentaethylenehexamine (PEHA), 3-(2-aminoethylamino)propylamine (N3 amine), propylenediamine (PDA), tetramethylenediamine (TMDA), pentamethylenediamine (PMDA), hexamethylenediamine (HMDA), heptamethylenediamine, octamethylenediamine (OMDA), dipropylene-triamine (DPTA), tripropylene-tetramine (TPTA), 4,7,10-Trioxa-tridecane-1,13-diamine (TTD), 4,4'- Diaminodicyclohexylmethane (MCDA), isophorone diamine (IPDA) and 4,9-Dioxado-decane-1 ,12-diamine (DODA).

4. The alkoxylated polymer according to claims 2 or 3, wherein the second amine (A2) is reacted with 0.1 mol to 10.0 mol, preferably 0.15 mol to 7.0 mol and even more preferably 0.2 to 4 mol, of the second alkylene oxide (AO2) per mol of NH-functionality of the second amine (A2).

5. The alkoxylated polymer according to any one of claims 1 to 4, wherein the aliphatic carboxylic acid or salts, esters or anhydrides thereof (B) comprise at least two carboxyl, ester or anhydride groups, preferably the aliphatic carboxylic acid or salts, esters or anhydrides thereof (B) is a dicarboxylic acid, di-ester or compound containing two anhydride groups or is selected from the group consisting of succinic acid, malic acid, malonic acid, tartaric acid, citric acid, levulinic acid, sebacic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, hexadecanedioic acid, heneicosanedioic acid, docosanedioic acid, triacontanedioic acid, iminodiacetic acid (IDA), itaconic acid, and alkali metal or ammonium salts, esters and anhydrides thereof.

6. The alkoxylated polymer according to any one of claims 1 to 5, wherein the aminopolycarboxylic acid or salts, esters or anhydrides thereof (C) comprise at least three carboxyl, ester or anhydride groups or are selected from the group consisting of methylglycinediacetic acid (MGDA), ethylenediaminedisuccinic acid (EDDS), nitrilotriacetic acid (NTA), N-hydroxyethylaminodiacetic acid, ethylenediaminetetraacetic acid (EDTA), N-(2hydroxyethyl)iminodiacetic acid (HEIDA), hydroxyethylenediaminetriacetic acid, N-hydroxyethyl-ethylenediaminetriacetic acid (HEDTA), hydroxyethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), glutamic acid-diacetic acid (GLDA), Ethylenediamine-N,N'-bis (2-hydroxyphenylacetic acid) (EDDHA), iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid, aspartic acid-N-monoacetic acid (ASMA), aspartic acid-N, N-diacetic acid (ASDA), aspartic acid-N- monopropionic acid (ASMP), N-(2-sulfomethyl) aspartic acid (SMAS), N-(2-sulfoethyl) aspartic acid (SEAS), N-(2-sulfomethyl) glutamic acid (SMGL), N-(2-sulfoethyl) glutamic acid (SEGL), N-methyliminodiacetic acid (MIDA), serine-N, N-diacetic acid (SEDA), isoserine-N, N-diacetic acid (ISDA), phenylalanine-N, N-diacetic acid (PHDA), anthranilic acid-N, N-diacetic acid (ANDA), sulfanilic acid-N, N-diacetic acid (SLDA), taurine-N, N-diacetic acid (TUDA), sulfomethyl-N, N-diacetic acid (SMDA) and alkali metal or ammonium salts, esters and anhydrides thereof.

7. The alkoxylated polymer according to any one of claims 1 to 6, wherein the alkanolamine (D)

(i) comprises at least two or three hydroxyl groups; or

8. The alkoxylated polymer according to any one of claims 1 to 7, wherein in the second reaction

(ii) 2 mol to 40 mol, preferably 3 mol to 30 mol of the first propylene oxide (PO1) is employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11); or (iii) 5 mol to 50 mol, preferably 15 mol to 45 mol of the first ethylene oxide (EO1) and 2 mol to 40 mol, preferably 3 mol to 30 mol of the first propylene oxide (PO1) are employed per mol of the sum of NH-functionality, -OH group and -COOH group of the first intermediate (11).

9. A process to prepare an alkoxylated polymer according to any one of claims 1 to 8 comprising carrying out the process steps according to any one of claims 1 to 8.

10. A compound that is the first intermediate (11) according to the first reaction of claim 1.

11 . Use of the alkoxylated polymer according to any one of claims 1 to 8 or the first intermediate (11) according to claim 10 in laundry detergents, in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil emulsion breaker, in pigment dispersions for ink jet inks, in formulations for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, in cementitious compositions and/or as dispersant for agrochemical formulations, preferably in cleaning compositions and/or in fabric and home care products.

12. Use according to claim 11 in cleaning compositions and/or in fabric and home care products, preferably in cleaning compositions for

(i) sebum removal, and/or

(ii) improved removal of oily/fatty stains, and/or

(iii) soil removal of particulate stains, and/or

(iv) dispersion and/or emulsification of soils, and/or

(v) modification of treated surface to improve removal upon later re-soiling, and/or

(vi) whiteness improvement, and/or

(vii) bleachable stains, and/or

(viii) dye transfer inhibition, and/or

(ix) color care, and/or most preferably in cleaning compositions for

(i) clay removal and/or (ii) removal of oily/fatty stains, each of the before mentioned options (i) to (ix) preferably for use in a laundry detergent formulation and/or a manual dish wash detergent formulation and/or in a formulation suitable for (pre)-treatment of textiles and/or soap bars, more preferably in a liquid laundry detergent formulation and/or a liquid manual dish wash detergent formulation.

13. A laundry detergent, cleaning composition, fabric and home care product, cosmetic formulation, crude oil emulsion breaker, pigment dispersion for ink jet inks, formulation for electro plating, as froth flotation agent in mineral processing, in waste water treatment, in deinking of recycled paper, cementitious composition and/or dispersant for agrochemical formulations, comprising at least one alkoxy I ated polymer according to any of claims 1 to 8 or the first intermediate (11) according to claim 10, preferably laundry detergent, cleaning composition and/or fabric and home care product, comprising at least one alkoxy lated polymer according to any of claims 1 to 8 or the first intermediate (11) according to claim 10.

14. The laundry detergent, cleaning composition, fabric or home care product according to claim 13 further comprising

(i) an antimicrobial agent selected from the group consisting of 2-phenoxyethanol and 4,4'-dichoro 2- hydroxydiphenylether; preferably comprising 2-phenoxyethanol in an amount ranging from 2ppm to 5% by weight of the composition; more preferably comprising 0.1 to 2% of phenoxyethanol or preferably comprising 4,4'-dichoro 2-hydroxydiphenylether in a concentration from 0.001 to 3%, more preferably 0.002 to 1%, even more preferably 0.01 to 0.6%, each by weight of the composition, and/or

(ii) at least one enzyme selected from the list consisting of lipases, hydrolases, amylases, DNases, proteases, cellulases, hemicellulases, phospholipases, esterases, mannanases, xylanases, dispersins, oxidoreductases, cutinases, pectate lyases, pectinases, lactases and peroxidases, and combinations of at least two of the foregoing types, preferably selected from one or more lipases, hydrolases, amylases, proteases, cellulases, and combinations of at least two of the foregoing types, more preferably at least one enzyme being selected from proteases and/or

(iii) at least one surfactant selected from the group consisting of anionic surfactants and non-ionic surfactants, and/or

(iv) at least one chelating agent selected from the group consisting of methylglycinediaceticacid (MGDA), ethylenediaminedisuccinic acid (EDDS), glutamic acid diacetate (GLDA), citric acid, iminodisuccinic acid, iminodiacetic acid and salts thereof.