Alkoxylated polyalkyleneimines or alkoxylated polyamines with improved biodegradability

Abstract

The present invention relates to a compound represented by general formula (I) [Formula 1] TIFF2023515059000026.tif20161, where variables E1-E5, R, B, y, and z are defined below. The present invention further relates to a method for preparing such an alkoxylated polyalkyleneimine or alkoxylated polyamine, as well as to the use of such compounds, for example in cleaning compositions and / or fabric and home care products. Furthermore, the present invention also relates to such compositions or products themselves.

Description

[Technical Field]

[0001] The present invention relates to a compound represented by general formula (I)

[0002] [ka] wherein variables E1-E5, R, B, y, and z are defined below. The present invention relates to an alkoxylated polyalkyleneimine or alkoxylated polyamine according to the above. [Background technology]

[0003] Various states have already introduced measures to ban microplastics, especially in cosmetic products. Active discussions are underway regarding this ban on insoluble microplastics as well as the future need for soluble polymers used in consumer products. Therefore, identifying new and better biodegradable components for such applications is highly desirable. This problem is primarily acute for polymers produced by radical polymerization based on carbon-only backbones, since carbon-only backbones (those without heteroatoms, e.g., oxygen) are particularly difficult to degrade by microorganisms.

[0004] The present invention further relates to methods for preparing such alkoxylated polyalkyleneimines or alkoxylated polyamines, and to the use of such compounds, for example in cleaning compositions and / or fabric and home care products. Additionally, the present invention also relates to such compositions or products themselves.

[0005] WO 2015 / 028191 relates to water-soluble alkoxylated polyalkyleneimines having polyethylene oxide inner blocks containing 5 to 18 polyethylene oxide units, a polyalkylene oxide middle block containing 1 to 5 polyalkylene oxide units, and polyethylene oxide outer blocks containing 2 to 14 polyethylene oxide units. The middle block is formed from polypropylene oxide units, polybutylene oxide units, and / or polypentene oxide units. WO 2015 / 028191 also relates to water-soluble alkoxylated polyamines.

[0006] WO2020 / 187648 also relates to polyalkoxylated polyalkyleneimines or alkoxylated polyamines according to general formula (I). The compounds described therein can be used, for example, in cosmetic formulations. However, the specific compounds disclosed in WO2020 / 187648 differ from the compounds of the present invention in terms of the definition of the substituents, such as E1 and E5, defined according to formula (IIa) or (IIb) in the present invention. Such substituents according to formula (IIa) and / or (IIb) are not disclosed in WO2020 / 187648.

[0007] GB-A2562172 relates to a specific functionalized polyalkyleneimine polymer according to general formula (I), which composition is used as a pigment dispersion. GB-A2562172 does not disclose any alkoxylated polyalkyleneimine or alkoxylated polyamine according to general formula (I) of the present invention, in which the substituents, e.g., E1 to E5, are defined according to general formula (IIa) and / or formula (IIb).

[0008] WO 95 / 32272 describes ethoxylated and / or propoxylated polyalkyleneamine polymers that enhance soil dispersancy performance, said polymers having an average ethoxylation / propoxylation per nitrogen of 0.5 to 10. Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide novel compounds based on a polyalkyleneimine or polyamine backbone, which, in addition, should have beneficial properties when used in compositions with regard to their biodegradability. [Means for solving the problem]

[0010] This object is achieved by the synthesis of compounds of general formula (I)

[0011] [ka] wherein each variable is defined as follows: R may be the same or different; i) linear or branched C2-C 12- an alkylene group or ii) a group represented by the following formula (III):

[0012] [ka] where each variable is defined as follows: R 10 , R 11 , R 12 represent the same or different linear or branched C2-C6 alkylene groups, d is an integer having a value in the range of 0 to 50. or iii) a C5-C optionally substituted with at least one C1-C3-alkyl 10 -represents a cycloalkylene group; B represents a continuation of the alkoxylated polyalkyleneimine by branching; y and z are each an integer having a value in the range of 0 to 150, provided that R is a C5-C optionally substituted with at least one C1-C3-alkyl. 10 - when it is a cycloalkylene group, both z and y are 0; E1, E2 and E4 represent the same or different residues according to formula (IIa) or the same or different residues according to formula (IIb), Residues according to formula (IIa) are

[0013] [ka] where each variable is defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group; R 2 In the general formula (I), when z is an integer of 1 or more, it is hydrogen and / or C1 to C 22 -Alkyl and / or C7-C 22 -aralkyl, or R 2 In the general formula (I), when z is 0, it is hydrogen and / or C1-C4 alkyl and / or C7-C 22 - represents aralkyl; R 3 is a linear or branched C1-C 22 -represents an alkylene group; m is an integer having a value of at least 1 to 10; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: Residues according to formula (IIb) are

[0014] [ka] where the variables are defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group; R 2 is hydrogen and / or C1-C 22 -Alkyl and / or C7-C 22 - represents aralkyl; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: E3 is hydrogen when E2 is a residue according to formula (IIa), or E3 is a residue according to formula (IIb); E5 is hydrogen when E4 is a residue according to formula (IIa), or E5 is a residue according to formula (IIb); 20 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa), and 50 to 100% of the total amount of E1 is a residue according to formula (IIb). This is achieved by the alkoxylated polyalkyleneimine or alkoxylated polyamine of the formula: DETAILED DESCRIPTION OF THE INVENTION

[0015] The alkoxylated compounds according to the present invention can be used in, for example, cleaning compositions and / or fabric and home care products.They provide at least the same, preferably even improved, anti-redeposition and cleaning performance in such compositions or products compared with the corresponding polymers or compounds according to the prior art, for example, in terms of soil redeposition and stain removal.In addition, the alkoxylated compounds according to the present invention provide improved biodegradability when used in such compositions or products, for example, cleaning compositions and / or fabric and home care products.

[0016] The alkoxylated compounds with improved biodegradability according to the present invention can be advantageously used in washing and cleaning compositions, where they assist surfactants in removing hydrophobic soils from fabrics or hard surfaces, thus improving the washing and cleaning performance of the formulations.In addition, they provide better dispersion of the removed soils in the washing or cleaning liquid, preventing them from re-depositing on the surface of the washed or cleaned materials.

[0017] For the purposes of the present invention, for example, R 2 C1 to C as defined above for the groups 22The definition -alkyl etc. means that the substituent (group or residue) is an alkyl group having 1 to 22 carbon atoms. The alkyl group may be linear or branched, or optionally cyclic. Alkyl groups having both cyclic and linear components are also included in this definition. The same applies to other alkyl groups, for example, C1-C4-alkyl groups. Examples of alkyl groups are methyl, ethyl, n-propyl, sec-propyl, n-butyl, sec-butyl, isobutyl, 2-ethylhexyl, tert-butyl (tert-Bu / t-Bu), pentyl, hexyl, heptyl, cyclohexyl, octyl, nonyl, decyl or dodecyl.

[0018] "C2~C 12 The term "-alkylene", as used herein, refers to a saturated divalent straight or branched hydrocarbon chain of 2, 3, 4, 5, 6 or up to 12 carbon atoms, examples of which include ethane-1,2-diyl ("ethylene"), propane-1,3-diyl, propane-1,2-diyl, 2-methylpropane-1,2-diyl, 2,2-dimethylpropane-1,3-diyl, butane-1,4-diyl, butane-1,3-diyl (=1-methylpropane-1,3 -diyl), butane-1,2-diyl ("1,2-butylene"), butane-2,3-diyl, 2-methyl-butane-1,3-diyl, 3-methyl-butane-1,3-diyl (= 1,1-dimethylpropane-1,3-diyl), pentane-1,4-diyl, pentane-1,5-diyl, pentane-2,5-diyl, 2-methylpentane-2,5-diyl (= 1,1-dimethylbutane-1,3-diyl) and hexane-1,6-diyl.

[0019] "C5~C 10 The term "cycloalkylene," as used herein, refers to a saturated divalent hydrocarbon of 5, 6, 7, 8, 9, or 10 carbon atoms, where all or at least some of the carbon atoms in each number form a cyclic moiety (ring). When not all of the carbon atoms in each number form a cyclic moiety, such remaining carbon atoms (i.e., carbon atoms not forming a cyclic moiety) are each a C5-C 10-cycloalkylene group, forming a methane-1,1-diyl ("methylene") or ethane-1,2-diyl ("ethylene") fragment. One of the two valencies of each methylene or ethylene fragment is attached to the adjacent nitrogen atom in general formula (I), while the second valency of the fragment is attached to the C5-C 10 - is attached to the cyclic fragment of the cycloalkylene group.

[0020] In other words, C5~C 10 -Cycloalkylene groups include, in addition to their cyclic fragments, some acyclic fragments, and are C5-C 10 A bridge or linker may be constructed between the cyclic fragment of the cycloalkylene group and the adjacent nitrogen atom in general formula (I). The number of such carbon linker atoms is usually 3 or less, preferably 1 or 2. For example, a C7-cycloalkylene group may contain one C6-cyclic part and one C1-linker.

[0021] Each hydrocarbon ring moiety may itself be unsubstituted or at least monosubstituted with C1-C3-alkyl. The carbon atoms of each C1-C3-alkyl substituent may be C5-C 10 It should be noted that the C-C alkylene group is not taken into account when determining the number of carbon atoms in the -cycloalkylene group. 10 The number of carbon atoms in a cycloalkylene group does not include any substituents, but is determined only by the number of carbon atoms in the cyclic fragment and any carbon linker atoms (methylene or ethylene fragments) that are optionally present.

[0022] C5~C 10 Examples of -cycloalkylene include cyclopentane-1,2-diyl, cyclohexane-1,2-diyl, cyclohexane-1,3-diyl, cyclohexane-1,4-diyl, 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl, cycloheptane-1,3-diyl or cyclooctane-1,4-diyl, each of the aforementioned groups being optionally at least monosubstituted by C1-C3-alkyl.

[0023] Each C5~C 10 The cycloalkylene groups are preferably used as a mixture of two or more individual cycloalkylene groups having the same ring size. It is particularly preferred to use a mixture of cyclohexane-1,3-diyls, each mono-substituted with methyl at the 2- or 4-position of the ring moiety. The ratio of the two components is preferably within the range of 95:5 to 75:25, most preferably about 85:15 (4-methyl to 2-methyl).

[0024] 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl is a C5-C cyclohexane-1,3-diyl derivative that has acyclic fragments in addition to its cyclic fragments. 10 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl is a preferred example of a -cycloalkylene group. In this particular case, the acyclic fragment is a C1-linker and the cyclic fragment is a C6-cyclic moiety, resulting in a C7-cycloalkylene group. 3-(methane-1,1-diyl)-cyclohexane-1,3-diyl may also be substituted with at least one C1-C3 alkyl, preferably with three methyl groups, in particular with 3,5,5-trimethyl. The latter is a fragment of isophoronediamine that can be used as a skeleton having the general formula (I).

[0025] For purposes of the present invention, the term "aralkyl" refers to, for example, R 2 As defined above for groups, it is meant that the substituent (group) is aromatic ("ar") in combination with an alkyl substituent ("alkyl"). The aromatic "ar" moiety may be monocyclic, bicyclic, or optionally polycyclic aromatic. In the case of polycyclic aromatics, the individual rings may optionally be fully or partially saturated. Preferred examples of aryl are phenyl, naphthyl, or anthracyl, especially phenyl.

[0026] In the context of the present invention, the term "polyalkyleneimine" differs from the corresponding term "polyamine," particularly with regard to the branching of the corresponding backbone. While polyamines in the context of the present invention are (predominantly) linear compounds with respect to their backbone (regardless of any alkoxylation) and containing primary and / or secondary amino moieties but not tertiary amino moieties within their backbone, corresponding polyalkyleneimines, according to the present invention, are (predominantly) branched molecules with primary and / or secondary amino moieties as well as mandatory tertiary amino moieties within their backbone (regardless of any alkoxylation), whereby the (linear) main chain branches into several side chains within the polymer backbone (basic framework). Polyalkyleneimines, both as backbone and alkoxylated compounds, are compounds falling within the definition of general formula (I), in which z is an integer of at least 1. In contrast, polyamines, both as backbone and alkoxylated compounds, are those compounds of formula (I), in which z is 0.

[0027] As a result, the alkoxylated polyalkyleneimines of the present invention have a basic framework (skeleton) comprising primary, secondary and tertiary amine nitrogen atoms linked by alkylene groups R (defined below) and in the form of the following moieties in a random arrangement: - primary amino moieties terminating the main and side chains of the basic framework, the hydrogen atoms of which are subsequently replaced by alkyleneoxy units:

[0028] [ka] a secondary amino moiety, the hydrogen atom of which is subsequently replaced by an alkyleneoxy unit:

[0029] [ka] - tertiary amino moieties that branch the main chain and side chains:

[0030] [ka]

[0031] For the sake of completeness, the variable B, which indicates the branching of the polyalkyleneimine backbone of the compounds according to general formula (I), including two, three or even higher branching, can be a fragment, such as -[-NH-R] y It is shown that the tertiary amino moiety may comprise -, H2N-R, or a combination thereof, wherein the tertiary amino moiety is not present within the backbone of the polyamine compound.

[0032] To obtain the respective alkoxylated compounds, the hydrogen atoms of the primary and / or secondary amino groups of the basic polyalkyleneimine or polyamine backbone are replaced by alkyleneoxy units of formula (IIa) or (IIb) as defined below: When E2 or E4 are defined according to general formula (IIa), the respective corresponding hydrogen atoms of the primary amino functions of the backbone (E3 or E5) remain unmodified due to the incorporation of an amide group.

[0033] In the context of the present invention, the term "polyalkyleneimine backbone" relates to a fragment of the alkoxylated polyalkyleneimine of the present invention that has not been alkoxylated. The polyalkyleneimine backbone is used in the present invention as an educt that is first reacted with at least one lactone or hydroxycarbon acid and then alkoxylated with at least one epoxide to obtain the alkoxylated polyalkyleneimine of the present invention ("alkoxylated compound"). The polyalkyleneimine itself (backbone or not the alkoxylated compound) is known to those skilled in the art. For example, the polyalkyleneimine backbone can be derived from a compound according to general formula (I) by replacing variables E1 to E5 with hydrogen atoms (H).

[0034] In the context of the present invention, the term "polyamine backbone" relates to a fragment of the alkoxylated polyamine of the present invention that has not been alkoxylated. The polyamine backbone is used in the present invention as an educt that is first reacted with at least one lactone or hydroxycarbon acid and then alkoxylated with at least one epoxide to obtain the alkoxylated polyamine of the present invention ("alkoxylated compound"). The polyamine itself (backbone or not the alkoxylated compound) is known to those skilled in the art. For example, the polyamine backbone can be derived from a compound according to general formula (I) by replacing variables E1 to E5 with hydrogen atoms (H).

[0035] In the context of the present invention, the term "NH-functionality" is defined as follows: in the case of (mainly) linear amines, such as di- and oligoamines, e.g., N4 amines or hexamethylenediamine, the structure itself gives information about the content of primary, secondary and tertiary amines. Primary amino groups (-NH2) have two NH-functionalities, secondary amino groups have only one NH-functionality, and tertiary amino groups consequently have no reactive NH-functionality. In the case of (mainly) branched polyethyleneimines, such as those obtained from the polymerization of the monomer ethyleneimine (C2H5N), each polymer (polyethyleneimine) contains a mixture of primary, secondary and tertiary amino groups. The exact distribution of primary, secondary, and tertiary amino groups can be determined as described in Lukovkin GM, Pshezhetsky VS, Murtazaeva GA: Europ. Polymer Journal 1973, 9, 559-565 and St. Pierre T., Geckle M.: ACS Polym. Prep. 1981, 22, 128-129. In the case of modification with lactone or hydroxy acid and alkylene oxide, polyethyleneimine consists of a 1:1:1 mixture of primary, secondary, and tertiary amino groups, and therefore, it is assumed that an amount similar to the molar mass of the monomer used, e.g., ethyleneimine, contributes, on average, one (reactive) NH-functional group. This is the molecular weight of the repeating unit.

[0036] The present invention is specified in more detail as follows:

[0037] The present invention relates to a compound represented by general formula (I)

[0038] [ka] wherein each variable is defined as follows: R may be the same or different; i) linear or branched C2-C 12- an alkylene group or ii) a group represented by the following formula (III):

[0039] [ka] where each variable is defined as follows: R 10 , R 11 , R 12 represent the same or different linear or branched C2-C6 alkylene groups, d is an integer having a value in the range of 0 to 50. or iii) a C5-C optionally substituted with at least one C1-C3-alkyl 10 -represents a cycloalkylene group; B represents an extension of the alkoxylated polyalkyleneimine by branching; y and z are each an integer having a value in the range of 0 to 150, provided that R is a C5-C optionally substituted with at least one C1-C3-alkyl. 10 - when it is a cycloalkylene group, both z and y are 0; E1, E2 and E4 represent the same or different residues according to formula (IIa) or the same or different residues according to formula (IIb), Residues according to formula (IIa) are

[0040] [ka] where each variable is defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group; R 2 In the general formula (I), when z is an integer of 1 or more, it is hydrogen and / or C1 to C 22 -Alkyl and / or C7-C 22 -aralkyl, or R 2 In the general formula (I), when z is 0, it is hydrogen and / or C1-C4 alkyl and / or C7-C 22 - represents aralkyl; R 3 is a linear or branched C1-C 22 -represents an alkylene group; m is an integer having a value of at least 1 to 10; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: Residues according to formula (IIb) are

[0041] [ka] where the variables are defined as follows: R 1 is C2~C 22 represents a -(1,2-alkylene) group; R 2 is hydrogen and / or C1-C 22 -Alkyl and / or C7-C 22 - represents aralkyl; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: E3 is hydrogen when E2 is a residue according to formula (IIa), or E3 is a residue according to formula (IIb); E5 is hydrogen when E4 is a residue according to formula (IIa), or E5 is a residue according to formula (IIb); 20 to 100% of the total amount of E2 and E4 is a residue according to formula (IIa), and 50 to 100% of the total amount of E1 is a residue according to formula (IIb). The present invention relates to an alkoxylated polyalkyleneimine or alkoxylated polyamine of the above formula (1).

[0042] For the sake of completeness, the variable B, which indicates the branching of the alkoxylated polyalkyleneimine compounds according to general formula (I), including two, three or even higher branching, can be a fragment, such as -[-NE-R] y It is shown that the tertiary amino moieties provided by backbone branching are absent in alkoxylated polyamine compounds according to general formula (I) because the variable z in formula (I) is 0 for such types of compounds.

[0043] In the compounds according to general formula (I), R are the same or different i) Linear or branched C2 to C 12- an alkylene group, preferably R is ethylene, propylene or hexamethylene; or ii) C5-C optionally substituted with at least one C1-C3-alkyl 10 -cycloalkylene group, preferably R is at least one C6-C7-cycloalkylene group substituted with at least one methyl or ethyl.

[0044] It is even more preferred for the alkoxylated compounds of the present invention that in formula (IIa) and / or (IIb), the variables are each defined as follows: R 1 represents 1,2-ethylene, 1,2-propylene or 1,2-butylene, most preferably 1,2-ethylene; and / or R 2 represents hydrogen and / or C1-C4-alkyl, preferably hydrogen, methyl and / or ethyl, most preferably hydrogen; and / or R 3 However, linear or branched C2 to C10 - represents an alkylene group, preferably a linear or branched C2-C5 alkylene group; and / or m is an integer having a value in the range of 1 to 5, preferably 1 to 3; and / or n is an integer having a value in the range of 8 to 40, preferably 10 to 25; and / or 50 to 100%, preferably 80 to 100%, even more preferably 90 to 100%, and most preferably more than 99% of the total amount of E2 and E4 are residues according to formula (IIa), and 80 to 100%, most preferably 85 to 95% of the total amount of E1 are residues according to formula (IIb).

[0045] Furthermore, for the alkoxylated compound according to the general formula (I) of the present invention, the weight average molecular weight (Mw) of the polyalkyleneimine skeleton or polyamine skeleton is preferably in the range of 50 to 10,000 g / mol, more preferably in the range of 500 to 5,000 g / mol, and more preferably in the range of 600 to 2,000 g / mol.

[0046] Those skilled in the art will appreciate that the respective weight average molecular weights (M W There are known methods for determining / measuring M. This can be done, for example, by size exclusion chromatography (e.g., GPC). Preferably, M W The values ​​are determined by the following method: OECD TG 118 (1996), 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 online at, for example, https: / / doi.org / 10.1787 / 9789264069848-en.

[0047] The alkoxylated polyalkyleneimine compounds according to formula (I) are preferably compounds in which the variables are each defined as follows: R is ethylene or propylene, preferably ethylene; The sum of y and z is an integer having a value within the range of 9 to 120, preferably within the range of 10 to 20.

[0048] It is even more preferred that for the alkoxylated polyalkyleneimine compounds according to general formula (I), the variables are defined as follows: R is ethylene or propylene, preferably ethylene; The sum of y and z is an integer having a value in the range of 9 to 120, preferably in the range of 10 to 20; R 1 represents 1,2-ethylene; R 2 represents hydrogen and / or C1-C4-alkyl, preferably hydrogen, methyl and / or ethyl, most preferably hydrogen; R 3 However, linear or branched C2 to C 10 - represents an alkylene group, preferably a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 5, preferably 1 to 3; n is an integer having a value in the range of 8 to 40, preferably 10 to 25; 50 to 100%, preferably 80 to 100%, even more preferably 90 to 100%, and most preferably more than 99% of the total amount of E2 and E4 are residues according to formula (IIa), and 80 to 100%, most preferably 85 to 95% of the total amount of E1 are residues according to formula (IIb).

[0049] In a preferred embodiment of the present invention, the alkoxylated polyalkyleneimine compound according to general formula (I) is a compound in which the variables are each defined as follows: R is ethylene; the sum of y and z is an integer having a value in the range of 10 to 20; R 1 represents 1,2-ethylene; R 2 represents hydrogen; R 3 represents a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 3; n is an integer having a value in the range of 10 to 25; 90-100%, most preferably more than 99%, of the total amount of E2 and E4 are residues according to formula (IIa), and 85-95% of the total amount of E1 are residues according to formula (IIb).

[0050] In another embodiment of the present invention, the alkoxylated compounds included in the definition of general formula (I) are alkoxylated polyamines. For those types of compounds, the variable z is 0.

[0051] The alkoxylated polyamine of the present invention is preferably, but not limited to, alkoxylated hexamethylenediamine, alkoxylated ethylenediamine, alkoxylated 1,3-diaminopropane, alkoxylated neopentanediamine, alkoxylated diethylenetriamine, alkoxylated octamethylenediamine, or alkoxylated 1,2-propylenediamine.

[0052] The R groups connecting the amine nitrogen atoms are the same or different linear or branched C2-C 12 -alkylene groups, preferably C2-C6-alkylene groups. A preferred branched alkylene is 1,2-propylene. Particularly preferred alkylene groups R are ethylene or hexamethylene. However, it is also possible for the group R to be an ether alkyl unit according to formula (III) defined above, or a C5-C6-alkylene group as defined above. 10 It is also preferably a -cycloalkylene group.

[0053] When the alkoxylated compound according to general formula (I) is an alkoxylated polyamine, it is preferred that the variables are defined as follows: y is an integer having a value in the range of 0 to 10; z is 0; R is the same or different, linear or branched C2-C 12- an alkylene group or a group represented by formula (III) d is 1 to 5; R 10 , R 11 , R 12 are independently selected from linear or branched C3-C4 alkylene groups. represents an ether alkyl unit conforming to the formula:

[0054] It is even more preferred that for those types of alkoxylated polyamine compounds according to formula (I): R 1 represents 1,2-ethylene; R 2 represents hydrogen and / or C1-C4-alkyl, preferably hydrogen, methyl and / or ethyl, most preferably hydrogen; R 3 However, linear or branched C2 to C 10 - represents an alkylene group, preferably a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 5, preferably 1 to 3; n is an integer having a value in the range of 8 to 40, preferably 10 to 25; y is an integer having a value in the range of 1 to 10; 50 to 100%, preferably 80 to 100%, even more preferably 90 to 100%, and most preferably more than 99% of the total amount of E2 and E4 are residues according to formula (IIa), and 80 to 100%, most preferably 90 to 100% of the total amount of E1 are residues according to formula (IIb).

[0055] In preferred embodiments of the alkoxylated polyamine compounds according to formula (I), the variables are defined as follows: R is ethylene or propylene; R 1 represents 1,2-ethylene; R 2represents hydrogen; R 3 represents a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 3; n is an integer having a value in the range of 10 to 25; y is an integer having a value in the range of 2 to 4; 90 to 100%, most preferably more than 99%, of the total amount of E2 and E4 are residues according to formula (IIa), and 90 to 100% of the total amount of E1 are residues according to formula (IIb).

[0056] In another embodiment of the invention, in which the compound according to general formula (I) is an alkoxylated polyamine, the variable R is based on a C5-C8-cycloalkylene group. The C5-C8-cycloalkylene group may be unsubstituted or at least monosubstituted with a C1-C3-alkyl. In this embodiment, it is preferred that the variables of general formula (I) are defined as follows: y is 0; z is 0; R is the same or different C5-C optionally substituted with at least one C1-C3-alkyl; 10 represents a cycloalkylene group, Preferably, R is at least one C6-C7-cycloalkylene group substituted with at least one methyl or ethyl, More preferably, R is at least one C6-cycloalkylene group monosubstituted with methyl or at least one C7-cycloalkylene group substituted with at least one methyl, preferably trisubstituted with methyl; Most preferably, R is a mixture of 4-methyl-cyclohexane-1,3-diyl and 2-methyl-cyclohexane-1,3-diyl.

[0057] It is even more preferred that for those types of alkoxylated polyamine compounds according to formula (I): R 1 represents 1,2-ethylene; R 2 represents hydrogen and / or C1-C4-alkyl, preferably hydrogen, methyl and / or ethyl, most preferably hydrogen; R 3 However, linear or branched C2 to C 10 - represents an alkylene group, preferably a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 5, preferably 1 to 3; n is an integer having a value in the range of 8 to 40, preferably 10 to 25; y is 0; 50 to 100%, preferably 80 to 100%, even more preferably 90 to 100%, and most preferably more than 99% of the total amount of E2 and E4 are residues according to formula (IIa), and 80 to 100%, most preferably 90 to 100% of the total amount of E1 are residues according to formula (IIb).

[0058] In preferred embodiments of the alkoxylated polyamine compounds according to formula (I), the variables are defined as follows: R is ethylene or propylene; R 1 represents 1,2-ethylene; R 2 represents hydrogen; R 3 represents a linear or branched C2-C5 alkylene group; m is an integer having a value in the range of 1 to 3; n is an integer having a value in the range of 10 to 25; y is 0; 90 to 100%, most preferably more than 99%, of the total amount of E2 and E4 are residues according to formula (IIa), and 90 to 100% of the total amount of E1 are residues according to formula (IIb).

[0059] In another embodiment of the present invention, the alkoxylated polyalkyleneimine or alkoxylated polyamine of the present invention comprises 1 to 30%, preferably 3 to 20%, most preferably 5 to 10% of residues according to formula (IV) relative to the total amount of residues according to formula (IIa) and formula (IIb).

[0060] The alkoxylated polyalkyleneimines or alkoxylated polyamines of the present invention may also be quaternized. A suitable degree of quaternization is up to 100%, in particular 10 to 95%. The quaternization is preferably carried out by dissolving C1 to C 22 -Alkyl group, C1-C4 alkyl group and / or C7-C 22 This is achieved by introducing an -aralkyl group, which can be carried out in a conventional manner by reaction with the corresponding alkyl halide and dialkyl sulfate.

[0061] Quaternization can be advantageous to tailor the alkoxylated polyalkyleneimines or alkoxylated polyamines to the particular compositions in which they are used, such as cosmetic compositions, to achieve better compatibility and / or phase stability of the formulation.

[0062] The quaternization of the alkoxylated polyalkyleneimines or alkoxylated polyamines is preferably carried out by quaternization of C1-C 22 Alkyl, C1-C4 alkyl group and / or C7-C 22 This is achieved by introducing aralkyl, aryl or alkylaryl groups, which can be carried out in conventional manner by reaction with the corresponding alkyl-, aralkyl-halides and dialkylsulfates.

[0063] Quaternization can be carried out, for example, by treating an alkoxylated polyamine or an alkoxylated polyalkyleneimine with an alkylating agent, for example a C1-C4-alkyl halide, such as methyl bromide, methyl chloride, ethyl chloride, methyl iodide, n-butyl bromide, isopropyl bromide, or an aralkyl halide, for example benzyl chloride, benzyl bromide, or a di-C1-C 22 -alkyl sulfates, in particular with dimethyl sulfate or diethyl sulfate. Suitable bases are, for example, sodium hydroxide and potassium hydroxide.

[0064] The amount of alkylating agent determines the amount of quaternization of amino groups in the polymer, ie, the amount of quaternized moieties.

[0065] The amount of quaternized moieties can be calculated from the difference in amine number between the non-quaternized and quaternized amines.

[0066] The amine number can be determined according to the method described in DIN 16945.

[0067] The quaternization can be carried out without using any solvent. However, a solvent or diluent such as water, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone, etc. may be used. The reaction temperature is usually within the range of 10°C to 150°C, preferably 50°C to 100°C.

[0068] Another subject of the present invention is a method for preparing the above-mentioned alkoxylated polyalkylenimines or alkoxylated polyamines, in which the polyalkylenimine or polyamine backbone is first reacted with at least one lactone and / or at least one hydroxycarbon acid, and then with at least one C2-C hydroxycarbon acid, to obtain the respective alkoxylated compound. 22 -React with epoxides.

[0069] It should be noted that the alkoxylation process itself, in which the backbone of a polyalkyleneimine or polyamine is reacted with an alkylene oxide, such as ethylene oxide or propylene oxide, is known to those skilled in the art. The same method, in which the respective backbone is first reacted with a lactone or a hydroxyl carbon acid, followed by the alkylation process, can also be applied to the present invention. The first step reaction between the respective backbone and a lactone, etc., is known to those skilled in the art.

[0070] In the process, per mole of NH functional groups in the polyalkyleneimine or polyamine, the respective polyalkyleneimine backbone or polyamine backbone is reacted with at least 0.05 mole, preferably at least 0.2 mole, of at least one lactone and / or at least one hydroxycarbon acid, followed by at least 5 moles of at least one C2-C 22 Preferably, it is reacted with an epoxide.

[0071] It should be noted that in the context of the method according to the invention, the primary amino moiety of each scaffold reacted with at least one lactone and / or at least one hydroxyl carbon acid in the first reaction step is transferred to an amide moiety, and one of the original two hydrogen atoms of each primary amino moiety is replaced by a fragment derived from the respective lactone or hydroxyl carbon acid, while the second hydrogen atom of the scaffold primary amino moiety is not replaced by this reaction. Moreover, such second hydrogen atom of the scaffold primary amino moiety is also transferred to an amide moiety when each intermediate scaffold is converted to at least one C2-C 22 -epoxide, they are not substituted in the second reaction step according to the invention. Furthermore, each fragment of the intermediate skeleton obtained in the first reaction step, which originates from at least one lactone and / or at least one hydroxyl carbon acid, is alkoxylated with at least one C2-C 22 -epoxide. The conversion of each step can be determined according to methods known to those skilled in the art, such as NMR spectroscopy. For example, both the first and second reaction steps can be carried out in the following manner, as shown in more detail in the experimental section: 13 C-NMR spectroscopy and / or 1 It can be monitored by 1 H-NMR spectroscopy.

[0072] In connection with the first step of the process according to the invention for preparing alkoxylated polyalkylenimines or alkoxylated polyamines according to the general formula (I) defined above, the respective polyalkylenimine or polyamine backbone is first reacted with at least one lactone and / or at least one hydroxycarbon acid. This first reaction step per se is known to those skilled in the art.

[0073] However, in this first reaction step, it is preferred that the reaction temperature is in the range of 50 to 200°C, more preferably 70 to 180°C, most preferably 100 to 160°C.

[0074] This first reaction step may be carried out in the presence of at least one solvent and / or at least one catalyst. However, it is preferred that each step in the first reaction step is carried out without any solvent and / or any catalyst. Suitable solvents are preferably selected from xylene, toluene, tetrahydrofuran (THF), methyl tert.butyl ether, or diethyl ether. Preferred catalysts are selected from alkali metal hydroxides or alkali metal alkoxides, such as KOMe, NaOMe, or other catalysts suitable for ring-opening polymerization with lactones, such as tin(II) octoate.

[0075] As mentioned above, the second step (alkoxylation) of the process according to the invention is known to those skilled in the art. The alkoxylation (second reaction step of the process according to the invention) can be carried out as a one-step reaction, or the alkoxylation can be divided into two or more separate steps.

[0076] In the present invention, the second step (alkoxylation) is preferably carried out as a single step reaction.

[0077] In this preferred embodiment, the alkoxylation is carried out in the presence of at least one catalyst and / or in the absence of water. In this single-step reaction of the alkoxylation step, the catalyst is preferably a basic catalyst. Examples of suitable catalysts include alkali metal and alkaline earth metal hydroxides, such as sodium hydroxide, potassium hydroxide, and calcium hydroxide; alkali metal alkoxides, particularly sodium and potassium C1-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. Alkali metal hydroxides and alkali metal alkoxides are preferred, particularly potassium hydroxide and sodium hydroxide. The amount of base typically used is 0.05 to 10% by weight, particularly 0.5 to 2% by weight, based on the total amount of polyalkyleneimine or polyamine and alkylene oxide.

[0078] An alternative procedure for the second reaction step (alkoxylation) is a two-step reaction, in which only the initial alkoxylation of the modified backbone of the polyalkyleneimine or polyamine obtained in the first step is first carried out. In this first part of the second step, the modified backbone of the polyalkyleneimine or polyamine is reacted with only a portion of the total amount of ethylene oxide used, which corresponds to about 1 mole of ethylene oxide per mole of NH moiety or NH functional group, respectively. This reaction (in the first part of the second step) is generally carried out in aqueous solution in the absence of a catalyst, at temperatures between 70 and 200°C, preferably between 80 and 160°C, and under pressures of up to 10 bar, in particular up to 8 bar.

[0079] Said second part of the alkoxylation reaction (the second step of the alternative process according to the invention) is typically carried out in the presence of the same type of catalyst as described above for the single-step alkoxylation reaction.

[0080] The second step of the alkoxylation can be carried out in water (variant a)) or in an organic solvent (variant b)). The process conditions specified below can be used for both steps of the alkoxylation reaction.

[0081] In variant a), the aqueous solution of the initial alkoxylated polyalkyleneimine or polyamine obtained in the first step is first dehydrated after the addition of the catalyst. This can be done in a simple manner by heating to 80-150°C and distilling off the water under a reduced pressure of less than 30 mbar. The subsequent reaction with alkylene oxide is typically achieved at 70-200°C, preferably 100-180°C, and a pressure of up to 10 bar, in particular up to 8 bar, with continued stirring in each case at about 100-160°C and constant pressure for about 0.5-4 hours.

[0082] Suitable reaction media for variant b) are, in particular, non-polar and polar aprotic organic solvents. Particularly suitable examples of non-polar aprotic solvents include aliphatic and aromatic hydrocarbons, such as hexane, cyclohexane, toluene and xylene. Particularly suitable examples of polar aprotic solvents are ethers, especially cyclic ethers, such as tetrahydrofuran and dioxane, N,N-dialkylamides, such as dimethylformamide and dimethylacetamide, and N-alkyllactams, such as N-methylpyrrolidone. Of course, it is also possible to use a mixture of these aprotic solvents. Preferred solvents are xylene and toluene.

[0083] Also in variant b), the solution obtained in the first step is first dehydrated after the addition of catalyst and solvent, advantageously by separating the water at a temperature of 120-180° C., preferably with the aid of a gentle nitrogen stream. The subsequent reaction with alkylene oxide can be achieved as in variant a).

[0084] In variant a), the alkoxylated polyalkyleneimine or polyamine is obtained directly in the substance, which can be converted into an aqueous solution if desired. In variant b), the organic solvent is typically removed and replaced with water. Of course, the product can also be isolated in the substance.

[0085] The amount of residues according to formula (IIa) or formula (IIb) in relation to the definition of the substituents E1 to E5 can be controlled by several factors, such as the stoichiometry of the educts used, the reaction temperatures in the individual steps, the amount and / or type of catalyst used, and / or the solvent selected.

[0086] In another preferred embodiment, the lactone is caprolactone, the hydroxycarbon acid is lactic acid, and / or the C2-C 22 - Epoxide is ethylene oxide.

[0087] In another preferred embodiment, the alkoxylated polyalkyleneimine or alkoxylated polyamine is additionally quaternized as described above, however, instead of or in addition to quaternization, it is also possible to sulfate the alkoxylated compound.

[0088] Another subject of the present invention is the use of the above-mentioned alkoxylated polyalkyleneimines or alkoxylated polyamines in laundry detergents, in fabric and home care products, in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions and / or as dispersants for pesticide formulations, preferably in cleaning compositions and / or fabric and home care products.

[0089] The alkoxylated polyalkyleneimines or alkoxylated polyamines of the present invention can be added to cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions, etc. However, the compounds of the present invention can also be added to (used in) cleaning or cleaning compositions.

[0090] Another subject of the present invention is therefore laundry detergents, cleaning compositions, fabric and home care products, cosmetic formulations, crude oil demulsifiers, pigment dispersions for inkjet inks, electroplating formulations, cementitious compositions and / or dispersants for pesticide formulations, comprising at least one alkoxylated polyalkyleneimine or alkoxylated polyamine as defined above.

[0091] Preferably, this is a laundry detergent, cleaning composition and / or fabric and home care product comprising at least one alkoxylated polyalkyleneimine or alkoxylated polyamine as defined above.

[0092] The alkoxylated polyalkyleneimine or alkoxylated polyamine of the present invention is present in the formulation at a concentration of 0.1 to 5% by weight, preferably 0.5 to 2% by weight.

[0093] The alkoxylated polyalkyleneimines or alkoxylated polyamines of the present invention can also be added to cleaning compositions comprising from about 1% to about 70% by weight of a surfactant system. The alkoxylated polyalkyleneimines or alkoxylated polyamines of the present invention can be present in the cleaning composition at a concentration of from about 0.1% to about 5% by weight of the composition, or from about 0.5% to about 2% by weight of the composition.

[0094] Cleansing Composition As used herein, the phrase "cleaning composition" includes compositions and formulations designed to clean soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric cleaning compositions, laundry pre-cleaners, laundry pre-treatments, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, post-rinse fabric treatments, ironing aids, dishwashing compositions, hard surface cleaning compositions, unit dose formulations, delayed delivery formulations, detergents contained on or within porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in light of the teachings herein. Such compositions may be used as laundry pre-treatments, laundry post-treatments, or may be added during the rinse or wash cycle of a laundry operation. The cleaning composition may have a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, bar, or flake.

[0095] The cleaning composition comprises a surfactant system in an amount sufficient to provide the desired cleaning properties. In some embodiments, the cleaning composition comprises from about 1% to about 70% surfactant system by weight of the composition. In other embodiments, the liquid cleaning composition comprises from about 2% to about 60% surfactant system by weight of the composition. In further embodiments, the cleaning composition comprises from about 5% to about 30% surfactant system by weight of the composition. The surfactant system may comprise a detersive surfactant selected from anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those skilled in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provides cleaning, stain removal, or laundering benefits to soiled materials.

[0096] The cleaning composition may also contain auxiliary cleaning additives. Suitable auxiliary cleaning additives include builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil release agents, polymeric dispersants, polymeric grease cleaners, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibitors, chelating agents, suds suppressors, softeners, and fragrances.

[0097] The compound of the present invention is C 10 ~C 15 The surfactant system may be utilized in laundry detergent or cleaning compositions comprising alkyl benzene sulfonate (LAS) and one or more co-surfactants selected from nonionic, cationic, anionic, or mixtures thereof. The choice of co-surfactant may depend on the desired benefit. In one embodiment, the co-surfactant is a nonionic surfactant, preferably C 12 ~C 18 In another embodiment, the co-surfactant is selected from an anionic surfactant, preferably C 10 ~C 18 Alkyl alkoxy sulfate (AE x S), where x is 1 to 30. In another embodiment, the co-surfactant is selected as a cationic surfactant, preferably dimethylhydroxyethyl lauryl ammonium chloride. 10 ~C 15 If alkylbenzene sulfonate (LAS) is included, the LAS is preferably used at a level ranging from about 9% to about 25%, or from about 13% to about 25%, or from about 15% to about 23% by weight of the composition.

[0098] The surfactant system may comprise from 0% to about 15%, or from about 0.1% to about 7%, or from about 1% to about 4%, by weight of the composition, of one or more co-surfactants selected from nonionic co-surfactants, cationic co-surfactants, anionic co-surfactants, and any mixtures thereof.

[0099] Non-limiting examples of nonionic co-surfactants include C 12 ~C 18 Alkyl ethoxylates, such as NEODOL® nonionic surfactants from Shell; C-C where the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units. 12 Alkylphenol alkoxylates; C with ethylene oxide / propylene oxide block alkyl polyamine ethoxylates 12 ~C 18 Alcohols and C6-C 12 Alkylphenol condensates, such as PLURONIC® from BASF; C as described in US Pat. No. 6,150,322 14 ~C 22 Medium-chain branched alcohols, BA; C as described in US 6,153,577, US 6,020,303 and US 6,093,856 14 ~C 22 Medium-chain branched alkyl alkoxylate, BAE x where x is 1 to 30; alkyl polysaccharides as described in U.S. Pat. No. 4,565,647 (Llenado, issued Jan. 26, 1986); alkyl polyglycosides as described, in particular, in U.S. Pat. No. 4,483,780 and U.S. Pat. No. 4,483,779; polyhydroxy fatty acid amides as described in U.S. Pat. No. 5,332,528; and ether-capped poly(oxyalkylated) alcohol surfactants as described in U.S. Pat. No. 6,482,994 and WO 01 / 42408.

[0100] Non-limiting examples of semi-polar nonionic co-surfactants include water-soluble amine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety containing about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety containing about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of about 10 to about 18 carbon atoms and a moiety selected from the group consisting of an alkyl moiety and a hydroxyalkyl moiety containing about 1 to about 3 carbon atoms (see WO 01 / 32816, US 4,681,704, and US 4,133,779).

[0101] Non-limiting examples of cationic co-surfactants include alkoxylate quaternary ammonium (AQA) surfactants described in US Pat. No. 6,136,769; dimethylhydroxyethyl quaternary ammonium described in US Pat. No. 6,004,922; dimethylhydroxyethyl lauryl ammonium chloride; polyamine cationic surfactants described in WO 98 / 35002, WO 98 / 35003, WO 98 / 35004, WO 98 / 35005, and WO 98 / 35006; cationic ester surfactants described in US Pat. No. 4,228,042, US Pat. No. 4,239,660, US Pat. No. 4,260,529, and US Pat. No. 6,022,844; and amino surfactants described in US Pat. No. 6,221,825 and WO 00 / 47708, particularly quaternary ammonium surfactants which may have up to 26 carbon atoms, including amidopropyldimethylamine (APA).

[0102] Non-limiting examples of anionic co-surfactants useful herein include C 10 ~C 20 Primary branched and random alkyl sulfates (AS); C 10 ~C 18 Secondary (2,3) alkyl sulfate; C 10 ~C 18 Alkyl alkoxy sulfate (AE xS) (wherein x is 1 to 30); C containing 1 to 5 ethoxy units 10 ~C 18 These include alkyl alkoxycarboxylates; mid-chain branched alkyl sulfates as described in US 6,020,303 and US 6,060,443; mid-chain branched alkyl alkoxy sulfates as described in US 6,008,181 and US 6,020,303; modified alkyl benzene sulfonates (MLAS) as described in WO 99 / 05243, WO 99 / 05242 and WO 99 / 05244; methyl ester sulfonates (MES); and alpha-olefin sulfonates (AOS).

[0103] The present invention also relates to the compounds of the present invention, as well as C8-C 18 The present invention relates to a composition comprising a surfactant system comprising a linear alkyl sulfonate surfactant and a co-surfactant.The composition may be in any form, i.e., liquid; solid, such as powder, granule, aggregate, paste, tablet, pouch, bar, gel; emulsion; type delivered in a two-compartment container; spray or foam detergent; wet wipe (i.e., cleaning composition combined with nonwoven material, for example, as described in US6,121,165 (Mackey et al.)); dry wipe activated by the consumer with water (i.e., cleaning composition combined with nonwoven material, for example, as described in US5,980,931 (Fowler et al.)); and other homogeneous or multi-phase consumer cleaning product forms.

[0104] In one embodiment, the cleaning composition of the present invention is a liquid or solid laundry detergent composition. In another embodiment, the cleaning composition of the present invention is a hard surface cleaning composition, and preferably, the hard surface cleaning composition is impregnated into a nonwoven substrate. As used herein, "impregnated" means that the hard surface cleaning composition is placed in contact with the nonwoven substrate so that at least a portion of the nonwoven substrate is permeated with the hard surface cleaning composition, preferably so that the hard surface cleaning composition saturates the nonwoven substrate. The cleaning composition can also be used in car care compositions for cleaning various surfaces, such as hardwood, tile, ceramic, plastic, leather, metal, and glass. The cleaning composition can also be designed for use in personal care and pet care compositions, such as shampoo compositions, body washes, liquid or solid soaps, and other cleaning compositions in which the surfactant is contacted at free hardness, as well as in all compositions requiring a hardness-resistant surfactant system, such as oil drilling compositions.

[0105] In another embodiment, the cleaning composition is a dishwashing cleaning composition, such as a liquid hand dishwashing composition, a solid automatic dishwashing composition, a liquid automatic dishwashing composition, and a tab / unit dose automatic dishwashing composition.

[0106] Very typically, the cleaning compositions herein, such as laundry detergents, laundry detergent additives, hard surface cleaners, synthetic and soap-based laundry bars, fabric softeners and fabric treatment liquids, solids, and all manner of treatment articles, will require some adjuvants, although certain simple formulation products, such as bleach additives, may require, for example, only oxygen bleach and the surfactants described herein. A comprehensive list of suitable laundry or cleaning adjuvants can be found in WO 99 / 05242.

[0107] Typical cleaning adjuncts include builders, enzymes, polymers not listed above, bleaches, bleach activators, catalytic materials, etc., excluding any materials already defined above. Other cleaning adjuncts herein may include various active ingredients or specialty materials such as suds boosters, suds suppressors (defoamers), etc., such as dispersant polymers other than those mentioned above (e.g., from BASF Corp. or Rohm & Haas), color spotting, silver care, anti-tarnish and / or rust inhibitors, dyes, fillers, disinfectants, alkalinity sources, hydrotropes, antioxidants, enzyme stabilizers, pro-perfumes, fragrances, solubilizers, carriers, processing aids, pigments, and, in the case of liquid formulations, solvents, chelating agents, dye transfer inhibitors, dispersants, brighteners, suds suppressors, dyes, structure elasticizing agents, fabric softeners, anti-abrasion agents, hydrotropes, processing aids, and other fabric, surface, and skin care agents. Suitable examples and use levels of such other cleaning adjuncts can be found in US Pat. No. 5,576,282, US Pat. No. 6,306,812 B1 and US Pat. No. 6,326,348 B1.

[0108] The alkoxylated polyethyleneimines and alkoxylated polyamines of the present invention may be used in compositions that include any of the known auxiliary materials, ingredients, and compositions, such as those found in WO 99 / 05242, U.S. Pat. No. 5,576,282, U.S. Pat. No. 6,306,812 B1, and U.S. Pat. No. 6,326,348 B1, and any of the other prior art documents mentioned and cited herein in this regard.

[0109] How to use The present invention includes a method for cleaning a target surface. As used herein, "target surface" may include such surfaces as fabrics, dishes, glass, and other kitchen utensil surfaces, hard surfaces, hair, or skin. As used herein, "hard surface" includes hard surfaces found in a typical home, such as hardwood, tile, ceramic, plastic, leather, metal, and glass. Such a method includes contacting a cleaning composition as previously defined herein, comprising an alkoxylated polyethyleneimine and / or an alkoxylated polyamine, in untreated form or diluted in a cleaning solution, with at least a portion of the target surface, and then optionally rinsing the target surface. Preferably, the target surface is subjected to a cleaning step before the optional rinsing step described above. For purposes of the present invention, cleaning includes, but is not limited to, scrubbing, wiping, and mechanical agitation.

[0110] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are ideally suited for use in home care (hard surface cleaning compositions) and / or laundry applications.

[0111] The pH of the cleaning composition solution is selected to be most complementary to the target surface to be cleaned, and can range over a wide pH range from about 5 to about 11. For personal care, e.g., skin and hair cleansing, such cleaning compositions preferably have a pH of about 5 to about 8, and for laundry cleaning compositions, a pH of about 8 to about 10. The cleaning composition is preferably used at a concentration of about 200 ppm to about 10,000 ppm in solution. The temperature of the water preferably ranges from about 5°C to about 100°C.

[0112] For use in laundry cleaning compositions, the cleaning composition is preferably used at a concentration of about 200 ppm to about 10,000 ppm in solution (or wash liquor). The water temperature is preferably in the range of about 5° C. to about 60° C. The water to fabric ratio is preferably about 1:1 to about 20:1.

[0113] The method may include contacting a nonwoven substrate impregnated with an embodiment of the cleaning composition of the present invention. As used herein, "nonwoven substrate" may include any conventional type of nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Examples of suitable commercially available nonwoven substrates include those sold under the trade names SONTARA® manufactured by DuPont and POLYWEB® manufactured by James River Corp.

[0114] As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are also ideally suited for use in liquid dish cleaning compositions. A method of using the liquid dish cleaning compositions of the present invention comprises contacting soiled dishes with an effective amount, typically about 0.5 ml to about 20 ml (per 25 dishes to be treated), of the liquid dish cleaning composition of the present invention diluted in water.

[0115] The following examples further illustrate the present invention without limiting its scope.

[0116] method E1-E5 = the amount of amine substituted with hydrogen, as described for polyethyleneimine in Lukovkin GM, Pshezhetsky VS, Murtazaeva GA: Europ. Polymer Journal 1973, 9, 559-565 and St. Pierre T., Geckle M.: ACS Polym. Prep. 1981, 22, 128-129. 13 It can be determined by the identification of primary, secondary and tertiary amino groups in C-NMR.

[0117] 13 C-NMR spectra are recorded in CDCl 3 at room temperature on a Bruker AV-401 instrument. 1 H-NMR spectra are recorded in CDCl 3 or CD 3 OD at room temperature on a Bruker AV-401 instrument.

[0118] The saponification number is determined in accordance with DIN EN ISO 3657:2013.

[0119] [Example] [Example 1] Polyethyleneimine reacted with 0.5 mol of caprolactone per mole of NH-functional group and ethoxylated with 20 mol of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol. 1a Polyethyleneimine reacted with 0.5 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 129.0 g of polyethyleneimine and heated to 50°C. At this temperature, 171.2 g of caprolactone is added within 1 hour. The temperature of the reaction mixture rises to 80°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 15 hours. 1 H-NMR shows complete conversion of caprolactone. 295.0 g of a pale orange oil are obtained. 13 C-NMR shows that all primary amines are converted to amides and that 10% of the total amount of secondary amines (E1) reacts with caprolactone. The saponification number is 52 mg KOH / g.

[0120] 1b Polyethyleneimine reacted with 0.5 mole of caprolactone per mole of NH-functional group and ethoxylated with 10 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 120.0 g of polyethyleneimine reacted with 0.5 moles of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 1a), and 1.3 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 528.6 g of ethylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 645.0 g of a light brown oil are obtained.

[0121] 1c Polyethyleneimine reacted with 0.5 mol of caprolactone per mole of NH-functional group and ethoxylated with 20 mol of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 250.0 g of polyethyleneimine, molecular weight 800 g / mol (Example 1b), which has been reacted with 0.5 mol of caprolactone per mol of NH-functional group and ethoxylated with 10 mol of ethylene oxide per mol of NH-functional group, and 0.4 g of potassium tert-butoxide, and the mixture is heated to 120 ° C. The vessel is purged with nitrogen three times. 203.7 g of ethylene oxide are added within 2 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120 ° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 ° C. 450.0 g of a light brown solid is obtained (saponification number: 9.0 mg KOH / g).

[0122] [Example 2] Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group and ethoxylated with 10 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol 2a Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol A 0.5 L four-neck vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 86.0 g of polyethyleneimine and heated to 90°C. At this temperature, 228.3 g of caprolactone is added within 1 hour. The temperature of the reaction mixture rises to 100°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 11 hours. 1 H-NMR shows complete conversion of caprolactone. 310.0 g of a pale orange oil are obtained (saponification number: 195 mg KOH / g). 13 C-NMR shows that all primary amines are converted to amides and that 15% of the total amount of secondary amines (E1) reacts with caprolactone.

[0123] 2b Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group and ethoxylated with 10 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 120.0 g of polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 2a), and 0.9 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 352.2 g of ethylene oxide are added within 5 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 440.0 g of a light brown oil is obtained.

[0124] [Example 3] Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group and ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 100.0 g of polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 2a), and 1.3 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged with nitrogen three times. 560.7 g of ethylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 659.0 g of a light brown solid are obtained (saponification number: 28.4 mg KOH / g).

[0125] [Example 4] Polyethyleneimine reacted with 2.0 moles of caprolactone per mole of NH-functional group and ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol 4a Polyethyleneimine reacted with 2.0 moles of caprolactone per mole of NH-functional group, molecular weight 800 g / mol A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 47.3 g of polyethyleneimine and heated to 90°C. At this temperature, 251.1 g of caprolactone is added within 1 hour. The temperature of the reaction mixture rises to 100°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 35 hours. 1 H-NMR shows complete conversion of caprolactone. 295.0 g of a pale orange oil are obtained (saponification number: 302 mg KOH / g). 13 C-NMR shows that all primary amines are converted to amides and that 10% of the total amount of secondary amines (E1) reacts with caprolactone.

[0126] 4b Polyethyleneimine reacted with 2.0 moles of caprolactone per mole of NH-functional group and ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 139.0 g of polyethyleneimine reacted with 2.0 moles of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 4a), and 1.2 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged with nitrogen three times. 451.4 g of ethylene oxide are added within 8 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 590.0 g of a viscous, light brown oil is obtained (saponification number: 65.7 mg KOH / g).

[0127] [Example 5] Polyethyleneimine reacted with 0.25 moles of lactide per mole of NH-functional group and ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol 5a Polyethyleneimine reacted with 0.25 moles of lactide per mole of NH-functional group, molecular weight 800 g / mol A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 172.3 g of polyethyleneimine and heated to 90°C. At this temperature, 145.6 g of lactide is added within 1 hour. The temperature of the reaction mixture rises to 110°C during the addition of lactide. After complete addition of lactide, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. 1 H-NMR shows complete conversion of lactide. 290 g of a pale orange oil are obtained.

[0128] 5b Polyethyleneimine reacted with 0.25 mol of lactide per mole of NH-functional group and ethoxylated with 20 mol of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 71.1 g of polyethyleneimine, molecular weight 800 g / mol (Example 5a), reacted with 0.25 moles of lactide per mole of NH-functional group, and 1.7 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 792.9 g of ethylene oxide are added within 15 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 860.0 g of a light brown, viscous oil is obtained (saponification number: 13.1 mg KOH / g).

[0129] [Example 6] Polyethyleneimine reacted with 0.5 mole of γ-butyrolactone per mole of NH-functional group and ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol 6a Polyethyleneimine reacted with 0.5 moles of γ-butyrolactone per mole of NH-functional group, molecular weight 800 g / mol A 0.5 L four-neck vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 172.0 g of polyethyleneimine and heated to 50°C. At this temperature, 172.2 g of γ-butyrolactone is added within 0.5 hours. The temperature of the reaction mixture rises to 55°C during the addition of γ-butyrolactone. After complete addition of γ-butyrolactone, the reaction mixture is heated to 100°C and stirred at 100°C for 18 hours. 1 H-NMR shows complete conversion of γ-butyrolactone. 340.0 g of a yellow viscous oil are obtained (saponification number: 100.6 mg KOH / g). 13 C-NMR shows that all primary amines are converted to amides and that 13% of the total amount of secondary amines (E1) reacts with γ-butyrolactone.

[0130] 6b Polyethyleneimine reacted with 0.5 mol of γ-butyrolactone per mole of NH-function and ethoxylated with 20 mol of ethylene oxide per mole of NH-function, molecular weight 800 g / mol A 2 L autoclave is charged with 82.0 g of polyethyleneimine reacted with 0.5 moles of γ-butyrolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 6a), and 1.8 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged with nitrogen three times. 840 g of ethylene oxide are added within 12 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 924.0 g of a light brown solid are obtained (saponification number: 8.7 mg KOH / g).

[0131] [Example 7] N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 4 moles of caprolactone / mole and ethoxylated with 80 moles of ethylene oxide / mole 7a N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 4 moles of caprolactone / mole A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 319.6 g of caprolactone and heated to 80°C. At this temperature, 122.0 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) is added within 1 hour. The temperature of the reaction mixture rises to 110°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 21 hours. 1 H-NMR shows complete conversion of caprolactone. 435.0 g of a pale yellow oil are obtained (saponification number: 167.3 mg KOH / g). 13 C-NMR shows that all primary amines are converted to amides and that secondary amines do not react with caprolactone.

[0132] 7b N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 4 moles of caprolactone / mole and ethoxylated with 80 moles of ethylene oxide / mole A 2 L autoclave is charged with 100.0 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) (Example 7a) reacted with 4 moles of caprolactone / mole and 1.4 g of potassium tert-butoxide, and the mixture is heated to 120 ° C. The vessel is purged with nitrogen three times. 583.2 g of ethylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120 ° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80 ° C. 680.0 g of a viscous, light brown oil is obtained (saponification number: 21.1 mg KOH / g).

[0133] [Example 8] Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, ethoxylated with 24 moles of ethylene oxide per mole of NH-functional group and propoxylated with 16 moles of propylene oxide per mole of NH-functional group, molecular weight 800 g / mol

[0134] 8a Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group and ethoxylated with 5 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 192.0 g of polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 2a), and 0.92 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged with nitrogen three times. 269.1 g of ethylene oxide are added within 6 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 464.0 g of a light brown, viscous oil is obtained (saponification number: 80.0 mg KOH / g).

[0135] 8b Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, ethoxylated with 24 moles of ethylene oxide per mole of NH-functional group and propoxylated with 16 moles of propylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 150.9 g of polyethyleneimine, molecular weight 800 g / mol (Example 8a), which has been reacted with 1.0 mole of caprolactone per mole of NH-functional group and ethoxylated with 5 moles of ethylene oxide per mole of NH-functional group, and 1.4 g of potassium tert-butoxide, and the mixture is heated to 120 ° C. The vessel is purged with nitrogen three times. 334.8 g of ethylene oxide is added within 4 hours. To complete the reaction, the mixture is reacted for another 2 hours at 120 ° C. 371.7 g of propylene oxide is added within 5 hours, followed by 5 hours of reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80 ° C. 464.0 g of a light brown, viscous oil is obtained (saponification number: 14.1 mg KOH / g).

[0136] [Example 9] Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group and propoxylated with 15 moles of propylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 105.0 g of polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, molecular weight 800 g / mol (Example 2a), and 1.4 g of potassium tert-butoxide, and the mixture is heated to 140° C. The vessel is purged three times with nitrogen. 582.3 g of propylene oxide are added within 6 hours. To complete the reaction, the mixture is reacted for another 6 hours at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 663.0 g of a light brown, viscous oil is obtained.

[0137] [Example 10] Polyethyleneimine reacted with 1.0 mole of caprolactone per mole of NH-functional group, propoxylated with 15 moles of propylene oxide per mole of NH-functional group, and ethoxylated with 24 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 2 L autoclave is charged with 205.7 g of polyethyleneimine, molecular weight 800 g / mol (Example 9), reacted with 1.0 mol of caprolactone per mol of NH-functional group and propoxylated with 15 mol of propylene oxide per mol of NH-functional group, and 0.42 g of potassium tert-butoxide, and the mixture is heated to 120° C. The vessel is purged three times with nitrogen. 211.4 g of ethylene oxide are added within 4 hours. To complete the reaction, the mixture is reacted for another 5 hours at 120° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 415.0 g of a light brown solid are obtained.

[0138] [Example 11] Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 11a Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 612.4 g of hexamethylenediamine and 5.4 g of potassium methylate (30% in methanol) and heated to 120°C. At this temperature, 150.4 g of caprolactone is added within 0.5 hours. After complete addition of caprolactone, the reaction mixture is stirred at 120°C for 3 hours. 1 H-NMR shows complete conversion of caprolactone. 750.0 g of a pale yellow oil is obtained which solidifies at room temperature.

[0139] 11b Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 145.4 g of hexamethylenediamine (Example 11a) reacted with 0.25 mol of caprolactone / mol and heated to 110° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 696.9 g of propylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 7 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 840.0 g of a very viscous, pale yellow oil is obtained (saponification number: 5.5 mg KOH / g).

[0140] [Example 12] Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 252.5 g of hexamethylenediamine (Example 11b) reacted with 0.25 mol of caprolactone / mol and propoxylated with 12 mol of propylene oxide / mol, and 0.97 g of potassium tert-butoxide. The mixture is heated to 110°C, and the vessel is purged with nitrogen three times. The vessel is heated to 140°C, and 348.5 g of propylene oxide is added within 5 hours. To complete the reaction, the mixture is reacted for another 10 hours at 140°C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 90°C. 600.0 g of a very viscous, light brown oil is obtained (saponification number: 4.8 mg KOH / g).

[0141] [Example 13] Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole and propoxylated with 60 moles of propylene oxide / mole A 2 L autoclave is charged with 168.3 g of hexamethylenediamine (Example 11b) reacted with 0.25 mol of caprolactone / mol and propoxylated with 12 mol of propylene oxide / mol, and 1.3 g of potassium tert-butoxide. The mixture is heated to 110°C, and the vessel is purged with nitrogen three times. The vessel is heated to 140°C, and 557.6 g of propylene oxide is added within 10 hours. To complete the reaction, the mixture is reacted for another 10 hours at 140°C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 90°C. 730.0 g of a very viscous, light brown oil is obtained (saponification number: 1.7 mg KOH / g).

[0142] [Example 14] Hexamethylenediamine reacted with 0.25 moles of caprolactone / mole, propoxylated with 60 moles of propylene oxide / mole, and ethoxylated with 40 moles of ethylene oxide / mole A 2 L autoclave is charged with 151.5 g of hexamethylenediamine (Example 11b) reacted with 0.25 mol of caprolactone / mol and propoxylated with 12 mol of propylene oxide / mol, and 1.8 g of potassium tert-butoxide. The mixture is heated to 110° C., and the vessel is purged with nitrogen three times. The vessel is heated to 140° C., and 502.0 g of propylene oxide is added within 8 hours. To complete the reaction, the mixture is reacted for another 2 hours at 140° C. 317.2 g of ethylene oxide is added within 5 hours, followed by 5 hours of reaction. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 960.0 g of a very viscous, light brown oil is obtained.

[0143] [Example 15] Hexamethylenediamine reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 15a Hexamethylenediamine reacted with 1 mole of caprolactone / mole A 2.0 L four-neck vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 631.0 g of hexamethylenediamine and heated to 50°C. 20.8 g of potassium methylate (30% in methanol) is added. 619.0 g of caprolactone is added within 0.5 hours, and the temperature is increased to 114°C. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. 1 H-NMR shows complete conversion of caprolactone. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 h. 1240.0 g of an orange viscous oil are obtained.

[0144] 15b Hexamethylenediamine reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 190.0 g of hexamethylenediamine (Example 15a) reacted with 1 mole of caprolactone / mole and heated to 110° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 572.4 g of propylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 7 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 760.0 g of a very viscous yellow oil is obtained (saponification number: 12.0 mg KOH / g).

[0145] [Example 16] Hexamethylenediamine reacted with 1 mole of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 94.0 g of hexamethylenediamine (Example 15a) reacted with 1 mole of caprolactone / mole and heated to 110° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 758.9 g of propylene oxide are added within 10 hours. To complete the reaction, the mixture is reacted for another 7 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 850.0 g of a very viscous yellow oil is obtained (saponification number: 7.9 mg KOH / g).

[0146] [Example 17] Hexamethylenediamine reacted with 1 mole of caprolactone / mole and propoxylated with 60 moles of propylene oxide / mole A 2 L autoclave is charged with 139.1 g of hexamethylenediamine (Example 15b) reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole, and 0.94 g of potassium tert-butoxide. The mixture is heated to 110°C and the vessel is purged with nitrogen three times. The vessel is heated to 140°C and 418.2 g of propylene oxide is added within 5 hours. To complete the reaction, the mixture is reacted for another 7 hours at 140°C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90°C. 556.0 g of a very viscous brown oil is obtained (saponification number: 5.4 mg KOH / g).

[0147] [Example 18] Hexamethylenediamine reacted with 1 mole of caprolactone / mole, propoxylated with 32 moles of propylene oxide / mole, and ethoxylated with 32 moles of ethylene oxide / mole A 2 L autoclave is charged with 231.8 g of hexamethylenediamine (Example 15b) reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole, and 1.5 g of potassium tert-butoxide. The mixture is heated to 110° C., and the vessel is purged with nitrogen three times. The vessel is heated to 140° C., and 290.4 g of propylene oxide is added within 4 hours. To complete the reaction, the mixture is reacted for another 2 hours at 140° C. 352.4 g of ethylene oxide is added within 7 hours, followed by 5 hours of reaction. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 870.0 g of a very viscous, light brown oil is obtained.

[0148] [Example 19] Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 19a Hexamethylenediamine reacted with 4 moles of caprolactone / mole A 2 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 232.4 g of hexamethylenediamine and 19.1 g of potassium methylate (30% in methanol) and heated to 120°C. At this temperature, 913.4 g of caprolactone are added within 0.5 hours. After complete addition of caprolactone, the reaction mixture is stirred at 120°C for 4 hours. Volatile compounds are removed in vacuo (30 mbar) at 80°C for 0.5 hours. 1 H-NMR shows complete conversion of caprolactone. 1130.0 g of a pale yellow oil are obtained.

[0149] 19b Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 402.0 g of hexamethylenediamine (Example 19a) reacted with 4 moles of caprolactone / mole and heated to 80° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 486.8 g of propylene oxide is added within 10 hours. To complete the reaction, the mixture is reacted for another 7 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 880.0 g of a very viscous yellow oil is obtained (saponification number: 87.5 mg KOH / g).

[0150] [Example 20] Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 20 moles of propylene oxide / mole A 2 L autoclave is charged with 96 g of hexamethylenediamine (Example 19a) reacted with 4 moles of caprolactone / mole and heated to 80° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 193.7 g of propylene oxide are added within 4 hours. The mixture is reacted for another 6 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 274.0 g of a very viscous yellow oil is obtained (saponification number: 72.2 mg KOH / g).

[0151] [Example 21] Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 96.0 g of hexamethylenediamine (Example 19a) reacted with 4 moles of caprolactone / mole and heated to 80° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 310.4 g of propylene oxide are added within 4 hours. The mixture is reacted for another 6 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 366.0 g of a very viscous, pale yellow oil is obtained (saponification number: 56.9 mg KOH / g).

[0152] [Example 22] N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 2 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 22a N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 2 moles of caprolactone / mole A 0.5 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 348.6 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) and 13.4 g of potassium methoxide (30% in methanol). 456.6 g of caprolactone are added within 0.75 hours. The temperature of the reaction mixture rises to 110°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. Volatile compounds are removed in vacuo (30 mbar) at 80°C for 0.5 hours. 1 H-NMR shows complete conversion of caprolactone. 801.0 g of a pale yellow oil are obtained.

[0153] 22b N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 2 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 296.0 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) (Example 22a) reacted with 2 moles of caprolactone / mole and heated to 140° C. The vessel is purged with nitrogen three times. 512.5 g of propylene oxide are added within 8 hours. The mixture is reacted for another 5 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 798.0 g of a viscous, light brown oil is obtained.

[0154] [Example 23] N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) reacted with 2 moles of caprolactone / mole and propoxylated with 64 moles of propylene oxide / mole A 2 L autoclave is charged with 217.6.0 g of N4 amine (N,N-bis(3-aminopropyl)ethylenediamine) (Example 22b) reacted with 2 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole, and 1.3 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. 606.3 g of propylene oxide is added within 10 hours. To complete the reaction, the mixture is reacted for another 5 hours at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 825.0 g of a viscous, light brown oil is obtained.

[0155] [Example 24] DETA (bis(2-aminoethyl)amine) reacted with 1.5 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 24a DETA (bis(2-aminoethyl)amine) reacted with 1.5 moles of caprolactone / mole A 1 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 309.5 g of DETA (bis(2-aminoethyl)amine) and 13.7 g of potassium methoxide (30% in methanol). 513.6 g of caprolactone are added within 0.75 hours. The temperature of the reaction mixture rises to 70°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. Volatile compounds are removed in vacuo (30 mbar) at 80°C for 0.5 hours. 1 H-NMR shows complete conversion of caprolactone. 801.0 g of a pale yellow oil are obtained.

[0156] 24b DETA (bis(2-aminoethyl)amine) reacted with 1.5 moles of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 219.5 g of DETA (bis(2-aminoethyl)amine) (Example 24a) reacted with 1.5 moles of caprolactone / mole and heated to 140° C. The vessel is purged with nitrogen three times. 557.6 g of propylene oxide are added within 10 hours. The mixture is reacted for another 5 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 767.0 g of a viscous, light brown oil is obtained.

[0157] [Example 25] DETA (bis(2-aminoethyl)amine) reacted with 1.5 moles of caprolactone / mole and propoxylated with 48 moles of propylene oxide / mole A 2 L autoclave is charged with 239.9 g of DETA (bis(2-aminoethyl)amine) (Example 24b), reacted with 1.5 mol of caprolactone / mol and propoxylated with 12 mol of propylene oxide / mol, and 1.2 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. 525.6 g of propylene oxide is added within 8 hours. To complete the reaction, the mixture is reacted for another 5 hours at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 770.0 g of a viscous, light brown oil is obtained.

[0158] [Example 26] 1,3-propanediamine reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 26a 1,3-propanediamine reacted with 1 mole of caprolactone / mole A 1 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 370.6 g of 1,3-propanediamine and 15.7 g of potassium methoxide (30% in methanol). 570.7 g of caprolactone is added within 0.75 hours. The temperature of the reaction mixture rises to 60°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. Volatile compounds are removed in vacuo (30 mbar) at 80°C for 0.5 hours. 1 H-NMR shows complete conversion of caprolactone. 935.0 g of a pale yellow oil are obtained.

[0159] 26b 1,3-propanediamine reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 188.3 g of 1,3-propanediamine (Example 26a) reacted with 1 mole of caprolactone / mole and heated to 140° C. The vessel is purged with nitrogen three times. 696.9 g of propylene oxide are added within 12 hours. To complete the reaction, the mixture is reacted for another 5 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 881.0 g of a viscous, light brown oil is obtained.

[0160] [Example 27] 1,3-propanediamine reacted with 1 mole of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 309.8 g of 1,3-propanediamine (Example 26b), reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole, and 1.1 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. 406.6 g of propylene oxide is added within 6 hours. To complete the reaction, the mixture is reacted for another 5 hours at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 718.0 g of a viscous, light brown oil is obtained.

[0161] [Example 28] MCDA (methylcyclohexyldiamine, mixture of isomers) reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole 28a MCDA (methylcyclohexyldiamine, mixture of isomers) reacted with 1 mole of caprolactone / mole A 1 L four-necked vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 128.4 g of MCDA (methylcyclohexyldiamine, mixture of isomers) and 4.0 g of potassium methoxide (30% in methanol). 114.1 g of caprolactone are added within 0.5 hours. The temperature of the reaction mixture rises to 60°C during the addition of caprolactone. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. Volatile compounds are removed in vacuo (30 mbar) at 80°C for 0.5 hours. 1 H-NMR shows complete conversion of caprolactone. 242.0 g of a pale yellow oil are obtained.

[0162] 28b MCDA (methylcyclohexyldiamine, mixture of isomers) reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole A 2 L autoclave is charged with 241.2 g of MCDA (methylcyclohexyldiamine, mixture of isomers) (Example 28a) reacted with 1 mole of caprolactone / mole and heated to 140°C. The vessel is purged with nitrogen three times. 348.5 g of propylene oxide are added within 5 hours. The mixture is reacted for another 5 hours at 140°C to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80°C. 585.0 g of a viscous, light brown oil is obtained.

[0163] [Example 29] MCDA (methylcyclohexyldiamine, mixture of isomers) reacted with 1 mole of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 353.8 g of MCDA (methylcyclohexyldiamine, mixture of isomers) (Example 28b), which has been reacted with 1 mole of caprolactone / mole and propoxylated with 12 moles of propylene oxide / mole, and 1.1 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. 348.5 g of propylene oxide are added within 6 hours. The mixture is reacted for another 5 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 80° C. 700.0 g of a viscous, light brown oil is obtained.

[0164] [Example 30] Hexamethylenediamine reacted with 1 mole of g-butyrolactone / mole and propoxylated with 12 moles of propylene oxide / mole 30a Hexamethylenediamine reacted with 1 mole of g-butyrolactone / mol A 2.0 L four-neck vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer, and nitrogen inlet is charged with 232.4 g of hexamethylenediamine and heated to 45°C. 6.7 g of potassium methylate (30% in methanol) is added. 172.2 g of g-butyrolactone is added within 1 hour, and the temperature is increased to 118°C. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 2 hours. 1 H-NMR shows complete conversion of caprolactone. Volatile compounds are removed in vacuo (30 mbar) at 80° C. for 0.5 h. 404.5 g of a light brown solid are obtained.

[0165] 30b Hexamethylenediamine reacted with 1 mole g-butyrolactone / mole and propoxylated with 12 moles propylene oxide / mole A 2 L autoclave is charged with 203.0 g of hexamethylenediamine (Example 30a) reacted with 1 mole of g-butyrolactone / mol and 1.8 g of potassium butoxide and heated to 110° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 696.9 g of propylene oxide is added within 15 hours. To complete the reaction, the mixture is reacted for another 10 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 899.0 g of a very viscous brown oil is obtained.

[0166] [Example 31] Hexamethylenediamine reacted with 1 mole of g-butyrolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 224.8 g of hexamethylenediamine (Example 30b) reacted with 1 mole of g-butyrolactone / mol and propoxylated with 12 moles of propylene oxide / mol and heated to 110° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 290.4 g of propylene oxide is added within 5 hours. The mixture is reacted for another 10 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 515.0 g of a viscous brown oil is obtained.

[0167] [Example 32] Hexamethylenediamine reacted with 1 mole of caprolactone / mole, propoxylated with 60 moles of propylene oxide / mole, and ethoxylated with 90 moles of ethylene oxide / mole A 2 L autoclave is charged with 209.0 g of hexamethylenediamine (Example 16) reacted with 1 mole of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole. The mixture is heated to 140°C and the vessel is purged with nitrogen three times. 162.6 g of propylene oxide is added within 10 hours. To complete the reaction, the mixture is reacted for another 23 hours at 140°C. 369.5 g of ethylene oxide is added within 7 hours, followed by 10 hours of reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80°C. 735.0 g of a very viscous, light brown oil is obtained.

[0168] [Example 33] Hexamethylenediamine reacted with 1 mole of caprolactone / mole, ethoxylated with 90 moles of ethylene oxide / mole, and propoxylated with 60 moles of propylene oxide / mole 33a Hexamethylenediamine reacted with 1 mole of caprolactone / mole and ethoxylated with 30 moles of ethylene oxide / mole A 2 L autoclave is charged with 120.0 g of hexamethylenediamine (Example 15a) reacted with 1 mole of caprolactone / mole and heated to 140° C. The vessel is purged with nitrogen three times. 685.0 g of ethylene oxide are added within 6 hours. The mixture is reacted for another 6 hours at 140° C. to complete the reaction. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 785.0 g of a very viscous brown oil is obtained.

[0169] 33b Hexamethylenediamine reacted with 1 mole of caprolactone / mole, ethoxylated with 90 moles of ethylene oxide / mole, and propoxylated with 60 moles of propylene oxide / mole A 2 L autoclave is charged with 120.0 g of hexamethylenediamine (Example 33a) reacted with 1 mole of caprolactone / mole and ethoxylated with 30 ethylene oxide / mole, and 1.1 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. 510.0 g of ethylene oxide is added within 6 hours. To complete the reaction, the mixture is reacted for another 6 hours at 140° C. 672.6 g of propylene oxide is added within 15 hours, followed by 15 hours of reaction at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 90° C. 1466.0 g of a very viscous brown oil is obtained.

[0170] [Example 34] Hexamethylenediamine reacted with 1 mole of caprolactone / mole and alkoxylated with a mixture of 90 moles of ethylene oxide / mole and 60 moles of propylene oxide / mole 34a Hexamethylenediamine reacted with 1 mole of caprolactone / mole and alkoxylated with a mixture of 15 moles of ethylene oxide / mole and 10 moles of propylene oxide / mole A 2 L autoclave is charged with 115.8 g of hexamethylenediamine (Example 15a) reacted with 1 mole of caprolactone / mole and heated to 140° C. The vessel is purged with nitrogen three times. A mixture of 330.4 g of ethylene oxide and 290.4 g of propylene oxide is added within 7 hours. To complete the reaction, the mixture is reacted for another 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 90° C. 736.0 g of a very viscous brown oil is obtained.

[0171] 34b Hexamethylenediamine reacted with 1 mole of caprolactone / mole and alkoxylated with a mixture of 90 moles of ethylene oxide / mole and 60 moles of propylene oxide / mole A 2 L autoclave is charged with 120.0 g of hexamethylenediamine (Example 34a) reacted with 1 mole of caprolactone / mole and alkoxylated with a mixture of 15 moles of ethylene oxide / mole and 10 moles of propylene oxide / mole, and 0.6 g of potassium tert-butoxide, and heated to 140° C. The vessel is purged with nitrogen three times. A mixture of 314.3 g of ethylene oxide and 276.3 g of propylene oxide is added within 7 hours. To complete the reaction, the mixture is reacted for an additional 6 hours at 140° C. The reaction mixture is stripped with nitrogen, and volatile compounds are removed in vacuo at 90° C. 718.0 g of a very viscous brown oil is obtained.

[0172] [Example 35] Hexamethylenediamine reacted with 1 mole of caprolactone / mole, propoxylated with 32 moles of propylene oxide / mole, and ethoxylated with 48 moles of ethylene oxide / mole A 2 L autoclave is charged with 211.0 g of hexamethylenediamine (Example 16) reacted with 1 mole of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole. The mixture is heated to 140°C and the vessel is purged with nitrogen three times. 214.0 g of ethylene oxide are added within 3 hours. To complete the reaction, the mixture is reacted for another 5 hours at 140°C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80°C. 420.0 g of a light brown solid is obtained.

[0173] [Example 36] Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole 36a Hexamethylenediamine reacted with 4 moles of caprolactone / mole A 0.5 L four-neck vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet is charged with 66.2 g of hexamethylenediamine and 5.4 g of potassium methylate (30% in methanol) and heated to 90°C. At this temperature, 260.2 g of caprolactone is added within 0.5 hours. After complete addition of caprolactone, the reaction mixture is heated to 120°C and stirred at 120°C for 7 hours. 1 H-NMR shows complete conversion of caprolactone. 320.0 g of a pale yellow oil are obtained (saponification number: 221.4 mg KOH / g). 13 C-NMR shows that 87.5% of the primary amines are converted to amides, with 12.5% ​​of the primary amines remaining unmodified.

[0174] 36b Hexamethylenediamine reacted with 4 moles of caprolactone / mole and propoxylated with 32 moles of propylene oxide / mole A 2 L autoclave is charged with 96.0 g of hexamethylenediamine (Example 8a) reacted with 4 moles of caprolactone / mole and heated to 80° C. The vessel is purged with nitrogen three times. The vessel is heated to 140° C. and 310.4 g of propylene oxide are added within 4 hours. To complete the reaction, the mixture is reacted for another 6 hours at 140° C. The reaction mixture is stripped with nitrogen and volatile compounds are removed in vacuo at 80° C. 366.0 g of a very viscous, pale yellow oil is obtained (saponification number: 56.9 mg KOH / g).

[0175] [Comparative Example 1] PEI800+20EO / NH synthesized as described in WO9532272

[0176] [Comparative Example] Polyethyleneimine ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol

[0177] [Comparative Example 1a] Polyethyleneimine ethoxylated with 1 mole of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A 5 L autoclave is charged with 1943.0 g of polyethyleneimine having an average molecular weight of 800 g / mol and 97.0 g of water. The reactor is purged with nitrogen three times and heated to 110°C. 1789.0 g of ethylene oxide are added within 14 hours. The reaction mixture is allowed to react for 5 hours to complete the reaction. Water and volatile compounds are removed in vacuo at 90°C. A very viscous yellow oil (3688.0 g, water content: 2.6%, pH: 11.05 (5% in water)) is obtained.

[0178] [Comparative example 1b] Polyethyleneimine ethoxylated with 20 moles of ethylene oxide per mole of NH-functional group, molecular weight 800 g / mol A product similar to Comparative Example 1a (144.6 g, 92.7% in water) and 4.34 g of potassium hydroxide (50% in water) are placed in a 2 L autoclave. The mixture is heated to 120°C under vacuum (<10 mbar) and stirred for 2 hours to remove water. The reactor is purged with nitrogen three times and the mixture is heated to 140°C. 1470.7 g of ethylene oxide are added within 14 hours. The mixture is reacted for 5 hours to complete the reaction. Volatile compounds are removed in vacuo. 1615.0 g of a slightly brown solid are obtained (melting point: 35.4°C).

[0179] biodegradation Biodegradation in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F. 30 mg / mL of the test substance was injected into wastewater taken from the Mannheim wastewater treatment plant and incubated in closed flasks at 25°C for 28 days. Oxygen consumption during this period was measured as the pressure change in the flask using an OxiTop® C (Xylem Analytics Germany Sales GmbH & Co KG). The evolved CO2 was absorbed using a NaOH solution. The amount of oxygen consumed by the microbial population during biodegradation of the test substance was expressed as % of ThOD (theoretical oxygen demand) after correction with a blank.

[0180] [Table 1]

[0181] [Table 2]

[0182] Application test for washing machines The soiled swatches are washed together with a cotton ballast cloth (3.5 kg) and one soil ballast sheet wfk SBL 2004 in a Miele domestic washing machine on the cotton shirt program at 30° C. After washing, the cloths are allowed to dry in air.

[0183] Wash performance is determined using MACH5 multi-area color measurement, which gives a calculated LAB value and ΔE between the unwashed stain and the washed stain. The higher the value, the better the performance.

[0184] [Table 3]

[0185] [Table 4]

[0186] [Table 5]

[0187] Primary cleaning performance for oil / grease stains To determine primary cleaning power, cleaning performance against 16 different oil / grease stains on cotton, polycotton, and polyester fabrics (CFT, Vlaardingen, The Netherlands) was measured by determining the color difference (Delta E) between the stains after cleaning and a clean white fabric using a reflectometer (Datacolor SF600 plus). Each experiment, involving 16 different circular oil / grease stains (lipstick, cosmetics, beef fat, frying grease, burnt butter, palm oil, sebum BEY, sebum Tefo, collar stain; all on different fabrics), was repeated six times, and the resulting data was used to calculate the average Delta E value.

[0188] These Delta E values ​​were used to calculate the so-called "normalized cleaning performance" (Delta Delta E) for each individual stain. The "normalized cleaning performance" (Delta Delta E) is the difference in performance between a laundry detergent containing the biodegradable amphiphilic alkoxylated polyalkyleneimine or alkoxylated polyamine polymer of the present invention or an equivalent polymer, and a laundry detergent that does not contain any of the biodegradable amphiphilic alkoxylated polyalkyleneimine or alkoxylated polyamine polymer of the present invention or an equivalent polymer.

[0189] Table 5 shows the laundry detergent compositions, Table 6 shows the wash test conditions, and Table 7 summarizes the resulting normalized cleaning performance. The normalized cleaning performance shown in Table 7 is the sum of the normalized cleaning performances for all 16 stains. The higher the sum of the Delta Delta E values, the greater the positive contribution to cleaning performance of the biodegradable amphiphilic alkoxylated polyalkyleneimine or alkoxylated polyamine polymers of the present invention or equivalent polymers, respectively.

[0190] [Table 6]

[0191] [Table 7]

[0192] [Table 8]

[0193] Normalized cleaning performance (Total Delta Delta E) of less than 10 is not significant / not observed.

Claims

1. General formula (I) 【Chemical 1】 wherein each variable is defined as follows: R may be the same or different; i) linear or branched C 2 ~C 12- an alkylene group or ii) a group represented by the following formula (III): 【Chemistry 2】 where each variable is defined as follows: R 10 , R 11 , R 12 are the same or different linear or branched C 2 ~C 6 represents an alkylene group, d is an integer having a value in the range of 0 to 50 or iii) at least one C 1 ~C 3 -C optionally substituted with alkyl 5 ~C 10 -represents a cycloalkylene group; B represents an extension of the alkoxylated polyalkyleneimine by branching; y and z are each an integer having a value in the range of 0 to 150, provided that R is at least one C 1 ~C 3 -C optionally substituted with alkyl 5 ~C 10 - when it is a cycloalkylene group, both z and y are 0; E1, E2 and E4 represent the same or different residues according to formula (IIa) or the same or different residues according to formula (IIb), Residues according to formula (IIa) are 【Chemistry 3】 where each variable is defined as follows: R 1 is C 2 ~C 22 represents a -(1,2-alkylene) group; R 2 In the general formula (I), when z is an integer of 1 or more, it is hydrogen or C 1 -C 4 -alkyl or C 7 ~C 22 -aralkyl, wherein the C 7 -C 22 -aralkyl contains a phenyl, naphthyl or anthracyl group, or R 2 In the general formula (I), when z is 0, it is hydrogen or C 1 ~C 4 -Alkyl or C 7 ~C 22 -aralkyl, wherein the C 7 -C 22 -aralkyl comprises a phenyl, naphthyl or anthracyl group; R 3 is a linear or branched C 1 ~C 22 -represents an alkylene group; m is an integer having a value of at least 1 to 10; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: Residues according to formula (IIb) are 【Chemistry 4】 where the variables are defined as follows: R 1 is C 2 ~C 22 represents a -(1,2-alkylene) group; R 2 is hydrogen or C 1 -C 4 alkyl or C 7 ~C 22 -aralkyl, wherein the C 7 -C 22 -aralkyl comprises a phenyl, naphthyl or anthracyl group; n is an integer having a value of at least 5 to 100 is an alkyleneoxy unit defined as: E3 is hydrogen when E2 is a residue according to formula (IIa), or E3 is a residue according to formula (IIb); E5 is hydrogen when E4 is a residue according to formula (IIa), or E5 is a residue according to formula (IIb); 20 to 100% of the total amount of E2 and E4 are residues according to formula (IIa), and 50 to 100% of the total amount of E1 are residues according to formula (IIb). Alkoxylated polyalkyleneimines or alkoxylated polyamines.

2. R is the same or different i) Linear or branched C 2 ~C 12- is an alkylene group, or ii) At least one C 1 ~C 3 -C optionally substituted with alkyl 5 ~C 10 -cycloalkylene group, 2. The alkoxylated polyalkyleneimine or alkoxylated polyamine of claim 1.

3. In formula (IIa) and / or (IIb), the variables are each defined as follows: R 1 represents 1,2-ethylene, 1,2-propylene or 1,2-butylene; and / or R 2 is hydrogen or C 1 ~C 4 -represents alkyl; and / or R 3 However, linear or branched C 2 ~C 10 represents an alkylene group; and / or m is an integer having a value in the range of 1 to 5; and / or n is an integer having a value in the range of 8 to 40; and / or 50 to 100% of the total amount of E2 and E4 are residues according to formula (IIa) and 80 to 100% of the total amount of E1 are residues according to formula (IIb); 3. The alkoxylated polyalkyleneimine or alkoxylated polyamine according to claim 1 or 2.

4. 4. The alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) of the polyalkyleneimine backbone or polyamine backbone is in the range of 50 to 10,000 g / mol.

5. The variables are defined as follows: R is ethylene or propylene; the sum of y and z is an integer having a value in the range of 9 to 120; 5. The alkoxylated polyalkyleneimine of any one of claims 1 to 4.

6. R is ethylene or propylene; the sum of y+z is an integer having a value in the range of 9 to 120; R 1 represents 1,2-ethylene; R 2 is hydrogen or C 1 ~C 4 -represents alkyl; R 3 However, linear or branched C 2 ~C 10 -represents an alkylene group; m is an integer having a value in the range of 1 to 5; n is an integer having a value in the range of 8 to 40; 50 to 100% of the total amount of E2 and E4 are residues according to formula (IIa) and 80 to 100% of the total amount of E1 are residues according to formula (IIb); 6. The alkoxylated polyalkyleneimine of claim 5.

7. The variables are defined as follows: R is ethylene; the sum of y+z is an integer having a value in the range of 10 to 20; R 1 represents 1,2-ethylene; R 2 represents hydrogen; R 3 However, linear or branched C 2 ~C 5 -represents an alkylene group; m is an integer having a value in the range of 1 to 3; n is an integer having a value in the range of 10 to 25; 90 to 100% of the total amount of E2 and E4 are residues according to formula (IIa) and 85 to 95% of the total amount of E1 are residues according to formula (IIb); 7. The alkoxylated polyalkyleneimine according to claim 5 or 6.

8. y is an integer having a value in the range of 0 to 10; z is 0; R is the same or different linear or branched C 2 ~C 12- an alkylene group or a group represented by formula (III) d is 1 to 5, R 10 , R 11 , R 12 are independently linear or branched C 3 ~C 4 alkylene groups) represents an ether alkyl unit conforming to 5. The alkoxylated polyamine of claim 1.

9. R 1 represents 1,2-ethylene; R 2 is hydrogen or C 1 ~C 4 -represents alkyl; R 3 However, linear or branched C 2 ~C 10 -represents an alkylene group; m is an integer having a value in the range of 1 to 5; n is an integer having a value in the range of 8 to 40; y is an integer having a value in the range of 1 to 10; 50 to 100% of the total amount of E2 and E4 are residues according to formula (IIa) and 80 to 100% of the total amount of E1 are residues according to formula (IIb); 9. The alkoxylated polyamine of claim 8.

10. R is ethylene or propylene; R 1 represents 1,2-ethylene; R 2 represents hydrogen; R 3 However, linear or branched C 2 ~C 5 -represents an alkylene group; m is an integer having a value in the range of 1 to 3; n is an integer having a value in the range of 10 to 25; y is an integer having a value in the range of 2 to 4; 90 to 100% of the total amount of E2 and E4 are residues according to formula (IIa), and 90 to 100% of the total amount of E1 are residues according to formula (IIb); 10. The alkoxylated polyamine of claim 8 or 9.

11. y is 0; z is 0; R is at least one C 1 ~C 3 - the same or different C optionally substituted with alkyl 5 ~C 10 represents a cycloalkylene group, 5. The alkoxylated polyamine of claim 1.

12. 12. The alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of claims 1 to 11, wherein up to 100% of the nitrogen atoms present in the alkoxylated polyalkyleneimine or alkoxylated polyamine are quaternized.

13. 13. Use of the alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of claims 1 to 12 in laundry detergents, in cleaning compositions, in fabric and home care products, in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cementitious compositions and / or as dispersants for pesticide formulations.

14. 13. A process for preparing the alkoxylated polyalkyleneimines or alkoxylated polyamines according to claims 1 to 12, comprising reacting the polyalkyleneimine or polyamine backbone first with at least one lactone and / or at least one hydroxycarbon acid to obtain the respective alkoxylated compound, followed by reacting the polyalkyleneimine or polyamine backbone with at least one C 2 ~C 22 - reacting with an epoxide.

15. For each mole of NH functional group in the polyalkyleneimine or polyamine, the respective polyalkyleneimine backbone or polyamine backbone is reacted with at least 0.05 moles of at least one lactone and / or at least one hydroxycarbon acid, followed by at least 5 moles of at least one C 2 ~C 22 15. The method of claim 14, wherein the hydroxybenzoate is reacted with an epoxide.

16. 16. The method according to claim 14 or 15, wherein the alkoxylated polyalkyleneimine or alkoxylated polyamine is additionally quaternized.

17. The lactone is caprolactone, the hydroxycarbon acid is lactic acid, and / or C 2 ~C 22 17. The method according to any one of claims 14 to 16, wherein the epoxide is ethylene oxide.

18. 13. A laundry detergent, cleaning composition, fabric and home care product, cosmetic formulation, crude oil demulsifier, pigment dispersion for inkjet ink, electroplating formulation, cementitious composition, and / or dispersant for pesticide formulation, comprising at least one alkoxylated polyalkyleneimine or alkoxylated polyamine according to any one of claims 1 to 12.

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