Carboxymethylated lysine-based polymers and compositions comprising same

Abstract

The present invention relates to a carboxymethylated lysine-based polymer comprising (A) from 60 to 99 mol% of structural units from lysine monomers, and (B) from 1 to 40 mol% of structural units from at least one dicarboxylic acid of formula (I) HOOC-R1-COOH or an amide-forming derivative thereof, and a method for preparing same, the carboxymethylated lysine-based polymer comprising (A) from 60 to 99 mol% of structural units from lysine monomers, and (B) from 1 to 40 mol% of structural units from at least one dicarboxylic acid of formula (I) HOOC-R1-COOH or an amide-forming derivative thereof, wherein R1 is a direct bond or an aliphatic linear alkylene group. The invention also relates to a detergent composition and a peroxy bleaching composition comprising a carboxymethylated lysine-based polymer.

Description

Technical Field

[0001] The present invention relates to a carboxymethylated lysine-based polymer, a method for preparing the same, a detergent composition comprising the carboxymethylated lysine-based polymer, and the use of the carboxymethylated lysine-based polymer in a detergent composition. Background Art

[0002] Today, dispersants play an important role in various industrial and household formulations, for example in laundry detergent formulations to prevent textile graying and in automatic dishwashing detergent formulations to prevent scale formation on utensils. The development of dispersants has always pursued the dispersion effect to avoid, for example, undesired phenomena such as scale formation or dirt deposition during the washing and cleaning processes.

[0003] Chelating agents are also important additives in industrial formulations (such as for papermaking) and household formulations (such as for washing and cleaning processes, especially in hard water areas).

[0004] In recent years, with the improvement of the public's environmental awareness and more environmental regulatory requirements worldwide, the new trend in additive development is to provide environmentally friendly phosphorus-free additives. Along with this trend, biodegradable dispersants and chelating agents pose new challenges to manufacturers.

[0005] Therefore, there is a need to provide a biodegradable chemical as a dispersant and / or chelating agent that can be used in industrial and household formulations. Summary of the Invention

[0006] The object of the present invention is to provide a biodegradable chemical as a dispersant and / or chelating agent, especially a biodegradable chemical having both chelating and dispersing functions.

[0007] It has been found that the object of the present invention can be achieved by a carboxymethylated lysine-based polymer obtained by polycondensation and carboxymethylation of monomers comprising lysine and at least one dicarboxylic acid.

[0008] In one aspect, the present invention relates to a carboxymethylated lysine-based polymer, which comprises

[0009] (A) 60 to 95 mol% of structural units derived from lysine monomers,

[0010] (B) 5 to 40 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative

[0011] HOOC-R1-COOH (I)

[0012] Wherein

[0013] R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, bis(alkyl)amino, alkylene, hydroxy, mercapto, amino, and halogen.

[0014] In another aspect, the present invention relates to a method for preparing a carboxymethylated lysine-based polymer, the method comprising - subjecting monomers comprising the following to thermal polycondensation:

[0015] (A) 60 to 99 mol% of lysine monomers,

[0016] (B) 1 to 40 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative

[0017] HOOC-R1-COOH (I)

[0018] wherein

[0019] R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, bis(alkyl)amino, alkylene, hydroxy, mercapto, amino, and halogen,

[0020] to obtain a lysine-based polymer, and

[0021] - subjecting the lysine-based polymer to carboxymethylation.

[0022] In yet another aspect, the present invention relates to a detergent composition or a peroxygen bleaching composition comprising a carboxymethylated lysine-based polymer as described in the first aspect.

[0023] In still another aspect, the present invention relates to the use of a carboxymethylated lysine-based polymer as described in the first aspect in a detergent composition or a peroxygen bleaching composition.

[0024] In a further aspect, the present invention relates to the use of a carboxymethylated lysine-based polymer as described in the first aspect as a chelating agent and / or a dispersing agent.

[0025] It has surprisingly been found that the carboxymethylated lysine-based polymers according to the present invention exhibit chelating and / or dispersing properties comparable to or even better than those of commercially available non-biodegradable chelating agents and dispersing agents, while having acceptable biodegradability. Detailed Description

[0026] The present invention will now be described in detail hereinafter. It should be understood that the present invention can be implemented in many different ways and should not be construed as limited to the embodiments set forth herein. Unless otherwise mentioned, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

[0027] As used herein, the singular forms "a / an" and "the" include plural referents unless the context clearly dictates otherwise.

[0028] As used herein, the terms "comprise / comprising" etc. are used interchangeably with "contain / containing" etc. and should be interpreted in a non-restrictive, open manner. That is, for example, additional components or elements may be present. The expressions "consisting of" or "consisting essentially of" or cognates may be included within "comprise" or cognates.

[0029] As used herein, the term "biodegradable" generally refers to a material that can be degraded by the action of naturally occurring microorganisms (such as bacteria, fungi, and algae), environmental heat, moisture, or other environmental factors.

[0030] As used herein, the term "lysine-based polymer" is intended to indicate a polymer in which lysine is present in a major molar proportion, for example, not less than 50 mol% of all monomers constituting the polymer.

[0031] As used herein, the term "carboxymethylated lysine-based polymer" is intended to refer to a lysine-based polymer that has been modified by carboxymethylation of the remaining free amino groups in the lysine-based polymer. It should be understood that the term "carboxymethylated lysine-based polymer" is intended to include the form in which the carboxyl groups introduced via carboxymethylation are partially or fully neutralized.

[0032] As used herein, the term "structural unit" is intended to refer to the smallest molecular residue produced by a corresponding monomer after polycondensation. It should be understood that if the monomer has an amino group that may remain in the polycondensation, the term "structural unit" may also refer to the molecular residue produced by the monomer after polycondensation and carboxymethylation.

[0033] Herein, the terms "one or more structural units from lysine monomers" and "one or more lysine structural units" are used interchangeably. Similarly, the terms "structural units from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives" and "one or more dicarboxylic acid structural units" are used interchangeably.

[0034] As used herein, unless the context clearly indicates otherwise, when referring to a carboxymethylated lysine-based polymer according to the present invention, the K-value refers to the corresponding parameter of the lysine-based polymer in the absence of carboxymethylation.

[0035] <Carboxymethylated lysine-based polymer>

[0036] The carboxymethylated lysine-based polymer according to the present invention comprises

[0037] (A) 60 to 99 mol% of structural units derived from lysine monomers,

[0038] (B) 1 to 40 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative

[0039] HOOC-R1-COOH (I)

[0040] wherein

[0041] R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylene, hydroxy, mercapto, amino, and halogen.

[0042] As used herein, the term "aliphatic straight-chain alkylene group" refers to a divalent group derived from an unsaturated or saturated acyclic hydrocarbon, which may optionally be interrupted by at least one heteroatom selected from O, S, and N. Typically, the alkylene group herein will have 1 to 24 carbon atoms (C1-C 24 -alkylene), preferably 1 to 18 carbon atoms (C1-C 18 -alkylene), more preferably 1 to 12 carbon atoms (C1-C 12 -alkylene). Examples of the aliphatic straight-chain alkylene group are especially alkylene and alkenylene.

[0043] As used herein, the term "alkylene" refers to a saturated divalent group derived from a straight-chain alkane, which may optionally be interrupted by at least one heteroatom selected from O, S, and N. Typically, the alkylene group herein will have 1 to 24 carbon atoms (C1-C 24 -alkylene), preferably 1 to 18 carbon atoms (C1-C 18 -alkylene), more preferably 1 to 12 carbon atoms (C1-C 12 -alkylene). Examples of the alkylene group are especially methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, hexadecamethylene, octadecamethylene, etc.

[0044] As used herein, the term "alkenylene" refers to an unsaturated divalent group derived from a straight-chain alkene, wherein any double bond is in an internal position. Typically, the alkenylene herein will have from 2 to 24 carbon atoms (C2-C 24 -alkenylene), preferably from 2 to 18 carbon atoms (C2-C 18 -alkenylene), more preferably from 2 to 12 carbon atoms (C2-C 12 -alkenylene). Examples of alkenylene are especially vinylene, 1,3-propenylene, 1,4-but-2-enylene, 1,5-pent-2-enylene, 1,6-hex-3-enylene, etc.

[0045] As used herein, the term "alkyl" in an alkyl moiety such as alkoxy, alkylthio, alkylamino, dialkylamino, etc. refers to a saturated straight-chain or branched hydrocarbon group typically having from 1 to 18 carbon atoms (C1-C 18 -alkyl), preferably from 1 to 12 carbon atoms (C1-C 12 -alkyl), more preferably from 1 to 8 carbon atoms (C1-C8-alkyl) or from 1 to 4 carbon atoms (C1-C4-alkyl). Examples of alkyl are especially methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 1-ethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, 2-methylhexyl, 1-ethylpentyl, 1-propylbutyl, 2-ethylpentyl, n-octyl, 1-methylheptyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1-propylpentyl, 2-propylpentyl, n-nonyl, etc.

[0046] As used herein, the term "alkoxy" refers to an alkyl attached via an oxygen atom, which may be represented by -O-alkyl, wherein the alkyl is as defined above.

[0047] As used herein, the term "alkylthio" refers to an alkyl attached via a sulfur atom, which may be represented by -S-alkyl, wherein the alkyl is as defined above.

[0048] As used herein, the terms "alkylamino" and "di(alkyl)amino" refer to an amino group (-NH2) in which the hydrogen atom is replaced by one or two alkyl groups, respectively, wherein the alkyl is as defined above.

[0049] As used herein, the term "alkylidene" refers to an unsaturated divalent group derived from an alkane having two valences on the same carbon atom, which may be represented by *=CR a R b wherein the asterisk (*) represents the position where the alkylidene is attached to the remainder, and R a and R bSupply H or alkyl, respectively. Typically, the alkylene groups herein will have 1 to 6 carbon atoms (C1-C6-alkylene), preferably 1 to 4 carbon atoms (C1-C4-alkylene). Examples of alkylene groups are especially methylene, ethylene, propylene, etc.

[0050] As used herein, the term "halogen" refers to fluorine, bromine, chlorine, and iodine.

[0051] In certain embodiments, the structural unit derived from lysine monomers contained in the carboxymethylated lysine-based polymers according to the present invention may be represented by

[0052]

[0053] (Lysine structural unit in ε-linkage form)(Lysine structural unit in α-linkage form)

[0054] wherein

[0055] R2 and R3 are each independently H, COOH, or COOM 1 / x , where M is a cation and x is the valence of the cation, particularly M is an alkali metal cation or a quaternary ammonium cation; and

[0056] * represents the position where the structural unit is attached to any other structural unit through an amide linkage bond.

[0057] It should be understood that each lysine structural unit as described above may be linked to a lysine structural unit of the same linkage form to form a polymer block, linked to a structural unit of another linkage form or a polymer block composed of a lysine structural unit of another linkage form, or linked to a dicarboxylic acid structural unit; and each lysine structural unit may be linked to two identical or different structural units.

[0058] The dicarboxylic acid structural unit contained in the carboxymethylated lysine-based polymers according to the present invention may be represented, for example, by formula (II)

[0059]

[0060] wherein

[0061] R1 is as defined hereinabove for formula (I),

[0062] * represents the position where the structural unit is attached to any other structural unit through an amide linkage bond.

[0063] It should be understood that each structural unit of formula (II) as described above may be linked to two lysine structural units of the same or different linkages.

[0064] It should also be understood that when R1 is a lower alkylene group substituted by an amino group (NH2), the dicarboxylic acid structural units contained in the carboxymethylated lysine-based polymers according to the invention can also be in any other possible form. The amino substituents are reactive with the carboxyl groups contained in the lysine monomers and the dicarboxylic acids and can form the corresponding amide linkage bonds.

[0065] In a specific embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond or an aliphatic straight-chain C1-C 24 -lower alkylene group which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C 18 -alkyl groups, unsubstituted or substituted C1-C 18 -alkoxy groups, unsubstituted or substituted C1-C 18 -alkylthio groups, unsubstituted or substituted C1-C 18 -alkylamino groups, di(C1-C 18 -alkyl)amino groups, C1-C6-lower alkylene groups, hydroxyl groups, mercapto groups, amino groups and halogen atoms.

[0066] In a preferred embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond or an aliphatic straight-chain C1-C 18 -lower alkylene group which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C 12 -alkyl groups, unsubstituted or substituted C1-C 12 -alkoxy groups, unsubstituted or substituted C1-C 12 -alkylthio groups, unsubstituted or substituted C1-C 12 -alkylamino groups, di(C1-C 12 -alkyl)amino groups, C1-C4-lower alkylene groups, hydroxyl groups, mercapto groups, amino groups and halogen atoms.

[0067] In a more preferred embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond or an aliphatic straight-chain C1-C 12 -lower alkylene group which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C8-alkyl groups, unsubstituted or substituted C1-C8-alkoxy groups, unsubstituted or substituted C1-C8-alkylthio groups, unsubstituted or substituted C1-C8-alkylamino groups, di(C1-C8-alkyl)amino groups, C1-C4-lower alkylene groups, hydroxyl groups, mercapto groups, amino groups and halogen atoms.

[0068] In a further preferred embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, unsubstituted or substituted C1-C4-alkoxy, unsubstituted or substituted C1-C4-alkylthio, unsubstituted or substituted C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

[0069] In a still more preferred embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C4-alkylene, hydroxy, mercapto and amino.

[0070] In a most preferred embodiment, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C2-alkylene, hydroxy and amino.

[0071] In particular, the carboxymethylated lysine-based polymer according to the invention comprises structural units (B) derived from at least one of the following: oxalic acid, malonic acid, succinic acid, maleic acid and fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

[0072] Preferably, the carboxymethylated lysine-based polymer according to the invention comprises

[0073] (A) 70 to 97 mol% of lysine structural units; and

[0074] (B) 3 to 30 mol% of dicarboxylic acid structural units.

[0075] More preferably, the carboxymethylated lysine-based polymer according to the invention comprises:

[0076] (A) 75 to 97 mol% lysine structural units; and

[0077] (B) 4 to 25 mol% dicarboxylic acid structural units.

[0078] Most preferably, the carboxymethylated lysine-based polymer according to the invention comprises

[0079] (A) 75 to 95 mol% lysine structural units; and

[0080] (B) 5 to 25 mol% dicarboxylic acid structural units.

[0081] The carboxymethylated lysine-based polymer according to the invention has a degree of modification (DM) by carboxymethylation of at least 20%, particularly at least 30%, preferably at least 50%, more preferably at least 70%, even more preferably at least 80%. Herein, the degree of modification (DM) is theoretically defined according to the following equation:

[0082]

[0083] The measurement of DM can be carried out as follows: hydrolyze the carboxymethylated lysine-based polymer and determine the number of moles of carboxymethyl groups, the number of moles of lysine structural units, and the number of moles of dicarboxylic acid structural units with amino groups when present, according to the resonance signals assigned to the corresponding protons in the hydrolysis products measured by 1 1H NMR in D2O. It should be understood that due to the limitations of the measurement method, the measured DM value may not be exactly the same as the theoretical value.

[0084] Preferably, the carboxymethylated lysine-based polymer according to the invention is prepared from a lysine-based polymer having a K-value in the range of 8 to 20, more preferably 9 to 15, and most preferably 9.5 to 13, where the K-value is determined as per DIN ISO 1628-1 at 23 °C using a 1 wt% solution of the corresponding lysine-based polymer in water. The K-value is generally referred to as the intrinsic viscosity and is an indirect measure of the molecular weight of the polymer.

[0085] The carboxymethylated lysine-based polymer according to the invention has a number average molecular weight (Mn) in the range of 400 to 10,000 g / mol, preferably 600 to 8,500 g / mol, more preferably 750 to 7,000 g / mol, and / or a weight average molecular weight (Mw) in the range of 500 to 3,500 g / mol, preferably 650 to 3,000 g / mol, more preferably 800 to 2,250 g / mol. The average molecular weight can be measured according to the methods described hereinafter.

[0086] Preferably, the carboxymethylated lysine-based polymer according to the present invention has a degree of modification (DM) by carboxymethylation of at least 30%, preferably at least 50%, more preferably at least 70%, and has a number average molecular weight (Mn) in the range of 600 to 8,500 g / mol, more preferably 750 to 7,000 g / mol and / or a weight average molecular weight (Mw) in the range of preferably 650 to 3,000 g / mol, more preferably 800 to 2,250 g / mol.

[0087] In particular, the carboxymethylated lysine-based polymer according to the present invention has a degree of modification (DM) by carboxymethylation of at least 50%, more preferably at least 70%, and has a number average molecular weight (Mn) in the range of 750 to 7,000 g / mol and / or a weight average molecular weight (Mw) in the range of 800 to 2,250 g / mol.

[0088] <Method for preparing a carboxymethylated lysine-based polymer>

[0089] There is no particular limitation on the method for preparing the carboxymethylated lysine-based polymer according to the present invention. Generally, the carboxymethylated lysine-based polymer according to the present invention can be prepared by a method comprising: thermal polycondensation of lysine and at least one dicarboxylic acid or its amide-forming derivative to provide a lysine-based polymer, and subsequent carboxymethylation of the lysine-based polymer.

[0090] In a specific embodiment, the present invention relates to a method for preparing a carboxymethylated lysine-based polymer, the method comprising

[0091] - thermally polycondensing monomers comprising:

[0092] (A) 60 to 95 mol% of lysine monomers,

[0093] (B) 5 to 40 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative

[0094] HOOC-R1-COOH (I)

[0095] where

[0096] R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylene, hydroxy, mercapto, amino and halogen,

[0097] to obtain a lysine-based polymer, and

[0098] - Carboxymethylate the lysine-based polymer.

[0099] Preferably, the method according to the invention comprises thermally polycondensing monomers comprising:

[0100] (A) 70 to 90 mol% of lysine monomers; and

[0101] (B) 10 to 30 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

[0102] More preferably, the method according to the invention comprises thermally polycondensing monomers comprising:

[0103] (A) 75 to 90 mol% of lysine monomers; and

[0104] (B) 10 to 25 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

[0105] Most preferably, the method according to the invention comprises thermally polycondensing monomers comprising:

[0106] (A) 80 to 90 mol% of lysine monomers; and

[0107] (B) 10 to 20 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

[0108] The lysine monomers can be in the form of, for example, lysine zwitterionic free base, lysine hydrochloride and / or lysine hydrate.

[0109] Suitable amide-forming derivatives of the dicarboxylic acid of formula (I) include, but are not limited to, its monoester and diester, anhydride, monoamide and diamide, and acyl halide.

[0110] In a further specific embodiment, R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 24 - alkylene group, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C 18 - alkyl, unsubstituted or substituted C1-C 18 - alkoxy, unsubstituted or substituted C1-C 18 - alkylthio, unsubstituted or substituted C1-C 18 - alkylamino, di(C1-C 18 - alkyl)amino, C2-C6-alkylene, hydroxy, mercapto, amino, and halogen.

[0111] In a preferred embodiment, R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 18-alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C 12 -alkyl, unsubstituted or substituted C1-C 12 -alkoxy, unsubstituted or substituted C1-C 12 -alkylthio, unsubstituted or substituted C1-C 12 -alkylamino, di(C1-C 12 -alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

[0112] In a more preferred embodiment, R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 12 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-alkoxy, unsubstituted or substituted C1-C8-alkylthio, unsubstituted or substituted C1-C8-alkylamino, di(C1-C8-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

[0113] In a further preferred embodiment, R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C4-alkyl, unsubstituted or substituted C1-C4-alkoxy, unsubstituted or substituted C1-C4-alkylthio, unsubstituted or substituted C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

[0114] In a still more preferred embodiment, R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C4-alkyl, C1-C4-alkylene, hydroxy, mercapto and amino.

[0115] In the most preferred embodiment, R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C4-alkyl, C1-C2-alkylene, hydroxy and amino.

[0116] In particular, at least one dicarboxylic acid of formula (I) is selected from oxalic acid, malonic acid, succinic acid, maleic acid and fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

[0117] The thermal polycondensation of lysine monomers and the dicarboxylic acid of formula (I) or its amide to form derivatives can be carried out via known methods.

[0118] Preferably, the lysine-based polymer thus obtained has a K-value in the range of 8 to 20, more preferably 9 to 15, and most preferably 9.5 to 13, as determined according to DIN ISO 1628-1 at 23 °C using a 1 wt% solution of the corresponding lysine-based polymer in water.

[0119] The carboxymethylation of the lysine-based polymer can also be carried out via known methods for the carboxymethylation of amino groups. For example, the carboxymethylation can be simply carried out via a carboxymethylating agent such as iodoacetic acid (as described in "Preparation and properties of poly(N ε ,N ε -dicarboxymethyl-L-Iysine)[Polymerization of N ε ,N ε -dicarboxymethyl-L-lysine] by Kazuo Uehara et al., Polymer, 1979, Vol. 20, 670-674), sodium chloroacetate (as described in US 2,860,164 A), etc. Alternatively, the carboxymethylation can be carried out via the reaction of the amino group with formaldehyde and hydrogen cyanide or sodium cyanide under the corresponding conditions, as described in US 2,860,164 A.

[0120] The carboxymethylated lysine-based polymer obtainable or obtained from the process according to the invention has a degree of modification (DM) by carboxymethylation of at least 20%, in particular at least 30%, preferably at least 50%, still preferably at least 70%, more preferably at least 80%.

[0121] The carboxymethylated lysine-based polymer obtainable or obtained from the process according to the invention has a number-average molecular weight (Mn) in the range of 400 to 10,000 g / mol, preferably 600 to 8,500 g / mol, more preferably 750 to 7,000 g / mol, and / or has a weight-average molecular weight (Mw) in the range of 500 to 3,500 g / mol, preferably 650 to 3,000 g / mol, more preferably 800 to 2,250 g / mol.

[0122] Preferably, the carboxymethylated lysine-based polymer obtainable or obtained from the process according to the invention has a degree of modification (DM) by carboxymethylation of at least 30%, preferably at least 50%, more preferably at least 70%, and has a number average molecular weight (Mn) in the range from 600 to 8,500 g / mol, more preferably from 750 to 7,000 g / mol and / or a weight average molecular weight (Mw) in the range preferably from 650 to 3,000 g / mol, more preferably from 800 to 2,250 g / mol.

[0123] In particular, the carboxymethylated lysine-based polymer obtainable or obtained from the process according to the invention may have a degree of modification (DM) by carboxymethylation of at least 50%, more preferably at least 70%, and has a number average molecular weight (Mn) in the range from 750 to 7,000 g / mol and / or a weight average molecular weight (Mw) in the range from 800 to 2,250 g / mol.

[0124] It has been found that the carboxymethylated lysine-based polymers according to the invention can be used as dispersants and / or chelating agents in detergent compositions and peroxy bleach compositions.

[0125] <Detergent composition>

[0126] According to the invention, a detergent composition can be any composition comprising a surfactant or a surfactant mixture to provide a cleaning effect. In particular, the detergent composition is a laundry detergent composition or a detergent composition for cleaning agents. The term "detergent composition for cleaning agents" includes cleaning agent compositions for household care and for industrial or institutional applications. In particular, the detergent composition for cleaning agents includes compositions for dishwashing, especially manual and automatic dishwashing and warewashing, and compositions for hard surface cleaning, such as but not limited to compositions for bathroom cleaning, kitchen cleaning, floor cleaning, pipe descaling, window cleaning, car cleaning (including truck cleaning), in addition to open plant cleaning, in-situ cleaning, metal cleaning, disinfectant cleaning, farm cleaning, high-pressure cleaning, but not laundry detergent compositions.

[0127] There are no restrictions on the formulation of the detergent composition. The carboxymethylated lysine-based polymer according to the invention can be used in any conventional formulation of a detergent composition such as a laundry detergent composition or a detergent composition for cleaning agents. It should be understood that, in addition to or instead of a chelating agent and / or a dispersing agent (which would otherwise be included in the conventional formulation of the detergent composition), the carboxymethylated lysine-based polymer according to the invention can be used in the detergent composition.

[0128] In some embodiments of the present invention, the laundry detergent composition comprises a carboxymethylated lysine-based polymer according to the present invention in an amount of from 0.5% to 30%, preferably from 1% to 25% and more preferably from 1% to 15% by weight based on the total solids content of the detergent composition, for example from 1% to 10% by weight.

[0129] In some other embodiments of the present invention, the cleaning detergent composition comprises a carboxymethylated lysine-based polymer according to the present invention in an amount of from 0.5% to 30%, preferably from 1% to 20%, more preferably from 1% to 10% by weight based on the total solids content of the detergent composition.

[0130] As an essential component for providing cleaning efficacy to the detergent composition, depending on the specific application and desired performance of the detergent composition, it may comprise at least one of cationic, anionic, nonionic and amphoteric surfactants.

[0131] Nonionic surfactant

[0132] Available nonionic surfactants may include, but are not limited to, (1) condensation products of alcohols with ethylene oxide, (2) alcohols with ethylene oxide and additional alkylene oxides, (3) polypropylene glycol with ethylene oxide, or (4) reaction products of ethylene oxide with ethylenediamine and propylene oxide, fatty acid amides, and semi-polar nonionic surfactants.

[0133] The condensation product of an alcohol with ethylene oxide is derived from, for example, an alcohol having a C8 to C 22 -alkyl, preferably C 10 to C 18 -alkyl, which may be straight-chain or branched, primary or secondary. The alcohol is condensed with about 1 to 25 mol and preferably with about 3 to 18 moles of ethylene oxide / mol of alcohol.

[0134] The condensation product of an alcohol with ethylene oxide and additional alkylene oxides can be constructed according to the scheme R-O-EO-AO or R-O-AO-EO, where R is a primary or secondary, branched or straight-chain C8 to C 22 -alkyl, preferably C 10 to C 18 -alkyl, EO is ethylene oxide and AO comprises an alkylene oxide, preferably propylene oxide, butylene oxide or pentylene oxide.

[0135] The condensation product of polypropylene glycol with ethylene oxide comprises a hydrophobic moiety preferably having a molecular weight of from about 1,500 to about 1,800. Addition of up to about 40 moles of ethylene oxide to this hydrophobic moiety results in an amphiphilic compound.

[0136] The condensation products of ethylene oxide with the reaction products of ethylenediamine and propylene oxide contain a hydrophobic portion consisting of the reaction products of ethylenediamine and propylene oxide and generally having a molecular weight of about 2,500 to about 3,000. Ethylene oxide is added up to a polyoxyethylene content of up to about 40% to about 80% by weight based on the hydrophobic unit and a molecular weight of about 5,000 to about 11,000.

[0137] The fatty acid amides may be those of the formula

[0138]

[0139] in

[0140] R 1 is an alkyl group having 7 to 21 and preferably 9 to 17 carbon atoms, and

[0141] R 2 are independently hydrogen, C1 to C4-alkyl, C1 to C4-hydroxyalkyl or (C2H4O) x H, where x varies from 1 to 3.

[0142] Preferred are C8 to C 20 - Fatty acid amides, such as monoethanolamide, diethanolamide and diisopropanolamide.

[0143] As semi-polar nonionic surfactants, there may be mentioned 18 -alkyl, preferably C 10 to C 14 -alkyl water-soluble amine oxides, water-soluble phosphine oxides and water-soluble sulfoxides. 10 -C 12 -Alkoxyethyl dihydroxyethylamine oxide.

[0144] In some embodiments, for example in automatic dishwashing compositions, weak or low foaming nonionic surfactants are preferred. In particular, mention may be made of the nonionic surfactants of formula (I), (II) and (III) below,

[0145] R 1 -O-(CH2CH2O) a -(CHR 2 CH2O)bR 3 (I),

[0146] in

[0147] R 1 Is a straight chain or branched C8 to C 22 -alkyl,

[0148] R 2and R 3 are each independently hydrogen or a straight-chain or branched C1 to C 10 alkyl group, where R 2 is preferably methyl, and

[0149] a and b are each independently 0 to 300;

[0150] R 4 -O-[CH2CH(CH3)O] c [CH2CH2O] d [CH2CH(CH3)O] e CH2CH(OH)R 5 (II),

[0151] where

[0152] R 4 is a straight-chain or branched aliphatic C4 to C 22 hydrocarbon group or a mixture thereof,

[0153] R 5 is a straight-chain or branched C2 to C 26 hydrocarbon group or a mixture thereof,

[0154] c and e are values between 0 and 40, and

[0155] d is a value of at least 15;

[0156] R 6 O-(CH2CHR 7 O) f (CH2CH2O) g (CH2CHR 8 O) h -CO-R 9 (III),

[0157] where

[0158] R 6 is a branched or unbranched C8 to C 16 alkyl group,

[0159] R 7 、R 8 are each independently H or a branched or unbranched C1 to C5 alkyl group, R 9 is an unbranched C5 to C 17 alkyl group,

[0160] f, h are each independently numbers from 1 to 5, and

[0161] g is a number from 13 to 35.

[0162] The surfactants of formula (I), (II) and (III) can be random copolymers or block copolymers, preferably in the form of block copolymers, as described in US 9796951 B2, which is incorporated herein by reference.

[0163] Anionic surfactant

[0164] Suitable anionic surfactants can include, but are not limited to, alkenyl- or alkylbenzenesulfonates, alkanesulfonates, olefinsulfonates, alkyl ester sulfonates, alkyl sulfates, alkyl ether sulfates, alkyl carboxylates (soaps). The counterions present are alkali metal cations (preferably sodium or potassium), alkaline earth metal cations (such as calcium or magnesium), as well as ammonium and substituted ammonium compounds (such as monoethanolammonium, diethanolammonium or triethanolammonium cations) and mixtures of the above cations therefrom.

[0165] The alkenyl- or alkylbenzenesulfonates can contain branched or straight-chain, optionally hydroxy-substituted alkenyl or alkyl groups, preferably straight-chain C9 to C 25 -alkyl.

[0166] Alkanesulfonates are available on an industrial scale in the form of secondary alkanesulfonates, where the sulfo group is attached to the secondary carbon atom of the alkyl moiety. The alkyl group can in principle be saturated, unsaturated, branched or straight-chain and optionally hydroxy-substituted. Preferred secondary alkanesulfonates contain straight-chain C9 to C 25 -alkyl, preferably C 10 to C 20 -alkyl and more preferably C 12 to C 18 -alkyl.

[0167] Olefinsulfonates are obtained by sulfonating C8 to C 24 and preferably C 14 to C 16 -α-olefins and then neutralizing. Due to their production process, these olefinsulfonates can contain small amounts of hydroxyalkanesulfonates and alkanedisulfonates.

[0168] Alkyl ester sulfonates are derived from, for example, straight-chain esters of C8 to C 20 -carboxylic acids (i.e., fatty acids), which are sulfonated with sulfur trioxide. Compounds of the following formula are preferred

[0169]

[0170] where

[0171] R’ is C8 to C 20 -alkyl, preferably C 10 to C 16-alkyl, and R” is C1 to C6-alkyl, preferably methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates, where R 1 is C 10 to C 16 -alkyl.

[0172] Alkyl sulfates are surfactants of the formula ROSO3M’, where R is C 10 to C 24 -alkyl and preferably C 12 to C 18 -alkyl. M’ is a counterion as described at the beginning of the anionic surfactants.

[0173] Alkyl ether sulfates have the general structure RO(A) m SO3M, where R is C 10 to C 24 -alkyl and preferably C 12 to C 18 -alkyl, where A is an alkoxy unit, preferably ethoxy, and m is a value from about 0.5 to about 6, preferably between about 1 and about 3, and M is a cation such as sodium, potassium, calcium, magnesium, ammonium or a substituted ammonium cation.

[0174] Alkyl carboxylates are commonly referred to by the term “soap”. Soaps can be made based on saturated or unsaturated, preferably natural straight-chain C8 to C 18 -fatty acids. Saturated fatty acid soaps include, for example, the salts of lauric acid, myristic acid, palmitic acid, stearic acid, erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids (such as coconut, palm kernel or tallow fatty acids). Known alkenyl succinates can also be used with or as an alternative to soaps.

[0175] Additional anionic surfactants are salts of acylamino carboxylic acids, acyl sarcosinates, fatty acid-protein condensation products obtained by the reaction of fatty acid chlorides with oligopeptides; salts of alkylsulfamoyl carboxylic acids; salts of alkyl and alkylaryl ether carboxylic acids; sulfonated polycarboxylic acids, alkyl and alkenyl glycerol sulfates (such as oleyl glycerol sulfate), alkylphenol ether sulfates, alkyl phosphates, alkyl ether phosphates, hydroxyethyl sulfonates (such as acyl hydroxyethyl sulfonates), N-acyl aminoethanesulfonates, alkyl succinates, sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 12 to C 18 -monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 12 to C 18 -diesters), sulfates of alkyl polysaccharides (such as alkyl polyglycosides and sulfates of alkyl polysaccharides, such as alkyl polyglycosides and alkyl polyethoxy carboxylates (such as of the formula RO(CH2CH2)k Those of CH2COOM, where R is C8 to C 22 -alkyl, k is a number from 0 to 10 and M is a cation).

[0176] Cationic surfactants

[0177] Suitable cationic surfactants can be R 1 N(CH3)3 + X - 、R 1 R 2 N(CH 3)2 + X - 、R 1 R 2 R 3 N(CH3) + X - or R 1 R 2 R 3 R 4 N + X - substituted or unsubstituted straight-chain or branched quaternary ammonium salts, where R 1 、R 2 、R 3 and R 4 are each independently unsubstituted C8 to C 24 -alkyl and preferably C8 to C 18 -alkyl, hydroxyalkyl having 1 to 4 carbon atoms, phenyl, C2 to C 18 -alkenyl, C7 to C 24 -aralkyl, (C2H4O) x H, where x is from about 1 to about 3, the alkyl may optionally contain one or more ester groups, and X is a suitable anion. Suitable cationic surfactants can also be cyclic quaternary ammonium salts.

[0178] Amphoteric / ampholytic surfactants

[0179] Suitable amphoteric surfactants can be aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic group can be straight-chain or branched and where one of the aliphatic substituents contains at least about 8 carbon atoms, or about 8 to about 18 carbon atoms, and at least one of the aliphatic substituents contains an anionic water-soluble group such as carboxylate, sulfonate, sulfate. Suitable amphoteric surfactants also include sarcosinates, glycinate, taurates and mixtures thereof. Examples of substances that are amphoteric surfactants are known in the art, for example from WO 2005095569A1.

[0180] The zwitterionic surfactants that can be used can be derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Suitable examples of zwitterionic surfactants include, but are not limited to, betaines such as alkyl betaines and alkylamido betaines such as N-alkyl-N,N-dimethyl-N-carboxymethyl betaines, N-(alkylamidopropyl)-N,N-dimethyl-N-carboxymethyl betaines, alkyl dimethoxy betaines, alkylamine oxides, and sulfobetaines and hydroxysulfobetaines such as N-alkyl-N,N-dimethylamino-1-propane sulfonates, each having a straight-chain or branched C8 to C 22 -alkyl, preferably C8 to C 18 -alkyl and more preferably C 12 to C 18 -alkyl.

[0181] In an exemplary embodiment of the present invention, based on the total solids content of the detergent composition, the laundry detergent composition may contain 0.1% to 80% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants, and nonionic surfactants. Some preferred laundry detergent compositions of the present invention may contain at least one anionic or nonionic surfactant.

[0182] In another exemplary embodiment of the present invention, based on the total solids content of the detergent composition, the detergent composition for cleaners may contain 0.1% to 80% by weight of at least one surfactant selected from anionic surfactants, amphoteric surfactants, and nonionic surfactants. Some preferred detergent compositions for cleaners of the present invention may contain at least one anionic or nonionic surfactant.

[0183] Builders

[0184] The detergent composition may further contain conventional builders for altering the performance characteristics of the detergent composition.

[0185] Suitable builders for the detergent composition may include, but are not limited to, chelating agents, ion exchangers and precipitating agents, bleaches, bleach activators, corrosion inhibitors, foam boosters, defoamers, dyes, fillers, color fixatives, optical brighteners, disinfectants, alkalis, antioxidants, thickeners, fragrances, solvents, solubilizers, softeners, and antistatic agents, such as complexing agents other than the carboxymethylated lysine-based polymers according to the present invention. As examples, some builders will be described below.

[0186] Typically, a detergent composition may comprise at least one builder selected from organic and inorganic builders. Examples of suitable inorganic builders are sodium sulfate or sodium carbonate or silicates, in particular disodium silicate and sodium metasilicate, zeolites, layered silicates, in particular those of the formula α-Na2Si2O5, β-Na2Si2O5 and δ-Na2Si2O5. Examples of suitable organic builders are fatty acid sulfonates, α-hydroxypropionic acid, alkali metal malonates, fatty acid sulfonates, alkyl and alkenyl disuccinates, tartrate diacetates, tartrate monoacetates, oxidized starches and polymeric builders (such as polycarboxylates and polyaspartic acid).

[0187] Based on the total solids content of the detergent composition, the detergent composition may comprise builders in a total amount of, for example, from 10% to 70% by weight, preferably up to 50% by weight. In the context of the present invention, the carboxymethylated lysine-based polymers according to the present invention are not counted as builders.

[0188] The detergent composition may comprise at least one defoamer selected from, for example, silicone oil and paraffin oil. Based on the total solids content of the detergent composition, the total amount of defoamer may be from 0.05% to 0.5% by weight.

[0189] The detergent composition may comprise at least one bleaching agent. The bleaching agent may be selected from chlorine bleaching agents and peroxide bleaching agents.

[0190] Peroxide bleaching agents may be selected from inorganic peroxide bleaching agents and organic peroxide bleaching agents. Preferred inorganic peroxide bleaching agents are selected from alkali metal percarbonates, alkali metal perborates and alkali metal persulfates. In solid detergent compositions for hard surface cleaning and in solid laundry detergent compositions, alkali metal percarbonates, in particular sodium percarbonate, are preferably used in coated form. Such coatings may be of organic or inorganic nature. Examples are glycerol, sodium sulfate, silicates, sodium carbonate and combinations thereof, such as combinations of sodium carbonate and sodium sulfate. Examples of organic peroxide bleaching agents are percarboxylic acids.

[0191] Suitable chlorine bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfonamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate. Based on the total solids content of the detergent composition, laundry detergent compositions and detergent compositions for cleaners may comprise chlorine bleaching agents in a total amount of, for example, from 3% to 10% by weight.

[0192] The detergent composition may further comprise at least one bleach activator, such as N-methylmorpholinium-acetonitrile salt (“MMA salt”), trimethylammonium acetonitrile salt, N-acylimides such as N-nonanoyl succinimide, 1,5-diacetyl-2,2-dioxohexahydro-1,3,5-triazine (“DADHT”) or nitrile quaternary ammonium salts (trimethylammonium acetonitrile salt). Further examples of bleach activators are tetraacetylethylenediamine (TAED) and tetraacetylhexanediamine.

[0193] The detergent composition may comprise at least one corrosion inhibitor. Examples of suitable corrosion inhibitors are triazoles, especially benzotriazole, bisbenzotriazole, aminotriazole, alkylaminotriazole, phenol derivatives such as hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol or pyrogallol. Based on the total solids content of the detergent composition, the detergent composition may comprise a corrosion inhibitor in a total amount of from 0.1% to 1.5% by weight.

[0194] The detergent composition may further comprise at least one enzyme. Examples of enzymes are lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase and peroxidase, especially protease. The enzyme may be comprised in the detergent composition, especially in a laundry detergent composition and a detergent composition for cleaning agents, in an amount of up to 5% by weight, such as from 0.1% to 3% by weight, or from 0.1% to 2% by weight, or even from 0.1% to 1% by weight, based on the total solids content of the detergent composition. The enzyme may be stabilized, for example, by at least one sodium salt of a C1 to C3-carboxylic acid or a C4 to C 10 -dicarboxylic acid.

[0195] Suitable types and dosages of conventional auxiliaries for detergent compositions, especially laundry detergent compositions and detergent compositions for cleaning agents, are well known in the art and can be found, for example, in WO 2017174413 A1, WO 2015187757A1, US 9796951 B2 and US20190136152 A1.

[0196] <Peroxy bleach composition>

[0197] Due to the strong oxidizing ability of peroxides, peroxy bleaching agents are widely used in various processes, such as textile whitening, cellulose fiber pulp whitening, hair bleaching and surface disinfection. It is known that peroxides are generally sensitive to heavy metal ions (such as Fe, Cu, Mn, Ni, Co, Zn, Pb and Cd ions) because heavy metal ions can catalyze the decomposition of peroxides. Even a small amount of heavy metal ions may inevitably have an adverse effect on the bleaching effect.

[0198] As a conventional measure to stabilize peroxides (such as hydrogen peroxide) against heavy metal ions, additives that can chelate or complex heavy metal ions (such as EDTA, DTPA, NTA) are often used in peroxy bleaching compositions containing hydrogen peroxide or hydrogen peroxide precursors that can generate hydrogen peroxide during the bleaching process.

[0199] It has been found that the carboxymethylated lysine-based polymers according to the present invention can be used as stabilizers for peroxy bleaching agents. In particular, the peroxy bleaching agents can be those conventionally used for bleaching cellulosic fiber materials such as wood, cotton, linen, jute, and other cellulosic materials (which can be in the form of individual fibers (such as wood pulp or cotton fibers) and yarns, tows, meshes, fabrics (woven or non-woven), and other aggregates of such fibers), as well as those used for bleaching synthetic textiles (including polyamides, viscose, rayon, and polyesters).

[0200] In an embodiment of the present invention, the carboxymethylated lysine-based polymer according to the present invention is included as a stabilizer in a peroxy bleaching composition for bleaching cellulosic fiber pulp. Cellulosic fiber pulp typically contains a certain amount of heavy metal ions (such as Fe, Cu, and Mn ions), which need to be masked so that the bleaching effect is not adversely affected.

[0201] In a specific embodiment, the peroxy bleaching composition for bleaching cellulosic fiber pulp is in the form of an aqueous hydrogen peroxide solution. The aqueous hydrogen peroxide solution typically contains inorganic alkali metal alkaline materials such as sodium hydroxide, sodium carbonate, sodium silicate, and mixtures thereof. The inorganic alkali metal alkaline materials are used to impart a desired pH in the range of 7.5 to 12.5 to the aqueous hydrogen peroxide solution. The carboxymethylated lysine-based polymer can be included in the aqueous hydrogen peroxide solution in an amount of 0.01% to 3% by weight, preferably 0.1% to 1% by weight, based on the total weight of the solution.

[0202] In another specific embodiment, the carboxymethylated lysine-based polymer and the peroxide component according to the present invention are separately included in a peroxy bleaching composition for bleaching cellulose fiber pulp. In this embodiment, the carboxymethylated lysine-based polymer and hydrogen peroxide are not mixed until both are incorporated into the cellulose fiber pulp to be bleached. The carboxymethylated lysine-based polymer can be incorporated into the cellulose fiber pulp at a dosage of 0.01% to 3% by weight, preferably 0.1% to 1% by weight, more preferably 0.2% to 0.8% by weight, based on the weight of the cellulose fiber pulp. The specific dosage of the carboxymethylated lysine-based polymer can vary depending on the heavy metal content of the pulp, the hydrogen peroxide dosage, the bleaching method, etc. It is also desirable to use an inorganic alkali metal alkaline material, such as sodium hydroxide, sodium carbonate, sodium silicate, and mixtures thereof, such that the bleaching is carried out at a pH in the range of 7.5 to 12.5.

[0203] The following examples are provided to illustrate the present invention but are not intended to limit the present invention.

[0204] Examples

[0205] Description of materials used in the examples:

[0206] Polymer PA-1: Sodium polyacrylate, aqueous solution, pH 8 (10%), solid content 40 wt%, Mw 4000 g / mol, commercially available from BASF

[0207] Polymer PA-2: Sodium polyacrylate, aqueous solution, pH 8 (10%), solid content 45 wt%, Mw 1200 g / mol, commercially available from BASF

[0208] Copolymer CP-1: Sodium copolymer of maleic acid and olefin, aqueous solution, solid content 25 wt%, Mw 12,000 g / mol, commercially available from BASF

[0209] Modified PEI-1: Carboxymethylated polyethyleneimine, aqueous solution, solid content 40%, commercially available from BASF

[0210] Modified PEI-2: Ethoxylated polyethyleneimine, Mw 14,000 g / mol, wt% N: 18.19, commercially available from BASF EDTA liquid: Tetrasodium ethylenediaminetetraacetate (EDTA-Na4), active substance content 40 wt%, commercially available from BASF MGDA granules: Trisodium methylglycine diacetate (MGDA-Na3), granules, active substance content 85%, commercially available from BASF

[0211] MGDA liquid: trisodium methylglycinediacetate (MGDA-Na3), aqueous solution, active substance content 40%, commercially available from BASF

[0212] Anionic surfactant AES: C 12 C 14 Alcohol ethoxysulfate (2EO), sodium salt, commercially available from BASF

[0213] Anionic surfactant DBS / LC: linear C 10 C 13 Alkylbenzenesulfonate, commercially available from BASF

[0214] Anionic surfactant LDBS 55: linear n-C 10 C 13 -alkylbenzenesulfonate, sodium salt, active substance content 55%, commercially available from BASF

[0215] Nonionic surfactant AEO-1: ethoxylated C 13 C 15 -oxo alcohol (7EO), commercially available from BASF

[0216] Nonionic surfactant AEO-2: ethoxylated C 12 C 14 -fatty alcohol, (7EO), commercially available from BASF

[0217] K12-18: coconut fatty acid, commercially available from Henkel

[0218] Protease: 150T, commercially available from Novozymes

[0219] Amylase: 12L, commercially available from Novozymes

[0220] White cotton fabrics: wfk 10A, wfk 80A, wfk 12A, from wfk Testgewebe GmbH, Brüggen, Deutschland; EMPA 221, from Swissatest Testmaterialien AG, Sankt Gallen, Schweiz; and T-shirts (plain knitted fabric, S+Z, 100% cotton), from MRCreation, Goethestraβe 86, 72461 Alzenau

[0221] White polyester / cotton fabric: wfk 20A, commercially available from wfk Testgewebe GmbH, Brueggen, Germany

[0222] White polyester fabric: wfk 30A, commercially available from wfk Testgewebe GmbH, Brueggen, Germany

[0223] White polyamide fabric: EMPA 406, commercially available from Swiss Test Materials AG, St. Gallen, Switzerland

[0224] Soiled fabrics:

[0225] EMPA 101 (cotton fabric soiled with carbon black and olive oil), commercially available from Swiss Test Materials AG, St. Gallen, Switzerland

[0226] EMPA 125 (cotton fabric soiled with a mixture of oily components and pigments), commercially available from Swiss Test Materials AG, St. Gallen, Switzerland

[0227] SBL 2004 (cotton fabric soiled with sebum), commercially available from wfk Testgewebe GmbH, Brueggen, Germany

[0228] wfk 10PF (cotton fabric soiled with pigment / vegetable fat), commercially available from wfk Testgewebe GmbH, Brueggen, Germany

[0229] wfk 20D (polyester / cotton fabric soiled with sebum), commercially available from wfk Testgewebe GmbH, Brueggen, Germany

[0230] CFT C-S-10 (cotton fabric soiled with butter fat), commercially available from CFT, NL-Vlaardingen, the Netherlands

[0231] CFT C-S-62 (cotton fabric soiled with lard), commercially available from CFT, NL-Vlaardingen, the Netherlands

[0232] CFT C-S-78 (cotton fabric soiled with soybean oil), commercially available from CFT, NL-Vlaardingen, the Netherlands

[0233] CFT PC-S-04 (polyester / cotton fabric soiled with colored olive oil), commercially available from CFT, NL-Vlaardingen, the Netherlands

[0234] Determination of molecular weight

[0235] The number-average (Mn) and weight-average (Mw) molecular weights of the modified polymers prepared in the following examples were determined by measuring the unmodified polylysine by gel permeation chromatography (GPC) and then converting the measured values to the molecular weights of the modified polymers based on the corresponding degree of modification (DM). The unmodified polymer was analyzed in an aqueous eluent containing 0.1 M NaCl and 0.1 wt% trifluoroacetic acid, through a cascade column (i.e., TSKgel G4000, G3000, G3000, 300 x 7.8 mm) at 35 °C and a flow rate of 0.8 ml / min. For analysis, the unmodified polymer was dissolved in the eluent at a concentration of 1.5 mg / ml at room temperature and filtered through a 0.22 μm membrane. After 2 h, 100 μl was injected into an Agilent 1100 chromatographic system. The relative molecular weights were characterized by refractive index detection relative to a calibration curve obtained with polyvinylpyrrolidone standards, ranging from 620 to 1,060,000 g / mol.

[0236] Preparation Example

[0237] Example 1: Preparation of carboxymethylated lysine-based polymer 1 with lys:asp = 80:20

[0238] A 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver was charged with an aqueous solution of 220 g of L-lysine (50 wt%) and 12.6 g of aspartic acid suspended in 10 g of water. The mixture was heated with stirring to an internal temperature of 160 °C for 3 h, with continuous water separation. Then, an additional 12.5 g of aspartic acid was introduced into the reactor. After a total reaction time of 3.5 h, the water was further distilled off under reduced pressure (900 mbar). Finally, 122 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 9.7. The molar ratio of lysine structural units to aspartic acid structural units was 87:13, as determined by 1 1H NMR.

[0239] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 41.9 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 75 g of D.I. water. Then, heat the solution to 70 °C for 5 h. Meanwhile, maintain the pH at 10 by controlling the addition of 48 wt% aqueous NaOH using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. After cooling the reaction mixture to 30 °C, adjust the pH of the solution to 6 using aqueous HCl. Then, precipitate the modified polymer with an excess of methanol (1:10 by weight) and filter. After three consecutive precipitation steps, dry the product in a vacuum oven at 40 °C for more than 16 h to obtain a final product with 100% solids content and 98 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR (2D), is 66%, and the determined molecular weights are M n n = 1304 g / mol and M w w = 2168 g / mol.

[0240] Example 2: Preparation of carboxymethylated lysine-based polymer 2 with lys:adi = 80:20

[0241] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver with an aqueous solution of 165 g of L-lysine (50 wt%) and 9.2 g of adipic acid suspended in 9.5 g of water. Heat the mixture with stirring to an internal temperature of 160 °C for 2 h 50 min, with continuous water separation. Then, introduce an additional 11.5 g of adipic acid into the reactor. Finally, collect 98 g of water distillate, and discharge the highly viscous polymer into a silicone container as quickly as possible while it is still hot and flowable. The K-value is measured to be 9.8. The molar ratio of lysine structural units to adipic acid structural units is 94:6, as determined by 1 1H NMR.

[0242] An 8.4 g of sodium chloroacetate, 25 g of lysine-based polymer and 75 g of D.I. water were charged into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. Then, the solution was heated up to 70 °C for 5 h. During the first 1.5 h, 33.5 g of sodium chloroacetate and 28.8 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions (every 0.5 h). After cooling the reaction mixture to 30 °C, the pH of the solution was adjusted to 4 using an aqueous HCl solution. Then, the modified polymer was precipitated with an excess of methanol (1:10 by weight) and filtered. After three consecutive precipitation steps, the product was dried in a vacuum oven at 40 °C for more than 16 h to obtain a final product with 100% solids content and 93 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR, was 104%, and the determined molecular weights were M n = 1089 g / mol and M w = 1439 g / mol.

[0243] Example 3: Preparation of carboxymethylated lysine-based polymer 3 with lys:ita = 80:20

[0244] An aqueous solution of 134 g of L-lysine (50 wt%) and 6.7 g of itaconic acid suspended in 8 g of water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h, with continuous water separation. Then, an additional 8.3 g of itaconic acid was introduced into the reactor. Finally, 80 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 10.6. The molar ratio of lysine structural units to itaconic acid structural units was 85:15, as determined by 1 1H NMR.

[0245] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 47.6 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 75 g of D.I. water. Then, heat the solution to 70 °C for 5 h. Meanwhile, use the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte to maintain the pH at 10 by controlling the addition of a 48 wt% aqueous NaOH solution. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 91 wt%, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR (2D), is 79%, and the determined molecular weights are M n = 1142 g / mol and M w = 1649 g / mol.

[0246] Example 4: Preparation of carboxymethylated lysine-based polymer 4 with lys:tar = 80:20

[0247] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver with an aqueous solution of 165 g of L-lysine (50 wt%) and 9.4 g of tartaric acid suspended in 9.5 g of water. Heat the mixture with stirring to an internal temperature of 160 °C for 2 h 25 min, with continuous water separation. Then, introduce an additional 11.8 g of tartaric acid into the reactor. Finally, 93 g of water distillate is collected, and the highly viscous polymer is discharged into a silicone container as quickly as possible while it is still hot and flowable. The K-value is measured to be 11.1. The molar ratio of lysine structural units to tartaric acid structural units is 78:22, as determined by 1 1H NMR.

[0248] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 41.6 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 75 g of D.I. water. Then, heat the solution to 70 °C for 5 h. Meanwhile, use the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte to maintain the pH at 10 by controlling the addition of a 48 wt% aqueous NaOH solution. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 92 wt%, as determined by 1Determined by ¹H NMR. As determined by 1 the degree of modification (DM) of the polymer determined by ¹H NMR is 79%, and the determined molecular weights are M n = 892 g / mol and M w = 1176 g / mol.

[0249] Example 5: Preparation of carboxymethylated lysine-based polymer 5 with lys:asp = 90:10

[0250] Charge 134 g of L-lysine (50 wt%), 13.6 g of aspartic acid, and 50 g of water into a 500 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, condenser with a vacuum connection, and Dean-Stark receiver. Heat the mixture with stirring to an internal temperature of 160 °C for 4 h 25 min, with continuous water separation. Finally, 62 g of water distillate is collected, and the highly viscous polymer is discharged as quickly as possible into a silicone container while it is still hot and flowable. The K-value is measured as 11.9. The molar ratio of lysine structural units to aspartic acid structural units is 90:10, as determined by 1 ¹H NMR.

[0251] Charge 9.4 g of sodium chloroacetate, 25 g of lysine-based polymer, and 75 g of D.I. water into a 250 ml four-necked flask equipped with a stirrer, internal thermometer, gas inlet tube, and condenser. Then, heat the solution to 70 °C for 5 h. During the first 1.5 h, add 37.7 g of sodium chloroacetate and 32.4 g of sodium hydroxide (50 wt%) in 3 portions (every 0.5 h) to the flask. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 85 wt%, as determined by 1 ¹H NMR. As determined by 1 the degree of modification (DM) of the polymer determined by ¹H NMR is 53% (2D), and the determined molecular weights are M n = 1357 g / mol and M w = 2868 g / mol.

[0252] Example 6: Preparation of carboxymethylated lysine-based polymer 6 with lys:asp = 80:20

[0253] A 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver was charged with 220 g of an aqueous solution of L-lysine (50 wt%) and 12.6 g of aspartic acid suspended in 10 g of water. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h 55 min, with continuous water separation. Then, an additional 12.5 g of aspartic acid was introduced into the reactor. After a total reaction time of 3 h 20 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 129 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.3. The molar ratio of lysine structural units to aspartic acid structural units was 80:20, as determined by 1 1H NMR.

[0254] An 83.7 g of sodium chloroacetate, 50 g of a lysine-based polymer, and 130 g of D.I. water were charged into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of a 48 wt% aqueous solution of NaOH using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solid content of 100% and an active substance content of 88 wt%, as determined by 1 1H NMR. As determined by 1 1H NMR (2D), the degree of modification (DM) of the polymer was 51%, and the determined molecular weights were M n = 1533 g / mol and M w = 5499 g / mol.

[0255] Example 7: Preparation of carboxymethylated lysine-based polymer 7 with lys:tar = 80:20

[0256] A 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver was charged with an aqueous solution of 165 g of L-lysine (50 wt%) and 9.5 g of tartaric acid suspended in 9.5 g of water. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h 25 min, with continuous water separation. Then, an additional 11.8 g of tartaric acid was introduced into the reactor. After a total reaction time of 2 h 45 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 96 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.7. The molar ratio of lysine structural units to tartaric acid structural units was 91:9, as determined by 1 1H NMR.

[0257] A 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 83.7 g of sodium chloroacetate, 50 g of a lysine-based polymer, and 130 g of D.I. water. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of a 48 wt% aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 79 wt%, as determined by 1 1H NMR. As determined by 1 1H NMR, the degree of modification (DM) of the polymer was 78%, and the determined molecular weights were M n = 1355 g / mol and M w = 2545 g / mol.

[0258] Example 8: Preparation of carboxymethylated lysine-based polymer 8 with lys:tar = 90:10

[0259] Into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a decompression connection, and a Dean-Stark receiver, 200 g of an aqueous solution of L-lysine (50 wt%) and 11.4 g of tartaric acid suspended in 20 g of water were charged. The mixture was heated with stirring to an internal temperature of 160 °C, with continuous water separation. After a reaction time of 2 h 55 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 130 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.0. The molar ratio of lysine structural units to tartaric acid structural units was 96:4, as determined by 1 1H NMR.

[0260] Into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser, 23.5 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 49 g of D.I. water were charged. Then, the solution was heated to 70 °C for 5 h. Meanwhile, using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte, the pH was maintained at 10 by controlling the addition of a 48 wt% aqueous NaOH solution. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solid content of 100% and an active substance content of 93 wt%, as determined by 1 1H NMR. As determined by 1 1H NMR, the degree of modification (DM) of the polymer was 30%, and the determined molecular weights were M n = 1278 g / mol and M w = 2650 g / mol.

[0261] Example 9: Preparation of a carboxymethylated lysine-based polymer 9 with lys:asp = 90:10

[0262] Into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a decompression connection, and a Dean-Stark receiver, 134 g of L-lysine, 13.6 g of aspartic acid, and 50 g of water were charged. The mixture was heated with stirring to an internal temperature of 160 °C for 4 h 25 min, with continuous water separation. Finally, 63 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.1. The molar ratio of lysine structural units to aspartic acid structural units was 90:10, as determined by 1 1H NMR.

[0263] Into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser, 94.2 g of sodium chloroacetate, 50 g of a lysine-based polymer, and 150 g of D.I. water were charged. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of 48 wt% aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with 100% solids content and 82 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR (2D), was 55%, and the determined molecular weights were M n = 1380 g / mol and M w = 2917 g / mol.

[0264] Example 10: Preparation of carboxymethylated lysine-based polymer 10 with lys:ita = 80:20

[0265] Into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver, an aqueous solution of 134 g of L-lysine (50 wt%) and 6.7 g of itaconic acid suspended in 8 g of water were charged. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h, with continuous water separation. Then, an additional 8.3 g of itaconic acid was introduced into the reactor. Finally, 78 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 10.1. The molar ratio of lysine structural units to itaconic acid structural units was 80:20, as determined by 1 1H NMR.

[0266] An 83.7 g of sodium chloroacetate, 50 g of lysine-based polymer and 130 g of D.I. water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of 48 wt% aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with 100% solids content and 94 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR (2D), was 86%, and the determined molecular weights were M n = 1152 g / mol and M w = 1664 g / mol.

[0267] Example 11: Preparation of carboxymethylated lysine-based polymer 11 with lys:glut = 80:20

[0268] 100 g of L-lysine, 25.2 g of glutamic acid and 80 g of water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h 35 min, with continuous water separation. Finally, 81 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 10.0. The molar ratio of lysine structural units to glutamic acid structural units was 79:21, as determined by 1 1H NMR.

[0269] An 83.7 g of sodium chloroacetate, 40 g of lysine-based polymer and 124 g of D.I. water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of 48 wt% aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with 100% solids content and 93 wt% active substance content, as determined by 1 1H NMR. As determined by 1The degree of modification (DM) of the polymer determined by ¹H NMR was 79%, and the determined molecular weights were M n = 1392 g / mol and M w = 2314 g / mol.

[0270] Example 12: Preparation of carboxymethylated lysine-based polymer 12 with lys:glut = 70:30

[0271] 100 g of L-lysine, 43.1 g of glutamic acid, and 80 g of water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C with continuous water separation. After a reaction time of 2 h 40 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 88 g of water distillate was collected, and the highly viscous polymer was discharged as quickly as possible into a silicone container while it was still hot and flowable. The K-value was measured to be 12.3. The molar ratio of lysine structural units to glutamic acid structural units was 80:20, as determined by 1 ¹H NMR.

[0272] 100.5 g of sodium chloroacetate, 60 g of lysine-based polymer, and 160 g of D.I. water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. The solution was then heated to 70 °C for 5 h. At the same time, the pH was maintained at 10 by controlling the addition of 48 wt% aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 96 wt%, as determined by 1 ¹H NMR. As determined by 1 The degree of modification (DM) of the polymer determined by ¹H NMR was 75%, and the determined molecular weights were M n = 1768 g / mol and M w = 6339 g / mol.

[0273] Example 13: Preparation of carboxymethylated lysine-based polymer 13 with lys:glut = 70:30

[0274] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a decompression connection, and a Dean-Stark receiver with 100 g of L-lysine, 43.1 g of glutamic acid, and 80 g of water. Heat the mixture with stirring to an internal temperature of 160 °C for 2 h 35 min, with continuous water separation. Finally, 80 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 10.1. The molar ratio of lysine structural units to glutamic acid structural units was 78:22, as determined by 1 1H NMR.

[0275] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 136.1 g of sodium chloroacetate, 65 g of a lysine-based polymer, and 202 g of D.I. water. Then, heat the solution to 70 °C for 5 h. Meanwhile, using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte, maintain the pH at 10 by controlling the addition of a 48 wt% aqueous NaOH solution. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solid content of 100% and an active substance content of 91 wt%, as determined by 1 1H NMR. As determined by 1 1H NMR, the degree of modification (DM) of the polymer was 118%, and the determined molecular weights were M n = 917 g / mol and M w = 998 g / mol.

[0276] Example 14: Preparation of carboxymethylated lysine-based polymer 14 with lys:adi = 80:20

[0277] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a decompression connection, and a Dean-Stark receiver with an aqueous solution of 165 g of L-lysine (50 wt%) and 9.2 g of adipic acid suspended in 9.5 g of water. Heat the mixture with stirring to an internal temperature of 160 °C for 2 h 50 min, with continuous water separation. Then, introduce an additional 11.5 g of adipic acid into the reactor, and further distill off the water under reduced pressure (667 mbar). Finally, 105 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.6. The molar ratio of lysine structural units to adipic acid structural units was 92:8, as determined by1 Determined by \(^1H\) NMR.

[0278] 8.4 g of sodium chloroacetate, 25 g of lysine-based polymer and 75 g of D.I. water were charged into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube and a condenser. Then, the solution was heated to 70 °C for 5 h. During the first 1.5 h, 33.5 g of sodium chloroacetate and 28.8 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions (every 0.5 h). After cooling the reaction mixture to 30 °C, the pH of the solution was adjusted to 4 using aqueous HCl solution. Then, the modified polymer was precipitated with an excess of methanol (1:10 by weight) and filtered. After three consecutive precipitation steps, the product was dried in a vacuum oven at 40 °C for more than 16 h to obtain a final product with a solid content of 100% and an active substance content of 89 wt%, as determined by 1 \(^1H\) NMR. As determined by 1 The degree of modification (DM) of the polymer determined by \(^1H\) NMR was 76%, and the determined molecular weights were \(M\) n = 1915 g / mol and \(M\) w = 4762 g / mol.

[0279] Example 15: Preparation of carboxymethylated lysine-based polymer 15 with lys:tar = 90:10

[0280] An aqueous solution (50 wt%) of 165 g of L-lysine and 9.4 g of tartaric acid suspended in 7.5 g of water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C, with continuous water separation. After a reaction time of 2 h 25 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 100 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.2. The molar ratio of lysine structural units to tartaric acid structural units was 91:9, as determined by 1 \(^1H\) NMR.

[0281] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 10.5 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 75 g of D.I. water. Then, heat the solution to 70 °C for 5 h. During the first 1.5 h, add 41.9 g of sodium chloroacetate and 36.0 g of sodium hydroxide (50 wt%) in three portions (every 0.5 h) to the flask. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with 100% solids content and 98 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR, is 106%, and the determined molecular weights are M n = 1895 g / mol and M w = 3941 g / mol.

[0282] Example 16: Preparation of carboxymethylated lysine-based polymer 16 with lys:adi = 90:10

[0283] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver with 165 g of an aqueous solution of L-lysine (50 wt%) and 9.2 g of adipic acid suspended in 7.5 g of water. Heat the mixture with stirring to an internal temperature of 160 °C with continuous water separation. After a reaction time of 2 h 45 min, further distill off the water under reduced pressure (900 mbar). Finally, collect 102 g of water distillate and discharge the highly viscous polymer into a silicone container as quickly as possible while it is still hot and flowable. The K-value is measured to be 12.2. The molar ratio of lysine structural units to adipic acid structural units is 92:8, as determined by 1 1H NMR.

[0284] Into a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser, 9.4 g of sodium chloroacetate, 25 g of a lysine-based polymer, and 75 g of D.I. water were charged. Then, the solution was heated to 70 °C for 5 h. During the first 1.5 h, 37.7 g of sodium chloroacetate and 32.4 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions (every 0.5 h). After cooling the reaction mixture to 30 °C, the pH of the solution was adjusted to 4 using an aqueous HCl solution. Then, the modified polymer was precipitated with an excess of methanol (1:10 by weight) and filtered. After three consecutive precipitation steps, the product was dried in a vacuum oven at 40 °C for more than 16 h to obtain a final product with a solid content of 100% and an active substance content of 89 wt%, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR, was 76%, and the determined molecular weights were M n = 1380 g / mol and M w = 2187 g / mol.

[0285] Example 17: Preparation of carboxymethylated lysine-based polymer 17 with lys:tar = 91:9

[0286] Into a 1000 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver, an aqueous solution of 556 g of L-lysine (50 wt%) and 31.7 g of tartaric acid suspended in 31.8 g of water were charged. The mixture was heated with stirring to an internal temperature of 160 °C for 3 h 5 min, with continuous water separation. Then, an additional 37.8 g of tartaric acid was introduced into the reactor, and the water was further distilled off under reduced pressure (900 mbar). Finally, 312 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 11.3.

[0287] 100.5 g of sodium chloroacetate, 60 g of polylysine copolymer, and 160.5 g of D.I. water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser. Then, the solution was heated to 70 °C for 5 h. Meanwhile, the pH was maintained at 10 by controlling the addition of 48% wt. aqueous NaOH solution using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte. The reaction mixture was treated and the product was purified in the same manner as described in Example 1 to obtain a final product with 100% solids content and 84 wt% active substance content, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR, was 94%, and the determined molecular weights were M n = 1018 g / mol and M w = 1343 g / mol. According to OECD 301F (manometric respirometry), the biodegradation rate after 56 days was 33%.

[0288] Example 18: Preparation of carboxymethylated lysine-based polymer 18 with lys:tar = 82:18, K-v 12.5, 13% DM

[0289] An aqueous solution (50 wt%) of 165 g of L-lysine and 9.4 g of tartaric acid suspended in 9.5 g of water were charged into a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver. The mixture was heated with stirring to an internal temperature of 160 °C for 2 h 21 min, with continuous water separation. Then, an additional 11.8 g of tartaric acid was introduced into the reactor. After a total reaction time of 2 h 40 min, the water was further distilled off under reduced pressure (900 mbar). Finally, 95 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.5.

[0290] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 6.6 g of sodium chloroacetate, 40 g of polylysine copolymer, and 50 g of D.I. water. Then, heat the solution to 70 °C for 5 h. Meanwhile, using the control unit of a Systag FlexyCube automated laboratory reactor equipped with a peristaltic pump and a pH probe with a high-temperature electrolyte, maintain the pH at 10 by controlling the addition of a 48% wt. aqueous NaOH solution. Treat the reaction mixture and purify the product in the same manner as described in Example 1 to obtain a final product with a solids content of 100% and an active substance content of 95 wt%, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1 1H NMR, is 13%, and the determined molecular weights are M n = 900 g / mol and M w = 1690 g / mol.

[0291] Comparative Example 1: Preparation of Carboxymethylated Polylysine Homopolymer 1

[0292] Charge a 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver with an aqueous solution of 100 g of L-lysine (50 wt%). Heat the mixture with stirring to an internal temperature of 160 °C for 45 minutes. Then, meteringly add an aqueous solution of 400 g of L-lysine (50 wt%) continuously over 3.5 h, with continuous water separation. After a reaction time of 1 h, further distill off the water under reduced pressure (670 mbar). Finally, 258 g of water distillate is collected, and the highly viscous polymer is discharged into a silicone container as quickly as possible while it is still hot and flowable. The K-value is measured to be 10.5.

[0293] Charge a 250 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser with 10.5 g of sodium chloroacetate, 19.1 g of polylysine, and 75 g of D.I. water. Then, heat the solution to 70 °C for 5 h. During the first 1.5 h, add 41.9 g of sodium chloroacetate and 36 g of sodium hydroxide (50 wt%) in three portions (every 0.5 h) to the flask. After cooling the reaction mixture to 30 °C, precipitate the modified polymer with an excess of methanol (1:10 by weight) and filter. After three consecutive precipitation steps, dry the product in a vacuum oven at 40 °C for more than 16 h to obtain a final product with a solids content of 100% and an active substance content of 94 wt%, as determined by 1 1H NMR. The degree of modification (DM) of the polymer, as determined by 1The degree of modification (DM) of the polymer determined by ¹H NMR is 89%, and the determined molecular weights are M n = 2112 g / mol and M w = 2560 g / mol.

[0294] Comparative Example 2: Preparation of Carboxymethylated Polylysine Homopolymer 2

[0295] A 500 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, a condenser with a vacuum connection, and a Dean-Stark receiver was charged with 100 g of an aqueous solution of L-lysine (5 wt%). The mixture was heated with stirring to an internal temperature of 160 °C for 45 minutes. Then, 400 g of an aqueous solution of L-lysine (50 wt%) was metered in continuously over 3.5 h, with continuous water separation. After a reaction time of 1 h, the water was further distilled off under reduced pressure (670 mbar). Finally, 264 g of water distillate was collected, and the highly viscous polymer was discharged into a silicone container as quickly as possible while it was still hot and flowable. The K-value was measured to be 12.2.

[0296] A 2000 ml four-necked flask equipped with a stirrer, an internal thermometer, a gas inlet tube, and a condenser was charged with 104.8 g of sodium chloroacetate, 250 g of polylysine, and 750 g of D.I. water. The solution was then heated to 70 °C for 5 h. During the first 1.5 h, 419.2 g of sodium chloroacetate and 360 g of sodium hydroxide (50 wt%) were added to the flask in 3 portions (every 0.5 h). The reaction mixture was treated and the product was purified in the same manner as described in Comparative Example 1 to obtain a final product with a solids content of 100% and an active substance content of 98 wt%. The degree of modification (DM) determined by 1 ¹H NMR is 70%, and the determined molecular weights are M n = 2429 g / mol and M w = 3825 g / mol.

[0297] Measurement of Chelating Properties

[0298] The chelating properties of the carboxymethylated lysine-based polymers according to the invention were investigated in terms of CaCO₃ dissolution (CCD) and hydrogen peroxide stability.

[0299] CaCO₃ Dissolution (CCD)

[0300] At room temperature, a 100 ml CaCO3 dispersion (0.005 mol / L) was titrated with a solution of 2.5 wt% polymer additive without stirring. Transmittance was recorded initially and when 5 mL, 10 mL, and 14 mL of the additive solution were added. Transmittance measurements were carried out at pH 11 using a photometer 662 from Metrohm (including Phototrode and Metrohm Titrino 716DMS) (the pH was adjusted to 11 and controlled by additional pH measurements with Metrohm 654). 100% transmittance means that the CaCO3 in the system is completely dissolved. The test results are summarized in Table 1.

[0301] Table 1

[0302]

[0303] Hydrogen peroxide stability

[0304] 100 mL of an aqueous solution containing Fe 3+ ions or Mn 2+ ions and an additive was prepared. Then, 6.67 g of a 30 wt% H2O2 solution was added to obtain a solution containing 2 wt% H2O2. The pH was adjusted to a constant value with NaOH or HCl. After stirring for a certain time, the remaining H2O2 content was determined by iodometric titration. The test results are summarized in Table 2.

[0305] Table 2

[0306]

[0307] a) Based on the active substance content, b) Based on the solid content

[0308] It can be seen that the carboxymethylated lysine-based polymer according to the present invention exhibits the desired chelating ability required for detergent compositions and an acceptable stabilizing ability required for peroxy bleach compositions.

[0309] Measurement of dispersion performance

[0310] The dispersion performance of the carboxymethylated lysine-based polymer according to the present invention was studied in terms of the CaCO3 dispersion capacity (CCDC).

[0311] The calcium carbonate dispersion capacity (CCDC) allows quantification of the ability of a polymer dispersant to inhibit the precipitation of calcium carbonate in an aqueous medium.

[0312] Dissolve the polymer additive based on 1.0 g of solid content in 100 ml of water. Then, add 10 ml of 10 wt% sodium carbonate solution. Adjust the pH value of the test solution to pH 11 with 1N NaOH. Titrate the test solution with 0.25M calcium acetate solution until it starts to become turbid. During the titration, keep the pH constant by adjusting with 1N NaOH or 1N HCl. The test results are summarized in Table 3.

[0313] Table 3

[0314]

[0315] The carboxymethylated lysine-based polymer according to the invention shows acceptable or desired dispersing properties as required for detergent compositions.

[0316] Application examples

[0317] The application of the carboxymethylated lysine-based polymer according to the invention in detergent formulations and in peroxy bleach formulations was studied.

[0318] Anti-greying properties of liquid laundry formulations

[0319] Simulate the washing process with a Launder-o-meter (LP2 Typ, SDL Atlas Inc., USA). Wash the white test fabric in the same beaker with 2.5 g of EMPA 101 and 2.5 g of SBL 2004 and 20 steel balls at 40 °C in a washing liquor containing a detergent with the formulation shown in Table 5, and then rinse and spin dry to complete the washing cycle. Repeat the washing cycle twice with a new clay dispersion and a new washing liquor. After rinsing in the third washing cycle, change the test fabric to air dry. The details of the washing cycle are summarized in Table 4.

[0320] The anti-greying properties are characterized by the ΔR value of the soiling relief of the fabric before and after washing, and are determined by measuring the fabric with a spectrophotometer Elrepho 2000 from Datacolor at 460 nm. The higher the ΔR value of the soiling relief, the better the performance. The results are summarized in Table 6.

[0321] Table 4

[0322]

[0323] Table 5

[0324]

[0325] a) Active substance content based on non-polymer components and

[0326] Solid content based on the polymer composition

[0327] Table 6

[0328]

[0329] It can be seen that laundry formulations containing the carboxymethylated lysine-based polymers according to the invention exhibit significant anti-graying properties, which are even comparable to formulations containing commercially available non-biodegradable polymer additives.

[0330] Primary detergency of liquid laundry formulations

[0331] According to the protocol described in Table 8, the primary detergency of the liquid laundry formulations shown in Table 7 was measured on a full scale using a household washing machine (Miele W1935 WPS WTL).

[0332] Table 7

[0333]

[0334] a) Active substance content based on non-polymeric components and

[0335] Solid content based on the polymer composition

[0336] Table 8

[0337]

[0338] The primary detergency is characterized by the ΔE value calculated according to DIN EN ISO 11664-4 (June 2012) according to the following equation:

[0339] ΔE = (ΔL *2 + Δa *2 + Δb *2 ) 1 / 2 ,

[0340] where

[0341] ΔL* = L* 洗涤 - L* 初始 ; Δa * = a* 洗涤 - a* 初始 ; and Δb * = b* 洗涤 - b* 初始 .

[0342] L was measured on the stained fabric before and after washing using a spectrophotometer MACH 5 from Colour Consult, supplied by CFT BV, Vlaardingen, the Netherlands* 、a * 、b * values. The higher the ΔE value, the better the performance.

[0343] The tests for each formulation were carried out twice, including washing according to the protocol described in Table 8 and characterization by ΔE, and the average value was given as the test result. The test results are summarized in Table 9.

[0344] Table 9

[0345]

[0346]

[0347] The test results show that laundry formulations containing the carboxymethylated lysine-based polymers according to the invention exhibit comparable or even better primary detergency than formulations containing commercially available non-biodegradable polymer additives or carboxymethylated lysine homopolymers.

[0348] Synergistic effect of carboxymethylated lysine-based polymers with enzymes in liquid laundry formulations

[0349] The liquid laundry formulation shown in Table 10 was used as the base formulation to measure the primary detergency with respect to blood, milk and ink according to the protocol described in Table 11.

[0350] Table 10

[0351]

[0352] a) Active substance content based on non-polymer components and

[0353] Solid content based on polymer components

[0354] Table 11

[0355] [[ID=4-six]]

[0356] The primary detergency performance was characterized by the ΔR value of the soiled fabric before and after washing, and was determined by measuring the fabric with a spectrophotometer Elrepho 2000 from Delta Color at 457 nm. The higher the ΔR value of the relief, the better the performance. The results are summarized in Table 12.

[0357] Table 12

[0358]

[0359] a) Enzyme: Lavergy Pro 104L, commercially available from BASF, and the amount is based on the active substance content

[0360] b) Polymer additive: polymer 16, amount based on solid content

[0361] From the test results of Formulations A and B, it can be seen that 3 wt% of the lysine-based polymer alone does not contribute to primary detergency, and 5 wt% of the lysine-based polymer alone provides an observable contribution to primary detergency. From the test results of Formulations C to F, it can also be seen that enzymes can contribute to primary detergency at various dosages.

[0362] Unexpectedly, Formulation G, which contains 3 wt% of a lysine-based polymer and 0.1 wt% of an enzyme, exhibits significantly improved primary detergency compared to Formulation C, which contains 0.1 wt% of an enzyme. That is, the combination of the lysine-based polymer and the enzyme provides a greater improvement in primary detergency than would be expected from a synergistic effect of the two. In other words, a synergistic effect of the lysine-based polymer and the enzyme is observed for Formulation G.

[0363] Likewise, for formulations H, I, J, and K, a synergistic effect of the lysine-based polymer and the enzyme was observed.

[0364] Anti-filming properties of automatic dishwashing preparations

[0365] Build-up testing was performed according to the general procedure as detailed in Table 13.

[0366] Table 13

[0367]

[0368] Composition of ballast dirt

[0369] Starch 0.5% potato starch, 2.5% gravy Fat 10.2% margarine Protein 5.1% egg yolk, 5.1% milk Others 2.5% tomato ketchup, 2.5% mustard, 0.1% benzoic acid, 71.4% water

[0370] The dishes were visually assessed after 30 cycles in a dark room under light behind an aperture stop using a grading scale from 10 (very good) to 1 (very poor). A rating of 1-10 for filming was obtained (1 = very severe filming, 10 = no filming).

[0371] Accumulation tests were performed with the formulations containing no phosphonate as shown in Table 14. The test results for the film formation evaluation are summarized in Table 15.

[0372] Table 14

[0373] a) Based on the active substance content of non-polymer components and

[0374] Based on the solid content of the polymer components

[0375] Table 15

[0376] Cutlery Glass Plastic Porcelain Total Blank 1.0 1.0 1.0 1.0 4.0 Polymer 2 5.0 4.0 4.3 2.7 16.0 Polymer 4 4.0 3.0 3.0 2.3 12.3 Polymer 17 4.0 3.0 3.0 2.3 12.3

[0377] The test results show that the dishwashing formulation containing the carboxymethylated lysine-based polymer according to the invention shows a distinct anti-filming effect.

[0378] Pulp bleaching application

[0379] An aqueous suspension containing 4.0 wt% of groundwood cellulose, 1.5 wt% of hydrogen peroxide (10%), 0.2 wt% of an additive (relative to the amount of cellulose fibers), 0.75 wt% of sodium hydroxide, and 2.0 wt% of sodium silicate is heated to 70 °C. After 1.5 h, the fibers are filtered, and then the filter cake is pressed and dried into paper sheets. The Tappi whiteness of the dried sheets is determined by a Datacolor DC 400 from Datacolor Inc. The test results are summarized in Table 16.

[0380] Table 16

[0381] a) Based on the active substance content, b) Based on the solids content

[0382] The test results show that the carboxymethylated lysine-based polymer according to the invention can stabilize hydrogen peroxide to an extent comparable to that of conventional non-biodegradable chelating agents.

[0383] Biodegradability of the carboxymethylated lysine-based polymer

[0384] The biodegradation of the polymer is tested after 4 weeks and 8 weeks respectively according to the standard manometric respirometry (OECD 301F).

[0385] Table 17

[0386] The test results show that the carboxymethylated lysine-based polymer according to the invention shows acceptable biodegradability and a distinct improvement in biodegradability compared to the carboxymethylated lysine homopolymer.

[0387] Anti-greying performance of liquid laundry formulations

[0388] Red clay

[0389] A Terg-o-meter (RHLG-IV, from ShanghaiBank Equipment Co., Ltd, China) using 12 cylinders with corresponding rotor blades as the washing unit generally follows GBT 13174-2008 to simulate the laundry process in the laboratory. The washing units are operated at the same agitation speed of 120 revolutions per minute (rpm) and each is filled with 1 L of water. White test fabrics are washed in the same cylinder with 10 g of a red clay and oil mixture in a washing liquor containing a detergent with the formulation shown in Table 18 at 30 °C. After washing, the fabrics are removed from the washing units, drained and rinsed twice in 10 L of tap water for 30 seconds. This washing cycle is repeated twice with fresh red clay and oil mixture and fresh washing liquor. After rinsing in the third washing cycle, the test fabrics are changed to air drying. The details of the washing cycles are summarized in Table 19.

[0390] The anti-graying performance is characterized by the ΔR value of the soiled fabric before and after washing and is determined by measuring the fabric with a spectrophotometer Elrepho 2000 from Delta Color at 457 nm. The higher the ΔR value of the remission, the better the performance. The results are summarized in Table 20.

[0391] Table 18

[0392]

[0393]

[0394] Table 19

[0395] a) Based on the active substance content of all ingredients

[0396] Table 20

[0397] Additive ΔR, total of all fabrics Blank 275.4 Modified PEI-2 267.9 Modified PEI-1 173.6 Polymer 8, lys:tar = 96:4, K-v 12.0, 30% DM 183.3 Polymer 18, lys:tar = 82:18, K-v 12.5, 13% DM 263.6

[0398] Better anti-graying performance can be observed with the polymers of the present invention compared to the blank sample and commercially modified PEI.

[0399] Yellow clay

[0400] A stir-type washing power washing machine (RHLG-IV, from Shanghai Bank Equipment Co., Ltd., China) using 12 cylinders each with corresponding rotor blades as the washing unit generally follows GBT 13174-2008 and simulates the laundry process in the laboratory. The washing units are operated at the same stirring speed of 120 revolutions per minute (rpm) and each is filled with 1 L of water. White test fabrics are washed together with 10 g of a yellow clay and oil mixture in the same cylinder at 30 °C in a washing liquor containing a detergent with the formulation shown in Table 21. After washing, the fabrics are removed from the washing unit, drained, and rinsed twice in 10 L of tap water for 30 seconds. This washing cycle is repeated twice with a new yellow clay and oil mixture and a new washing liquor. After rinsing in the third washing cycle, the test fabrics are changed to air drying. The details of the washing cycle are summarized in Table 22.

[0401] The anti-greying performance is characterized by the ΔR value of the soiling relief of the dirty fabrics before and after washing and is determined by measuring the fabrics with a spectrophotometer Elrepho 2000 from Delta Color at 457 nm. The higher the ΔR value of the soiling relief, the better the performance. The results are summarized in Table 23.

[0402] Table 21

[0403]

[0404] Table 22

[0405]

[0406] a) Active substance content based on all ingredients

[0407] Table 23

[0408]

[0409]

[0410] Improved anti-greying performance can be observed with the polymers of the present invention compared to the blank sample and commercially modified PEI.

[0411] Primary detergency of liquid laundry formulations

[0412] According to the protocol described in Table 25, the primary detergency of the liquid laundry formulations shown in Table 24 is measured at full scale using a household washing machine (Media MG80T1WS). The results are summarized in Table 26.

[0413] Table 24

[0414] a) Active substance content based on all ingredients

[0415] Table 25

[0416]

[0417]

[0418] Table 26

[0419] Better primary detergency performance was observed with the polymers of the present invention compared to blank samples and commercially modified PEI.

Claims

1. A carboxymethylated lysine-based polymer, comprising (A) 60 to 99 mol% of structural units derived from lysine monomers, (B) 1 to 40 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative HOOC-R1-COOH (I) wherein R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, bis(alkyl)amino, alkylene, hydroxy, mercapto, amino and halogen.

2. The carboxymethylated lysine-based polymer according to claim 1, which comprises a structural unit (B) derived from at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof, wherein, R1 is a direct bond or an aliphatic straight-chain C1-C 24 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C 18 -alkyl group, unsubstituted or substituted C1-C 18 -alkoxy group, unsubstituted or substituted C1-C 18 -alkylthio group, unsubstituted or substituted C1-C 18 -alkylamino group, di(C1-C 18 -alkyl)amino group, C1-C6-alkylene group, hydroxyl group, mercapto group, amino group and halogen.

3. The carboxymethylated lysine-based polymer according to claim 1, which comprises a structural unit (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative, wherein, R1 is a direct bond or an aliphatic straight-chain C1-C 18 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C 12 -alkyl, unsubstituted or substituted C1-C 12 -alkoxy, unsubstituted or substituted C1-C 12 -alkylthio, unsubstituted or substituted C1-C 12 -alkylamino, di(C1-C 12 -alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

4. The carboxymethylated lysine-based polymer according to claim 1, which comprises a structural unit (B) derived from at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof, wherein, R1 is a direct bond or an aliphatic straight-chain C1-C 12 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-alkoxy, unsubstituted or substituted C1-C8-alkylthio, unsubstituted or substituted C1-C8-alkylamino, di(C1-C8-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino, and halogen.

5. The carboxymethylated lysine-based polymer according to claim 1, which comprises structural units (B) from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein, R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, unsubstituted or substituted C1-C4-alkoxy, unsubstituted or substituted C1-C4-alkylthio, unsubstituted or substituted C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

6. The carboxymethylated lysine-based polymer according to claim 1, which comprises a structural unit (B) derived from at least one dicarboxylic acid of formula (I) or an amide-forming derivative thereof, wherein, R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C4-alkylene, hydroxy, mercapto and amino.

7. The carboxymethylated lysine-based polymer according to claim 1, which comprises structural units (B) derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivatives, wherein, R1 is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C2-alkylene, hydroxy and amino, preferably at least one of oxalic acid, malonic acid, succinic acid, maleic acid and fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid.

8. The carboxymethylated lysine-based polymer according to any one of the preceding claims, comprising (A) 70 to 97 mol% of structural units derived from lysine monomers; and (B) 3 to 30 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

9. The carboxymethylated lysine-based polymer according to any one of the preceding claims, comprising (A) 75 to 97 mol% of structural units derived from lysine monomers; and (B) 4 to 25 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

10. The carboxymethylated lysine-based polymer according to any one of the preceding claims, comprising (A) 75 to 95 mol% of structural units derived from lysine monomers; and (B) 5 to 25 mol% of structural units derived from at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

11. The carboxymethylated lysine-based polymer according to any one of the preceding claims, having a degree of modification by carboxymethylation of at least 20%, particularly at least 30%, preferably at least 50%, more preferably at least 70%, even more preferably at least 80%.

12. The carboxymethylated lysine-based polymer according to any one of the preceding claims, wherein, The carboxymethylated lysine-based polymer is prepared from a lysine-based polymer having a K-value in the range of 8 to 20, more preferably 9 to 15, and most preferably 9.5 to 13; or wherein the carboxymethylated lysine-based polymer has a number-average molecular weight (Mn) in the range of 400 to 10,000 g / mol, preferably 600 to 8,500 g / mol, more preferably 750 to 7,000 g / mol and / or a weight-average molecular weight (Mw) in the range of 500 to 3,500 g / mol, preferably 650 to 3,000 g / mol, more preferably 800 to 2,250 g / mol.

13. A method for preparing a carboxymethylated lysine-based polymer, the method comprising - subjecting monomers comprising the following to thermal polycondensation: (A) 60 to 95 mol% of lysine monomers, (B) 5 to 40 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative HOOC-R1-COOH (I) wherein R1 is a direct bond or an aliphatic straight-chain alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted alkyl, unsubstituted or substituted alkoxy, unsubstituted or substituted alkylthio, unsubstituted or substituted alkylamino, di(alkyl)amino, alkylene, hydroxy, mercapto, amino, and halogen, to obtain a lysine-based polymer, and - carboxymethylating the lysine-based polymer.

14. The method according to claim 13, wherein R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 24 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C 18 -alkyl, unsubstituted or substituted C1-C 18 -alkoxy, unsubstituted or substituted C1-C 18 -alkylthio, unsubstituted or substituted C1-C 18 -alkylamino, di(C1-C 18 -alkyl)amino, C1-C6-alkylene, hydroxy, mercapto, amino and halogen.

15. The method according to claim 13, wherein, R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 18 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C 12 -alkyl, unsubstituted or substituted C1-C 12 -alkoxy, unsubstituted or substituted C1-C 12 -alkylthio, unsubstituted or substituted C1-C 12 -alkylamino, di(C1-C 12 -alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

16. The method according to claim 13, wherein, R1 in formula (I) is a direct bond or an aliphatic straight-chain C1-C 12 -alkylene group, which is unsubstituted or substituted by at least one group selected from the following: unsubstituted or substituted C1-C8-alkyl, unsubstituted or substituted C1-C8-alkoxy, unsubstituted or substituted C1-C8-alkylthio, unsubstituted or substituted C1-C8-alkylamino, di(C1-C8-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

17. The method according to claim 13, wherein R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, unsubstituted or substituted C1-C4-alkoxy, unsubstituted or substituted C1-C4-alkylthio, unsubstituted or substituted C1-C4-alkylamino, di(C1-C4-alkyl)amino, C1-C4-alkylene, hydroxy, mercapto, amino and halogen.

18. The method according to claim 13, wherein, R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C4-alkylene, hydroxy, mercapto and amino.

19. The method according to claim 13, wherein R1 in formula (I) is a direct bond, C1-C 12 -alkylene or C2-C 12 -alkenylene, which is unsubstituted or substituted by at least one group selected from: unsubstituted or substituted C1-C4-alkyl, C1-C2-alkylene, hydroxy and amino.

20. The method according to claim 13, wherein At least one dicarboxylic acid of formula (I) is selected from oxalic acid, malonic acid, succinic acid, maleic acid, and fumaric acid, tartaric acid, aspartic acid, glutaric acid, itaconic acid, glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid.

21. The method according to any one of claims 13 to 20, the method comprising thermally polycondensing monomers comprising: (A) 70 to 90 mol% of lysine monomers, and (B) 10 to 30 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative; Preferably (A) 75 to 90 mol% of lysine monomers, and (B) 10 to 25 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative; More preferably (A) 80 to 90 mol% of lysine monomers, and (B) 10 to 20 mol% of at least one dicarboxylic acid of formula (I) or its amide-forming derivative.

22. The method according to any one of claims 13 to 21, wherein The lysine-based polymer has a K-value in the range of 8 to 20, more preferably 9 to 15, and most preferably 9.5 to 13.

23. The method according to any one of claims 13 to 22, wherein, The carboxymethylated lysine-based polymer has a degree of modification by carboxymethylation of at least 20%, particularly at least 30%, preferably at least 50%, still preferably at least 70%, more preferably at least 80%.

24. The method according to any one of claims 13 to 23, wherein, The carboxymethylated lysine-based polymer has a number average molecular weight (Mn) in the range of 400 to 10,000 g / mol, preferably 600 to 8,500 g / mol, more preferably 750 to 7,000 g / mol, and / or has a weight average molecular weight (Mw) in the range of 500 to 3,500 g / mol, preferably 650 to 3,000 g / mol, more preferably 800 to 2,250 g / mol.

25. A carboxymethylated lysine-based polymer obtainable or obtained by the method according to any one of claims 13 to 24.

26. A detergent composition comprising a carboxymethylated lysine-based polymer according to any one of the preceding claims 1 to 12 or 25, preferably a laundry detergent composition or a detergent composition for cleaning agents, such as an automatic dishwashing detergent composition.

27. The detergent composition according to claim 26, wherein, The detergent composition comprises at least one surfactant selected from anionic surfactants, amphoteric surfactants, and nonionic surfactants, preferably anionic surfactants, in an amount of 0.1% to 80% by weight based on the total solids content of the detergent composition.

28. The detergent composition according to claim 26 or 27, wherein, The detergent composition comprises the carboxymethylated lysine-based polymer in an amount of from 0.5% to 30% by weight, preferably from 1% to 25% by weight, and more preferably from 1% to 15% by weight based on the total solids content of the detergent composition.

29. The detergent composition according to any one of claims 26 to 28, wherein, The detergent composition comprises at least one enzyme selected from the group consisting of: lipase, hydrolase, amylase, protease, cellulase, esterase, pectinase, lactase and peroxidase, preferably protease.

30. The detergent composition according to any one of claims 26 to 29, wherein, The detergent composition comprises the at least one enzyme, especially protease, in an amount of up to 5% by weight, such as from 0.1% to 3% by weight based on the total solids content of the detergent composition.

31. A peroxybleaching composition comprising the carboxymethylated lysine-based polymer according to any one of claims 1 to 12 or 25, the peroxybleaching composition being particularly useful for bleaching cellulosic fiber materials, preferably for bleaching cellulosic fiber pulp.

32. The peroxybleaching composition according to claim 31, which comprises hydrogen peroxide or a precursor of hydrogen peroxide.

33. The peroxybleaching composition according to claim 31 or 32, which is in the form of an aqueous hydrogen peroxide solution, the aqueous hydrogen peroxide solution preferably comprising the carboxymethylated lysine-based polymer in an amount of from 0.01% to 3% by weight, preferably from 0.1% to 1% by weight based on the total weight of the solution.

34. A method for bleaching cellulosic fiber pulp with a peroxybleaching agent, wherein the carboxymethylated lysine-based polymer according to claims 1 to 12 or 25 is used as a stabilizer for the peroxybleaching agent.

35. The method according to claim 34, wherein The carboxymethylated lysine-based polymer is incorporated into the cellulosic fiber pulp in a dosage of from 0.01% to 3% by weight, preferably from 0.1% to 1% by weight, more preferably from 0.2% to 0.8% by weight based on the weight of the cellulosic fiber pulp.

36. Use of the carboxymethylated lysine-based polymer according to any one of claims 1 to 12 or 25 in a detergent composition or a peroxybleaching composition.

37. Use of the carboxymethylated lysine-based polymer according to any one of claims 1 to 12 or 25 as a chelating agent and / or a dispersing agent.

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