Glycerol ester alkoxylates

Abstract

Mixtures of glycerol ester alkoxylates are described. They are preferably used as thickener or softening agents. Liquid laundry compositions containing the mixture of glycerol ester alkoxylates are preferably fabric conditioner compositions or liquid laundry detergent compositions.

Description

[0001] GLYCEROL ESTER ALKOXYLATES

[0002] The present invention relates to specific mixtures of glycerol ester alkoxylates; to a method for their preparation; to alkoxylation products obtainable by this preparation method; to specific compositions comprising the mixtures of glycerol ester alkoxylates or the alkoxylation products and one or more specific solvents; to liquid laundry compositions comprising the mixtures of glycerol ester alkoxylates or the alkoxylation products and water but no esterquat; and to specific uses of the mixtures of glycerol ester alkoxylates or the alkoxylation products or of the liquid laundry compositions.

[0003] While laundering, in addition to cleaning clothes, many end consumers also want to make their clothes softer. In order to achieve this when using liquid laundry detergent compositions, these end consumers usually have to use fabric conditioner compositions in addition to the liquid laundry detergent compositions. This is due to the fact, that the softening agents used in fabric conditioner compositions, e.g. esterquats, are not stable in most liquid laundry detergent compositions.

[0004] Therefore, it was an object of the present invention to provide new softening agents which can be used in liquid laundry detergent compositions that provide, in addition to cleaning, also a softening effect to the clothes.

[0005] Surprisingly, it has been found that this object can be solved by mixtures of glycerol ester alkoxylates selected from the substances of the following formula (I) wherein

[0006] R1, R2and R3are, independent from each other, selected from linear or branched alkylene groups (CmH2m) with m being 2 or 3 or mixtures thereof; x, y and z are, independent from each other, integer numbers from 0 to 300, where at least one of the variables x, y and z is 1 or an integer number greater than 1 , preferably are, independent from each other, integer numbers from 1 to 250, more preferably from 2 to 200, even more preferably from 5 to 150, particularly preferably from 10 to 120, extraordinarily preferably from 15 to 110 and especially preferably from 20 to 100;

[0007] R4, R5and R6are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 8 to 30 carbon atoms or mixtures thereof, preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 30 carbon atoms or mixtures thereof, more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 24 carbon atoms or mixtures thereof, even more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 20 carbon atoms or mixtures thereof, and particularly preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 14 to 20 carbon atoms or mixtures thereof, and wherein in the definitions of R4, R5and R6above, at least one of R4, R5and R6has a meaning different from hydrogen (acyl group); characterized in that x+y+z is, based on a molar average, a number from 50 to 300, preferably from 60 to 300, more preferably from 70 to 280, even more preferably from 85 to 250 and particularly preferably from 90 to 250; at least 70 mol%, preferably at least 75 mol%, more preferably at least 80 mol% and even more preferably at least 85 mol% of the glycerol ester alkoxylates of the formula (I) in the mixture, in each case based on the total amount of the glycerol ester alkoxylates of the formula (I) in the mixture, are glycerol ester alkoxylates of the formula (I), wherein all of the groups R4, R5and R6have a meaning different from hydrogen (acyl groups); and at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol% and particularly preferably at least 70 mol% of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 18 carbon atoms or mixtures thereof, in each case based on the total amount of the linear or branched, preferably linear, saturated or unsaturated acyl groups R4, R5and R6.

[0008] Therefore, a subject matter of the present invention is mixtures of glycerol ester alkoxylates selected from the substances of the following formula (I)

[0009] wherein

[0010] R1, R2and R3are, independent from each other, selected from linear or branched alkylene groups (CmH2m) with m being 2 or 3 or mixtures thereof; x, y and z are, independent from each other, integer numbers from 0 to 300, where at least one of the variables x, y and z is 1 or an integer number greater than 1 , preferably are, independent from each other, integer numbers from 1 to 250, more preferably from 2 to 200, even more preferably from 5 to 150, particularly preferably from 10 to 120, extraordinarily preferably from 15 to 110 and especially preferably from 20 to 100;

[0011] R4, R5and R6are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 8 to 30 carbon atoms or mixtures thereof, preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 30 carbon atoms or mixtures thereof, more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 24 carbon atoms or mixtures thereof, even more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 20 carbon atoms or mixtures thereof, and particularly preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 14 to 20 carbon atoms or mixtures thereof, and wherein in the definitions of R4, R5and R6above, at least one of R4, R5and R6has a meaning different from hydrogen (acyl group); characterized in that x+y+z is, based on a molar average, a number from 50 to 300, preferably from 60 to 300, more preferably from 70 to 280, even more preferably from 85 to 250 and particularly preferably from 90 to 250; at least 70 mol%, preferably at least 75 mol%, more preferably at least 80 mol% and even more preferably at least 85 mol% of the glycerol ester alkoxylates of the formula (I) in the mixture, in each case based on the total amount of the glycerol ester alkoxylates of the formula (I) in the mixture, are glycerol ester alkoxylates of the formula (I), wherein all of the groups R4, R5and R6have a meaning different from hydrogen (acyl groups); and at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol% and particularly preferably at least 70 mol% of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 18 carbon atoms or mixtures thereof, in each case based on the total amount of the linear or branched, preferably linear, saturated or unsaturated acyl groups R4, R5and R6. In the inventive mixtures of glycerol ester alkoxylates of the formula (I), those of the groups R4, R5and R6, which have a meaning different from hydrogen, are referred to as “acyl groups”.

[0012] In the inventive mixtures of glycerol ester alkoxylates of the formula (I), the single acyl groups R4, R5and R6consist of a carbonyl group C=O and a hydrocarbon residue, without further substituents, e.g. without hydroxyl groups, on the hydrocarbon residue.

[0013] More preferably, acyl groups R4, R5and R6are of the formula -C(=O)-R4a, -C(=O)-R5aand -C(=O)-R6a, respectively, wherein the residues R4a, R5aand R6acomprise one carbon atom less than the respective acyl groups R4, R5and R6and are, independent from each other, selected from linear or branched, preferably linear, saturated alkyl groups, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups, or mixtures thereof. For example, in this more preferred embodiment of the invention, in case R4, R5and R6are, independent from each other, selected from linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 8 to 30 carbon atoms or mixtures thereof, R4a, R5aor R6aare, independent from each other, selected from linear or branched, preferably linear, saturated alkyl groups comprising from 7 to 29 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups comprising from 7 to 29 carbon atoms, or mixtures thereof.

[0014] In a single glycerol ester alkoxylate molecule of the formula (I), an acyl group R4, R5or R6forms an ester bond, either (i) with an oxygen atom of one of the structural units -[R1O]-, -[R2O]- or -[R3O]- or (ii) with an oxygen atom of the glycerol residue -O-CH2-CH(O-)-CH2-O-.

[0015] WO 93 / 10072 A1 discloses the preparation of esters of fatty acids with ethoxylated polyols by (a) ethoxylating polyols in the presence of basic catalysts at high temperatures with 80 to 150 moles ethylene oxide per mol polyol and then (b) reacting the reaction product with 1 to 1 .3 moles fatty acids per mole of hydroxyl groups contained in the original polyol, in the presence of acid catalysts. These esters are useful as thickeners of aqueous solutions of surface active agents.

[0016] If present, the structural units -[R1O]-, -[R2O]- and -[R3O]- in the glycerol ester alkoxylates of the formula (I) are, independent from each other, selected from [(C2H4)O] or [(C3H6)O].

[0017] If present, the structural units of the formula -[R1O]x-, -[R2O]y- and -[R3O]z- in a single glycerol ester alkoxylate molecule of the formula (I), independent from each other, may consist of one or more [(C2H4)0]-groups, may consist of one or more [(C3He)O]- groups or may consist of a mixture of [(C2H4)O]- and [(C3He)0]-groups.

[0018] Within a single glycerol ester alkoxylate molecule of the formula (I), the structural units -[R1O]x-, -[R2O]y- and -[R3O]z- may be the same or different.

[0019] The groups [(C2H4)O], if present in the structural units of the formula -[R1O]x-, -[R2O]y- and / or -[R3O]z- of the glycerol ester alkoxylates of the formula (I), preferably are of the formula -CH2-CH2-O-.

[0020] The groups [(CsHeJO], if present in the structural units of the formula -[R1O]x-, -[R2O]y- and / or -[R3O]z- of the glycerol ester alkoxylates of the formula (I), preferably are of the formula -CH(CH3)-CH2-O- or -CH2-CH(CH3)-O-, i.e. of the formula

[0021] In the case that [(C2H4)O]- and [(C3He)]0-groups exist in a structural unit of the formula -[R1O]x-, -[R2O]y- and / or -[R3O]z-, they may be arranged blockwise, alternating, periodically and / or statistically, preferably blockwise and / or statistically. This means that in a structural unit of the formula -[R1O]x-, -[R2O]y- and / or -[R3O]z-, the groups [(C2H4)O] and [(CsHeJO] may be arranged, for example, in a purely statistically or blockwise form but may also be arranged in a form which could be considered as both, statistical and blockwise, e.g. small blocks of [(C2H4)O] and [(CaHejO] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [(C2H4)O] and [(CaHejO] exist.

[0022] Any of the groups [(C2H4)O] and [(CaHejO] can be linked to -R4, -R5, -R6and an oxygen of the glycerol backbone in a glycerol ester alkoxylate molecule of the formula (I). This means, for example, that all, -R4, -R5, -R6and the oxygens of the glycerol backbone in a glycerol ester alkoxylate molecule of the formula (I), may be connected to a [(C2H4)0]-group, they may all be connected to a [(CaHejO]- group or they may be connected independently from one another to either group selected from [(C2H4)O] and [(CaHejO].

[0023] In a preferred embodiment of the invention, the structural units -[R10]-, -[R2O]- and -[R3O]- in the mixture of glycerol ester alkoxylates of the formula (I) are [(C2H4)O].

[0024] Preferably, the variables x, y and z in the mixture of glycerol ester alkoxylates of the formula (I) are, based on a molar average, independent from each other, numbers from 0 to 150, more preferably from 0 to 125, even more preferably from 0 to 1 10, particularly preferably from 0 to 100, and extraordinarily preferably from 0 to 90, and wherein in the definitions above in this paragraph at least one of the variables x, y, and z is, based on a molar average, a number greater than 0.

[0025] In a more preferred embodiment of the invention, the variables x, y and z in the mixture of glycerol ester alkoxylates of the formula (I) are, based on a molar average, independent from each other, numbers from 2 to 149, even more preferably from 5 to 125, particularly preferably from 10 to 1 10, extraordinarily preferably from 20 to 100 and especially preferably from 30 to 90.

[0026] The variables x, y, and z are the same or different and are independently integer numbers for each single glycerol ester alkoxylate molecule of the formula (I) in the mixture according to the invention and may be the same or different for the various glycerol ester alkoxylate molecules in the mixture according to the invention.

[0027] The sum x+y+z is an integer number for each single glycerol ester alkoxylate molecule of the formula (I) in the mixture according to the invention and may be the same or different for the various glycerol ester alkoxylate molecules in the mixture according to the invention. Preferably, the sum x+y+z for a single glycerol ester alkoxylate molecule of the formula (I) in the mixture according to the invention is selected from integer numbers from 5 to 600, more preferably is selected from integer numbers from 10 to 500, even more preferably is selected from integer numbers from 20 to 400, and particularly preferably is selected from integer numbers from 30 to 300.

[0028] In a preferred embodiment of the invention, in the inventive mixtures of glycerol ester alkoxylates of the formula (I), at least 20 mol%, preferably at least 25 mol%, more preferably at least 30 mol%, even more preferably at least 35 mol% and particularly preferably at least 40 mol% of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), are linear or branched, preferably linear, unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, unsaturated acyl groups comprising 16 to 18 carbon atoms or mixtures thereof, in each case based on the total amount of the acyl groups R4, R5and R6.

[0029] In a further preferred embodiment of the invention, in the inventive mixtures of glycerol ester alkoxylates of the formula (I), the groups R4, R5and R6are selected from hydrogen, acyl groups derived from palm oil, rape seed oil, refined rape seed oil, sunflower oil, high oleic sunflower oil, or mixtures thereof.

[0030] In the context of the present invention, “high oleic sunflower oil” refers to a sunflower oil, wherein the amount of the oleic acid residues in the oil, based on the total amount of fatty acid residues in the oil, is at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol% and even more preferably at least 80 mol%. "Refined rape seed oil" refers to a rapeseed oil wherein undesired impurities have been reduced or removed.

[0031] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises acyl groups with 16 carbon atoms and acyl groups with 18 carbon atoms, the molar ratio of the acyl groups with 16 carbon atoms to the acyl groups with 18 carbon atoms preferably is not 1 :1 .

[0032] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated and unsaturated acyl groups with 16 carbon atoms and saturated and unsaturated acyl groups with 18 carbon atoms, the molar ratio of the sum of the saturated and unsaturated acyl groups with 16 carbon atoms to the sum of the saturated and unsaturated acyl groups with 18 carbon atoms preferably is < 1 .0 and more preferably < 0.9.

[0033] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated acyl groups with 16 carbon atoms and saturated acyl groups with 18 carbon atoms, the molar ratio of the saturated acyl groups with 16 carbon atoms to the saturated acyl groups with 18 carbon atoms preferably is > 1 .0, more preferably > 1 .2 and even more preferably > 1 .5.

[0034] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated and unsaturated acyl groups with 16 carbon atoms and saturated acyl groups with 18 carbon atoms, the molar ratio of the sum of the saturated and unsaturated acyl groups with 16 carbon atoms to the saturated acyl groups with 18 carbon atoms preferably is > 1 .0, more preferably > 1 .2 and even more preferably > 1.5.

[0035] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises acyl groups with 16 carbon atoms and acyl groups with 18 carbon atoms, the weight ratio of the acyl groups with 16 carbon atoms to the acyl groups with 18 carbon atoms preferably is not 1 :1 . In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated and unsaturated acyl groups with 16 carbon atoms and saturated and unsaturated acyl groups with 18 carbon atoms, the weight ratio of the sum of the saturated and unsaturated acyl groups with 16 carbon atoms to the sum of the saturated and unsaturated acyl groups with 18 carbon atoms preferably is < 1 .0 and more preferably < 0.9.

[0036] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated acyl groups with 16 carbon atoms and saturated acyl groups with 18 carbon atoms, the weight ratio of the saturated acyl groups with 16 carbon atoms to the saturated acyl groups with 18 carbon atoms preferably is > 1 .0, more preferably > 1 .2 and even more preferably > 1 .5.

[0037] In case the mixture of glycerol ester alkoxylates of the formula (I) comprises saturated and unsaturated acyl groups with 16 carbon atoms and saturated acyl groups with 18 carbon atoms, the weight ratio of the sum of the saturated and unsaturated acyl groups with 16 carbon atoms to the saturated acyl groups with 18 carbon atoms preferably is > 1 .0, more preferably > 1 .2 and even more preferably > 1.5.

[0038] Glycerol ester alkoxylates are already known in the prior art. Glycerol ester ethoxylates of the prior art are e. g. described in WO 2020 / 239750 A1 , WO 2020 / 239760 A1 , WO 2021 / 078807 A1 , EP 4 067 468 A1 ,

[0039] WO 2023 / 057335 A1 or WO 2023 / 083995 A1 . Glycerol ester ethoxylates are also disclosed in CN 111234199 A, e.g. as latex paint thickening rheological agents.

[0040] Glycerol ester alkoxylates may be produced by the reaction of glycerol ester such as triglyceride with alkylene oxide e.g. using catalysts based on calcium or magnesium. An alternative route to prepare glycerol ester alkoxylates is a transesterification reaction of a methyl ester or esterification reaction of a carboxylic acid with an alkoxylated glycerol.

[0041] The inventive mixture of glycerol ester alkoxylates of the formula (I) may advantageously be prepared by insertion alkoxylation, e.g. by alkoxylation of glycerol esters such as triglycerides using an alkaline earth metal catalyst.

[0042] A further subject matter of the invention is a method for preparing an inventive mixture of glycerol ester alkoxylates of the formula (I), in particular an inventive mixture of glycerol ester alkoxylates of the formula (I) wherein

[0043] R1, R2, R3, x, y, z, R4, R5, R6, and the sum of x + y + z, based on a molar average, are as defined above, and the amount of the glycerol ester alkoxylates of the formula (I), wherein all of the groups R4, R5and R6have a meaning different from hydrogen, is as defined above, and the amount of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), and are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 18 carbon atoms or mixtures thereof, is as defined above, from ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide and a mixture of glycerol esters of the formula (II) wherein R4, R5and R6in the mixture of the glycerol esters of the formula (II) have the same meaning as in the mixture of the glycerol ester alkoxylates of the formula (I), characterized in that in the method a catalyst (C) based on an alkaline earth metal is used.

[0044] In the inventive method for preparing an inventive mixture of glycerol ester alkoxylates of the formula (I), R4, R5and R6in the mixture of the glycerol esters of the formula (II) have the same meaning as in the mixture of the glycerol ester alkoxylates of the formula (I).

[0045] This e.g. means, that

[0046] R4, R5and R6in the mixture of the glycerol esters of the formula (II), are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 8 to 30 carbon atoms or mixtures thereof, and wherein, in the single glycerol ester molecules of the formula (II), at least one of the groups R4, R5and R6has a meaning different from hydrogen (acyl group), and at least 70 mol% of the glycerol esters of the formula (II) in the mixture of the glycerol esters of the formula (II), based on the total amount of the glycerol esters of the formula (II) in the mixture of the glycerol esters of the formula (II), are glycerol esters of the formula (II), wherein all of the groups R4, R5and R6have a meaning different from hydrogen (acyl groups), and in the mixture of the glycerol esters of the formula (II), at least 30 mol% of those groups R4, R5and R6, which have a different meaning from hydrogen (acyl groups), are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof, based on the total amount of the linear or branched, preferably linear, saturated or unsaturated acyl groups R4, R5and R6.

[0047] Preferably, triglycerides of the formula (II) are used for the preparation of the inventive mixtures of alkoxylates of the formula (I) and are not admixed with other reactants that contain any free hydroxyl groups.

[0048] Preferably, in the method according to the invention, the catalyst (C) is obtainable by a reaction involving

[0049] (a) an alkaline earth metal compound (A) and

[0050] (b) one or more substances selected from the group consisting of a carboxylic acid (B) preferably comprising 3 to 60, more preferably 3 to 46, carbon atoms; a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol; an alcohol solvent; and mixtures including any of the foregoing, and

[0051] (c) a strong acid (AC).

[0052] The carboxylic acid (B) mentioned under component (b) above may e. g. be a carboxylic acid, wherein the carboxylic acid function -COOH is connected to a hydrocarbon group but may also e. g. be a carboxylic acid wherein the carboxylic acid function -COOH is connected to a hydrocarbon group that contains or is interrupted by ether functions.

[0053] The alcohol mentioned in component (b) is an alcohol wherein the hydroxyl function -OH is bonded to a hydrocarbyl group. Preferably, in the method according to the invention, the alcohol solvent is an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water.

[0054] Preferably, in the method according to the invention the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium sulfate, magnesium phosphate, calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, calcium phosphate, strontium hydroxide, strontium acetate, strontium carbonate, strontium sulfate, strontium phosphate, barium hydroxide, barium acetate, barium carbonate, barium sulfate, and barium phosphate. In a more preferred embodiment of the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, and calcium phosphate. In another more preferred embodiment of the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, calcium hydroxide, calcium acetate, strontium hydroxide, strontium acetate, barium hydroxide, and barium acetate. Particularly preferably, in the method according to the invention, the alkaline earth metal compound (A) is selected from the group consisting of calcium acetate and calcium hydroxide.

[0055] Preferably, in the method according to the invention, the strong acid (AC) is an acid which has a PKA value of 3 or less, more preferably is selected from the group consisting of acids of sulfur oxides and phosphorus oxides, even more preferably from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids (among the sulfonic acids methane sulfonic acid is preferred), phosphorus acid, phosphorous acid and phosphonic acids (among the phosphonic acids methane phosphonic acid is preferred) and particularly preferably from the group consisting of sulfuric acid, sulfurous acid and methane sulfonic acid. Extraordinarily preferably, in the method according to the invention, the strong acid (AC) is sulfuric acid. Preferably, in the method according to the invention, the molar ratio of the alkaline earth metal compound (A) to the strong acid (AC) is from 1 .0:0.1 to 1 .0:1 .0, more preferably from 1 .0:0.2 to 1 .0:0.9 and even more preferably from 1 .0:0.3 to 1 .0:0.8.

[0056] Preferably, in the method according to the invention, the polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol is a polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol.

[0057] Preferably, in the method according to the invention, the C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol is a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and more preferably is a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol.

[0058] Preferably, in the method according to the invention, volatile components are removed before the catalyst (C) is used for the preparation of the mixture of glycerol ester alkoxylates of the formula (I).

[0059] In one preferred embodiment of the method according to the invention, a carboxylic acid (B) is used in the preparation of the catalyst (C).

[0060] Preferably, in the method according to the invention, the molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1 :1 to 1 :5.

[0061] Preferably, the carboxylic acid (B) is represented by formula (III),

[0062] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0063] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to C18 hydrocarbyl groups, q is 0 or 1 , and p is, based on molar average, a number from 0 to 11 , preferably from 1 to 11 , more preferably from 1 to 9, and even more preferably from 2 to 7.

[0064] In a more preferred embodiment of the invention, the carboxylic acid (B) is represented by formula (III),

[0065] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0066] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups, q is 0, and p is 0, and preferably is isononanoic acid or oleic acid.

[0067] In another more preferred embodiment of the invention, the carboxylic acid (B) is represented by formula (III),

[0068] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0069] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups, q is 1 , and p is, based on molar average, a number from 0 to 11 , preferably from 1 to 11 , more preferably from 1 to 9, and even more preferably from 2 to 7, and preferably, R4is oleyl, q is 1 , and p is, based on molar average, 5.

[0070] In one preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0071] (a) calcium hydroxide and

[0072] (b) a carboxylic acid (B), which is represented by formula (III), R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0073] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups, q is 0, and p is 0, and preferably is isononanoic acid, and an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and

[0074] (c) sulfuric acid.

[0075] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0076] (a) calcium hydroxide and

[0077] (b) a carboxylic acid (B), which is represented by formula (III),

[0078] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0079] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups, q is 1 , and p is, based on molar average, a number from 0 to 11 , preferably from 1 to 1 1 , more preferably from 1 to 9, and even more preferably from 2 to 7, and preferably, R4is oleyl, q is 1 , and p is, based on molar average, 5, and an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and

[0080] (c) a strong acid and preferably sulfuric acid. In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0081] (a) calcium acetate and

[0082] (b) a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such polyalkylene glycols, and

[0083] (c) sulfuric acid.

[0084] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0085] (a) calcium acetate and

[0086] (b) a carboxylic acid (B), which is represented by formula (III),

[0087] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0088] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to Cis hydrocarbyl groups, q is 0, and p is 0, and preferably, is oleic acid, and a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol, preferably a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and more preferably a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such alkyl-capped polyalkylene glycols, and

[0089] (c) sulfuric acid.

[0090] In another preferred embodiment of the invention, the catalyst (C) is obtainable by a reaction involving

[0091] (a) calcium acetate and (b) an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, and

[0092] (c) sulfuric acid.

[0093] In the inventive method for preparing the mixture of alkoxylates of the formula (I), the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more glycerol esters of the formula (II) preferably is from 50:1 to 300:1 , more preferably from 60:1 to 300:1 , even more preferably from 70:1 to 280:1 , particularly preferably from 85:1 to 250:1 , and extraordinarily preferably from 90:1 to 250:1.

[0094] The molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) (molar ratio (A):(B)) in the preparation of the catalyst (C) preferably is from 1 :1 to 1 :5. More preferably, the molar ratio (A):(B) is from 1 :1 .5 to 1 :4, even more preferably from 1 :1 .8 to 1 :2.2 and particularly preferably from 1 :1 .9 to 1 :2.1 . In an extraordinarily preferred embodiment of the invention, the molar ratio of (A):(B) in the preparation of the catalyst (C) is approximately 1 :2.

[0095] In one preferred embodiment of the invention, the reaction for the preparation of the catalyst (C) is carried out in the presence of at least one polar solvent, more preferably a polar solvent comprising at least one hydroxyl group, even more preferably at least one alcohol having 1 to 5 carbon atoms or a mixture thereof with water. In a particularly preferred embodiment, the polar solvent is propan-2-ol or a mixture thereof with water. In another particularly preferred embodiment, the polar solvent is ethanol or a mixture thereof with water.

[0096] It is advisable to perform the reaction for obtaining the catalyst (C) in the presence of an acid (AC) which has a PKA value of 3 or less, preferably 2 or less, more preferably 0 or less, and often -3 or less.

[0097] Preferably, the acid (AC) is selected from the group consisting of acids of sulfur oxides and phosphorus oxides, more preferably from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids (among the sulfonic acids methane sulfonic acid is preferred), phosphorus acid, phosphorous acid and phosphonic acids (among the phosphonic acids methane phosphonic acid is preferred). Sulfuric acid, sulfurous acid and methane sulfonic acid are of particular interest.

[0098] In a particularly preferred embodiment of the invention, the reaction for obtaining the catalyst (C) is performed in the presence of sulfuric acid.

[0099] It is particularly advantageous to prepare the alkaline earth metal catalyst (C) by first allowing the alkaline earth metal compound (A) to react with the carboxylic acid (B), preferably in a solvent as described above, after which the reaction mixture is further treated with the acid (AC).

[0100] It is also particularly advantageous to prepare the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in a polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such polyalkylene glycols, or in a C1-C18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol, preferably a methyl-capped polyalkylene glycol having a molecular weight from 100 g / mol to 1500 g / mol and more preferably a methyl-capped polyethylene glycol having a molecular weight from 100 g / mol to 1500 g / mol or mixtures of such alkyl-capped polyalkylene glycols, optionally in the presence of water, after which the reaction mixture is further treated with the acid (AC). The dispersing step may be performed in the presence of a carboxylic acid (B), which is represented by formula (III),

[0101] R4-[O]q-[CH2CH2-O]P-CH2COOH (III) wherein

[0102] R4is selected from saturated or unsaturated, linear or branched Ci to C30 hydrocarbyl groups, preferably Ci to C22 hydrocarbyl groups, and more preferably Ce to C18 hydrocarbyl groups, q is 0, and p is 0, and preferably is oleic acid. It is also particularly advantageous to prepare the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan- 2-ol, or a mixture thereof with water, after which the reaction mixture is further treated with the acid (AC).

[0103] For the reaction by which the alkaline earth metal catalyst (C) is obtained, any common reactor may be employed, preferably a reactor with an agitating / mixing means, such as, e.g., a magnetic stirrer, a mechanical stirrer, a static mixer, a blender, a batch disperser, or a Rotor-Stator disperser.

[0104] The preparation of the catalyst (C) is preferably carried out under a pressure of from 0.5 to 2 bar, more preferably from 0.8 to 1 .5 bar, even more preferably from 0.9 to 1 .2 bar. In a preferred embodiment of the invention, the catalyst is prepared under atmospheric pressure. Furthermore, the catalyst (C) is preferably prepared at a temperature of from -30 °C to 80 °C, preferably from -10 °C to 60 °C, more preferably from 0 °C to 50 °C. In a preferred embodiment of the invention, the catalyst is prepared at a temperature of from 20 to 40 °C, especially at room temperature.

[0105] The thus prepared alkaline earth metal catalyst (C), preferably the calcium catalyst, typically has a content of alkaline earth metal ions, preferably Ca2+ions, that is from 0.5 to 10 wt.-%, often from 1 to 7 wt.-%, often from 2.0 to 5.5 wt.-%.

[0106] Optionally, the catalyst may be purged of volatile components, such as the solvent, water and other volatile byproducts by employing commonly used methods. Preferably, the volatile components are removed in vacuo, e.g. under a pressure below 0.8 bar, preferably below 0.3 bar, more preferably below 0.1 bar, and / or at elevated temperatures, e.g. 50 to 180 °C, preferably 70 to 150 °C, more preferably 80 to 140 °C. In a particularly preferred embodiment of the invention, the volatile compounds are removed on a rotary evaporator at a pressure below 0.1 bar and a temperature of from 80 °C to 140 °C.

[0107] Preferably, the method of the invention for preparing a mixture of glycerol ester alkoxylates of the formula (I) according to the invention comprises the steps of i) introducing the catalyst (C) as defined above and one or more glycerol esters of the formula (II) as described above into a pressure-resistant reactor; ii) optionally replacing the air in the reactor with nitrogen or other protective gas; iii) optionally drying the reactor content at a temperature of from 50 to 200 °C and / or a pressure below 0.8 bar; iv) heating the content of the reactor to a temperature of from 80 °C to 200 °C; v) optionally pressurizing the reactor with nitrogen or other protective gas to a pressure of from 0.3 bar to 3.5 bar above atmospheric pressure; vi) pressurizing the reactor with alkylene oxide gas selected from the group consisting of ethylene oxide gas, propylene oxide gas and mixtures of ethylene oxide gas and propylene oxide gas to a pressure of from 1 .5 bar to 10 bar above atmospheric pressure with the proviso that the pressure is above the pressure prior to step vi); vii) allowing the mixture to react until the pressure in the reactor is constant.

[0108] In step i), the catalyst (C) may be introduced as obtained from the reaction of its preparation described above directly, or in its form that has been purged of volatile compounds, but preferably as obtained from the reaction of its preparation described above directly. The glycerol esters of formula (II) may be introduced in their raw form or may be purified prior to use.

[0109] The catalyst (C) is preferably introduced into the reactor in an amount from 0.5 to 5 wt.-%, preferably from 1 to 3 wt.-%, more preferably from 1 to 2 wt.-% based on the total weight of the mixture of glycerol esters of formula (II) and alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide.

[0110] The pressure-resistant reactor is not particularly limited but is designed to withstand the pressures employed in the process, thus that it is not damaged during the process. Preferably, the reactor is designed to withstand pressures both above 10 bar, more preferably above 15 bar, and below 0.01 bar, more preferably below 0.001 bar. Preferably, the pressure-resistant reactor is an autoclave, more preferably an autoclave equipped with an agitating means such as a magnetic or a mechanical stirrer.

[0111] Generally, the replacement of air in the reactor with nitrogen or other protective gas is not necessarily required, because the mixture of glycerol ester alkoxylates of the formula (I) according to the invention would at least partially be generated in the process. However, air, particularly oxygen, in the reactor may lead to safety concerns during alkoxylation reactions in general and decomposition products due to oxidation and / or hydrolysis of the employed materials and of the generated products, especially at elevated temperatures. Therefore, it is advisable to carry out step ii) of the method of the invention after step i).

[0112] In general, the step of drying the reactor content is also not necessarily required, because the mixture of glycerol ester alkoxylates of the formula (I) according to the invention would at least partially be generated in the process. However, water and alcohols may facilitate hydrolysis and transesterification of the employed materials and of the generated products under the reaction conditions. Especially if in step i) the catalyst (C) is introduced into the reactor as obtained from the reaction of its preparation described above directly, it is advisable to carry out the drying step, since the directly obtained catalyst (C) typically contains residues of polar solvents or their mixtures with water. In case the catalyst (C) is purged of volatile components before introducing it into the reactor, the drying step iii) may be omitted. Nevertheless, in this case it may be advisable to carry out step iii) since volatile components may also be present as impurities in the one or more glycerol esters of formula (II). Therefore, in particularly preferred embodiments, step iii) is carried out.

[0113] The step iii) of drying the reactor content is typically performed at a temperature of from 50 °C to 200 °C, preferably of from 50 °C to 180 °C, more preferably of from 60 °C to 150 °C, even more preferably of from 70 °C to 130 °C, particularly preferably of from 80 °C to 120 °C, and at a pressure below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar. The thus generated vacuum is preferably a dynamic vacuum.

[0114] The vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Furthermore, it is advisable to reduce the pressure and increase temperature in the reactor gradually to prevent boiling retardation. In a particularly preferred embodiment, the step of drying the reactor content is carried out at a temperature of from 80 °C to 120 °C and a pressure below 0.01 bar, preferably over a period of at least 15 minutes, more preferably over a period of at least 30 minutes, even more preferably over a period of at least 1 hour. It is particularly preferred to dry the content of the reactor to constant mass.

[0115] After the drying step iii), the fluid line between the vacuum pump and the reactor is interrupted, to ensure that the components added to the reactor after the drying remain in the reactor and are not directly withdrawn therefrom. Furthermore, it is preferable to compensate the vacuum in the reactor with nitrogen or other protective gas before carrying out the further steps, to reduce the risk of air entering the reactor.

[0116] Step iv) of heating the content of the reactor is generally performed at a temperature of from 80 °C to 200 °C, preferably from 120 °C to 190 °C, more preferably from 160 °C to 180 °C. This temperature is maintained at least until step vi) is finished, preferably until step vii) is finished. After setting the temperature in step iv), the reactor may be optionally pressurized in step v) with nitrogen or other protective gas to a pressure of from 0.3 to 3.5 bar, preferably of from 0.4 to 3.3 bar, more preferably of from 0.5 to 3.0 bar, even more preferably of from 0.7 to 2.5 bar and particularly preferably of from 0.8 to 2.2 bar above atmospheric pressure. By carrying out this step v), alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide introduced in the following step is diluted with the protective gas, thus that pressure-controlled dosage of alkylene oxide into the reactor is facilitated.

[0117] In step vi) the reactor is further pressurized with alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to a total internal pressure of from 1 .5 to 10 bar, preferably from 2 to 8 bar, more preferably from 3 to 6 bar, even more preferably from 4 to 5 bar, above atmospheric pressure, with the proviso that the pressure in step vi) is above the pressure before step vi).

[0118] During step vii), after introduction of the intended amount of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide, the alkylene oxide inlet is closed and the reaction is allowed to proceed until the pressure in the reactor is constant.

[0119] In the sense of the invention, the pressure is considered constant, if it does not change by more than 0.05 bar over a period of 15 minutes, preferably 30 minutes, more preferably 1 hour. It is particularly preferred that the pressure in the reactor does not change by more than 0.01 bar over a period of 1 hour.

[0120] After completion of step vii), it is advisable to remove residual alkylene oxide from the reactor before isolating the mixture of glycerol ester alkoxylates of the formula (I) according to the invention, in order to prevent any unwanted reactions with alkylene oxide from taking place after isolation of the product. Preferably, residual alkylene oxide is removed from the reactor by cooling the reactor content to a temperature of from 50 to 120 °C, more preferably from 70 to 100 °C and even more preferably from 85 to 95 °C, and employing a pressure of below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar. The thus generated vacuum is preferably a dynamic vacuum. The vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Removal of residual alkylene oxide under these conditions is preferably carried out for at least 10 minutes, more preferably at least 30 minutes and even more preferably at least 1 hour.

[0121] The method of isolation of the mixture of glycerol ester alkoxylates of the formula (I) according to the invention is not particularly limited. However, it is preferable to isolate the product at elevated temperatures, specifically at temperatures of from 50 to 150 °C, preferably from 60 to 140 °C, more preferably from 80 to 120 °C. At these temperatures, the mixture of glycerol ester alkoxylates of the formula (I) according to the invention is typically in a liquid state and has a sufficiently low viscosity, and therefore may be transferred out of the reactor more easily than in the solid state, e.g. by pouring the product out of the reactor or via a bottom valve, thereby minimizing the amount of residues in the reactor. Thus, the subsequent cleaning and maintenance of the reactor is also facilitated.

[0122] The method for preparing a mixture of glycerol ester alkoxylates of the formula (I) according to the invention using the catalyst (C) described above may be interrupted at any stage, and continued at a later point in time, without the reaction time being significantly increased.

[0123] In a preferred embodiment of the invention, the sum x+y+z in the inventive mixtures of alkoxylates of the formula (I), is, based on a molar average, a number from 90 to 200, more preferably from 90 to 190 and even more preferably from 90 to 1 10 or from 160 to 190. In a particularly preferred embodiment of the invention, the sum x+y+z in the inventive mixtures of alkoxylates of the formula (I), is, based on a molar average, a number from 90 to 110. In another particularly preferred embodiment of the invention, the sum x+y+z in the inventive mixtures of alkoxylates of the formula (I), is, based on a molar average, a number from 160 to 190. Accordingly, in a preferred embodiment of the inventive method for preparing the inventive mixtures of alkoxylates of the formula (I), the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more glycerol esters of the formula (II) is from 90:1 to 200:1 , more preferably from 90:1 to 190:1 and even more preferably from 90:1 to 110:1 or from 160:1 to 190:1 . In a particularly preferred embodiment of the inventive method for preparing the inventive mixtures of alkoxylates of the formula (I), the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more glycerol esters of the formula (II) is from 90:1 to 1 10:1 . In another particularly preferred embodiment of the inventive method for preparing the inventive mixtures of alkoxylates of the formula (I), the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more glycerol esters of the formula (II) is from 160:1 to 190:1 . In the preferred inventive mixtures of glycerol ester alkoxylates of the formula (I) mentioned in this paragraph above, the groups R4, R5and R6are preferably selected from hydrogen, acyl groups derived from palm oil, rape seed oil, refined rapeseed oil, sunflower oil, high oleic sunflower oil, or mixtures thereof and more preferably selected from hydrogen, acyl groups derived from palm oil, rape seed oil, refined rape seed oil, high oleic sunflower oil, or mixtures thereof.

[0124] The mixture of glycerol ester alkoxylates of the formula (I) according to the invention may occur together with starting material used for its preparation, in particular glycerol ester in case the inventive mixture is prepared by alkoxylation of glycerol esters (in the following referred to as “composition A”). In case glycerol ester is present in the compositions A, the glycerol ester may be present in an amount of 0.1 wt.-% or more, or 0.25 wt.-% or more, or 0.5 wt.-% or more, or 1 .0 wt.-% or more, in each case based on the total weight of the composition A. In case glycerol ester is present in the compositions A, the glycerol ester is present in an amount of preferably less than 20.0 wt.-%, more preferably less than 10.0 wt.-%, even more preferably less than 5.0 wt.-%, particularly preferably less than 2.0 wt.-% and extraordinarily preferably less than 1 .0 wt.-%, in each case based on the total weight of the composition A.

[0125] During the preparation of the mixture according to the invention, by-products may be formed. The formation of by-products in chemical reactions is quite normal since these reactions usually do not take place with a selectivity of 100 %. However, in case by-products are formed during the preparation of the mixture according to the invention, these by-products are formed in an amount of preferably less than 25.0 wt.-%, more preferably less than 20.0 wt.-%, even more preferably less than 15.0 wt.-%, particularly preferably less than 10.0 wt.-%, extraordinarily preferably less than 6.0 wt.-% and especially preferably less than 5.0 wt.-%, in each case based on the combined total weight of the mixture according to the invention and the by-products, and in particular in case the inventive mixture is prepared by a method according to the invention.

[0126] Starting material, and in particular glycerol ester, occurring together with the mixture according to the invention is considered to form part of the by-products.

[0127] Furthermore, the mixture according to the invention may be purified after its preparation and prior to its use, e.g. by distilling, stripping or filtering-off byproducts, but in a preferred embodiment, the mixture may be used as obtained without prior purification.

[0128] A further subject matter of the invention is an alkoxylation product obtainable by the inventive method described above for preparing a mixture according to the invention. The alkoxylation product comprises a mixture of glycerol ester alkoxylates of the formula (I) according to the invention and may optionally comprise further substances such as starting materials or reactants, in particular glycerol esters of the formula (II), and / or by-products.

[0129] The inventive mixtures of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product may also be bio-based. Bio-based glycerol ester alkoxylates of formula (I) can, for example, be prepared from (i) glycerol esters of the formula (II) such as triglycerides and (ii) ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide, wherein at least a part of one of the aforementioned alkylene oxides is bio-based.

[0130] Bio-based ethylene oxide can be obtained from bio-ethanol, which can be obtained from natural sources like corn, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol is then dehydrated to produce bio-ethylene. The bioethylene is then oxidized with oxygen over a silver catalyst to produce bio-based ethylene oxide.

[0131] Bio-based propylene oxide can be obtained from

[0132] 1 ) bio-glycerol, which can be obtained from biodiesel production, hydrolysis of vegetable oils, or fermentation of sugars. Bio-glycerol is then converted to acrolein via dehydration. Acrolein is hydrogenated to produce bio-propanol and subsequently dehydrated to provide bio-propylene, which is epoxidized to produce propylene oxide using hydrogen peroxide; or

[0133] 2) bio-ethanol, which can be obtained from natural sources like corn, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol is then dehydrated to produce bio-ethylene. The bio-ethylene is then catalytically dimerized to bio-butene. Bio-butene and bio-ethylene are then converted to bio- propylene via metathesis. The bio-propylene is then catalytically converted to propylene oxide.

[0134] Preferably, the materials used to prepare the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product are bio-based and derived from natural sources. More preferably, the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product has at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt.-% and particularly preferably 100 wt.-% bio-based carbon content, in each case relative to the total mass of carbon in the mixture of alkoxylates of the formula (I) or relative to the total mass of carbon in the alkoxylation product, respectively. Preferably, the hydroxyl number of the alkoxylation product according to the invention is smaller than 15 mg KOH / g, more preferably smaller than 10 mg KOH / g and even more preferably smaller than 5 mg KOH / g. The hydroxyl number is measured according to DIN EN ISO 4629-2.

[0135] Mixtures of glycerol ester alkoxylates of the formula (I) which have been prepared via insertion alkoxylation as described above or the inventive alkoxylation products show an advantageous biodegradability.

[0136] A further subject matter of the invention is compositions comprising the inventive mixtures of glycerol ester alkoxylates or the inventive alkoxylation products, preferably in an amount from 10 to 90 wt.-%, more preferably in an amount from 15 to 85 wt.-% and even more preferably in an amount from 20 to 80 wt.-%, in each case based on the total weight of the compositions, and one or more solvents selected from the group consisting of water, ethanol, propanol, isopropanol, butanol, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol, preferably in an amount from 10 to 90 wt.-%, more preferably in an amount from 15 to 85 wt.-% and even more preferably in an amount from 20 to 80 wt.-%, in each case based on the total weight of the compositions and even more preferably, the compositions comprise water and a second solvent different from water and selected from the group above. These compositions do not contain esterquat. They are liquid solutions or liquid dispersions at one atmosphere (1 atm = 101325 Pascal), preferably above 60°C, more preferably above 50°C, even more preferably above 45°C, particularly preferably above 40°C and extraordinarily preferably above 20°C.

[0137] Esterquats are quaternary ammonium compounds comprising one or more ester groups, wherein 4 groups different from hydrogen are bound to the nitrogen atom of the quaternary ammonium group. In the context of the present invention, the one or more acids underlying the one or more acid parts of the one or more ester groups of the esterquats preferably are selected from fatty acids. A further subject matter of the invention is liquid laundry compositions comprising

[0138] Z1 ) the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product and

[0139] Z2) water, whereby the liquid laundry compositions do not contain esterquat.

[0140] EP 3 290 500 A1 describes agents with polyoxyalkylene carboxylate and glycolipid comprising rhamnolipid, sophorolipid, cellobioselipid, trehaloselipid, mannosylerythritollipid, for the use as laundry detergent, care product or cleaning medium.

[0141] WO 2021 / 099095 A1 discloses a liquid laundry detergent composition comprising linear alkyl benzene sulphonate (LAS) and from 0.1 to 10% wt. ethoxylated glycerol ester (EGE), wherein the weight ratio (LAS:EGE) is from 0.5:1 to 2:1 , wherein said composition comprises less than 2% weight alkali-metal alkyl ether sulphate and wherein the composition comprises less than 0.1% wt. magnesium sulphate heptahydrate.

[0142] WO 2024 / 017614 A1 discloses a concentrated liquid composition for forming a liquid detergent on dilution in water comprising: a) 20 to 90% by weight of an anionic surfactant with an alkylamine or alkanolamine counterion; b) an alkoxylated polyol polyester comprising at least three alkoxylates and at least two C8 to C40 fatty acid ester; and c) a cosurfactant selected from cationic surfactant, amphoteric surfactant and combinations thereof, wherein the composition comprises less than 10% by weight water. US 2007 / 0199157 A1 describes an enhanced fabric conditioner comprising a fabric conditioner and ethoxylated propoxylated triglycerides, ethoxylated propoxylated sorbitol.

[0143] EP 0 569 847 A1 discloses alkoxylated natural oils and fats as nitrogen-free active ingredient component in fabric softener formulations and their use therefor. The alkoxylated natural oils and fats may be used both on their own and in mixture with conventional nitrogen-containing cationic active ingredient components with and without the addition of dispersants, emulsifiers and / or solubilisers.

[0144] In a preferred embodiment, the inventive liquid laundry compositions are fabric conditioner compositions and comprise the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1 ) in an amount from 0.1 to 20 wt.-%, preferably in an amount from 0.5 to 17 wt.-%, more preferably in an amount from 1 to 15 wt.-% and even more preferably in an amount from 3 to 12 wt.-%, in each case based on the total weight of the fabric conditioner composition.

[0145] The fabric conditioner compositions of the invention comprise water of component Z2) preferably in an amount from 80 to 99.9 wt.-%, more preferably in an amount from 83 to 99.5 wt.-%, even more preferably in an amount from 85 to 99 wt.-% and particularly preferably in an amount from 88 to 97 wt.-%, in each case based on the total weight of the fabric conditioner compositions.

[0146] In addition to the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1 ) and water of component Z2), the fabric conditioner compositions of the invention may comprise one or more optional ingredients, e.g. nonionic surfactants, cationic surfactants different from esterquats, fragrances, preservatives or thickeners.

[0147] Suitable nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, polyhydroxy alkyl fatty acid amide and N-acyl N-alkyl derivatives of glucosamine ("glucamides"). Mixtures of nonionic surfactants may be used.

[0148] Suitable cationic surfactants different from esterquats include quaternary ammonium compounds having alkyl chains attached directly to the nitrogen atoms in the ammonium.

[0149] In another preferred embodiment of the invention, the inventive liquid laundry compositions are liquid laundry detergent compositions and comprise a further component Z3)

[0150] Z3) one or more anionic or nonionic surfactants or mixtures thereof.

[0151] In a preferred embodiment, the pH value of the inventive liquid laundry detergent compositions is between 6 and 11 , preferably between 6 and 10 and more preferably between 6 and 9.

[0152] The inventive liquid laundry detergent compositions have the advantage that they contain the mixture of glycerol ester alkoxylates of formula (I) or the alkoxylation product of component Z1) and can be used for treating fabrics through washing to improve the softness of the fabrics after the washed fabrics are dried.

[0153] The mixture of glycerol ester alkoxylates of formula (I) or the alkoxylation product of component Z1) furthermore shows beneficial compatibility with other ingredients in the inventive liquid laundry detergent compositions, and a beneficial thickening effect in the inventive liquid laundry detergent compositions.

[0154] The one or more anionic or nonionic surfactants of component Z3) of the inventive liquid laundry detergent compositions are preferably selected from the group consisting of sulfates, sulfonates, soaps, alcohol ethoxylates, glucamides, alkyl polyglycosides and mixtures thereof. Suitable anionic surfactants that may be used are any of the conventional anionic surfactant types typically used in detergent products. These include alkyl sulfonates, alkyl ether sulfates, alkyl sulfates, alkyl ester sulfonates and soaps. Preferred anionic surfactants are alkylbenzene sulfonates, alkyl ether sulfates, alkyl sulfates and soaps.

[0155] Preferred alkyl sulfonates are alkylbenzene sulfonates, particularly linear alkylbenzene sulfonates (LAS) having an alkyl chain length of Cs-Cis. Possible counter ions for concentrated alkaline liquids are ammonium ions, e.g. those generated by the neutralization of alkylbenzene sulfonic acid with one or more ethanolamines, for example monoethanolamine (MEA) and triethanolamine (TEA), or alternatively, alkali metals, e.g. those arising from the neutralization of alkylbenzene sulfonic acid with alkali hydroxides. The linear alkyl benzene sulfonate surfactants may be LAS with an alkyl chain length of preferably from 8 to 15 and more preferably from 12 to 14. The neutralization of the acid may be performed before addition to the liquid laundry detergent compositions of the invention or during the process of formulating the liquid laundry detergent compositions of the invention through excess addition of neutralizing agent.

[0156] Preferred alkyl ether sulfates (AES) are alkyl polyethoxylate sulfate anionic surfactants of the formula

[0157] R7O(C2H4O)aSO3M+wherein

[0158] Fb is a saturated or unsaturated alkyl chain having preferably from 10 to 22 carbon atoms, and more preferably from 12 to 16 carbon atoms,

[0159] M+is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers, and a averages preferably from 1 to 15, more preferably from 1 to 3 and even more preferably is 3. Preferred alkyl sulfates (AS) are surfactants of the formula

[0160] R8OSO3M+wherein

[0161] R8is a linear or branched alkyl chain having preferably from 8 to 24 carbon atoms, and more preferably from 12 to 18 carbon atoms, and

[0162] M+is a cation which makes the compound water-soluble, preferably an ammonium cation, a substituted ammonium cation, an alkali metal cation, or other material chosen from the list of buffers.

[0163] Soaps are preferably fatty acids and more preferably linear saturated or unsaturated fatty acids having from 10 to 18 carbon atoms.

[0164] Suitable nonionic surfactants include primary and secondary alcohol ethoxylates, especially C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 35 moles of ethylene oxide per mole of alcohol, and more especially the C10-C15 primary and secondary aliphatic alcohols ethoxylated with an average of from 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, polyhydroxy alkyl fatty acid amide and N-acyl N-alkyl derivatives of glucosamine ("glucamides"). Mixtures of nonionic surfactants may be used.

[0165] The liquid laundry detergent compositions of the invention comprise the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1) preferably in an amount from 0.01 to 50 wt.-%, more preferably in an amount from 0.1 to 40 wt.-%, even more preferably in an amount from 0.2 to 30 wt.-% and particularly preferably in an amount from 0.5 to 25 wt.-%, in each case based on the total weight of the liquid laundry detergent compositions.

[0166] The liquid laundry detergent compositions of the invention comprise water of component Z2) preferably in an amount from 2 to 90 wt.-%, more preferably in an amount from 2 to 85 wt.-%, even more preferably in an amount from 15 to 80 wt.-% and particularly preferably in an amount from 25 to 75 wt.-%, in each case based on the total weight of the liquid laundry detergent compositions.

[0167] The liquid laundry detergent compositions of the invention comprise the one or more anionic or nonionic surfactants of component Z3) preferably in an amount from 0.01 to 80 wt.-%, more preferably in an amount from 0.1 to 70 wt.-%, even more preferably in an amount from 1 to 60 wt.-% and particularly preferably in an amount from 5 to 55 wt.-%, in each case based on the total weight of the liquid laundry detergent compositions.

[0168] In addition to the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1), water of component Z2), and the one or more anionic or nonionic surfactants or mixtures thereof of component Z3), the liquid laundry detergent compositions of the invention may comprise one or more optional ingredients, e.g. they may comprise conventional ingredients commonly used in liquid laundry detergent compositions. Examples of optional ingredients include, but are not limited to builders, bleaching agents, bleach active compounds, bleach activators, bleach catalysts, photobleaches, dye transfer inhibitors, colour protection agents, anti-redeposition agents, dispersing agents, fabric softening and antistatic agents different from esterquats, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodour reducers, preservatives, disinfecting agents, hydrotropes, fibre lubricants, anti-shrinkage agents, buffers, fragrances, processing aids, colorants, dyes, pigments, anti-corrosion agents, fillers, stabilizers and other conventional ingredients for liquid laundry detergent compositions.

[0169] Polyalkoxylated polyethyleneimine

[0170] For detergency boosting, it is advantageous to use a polymer in the liquid laundry detergent compositions of the invention. This polymer is preferably a polyalkoxylated polyethyleneimine (EPEI). Polyethylene imines are materials composed of ethylene imine units -CH2CH2NH- and, where branched, the hydrogen on the nitrogen is replaced by another chain of ethylene imine units. These polyethyleneimines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like.

[0171] Soil release polymers

[0172] Soil release polymers enhance soil removal during laundering by modifying the surface of the fabric that is laundered, preferably by increasing surface polarity. Typical soil release polymers are obtainable from polymerization of terephthalic acid or its salts or its dialkyl esters; and alkylene glycol, preferably propylene glycol and / or ethylene glycol; and alcohol alkoxylates.

[0173] Other Polymers

[0174] In addition to the optional EPEI and optional soil release polymers, the liquid laundry detergent compositions of the invention may comprise other polymeric materials, for example dye transfer inhibition polymers, anti-redeposition polymers and cotton soil release polymers, especially those based on modified cellulosic materials. Especially, if EPEI is not present, the liquid laundry detergent compositions of the invention may further comprise a polymer of polyethylene glycol and vinyl acetate, for example the lightly grafted copolymers described in WO 2007 / 138054. Such amphiphilic graft polymers based on water soluble polyalkylene oxides as graft base and side chains formed by polymerisation of a vinyl ester component have the ability to enable reduction of surfactant levels whilst maintaining high levels of oily soil removal.

[0175] Hydrotropes

[0176] In the context of this invention a hydrotrope is a solvent that is neither water nor conventional surfactant that aids the solubilisation of the surfactants and other components, especially polymer and sequestrant, in the liquid to render it isotropic. Among suitable hydrotropes there may be mentioned as preferred: monopropylene glycol (MPG), glycerol, sodium cumene sulfonate, ethanol, other glycols, e. g. dipropylene glycol, diethers and urea. MPG and glycerol are preferred hydrotropes. Enzymes

[0177] It is preferable that one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, lipase, amylase, DNase, and cellulase may be present in the liquid laundry detergent compositions of the invention. Less preferred additional enzymes may be selected from esterase, peroxidase and oxidase. The enzymes are preferably present with corresponding enzyme stabilizers. The total enzyme content in the liquid laundry detergent compositions of the invention is preferably from 0 to 5 wt.-%, more preferably from 0.2 to 4 wt.-% and even more preferably from 0.4 to 2 wt.-%, in each case based on the total weight of the liquid laundry detergent composition.

[0178] Sequestrants

[0179] Sequestrants are preferably included. Preferred sequestrants include organic phosphonates, alkanehydroxy phosphonates and carboxylates available under the DEQUEST trademark from Thermphos. The preferred sequestrant level is less than 10 wt.-% and preferably less than 5 wt.-% of the liquid laundry detergent composition of the invention. A particularly preferred sequestrant is HEDP (1 -Hydroxyethylidene-1 ,1 -diphosphonic acid). Also suitable but less preferred as it gives inferior cleaning results is diethylenetriamine penta(methylene phosphonic acid) (DTPMP) or Heptasodium DTPMP.

[0180] Buffers

[0181] In addition to agents optionally included for the generation of anionic surfactants, e.g. from LAS or fatty acids, the presence of buffer is preferred for pH control. Possible buffers are one or more ethanolamines, e.g. monoethanolamine (MEA) or triethanolamine (TEA). They are preferably used in the liquid laundry detergent compositions of the invention at levels of from 1 to 15 wt.-%, based on the total weight of the liquid laundry detergent composition. Other suitable amino alcohol buffer materials may be selected from the group consisting of compounds having a molecular weight above 61 g / mol, which includes MEA. Suitable materials also include, in addition to the already mentioned materials: monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoamino hexanol, 2-[(2-methoxyethyl) methylamino]-ethanol, propanolamine, N-methylethanolamine, diethanolamine, monobutanolamine, isobutanolamine, monopentanolamine, 1 -amino-3-(2-methoxyethoxy)-2-propanol, 2-methyl-4-(methylamino)-2-butanol and mixtures thereof.

[0182] Potential alternatives to amino ethanol buffers are alkali hydroxides such as sodium hydroxide or potassium hydroxide.

[0183] Builders

[0184] Further washing and cleaning ingredients which may be present in the liquid laundry detergent compositions of the invention include inorganic and / or organic builders in order to reduce the degree of hardness of the water. These builders may be present in the liquid laundry detergent compositions of the invention in amounts of from about 5 to about 80 wt.-%, based on the total weight of the liquid laundry detergent compositions. Inorganic builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, silicates, carbonates, sulfates and aluminosilicates.

[0185] Suitable organic builders include polycarboxyl compounds, such as, for example, ether polycarboxylates, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6- trisulfonic acid and carboxymethyloxysuccinic acid, the alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as, for example, ethylenediaminetetraacetic acid and nitrilotriacetic acid, and also polycarboxylic acids, such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof. Builders based on citrates, for example citric acid and its soluble salts, in particular the sodium salt, are preferred polycarboxylic acid builders.

[0186] It may be advantageous to include fluorescer and / or bleach catalyst in the liquid laundry detergent compositions of the invention as further high efficiency performance additives. Perfume and colorants will also desirably be included. The liquid laundry detergent compositions of the invention may additionally contain viscosity modifiers, foam boosting agents, preservatives (e. g. bactericides), pH buffering agents, polyelectrolytes, anti-shrinking agents, anti-wrinkle agents, anti-oxidants, sunscreens, anti-corrosion agents, drape imparting agents, antistatic agents and ironing aids. The liquid laundry detergent compositions of the invention may further comprise pearlisers and / or opacifiers or other visual cues and shading dye.

[0187] Solvents

[0188] Additional solvents different from water may be also used to advantageously mix all ingredients, to improve stability or to achieve a certain viscosity of the liquid laundry detergent compositions of the invention. These solvents comprise ethanol, propanol, butanol, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol, 1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol, butyl glycol, butyl diglycol, butyl polyglycol or mixtures thereof.

[0189] Form, packaging and dosing

[0190] The liquid laundry detergent compositions of the invention are in liquid form, including a gel form. The liquid laundry detergent compositions of the invention may be packaged as unit doses in a polymeric film soluble in the wash water. Alternatively, the liquid laundry detergent compositions of the invention may be supplied in multidose plastics packs with a top or bottom closure. A dosing measure may be supplied with the pack either as a part of the cap or as an integrated system.

[0191] The inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product may advantageously be used as thickener in inventive liquid laundry compositions.

[0192] A further subject matter of the invention is the use of the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product as thickener in an inventive liquid laundry composition, preferably in a fabric conditioner composition comprising water but no esterquat or in a liquid laundry detergent composition comprising water but no esterquat, and more preferably in an inventive fabric conditioner composition or in an inventive liquid laundry detergent composition.

[0193] The inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product may advantageously be used as softening agent.

[0194] A further subject matter of the invention is the use of the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product as softening agent, preferably in a liquid laundry composition, more preferably in a fabric conditioner composition or in a liquid laundry detergent composition, even more preferably in a fabric conditioner composition comprising no esterquat or in a liquid laundry detergent composition comprising no esterquat, and particularly preferably in an inventive fabric conditioner composition or in an inventive liquid laundry detergent composition.

[0195] The inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product may advantageously be used for treating fabrics by washing to maintain water absorbency of fabrics.

[0196] A further subject matter of the invention is the use of the inventive mixture of glycerol ester alkoxylates of the formula (I) or the inventive alkoxylation product for treating fabrics by washing to maintain water absorbency of fabrics, preferably in a liquid laundry composition, more preferably in a fabric conditioner composition or in a liquid laundry detergent composition, even more preferably in a fabric conditioner composition comprising no esterquat or in a liquid laundry detergent composition comprising no esterquat, and particularly preferably in an inventive fabric conditioner composition or in an inventive liquid laundry detergent composition.

[0197] When treated with liquid laundry compositions that contain esterquats, preferably fabric conditioner compositions or liquid laundry detergent compositions that contain esterquats and more preferably fabric conditioner compositions that contain esterquats, fabrics become more hydrophobic and do not absorb water or sweat in a desired amount of time.

[0198] The inventive liquid laundry compositions, preferably the inventive fabric conditioner compositions or the inventive liquid laundry detergent compositions, and more preferably the inventive fabric conditioner compositions, may advantageously be used for treating fabrics by washing to maintain water absorbency of fabrics.

[0199] A further subject matter of the invention is the use of the inventive liquid laundry compositions, preferably the inventive fabric conditioner compositions or the inventive liquid laundry detergent compositions, and more preferably the inventive fabric conditioner compositions, for treating fabrics by washing to maintain water absorbency of fabrics.

[0200] The inventive liquid laundry detergent compositions may advantageously be used in a method of washing a textile.

[0201] A further subject matter of the invention is a method of washing a textile comprising the step of contacting the textile with an aqueous solution comprising an inventive liquid laundry detergent composition, preferably at a temperature between 10°C and 90°C, furthermore preferably for a time between 5 minutes and 4 hours, and more preferably in a washing machine.

[0202] In the inventive method of washing a textile, the concentration of the inventive liquid laundry detergent compositions in the wash liquor is typically from 0.01 g / L to 50 g / L in water, preferably from 0.05 g / L to 20 g / L in water, more preferably from 0.1 g / L to 15 g / L in water, even more preferably from 0.5 g / L to 10 g / L in water, and particularly preferably from 1 g / L to 8 g / L in water.

[0203] A further subject matter of the invention is the use of the inventive liquid laundry detergent compositions to treat fabrics while laundering to achieve cleaning of the fabrics. A further subject matter of the invention is a method of treating a textile in a wash process comprising the following steps 1 ), 2) and 3): step 1 ), main wash cycle: contacting the textile with an aqueous solution comprising a liquid laundry detergent composition, preferably at a temperature between 10°C and 90°C, furthermore preferably for a time between 5 minutes and 4 hours, and more preferably in a washing machine; step 2), rinse cycle: rinsing the textile at least once with water, preferably at a temperature between 10°C and 90°C, furthermore preferably for a time between 5 minutes and 4 hours, and more preferably in a washing machine; and step 3), last rinse cycle: contacting the textile with a fabric conditioner composition, preferably at a temperature between 10°C and 90°C, furthermore preferably for a time between 5 minutes and 4 hours, and more preferably in a washing machine, wherein either the liquid laundry detergent composition is an inventive liquid laundry detergent composition or the fabric conditioner composition is an inventive fabric conditioner composition and preferably, the liquid laundry detergent composition is an inventive liquid laundry detergent composition and the fabric conditioner composition is an inventive fabric conditioner composition.

[0204] A further subject matter of the invention is the use of the inventive liquid laundry composition for treating fabrics by washing, preferably of the inventive fabric conditioner composition or of the inventive liquid laundry detergent composition for treating fabrics by washing, and more preferably of the inventive fabric conditioner composition for treating fabrics by washing in the last rinse cycle of a wash process in a concentration from 0.5 to 20 g / L in water, preferably from 1 to 15 g / L in water and more preferably from 2 to 10 g / L in water, and / or of the inventive liquid laundry detergent composition for treating fabrics by washing in the main wash cycle of a wash process in a concentration from 0.01 g / L to 50 g / L in water, preferably from 0.05 g / L to 20 g / L in water, more preferably from 0.1 g / L to 15 g / L in water, even more preferably from 0.5 g / L to 10 g / L in water, and particularly preferably from 1 g / L to 8 g / L in water. A preferred embodiment of the invention is the use of the inventive fabric conditioner compositions in the last rinse cycle of a wash process in a concentration from 0.5 to 20 g / L in water, more preferably from 1 to 15 g / L in water and even more preferably from 2 to 10 g / L in water.

[0205] The inventive liquid laundry compositions may advantageously be used for treating fabrics by washing to soften fabrics.

[0206] A further subject matter of the invention is the use of the inventive liquid laundry composition for treating fabrics by washing to soften fabrics and preferably of the inventive fabric conditioner composition or of the inventive liquid laundry detergent composition for treating fabrics by washing to soften fabrics.

[0207] A more preferred embodiment of the invention is the use of the inventive fabric conditioner compositions for treating fabrics by washing to soften fabrics.

[0208] Another more preferred embodiment of the invention is the use of the inventive liquid laundry detergent compositions for treating fabrics by washing to soften fabrics.

[0209] Further preferred embodiments of the invention may arise from the combination of above-described preferred embodiments.

[0210] EXAMPLES

[0211] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto.

[0212] Example 1 : Synthesis of inventive glycerol ester alkoxylates 1-1 , I-2, I-3, I-4, I-5 and I-6 (from high oleic sunflower oil, palm oil and refined rapeseed oil) Preparation of calcium catalyst

[0213] A mixture of 1047.0 g of a carboxylic acid under the trade name “Emulsogen™ COL 050” marketed by Clariant Produkte (Deutschland) GmbH, 55.8 g of calcium hydroxide and 360.6 g of propan-2-ol was agitated at ambient temperature for 5 minutes with a batch disperser (Ultra Turrax from IKA Werke GmbH & Co KG). After this, 44.2 g of concentrated sulfuric acid were added over two minutes and the mixture was again agitated for 5 minutes with the batch disperser, providing a catalyst with a Ca2+content of 2.00 wt.-%.

[0214] General alkoxylation procedure

[0215] The glycerol ester of the corresponding oil and the catalyst were placed into a glass autoclave, which was then flushed with nitrogen by alternatingly applying vacuum and introducing nitrogen (3 cycles). The mixture was dried under aspirator vacuum at 120°C for 15 minutes. The pressure in the autoclave was restored to ambient with nitrogen and heated to 160°C. At this temperature the autoclave was pressurized with nitrogen to a pressure of 1 .0 bar above atmospheric pressure, after which pressure-controlled dosage of alkylene oxide, preferably ethylene oxide, took place up to a maximum pressure of 5.5 bar above atmospheric pressure.

[0216] The alkoxylation is carried out in a semi-batch process with automated dosage of additional alkylene oxide within a given temperature window and up to the specified maximum pressure. The pressure is adjusted according to the increased filling volume of the vessel. After introduction of the intended amount of alkylene oxide and closing the alkylene oxide inlet, the reaction was continued until the pressure became constant.

[0217] The reactor content was cooled to 100°C and aspirator vacuum was applied for 60 minutes to remove residual alkylene oxide. The temperature was reduced to 80°C and the final product was transferred into storage vessels and analyzed. The typical batch scale was 400 g to 2000 g. The uptake of the intended amount of alkylene oxide is assured by gravimetry and by determination of the saponification value according to DIN EN ISO 3681 . The materials employed in example 1 are shown in the following Table 1 (molar equivalents):

[0218] Table 1 Synthesis of inventive glycerol ester alkoxylates 1-1 , I-2, I-3, I-4, I-5, and I-6

[0219] Example 2: Synthesis of comparative alkoxylates C-1 , C-2 (from coconut oil, castor oil)

[0220] The preparation followed the general procedure described in example 1 .

[0221] The materials employed and reaction times to constant pressure in the synthesis in example 2 are shown in the following Table 2 (molar equivalents):

[0222] Table 2 Synthesis of comparative glycerol ester alkoxylates C-1 and C-2

[0223] The acyl groups comprising 16 to 20 carbon atoms in C-1 are less than 30 mol%, based on the total amount of the acyl groups in C-1 .

[0224] The acyl groups comprising 16 to 20 carbons in C-2 contain OH substitution. Example 3: Synthesis of a comparative example - palm oil ethoxylate 100 EO via transesterification C-3

[0225] Ethoxylation of glycerol:

[0226] Glycerol (477 g) and sodium hydroxide (10 g) were placed into a metal autoclave, which was then flushed with nitrogen by alternatingly applying vacuum and introducing nitrogen (3 cycles). The mixture was dried under aspirator vacuum at 140°C for 120 minutes. The pressure in the autoclave was restored to ambient with nitrogen and then pressurized with nitrogen to a pressure of 1 .0 bar above atmospheric pressure, after which pressure-controlled dosage of ethylene oxide (3425 g) took place up to a maximum pressure of 8.5 bar above atmospheric pressure.

[0227] The ethoxylation is carried out in a semi-batch process with automated dosage of additional ethylene oxide within a given temperature window and up to the specified maximum pressure. The pressure is adjusted according to the increased filling volume of the vessel. After introduction of the intended amount of ethylene oxide and closing the ethylene oxide inlet, the reaction was continued until the pressure became constant.

[0228] The reactor content was cooled to 100°C and aspirator vacuum was applied for 120 minutes to remove residual ethylene oxide. The temperature was reduced to 80°C and the ethoxylated glycerol was transferred into storage vessels and analyzed. The uptake of the intended amount of ethylene oxide, on average 100 mol ethylene oxide per 1 mol glycerol, is assured by gravimetry and by determination of the hydroxyl value according to DIN EN ISO 4629-2.

[0229] Transesterification of the ethoxylated glycerol:

[0230] The resulting product from the ethoxylation of glycerol (900 g), Palmere C1618 DPO (C16 / 18 fatty acid methyl ester obtained from transesterification of palm oil with methanol, 288 g) and p-toluene sulfonic acid (4.2 g) were placed into a 2000 mL 4-neck flask, equipped with a heated Vigreux column with water separator.

[0231] The headspace was flushed with nitrogen and a constant light nitrogen stream was applied, which was maintained for the complete reaction. The Vigreux column was heated to 100°C and subsequently, the reaction mixture was stirred at 170°C for 35 hours. The reaction was monitored by collecting and measuring the distilled methanol. After sufficient conversion, the mixture was cooled and transferred into storage vessels for further analysis. The acid number of the final product was determined by titration according to DIN EN ISO 2114 to be below 8 mg KOH / g.

[0232] The glycerol ester alkoxylate C-3 was obtained as a mixture comprising less than 70 mol% tri-esters.

[0233] Example 4: Thickening of liquid laundry detergent composition

[0234] A series of exemplary liquid laundry detergent compositions containing no glycerol ester alkoxylate (reference composition A and G), containing inventive glycerol ester alkoxylates (inventive composition B, C, D, H and I) or containing comparative glycerol ester alkoxylates (comparative composition E, F, J and K) were prepared according to Table 3.

[0235] Key to ingredients used in the compositions of Table 3:

[0236] Fatty Acid is a C12-18 stripped palm kernel fatty acid

[0237] GEA is glycerol ester alkoxylate

[0238] LAS is C12-14 linear alkylbenzene sulfonate, sodium salt

[0239] MEE is a methyl ester ethoxylate with C16 / 18 acyl group and on average 10 EG

[0240] Nl 7EO is C12-15 alcohol ethoxylate 7EO nonionic

[0241] SLES 2EO is sodium lauryl ether sulfate with 2 moles EO Table 3 Liquid laundry detergent compositions for performance testing

[0242] a.m.: active matter; Comp.: Comparative; Inv.: Inventive; Ref.: Reference

[0243] The viscosities of the compositions of Table 3 were determined using a Haake MARS Modular Advanced Rheometer System equipped with a Rotor C60 / 10Ti L and a lower plate TMP60, at a temperature of 25 °C and at a shear rate of 20 s-1for 1 minute. The results are summarized in Table 4.

[0244] Table 4 Viscosity of liquid laundry detergent compositions

[0245] The results in Table 4 show that the inventive alkoxylates had much better thickening effect than the comparative alkoxylates in the liquid laundry detergent compositions. Example 5: Fabric conditioning through the wash

[0246] Treatment of cotton fabric:

[0247] Liquid laundry detergent compositions A (reference) and C (inventive) from Table 3 were diluted in 800 mL tap water in 1 L Tergotometer beakers to prepare 4.3 g / L liquid laundry detergent composition wash liquor. In each wash, 4 pieces of cotton towel swatches (10 x 10 cm) were added. The cotton towel swatches were then washed in the prepared wash liquor using a Tergotometer at 40°C for 30 minutes. The cotton towel swatches were then taken out of the wash liquor and rinsed with tap water three times. Excess water from the swatches was then wringed out. The swatches were then line-dried overnight.

[0248] Panel test to evaluate conditioning effect:

[0249] A group of 18 people was involved in a panel test to compare the softness of swatches washed with (i) the reference composition A and (ii) the inventive composition C. Each person was given two swatches: one was washed with the reference composition A and the other one was washed with the inventive composition C. He / She was then asked to touch and feel both swatches and then to pick the swatch, which felt softer than the other one. The panel test result is shown in Table 5.

[0250] Table 5 Panel test result Example 6: Biodegradability comparison of the inventive glycerol ester alkoxylate I-3 and the comparative glycerol ester alkoxylate C-3

[0251] The inventive glycerol ester alkoxylate I-3 and the comparative glycerol ester alkoxylate C-3 were subjected to a biodegradability test according to the OECD 301 guideline (Test F; see also: https: / / www.oecd-ilibrary.org / environment / test-no- 301 -ready-biodegradability_9789264070349-en). The test was conducted at 21 °C in a BOD Direct Plus System from Hach Lange over a time period of 28 days.

[0252] Surface water was used as the inoculum. The same inoculum was used for both tests and the tests were performed in duplicate. The results of the biodegradability tests are shown in Table 6.

[0253] Table 6 Biodegradability test results

[0254] Example 7: Water absorbency test using a fabric conditioner composition comprising the inventive glycerol ester alkoxylate I-2

[0255] Inventive fabric conditioner composition L was prepared by mixing 5 g of the inventive glycerol ester alkoxylate I-2 with 95 g of water.

[0256] As test fabric, white cotton standard swatches (WFK 10A from WFK Testgewebe GmbH, 8x10 cm) were used. The fabrics were washed at 40°C for 30 minutes using a Tergotometer with 800 g of wash liquor, which contained 4 g / L of a commercial liquid laundry detergent and then rinsed with water for 5 minutes.

[0257] The washed swatches were then divided into two groups. Each group had 4 pieces of washed swatches. One group was then washed at room temperature for 30 minutes using a Tergotometer with 800 g of wash liquor, which contained 3 g / L of a commercial fabric conditioner (Vernel Hautsensitiv from Henkel), which contains esterquat, and then dried overnight. Another group was then washed at room temperature for 30 minutes using a Tergotometer with 800 g of wash liquor, which contained 3 g / L of the inventive fabric conditioner composition L, which did not contain esterquat, and then dried overnight.

[0258] Each piece of cotton swatch was then mounted in an embroidery hoop so that the surface of the swatch was taut and free of wrinkles but without distorting the structure of the swatch. To the center of each mounted swatch, 1 waterdrop of 50 pL was dropped using an Eppendorf pipette and the stopwatch was started immediately. The stopwatch was then stopped as soon as the waterdrop was completely absorbed by the swatch. The time each swatch needed to absorb the waterdrop was then recorded. The average time for the swatches within the same group to absorb the waterdrop was then calculated and listed in Table 7.

[0259] Table 7 Water absorbency of washed swatches

Claims

PATENT CLAIMS1 . A mixture of glycerol ester alkoxylates selected from the substances of the following formula (I)whereinR1, R2and R3are, independent from each other, selected from linear or branched alkylene groups (CmH2m) with m being 2 or 3 or mixtures thereof; x, y and z are, independent from each other, integer numbers from 0 to 300, where at least one of the variables x, y and z is 1 or an integer number greater than 1 , preferably are, independent from each other, integer numbers from 1 to 250, more preferably from 2 to 200, even more preferably from 5 to 150, particularly preferably from 10 to 120, extraordinarily preferably from 15 to 110 and especially preferably from 20 to 100;R4, R5and R6are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 8 to 30 carbon atoms or mixtures thereof, preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 30 carbon atoms or mixtures thereof,more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 24 carbon atoms or mixtures thereof, even more preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 12 to 20 carbon atoms or mixtures thereof, and particularly preferably are, independent from each other, selected from hydrogen, linear or branched, preferably linear, saturated or unsaturated acyl groups comprising from 14 to 20 carbon atoms or mixtures thereof, and wherein in the definitions of R4, R5and R6above, at least one of R4, R5and R6has a meaning different from hydrogen (acyl group); characterized in that x+y+z is, based on a molar average, a number from 50 to 300, preferably from 60 to 300, more preferably from 70 to 280, even more preferably from 85 to 250 and particularly preferably from 90 to 250; at least 70 mol%, preferably at least 75 mol%, more preferably at least 80 mol% and even more preferably at least 85 mol% of the glycerol ester alkoxylates of the formula (I) in the mixture, in each case based on the total amount of the glycerol ester alkoxylates of the formula (I) in the mixture, are glycerol ester alkoxylates of the formula (I), wherein all of the groups R4, R5and R6have a meaning different from hydrogen (acyl groups); and at least 30 mol%, preferably at least 40 mol%, more preferably at least 50 mol%, even more preferably at least 60 mol% and particularly preferably at least 70 mol% of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), are linear or branched, preferably linear, saturated or unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, saturated or unsaturated acyl groupscomprising 16 to 18 carbon atoms or mixtures thereof, in each case based on the total amount of the linear or branched, preferably linear, saturated or unsaturated acyl groups R4, R5and R6.

2. The mixture of glycerol ester alkoxylates according to claim 1 , characterized in that at least 20 mol%, preferably at least 25 mol%, more preferably at least 30 mol%, even more preferably at least 35 mol% and particularly preferably at least 40 mol% of those groups R4, R5and R6, which have a meaning different from hydrogen (acyl groups), are linear or branched, preferably linear, unsaturated acyl groups comprising 16 to 20 carbon atoms or mixtures thereof and preferably are linear or branched, preferably linear, unsaturated acyl groups comprising 16 to 18 carbon atoms or mixtures thereof, in each case based on the total amount of the acyl groups R4, R5and R6.

3. The mixture of glycerol ester alkoxylates according to claim 1 or 2, characterized in that the groups R4, R5and R6are selected from hydrogen, acyl groups derived from palm oil, rape seed oil, refined rape seed oil, sunflower oil, high oleic sunflower oil, or mixtures thereof.

4. A method for preparing a mixture of glycerol ester alkoxylates of the formula (I) as claimed in one or more of claims 1 to 3 from ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide and a mixture of glycerol esters of the formula (II)wherein R4, R5and R6in the mixture of the glycerol esters of the formula (II) have the same meaning as in the mixture of the glycerol ester alkoxylates of the formula (I), characterized in that in the method a catalyst (C) based on an alkaline earth metal is used.

5. Alkoxylation product obtainable by a method according to claim 4.

6. A composition comprising the mixture of glycerol ester alkoxylates as claimed in one or more of claims 1 to 3 or the alkoxylation product as claimed in claim 5, preferably in an amount from 10 to 90 wt.-%, more preferably in an amount from 15 to 85 wt.-% and even more preferably in an amount from 20 to 80 wt.-%, in each case based on the total weight of the composition, and one or more solvents selected from the group consisting of water, ethanol, propanol, isopropanol, butanol, ethylene glycol, 1 ,2-propylene glycol, 1 ,3-propylene glycol,1 ,2-butylene glycol, 1 ,3-butylene glycol, 1 ,4-butylene glycol, butyl glycol, butyl diglycol and butyl polyglycol, preferably in an amount from 10 to 90 wt.-%, more preferably in an amount from 15 to 85 wt.-% and even more preferably in an amount from 20 to 80 wt.-%, in each case based on the total weight of the composition and even more preferably, the composition comprises water and a second solvent different from water and selected from the group above, characterized in that the composition does not contain esterquat.

7. A liquid laundry composition comprisingZ1 ) the mixture of glycerol ester alkoxylates of the formula (I) as claimed in one or more of claims 1 to 3 or the alkoxylation product as claimed in claim 5 andZ2) water, characterized in that the liquid laundry composition does not contain esterquat.

8. The liquid laundry composition according to claim 7, characterized in that it is a fabric conditioner composition and comprises the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1) in an amount from 0.1 to 20 wt.-%, preferably in an amount from 0.5 to 17 wt.-%, more preferably in an amount from 1 to 15 wt.-% and even more preferably in an amount from 3 to 12 wt.-%, in each case based on the total weight of the fabric conditioner composition.

9. The liquid laundry composition according to claim 7, characterized in that it is a liquid laundry detergent composition and comprises a further component Z3) Z3) one or more anionic or nonionic surfactants or mixtures thereof.

10. The liquid laundry detergent composition according to claim 9, characterized in that the one or more anionic or nonionic surfactants of component Z3) are selected from the group consisting of sulfates, sulfonates, soaps, alcohol ethoxylates, glucamides, alkyl polyglycosides and mixtures thereof.11 . The liquid laundry detergent composition according to claim 9 or 10, characterized in that it comprises the mixture of glycerol ester alkoxylates of the formula (I) or the alkoxylation product of component Z1) in an amount from 0.01 to 50 wt.-%, preferably in an amount from 0.1 to 40 wt.-%, more preferably in an amount from 0.2 to 30 wt.-% and even more preferably in an amount from 0.5 to 25 wt.-%, in each case based on the total weight of the liquid laundry detergent composition.

12. The liquid laundry detergent composition according to one or more claims of 9 to 11 , characterized in that it comprises the one or more anionic or nonionic surfactants of component Z3) in an amount from 0.01 to 80 wt.-%, preferably in an amount from 0.1 to 70 wt.-%, more preferably in an amount from 1 to 60 wt.-% and even more preferably in an amount from 5 to 55 wt.-%, in each case based on the total weight of the liquid laundry detergent composition.

13. Use of the mixture of glycerol ester alkoxylates of the formula (I) as claimed in one or more of claims 1 to 3 or of the alkoxylation product as claimed in claim 5 as thickener in a liquid laundry composition as claimed in claim 7, preferably in a fabric conditioner composition comprising water but no esterquat or in a liquid laundry detergent composition comprising water but no esterquat, and more preferably in a fabric conditioner composition as claimed in claim 8 or in a liquid laundry detergent composition as claimed in one or more of claims 9 to 12.

14. Use of the mixture of glycerol ester alkoxylates of the formula (I) as claimed in one or more of claims 1 to 3 or of the alkoxylation product as claimed in claim 5 as softening agent, preferably in a liquid laundry composition, more preferably in a fabric conditioner composition or in a liquid laundry detergent composition, even more preferably in a fabric conditioner composition comprising no esterquat or in a liquid laundry detergent composition comprising no esterquat, and particularly preferably in a fabric conditioner composition as claimed in claim 8 or in a liquid laundry detergent composition as claimed in one or more of claims 9 to 12.

15. Use of the mixture of glycerol ester alkoxylates of the formula (I) as claimed in one or more of claims 1 to 3 or of the alkoxylation product as claimed in claim 5 for treating fabrics by washing to maintain water absorbency of fabrics, preferably in a liquid laundry composition, more preferably in a fabric conditioner composition or in a liquid laundry detergent composition, even more preferably in a fabric conditioner composition comprising no esterquat or in a liquid laundry detergent composition comprising no esterquat, and particularly preferably in a fabric conditioner composition as claimed in claim 8 or in a liquid laundry detergent composition as claimed in one or more of claims 9 to 12.

16. Use of the liquid laundry composition as claimed in one or more of claims 7 to 12 for treating fabrics by washing, preferably of the fabric conditioner composition as claimed in claim 8 or of the liquid laundry detergent composition as claimed in one or more of claims 9 to 12 for treating fabrics by washing, and more preferably of the fabric conditioner composition as claimed in claim 8 for treating fabrics by washing in the last rinse cycle of a wash process in a concentration from0.5 to 20 g / L in water, preferably from 1 to 15 g / L in water and more preferably from 2 to 10 g / L in water, and / or of the liquid laundry detergent composition as claimed in one or more of claims 9 to 12 for treating fabrics by washing in the main wash cycle of a wash process in a concentration from 0.01 g / L to 50 g / L in water, preferably from 0.05 g / L to 20 g / L in water, more preferably from 0.1 g / L to 15 g / L in water, even more preferably from 0.5 g / L to 10 g / L in water, and particularly preferably from 1 g / L to 8 g / L in water.

17. Use of the liquid laundry composition as claimed in one or more of claims 7 to 12 for treating fabrics by washing to soften fabrics and preferably of the fabric conditioner composition as claimed in claim 8 or of the liquid laundry detergent composition as claimed in one or more of claims 9 to 12 for treating fabrics by washing to soften fabrics.

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