Polyester compounds and their uses

Abstract

A polyester comprising at least one diacid-based constitutional unit, at least one diol-based constitutional unit, and at least one polyol-based constitutional unit, wherein the diacid-based constitutional unit comprises a group of formula (I): [Case 1] TIFF2024524628000011.tif39170, R 1 is of the general formula CH 2 -CH 2 -O(AO) x -H, x is a number from 0 to 75, AO is an alkylene oxide selected from ethylene oxide and combinations of ethylene oxide with at least one of propylene oxide and butylene oxide, the polyol building blocks are derived from a compound having at least three alcoholic hydroxyl groups, the asterisk indicates attachment to the diol or polyol building blocks through an ester oxygen atom, and the molar ratio of the diacid based building blocks to the sum of the diol and polyol building blocks is in the range of 2:1 to 1:2.

Description

[Technical field]

[0001] The present invention relates to a polyester comprising at least one diacid-based constitutional unit, at least one diol-based constitutional unit, and at least one polyol-based constitutional unit, wherein the diacid-based constitutional unit comprises a group of formula (I): [ka] In the formula, R 1 is the general formula CH2-CH2-O(AO) x -X 1 where x is a number from 0 to 75, and X 1 is methyl or hydrogen, AO is an alkylene oxide selected from ethylene oxide and combinations of ethylene oxide with at least one of propylene oxide and butylene oxide; the polyol building blocks are derived from a compound having y hydroxyl groups per molecule, where y is at least 3; The asterisk indicates attachment to the diol or polyol building block through the ester oxygen atom; The molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) ranges from 2:1 to 1:2. [Background technology]

[0002] Polyaspartates are polymers that contain mono-N-substituted aspartic acid units in their structure. Despite the name, such polymers are synthesized not from aspartic acid but from unsaturated polyesters (UPEs) and primary amines by aza-Michael addition. The product of this reaction contains a polyester backbone with side chains linked to the backbone through secondary amine groups.

[0003] U.S. Patent Application Publication No. 2005 / 0059791 A1, for example, describes flexible polyaspartic esters formed by reacting diethyl maleate with 1,4-butanediol, followed by addition of a polyamine such as 1,6-hexanediamine.

[0004] In laundry formulations, it is a common problem to disperse solid inorganic particles such as clay. Inorganic particles can be derived from soils such as clay, silica and oxide ions. During the washing process, they are removed from the laundry, dispersed in the washing liquor and removed together with the washing liquor. Several structures such as alkoxylated polytriethanolamine have been proposed, see for example WO2009 / 060409. However, the compounds proposed are generally not biodegradable.

[0005] Detergent formulators are continually challenged to develop improved products for removing various soils and stains from fabrics and hard surfaces. Removal of particulate stains has been a particularly difficult problem. This challenge has been highlighted by the recent high interest and drive to incorporate sustainable, bio-based and / or biodegradable components into laundry detergents and manual dishwashing. This has resulted in an increased market demand for detergent ingredients with satisfactory performance profiles combined with significantly improved biodegradability. Summary of the Invention [Problem to be solved by the invention]

[0006] It was therefore an object of the present invention to provide an additive for laundry formulations which exhibits good properties in laundry applications, for example with regard to cleaning properties, in particular with regard to the dispersion of inorganic particles, and which is biodegradable. Furthermore, it was an object of the present invention to provide a process for producing such an additive, and the object was to provide a laundry formulation with good solid inorganic particle dispersion properties, without the need to use non-biodegradable additives. [Means for solving the problem]

[0007] Thus, polyesters as defined at the outset have been found, hereinafter also referred to as inventive polyesters, which are described in more detail below.

[0008] The polyester of the present invention comprises at least one diacid-based constitutional unit, at least one diol-based constitutional unit, and at least one polyol-based constitutional unit, the diacid-based constitutional unit being represented by the formula (I): [ka] The group includes:

[0009] In formula (I), the asterisk indicates attachment to the diol or polyol building block through the ester oxygen atom.

[0010] Preferably, the polyester of the present invention contains two or more, for example from 2 to 20, preferably from 3 to 10, constitutional units according to formula (I) per molecule.

[0011] It is understood that the polyester of the present invention is not usually one pure compound, but a mixture of various compounds containing the same constitutional units but arranged differently, and has a molecular weight distribution as seen below.

[0012] R 1 is represented by the general formula CH2-CH2-O(AO) x -X 1 where x is a number from 0 to 75, preferably 0 or 12 to 30. 1 may be methyl; X 1 is preferably hydrogen.

[0013] AO is an alkylene oxide selected from ethylene oxide (CH2CH2-O, hereinafter also referred to as EO), and a combination of ethylene oxide with at least one of propylene oxide (CH2CH(CH3)-O, hereinafter also referred to as PO) and butylene oxide (CH2CH(C2H5)-O, hereinafter also referred to as BuO). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] In one embodiment of the present invention, x is 0 or in the range of 1 to 30, and R 1 In the formula (I), the majority of AO is ethylene oxide, and more preferably, x is in the range of 12 to 30, and the majority of all AO is EO. For example, R 1 is the formula (EO) x1 (PO) x2 -H may be present, where x1 is in the range of 8 to 20 and x2 is in the range of 1 to 5.

[0015] In certain embodiments, x ranges from 12 to 25 and all AO are EO.

[0016] In particular, in embodiments where x is greater than 2, for example 2 to 75, the value of x represents an average, meaning the average of numbers.

[0017] The diol building blocks may be based on an aliphatic or cycloaliphatic diol, e.g. a C2-C8 alkanediol or a C4-C7 cycloalkanediol, preferably a C2-C8 alkanediol, unsubstituted or substituted with one or more methyl or ethyl groups. The diol building blocks may be derived from one or at least two different aliphatic or cycloaliphatic diols, preferably one. "Based on" in this context means that the majority of the hydroxyl groups are included in the polyester of the invention in esterified form.

[0018] Examples of C2-C8 alkanediols are ethylene glycol, propane-1,2-diol, propane-1,3-diol, 2,2-dimethyl-propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1,4-diol, butane-2,3-diol, pentane-1,2-diol, pentane-1,3-diol, pentane-1,4-diol, pentane-1,5-diol, pentane-2,3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane- 1,6-diol, hexane-2,5-diol, heptane-1,2-diol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-decanediol, 1,12-dodecanediol, 1,2-dodecanediol, 1,5-hexadiene-3,4-diol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and pinacol. Preferred examples are ethylene glycol, triethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 2,5-dimethyl-2,5-hexanediol and 2-ethyl-1,3-hexanediol.

[0019] Examples of C4-C7 cycloalkanediols are 1,2-cyclopentanediol, 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cycloheptanediol, which are usually present as mixtures of isomers.

[0020] In another embodiment of the present invention, the diol building block is diethylene glycol, triethylene glycol, tetraethylene glycol, or an alkylene glycol having an average molecular weight M of, for example, 200 to 500 g / mol. nIn another embodiment of the invention, the diol building block is based on a polyethylene glycol having an average molecular weight M of, for example, 280 to 750 g / mol. n The polypropylene glycol is based on

[0021] The polyol building blocks are derived from compounds having at least three hydroxyl groups per molecule, for example three ("triol", y=3) or four ("tetrol", y=4) or six ("hexol", y=6), with triols being preferred. In the context of the present invention, the term "hydroxyl group" refers to a primary or secondary alcohol group. Examples of triol building blocks are glycerol, butane-1,2,3-triol, butane-1,2,4-triol, pentane-1,2,3-triol, pentane-1,2,4-triol, pentane-1,2,5-triol, hexane-1,2,3-triol, hexane-1,2,4-triol, hexane-1,2,5-triol, hexane-1,2,6-triol, hexane-1,3,4-triol, hexane-1,3,5-triol, hexane-1,3,6-triol, hexane-1,4,5-triol, tetrahydrofuran-2,3,4-triol, tetrahydrofuran-2,3,5-triol, 2-(hydroxymethyl)tetrahydrofuran-3,4-diol, 5-(hydroxymethyl)tetrahydrofuran-2,4-diol, (3-hydroxytetrahydrofuran-2,5-diol), The hydroxytetrahydrofuran-2-yl)dimethanol, 1-(3-hydroxytetrahydrofuran-2-yl)ethane-1,2-diol, 1-(4-hydroxytetrahydrofuran-2-yl)ethane-1,2-diol, 2-(2-hydroxyethyl)tetrahydrofuran-3,4-diol, 2-(1-hydroxyethyl)tetrahydrofuran-3,4-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,3-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,4-diol, 6-(hydroxymethyl)tetrahydro-2H-pyran-2,5-diol, 1,trimethylolmethane, 1,1,1-trimethylolethane and 1,1,1-trimethylolpropane, as well as ethoxylated, propoxylated and / or butoxylated derivatives thereof and mixtures of at least two of the aforementioned.Preferred examples of triol building blocks are based on glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane ("TMP"), 1,1,1-trimethylolethane, trimethylolmethane, and mixtures of at least two of the foregoing. "Based on" and "derived from" in this context mean that the majority of the hydroxyl groups are included in the polyester of the invention in esterified form.

[0022] Further examples of triol building blocks are those derived from any of the ethoxylates and propoxylates described above, such as the ethoxylates and propoxylates of glycerol or TMP, in such embodiments, the molar ratio of ethoxylate or propoxylate per mole of glycerol or TMP, respectively, ranges from 1:1 to 50:1.

[0023] Examples of tetrol building blocks are those derived from pentaerythritol, diglycerol, trimethylolpropane dimer, erythritol, or ethoxylate, propoxylate or mixed ethoxylate / propoxylate oligomers and polymers based on the above-mentioned tetrols as starting components. More preferably, the tetrol building blocks are derived from pentaerythritol and diglycerol.

[0024] An example of a hexol building block is one derived from sorbitan.

[0025] In the polyesters of the invention, the molar ratio of diacid-based building blocks to the sum of diol and polyol building blocks (the latter multiplied by 2 / y) is in the range of from 2:1 to 1:2, preferably from 3:2 to 2:3, more preferably from 1.2:1 to 1:1.2, even more preferably from 1.1:1 to 1:1.1 and in particular 1:1.

[0026] Thus, (moles of diacid-based building blocks) / [(moles of diol-based building blocks)+2 / y(moles of polyol-based building blocks) is in the range of 2:1 to 1:2, preferably 3:2 to 2:3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, especially 1:1.

[0027] In one embodiment of the present invention, the molar ratio of the diol constituent units to the polyol constituent units multiplied by 2 / y is in the range of 1:1 to 4:1.

[0028] In a preferred embodiment of the present invention, all of the polyol constituent units are triol constituent units, and the molar ratio of the diol constituent units to the polyol constituent units multiplied by 2 / 3 is in the range of 2:1 to 1:1.5, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, and particularly 1:1.

[0029] In one embodiment of the present invention, the average molecular weight M of the polyester of the present invention is n The average molecular weight M is in the range of 3,000 to 10,000 g / mol. n can be measured by gel permeation chromatography ("GPC"). Suitable mobile phases are hexafluoroisopropanol ("HFIP"), dimethylacetamide ("DMAc"), tetrahydrofuran ("THF") and water.

[0030] In one embodiment of the present invention, the average molecular weight M of the polyester of the present invention is w The average molecular weight M is in the range of 5,000 to 30,000 g / mol. w can be measured by GPC. Suitable mobile phases are HFIP, DMAc, THF and water.

[0031] In one embodiment of the present invention, the polydispersity M of the polyester of the present invention w / M n is 1:10, and preferably in the range of 1.5 to 5.

[0032] In one embodiment of the present invention, the unsaturated polyester after step (a) has a hydroxyl number in the range of 20 to 150 mg KOH / g according to DIN 53240 (2016).

[0033] In one embodiment of the invention, the polyesters of the invention have a total amino number in the range of 30 to 50 mg KOH / g according to ASTM D2074-07.

[0034] In one embodiment of the present invention, the glass transition temperature of the polyester of the present invention ranges from −5° C. to 41° C., as measured by differential scanning calorimetry (DSC).

[0035] In one embodiment of the present invention, the polyesters of the present invention have some carbon-carbon double bonds. Such carbon-carbon double bonds preferably have the (E)-configuration (or trans-, etc.). They are 1 It can be determined by H-NMR spectroscopy. In one embodiment of the invention, the molar percentage of carbon-carbon double bonds corresponds to a range of 5-10 ester building blocks.

[0036] In one embodiment of the present invention, the polyester of the present invention may comprise additional building blocks based on alkanedicarboxylic acids, such as, for example, adipic acid, succinic acid, or glutaric acid, for example in a molar ratio of diacid-based building blocks according to formula (I) to alkanedicarboxylic acid-based building blocks in the range of 10:1 to 2:1. In terms of the molar ratio of diol building blocks to polyol building blocks, such alkanedicarboxylic acid-based building blocks are then replaced by diacid-based building blocks according to formula (I). However, in a preferred embodiment, the polyester of the present invention does not comprise such additional building blocks.

[0037] Preferably, the polyester of the present invention does not contain any constitutional units derived from monoalkanols and monocarboxylic acids.

[0038] It has been found that the above-mentioned good properties can be obtained by using a mixture of diols and polyols in a specific range, i.e., in a molar ratio of 2:1 to 1:2, based on hydroxyl groups, to adjust the branching degree of the polyester of the present invention. It has been found that the solution viscosity of the polyester of the present invention is extremely low. In addition, the polyester of the present invention is biodegradable.

[0039] Thus, another aspect of the present invention is (a) reacting an activated α,β-ethylenically unsaturated dicarboxylic acid with a mixture of at least one diol and at least one polyol, wherein the activated unsaturated dicarboxylic acid is selected from the group consisting of activated maleic acid, activated itaconic acid, and activated fumaric acid, and the molar ratio of the carboxyl groups of the activated α,β-ethylenically unsaturated dicarboxylic acid to the sum of the hydroxyl groups of the diol and polyol is in the range of 2:1 to 1:2; (b) The product obtained in step (a) is treated with R 1 2 is a process for producing a polyester of the present invention, comprising the step of reacting with —NH2.

[0040] Said process is also referred to below as the inventive process, and its steps are also referred to as step (a) or step (b), respectively. The activated α,β-ethylenically unsaturated dicarboxylic acid and the diol and polyol are both also referred to as starting materials. The inventive process is described in more detail below.

[0041] In step a), an activated α,β-ethylenically unsaturated dicarboxylic acid is reacted with a mixture of at least one diol and at least one polyol.

[0042] Examples of α,β-ethylenically unsaturated dicarboxylic acids are maleic acid, itaconic acid, fumaric acid, with maleic acid being preferred. Since carrying out step (a) with the acid itself requires drastic reaction conditions, step a) is carried out with so-called activated α,β-ethylenically unsaturated dicarboxylic acids. Activation can be carried out by using dichlorides of α,β-ethylenically unsaturated dicarboxylic acids, C1-C4 alkyl diesters of α,β-ethylenically unsaturated dicarboxylic acids, or anhydrides in the case of maleic acid, respectively. Particularly preferred examples are the dimethyl ester of maleic acid, the diethyl ester of maleic acid, and maleic anhydride.

[0043] Examples of suitable diols and polyols are disclosed above. Preferred examples are ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and ethylene glycols having an average molecular weight M of, for example, 200 to 500 g / mol. n In another embodiment of the invention, the diol is dipropylene glycol, tripropylene glycol, tetrapropylene glycol, or polyethylene glycol having an average molecular weight M of, for example, 280 to 750 g / mol. n The polypropylene glycol is selected from those having the formula:

[0044] Examples of polyols are selected from compounds having at least three hydroxyl groups per molecule, for example three ("triols", y=3) or four ("tetrols", y=4) or six ("hexols", y=6), with triols being preferred. Examples of preferred triols are glycerol, butane-1,2,4-triol, n-pentane-1,2,5-triol, n-pentane-1,3,5-triol, n-hexane-1,2,6-triol, n-hexane-1,2,5-triol, n-hexane-1,3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane ("TMP"), 1,1,1-trimethylolethane, trimethylolmethane, and mixtures of at least two of the above in the present context.

[0045] Further examples of triols are the ethoxylates and propoxylates of any of the foregoing, such as ethoxylates of glycerol or TMP, in such embodiments, the molar ratio of ethoxylate or propoxylate per mole of glycerol or TMP, respectively, ranges from 1:1 to 50:1.

[0046] Examples of tetrols are pentaerythritol, diglycerol, trimethylolpropane dimer, erythritol or ethoxylate, propoxylate or mixed ethoxylate / propoxylate oligomers and polymers based on the abovementioned tetrols as starting components. More preferably, the tetrols are selected from pentaerythritol and diglycerol.

[0047] An example of a hexol is sorbitan.

[0048] In step (a), the molar ratio of the carboxyl groups of the activated α,β-ethylenically unsaturated dicarboxylic acid to the sum of the hydroxyl groups of the diol and polyol is in the range of 2:1 to 1:2, preferably 3:2 to 2:3, more preferably 1.2:1 to 1:1.2, even more preferably 1.1:1 to 1:1.1, in particular 1:1.

[0049] In one embodiment of step (a), an activated alkanedicarboxylic acid such as an activated adipic acid, an activated succinic acid, or an activated glutaric acid is added, for example, in a molar ratio of activated α,β-ethylenically unsaturated dicarboxylic acid to activated alkanedicarboxylic acid in the range of 10:1 to 2:1. The addition of the activated alkanedicarboxylic acid does not change the overall molar ratio of activated carboxyl groups to activated hydroxyl groups. The activation of the carboxyl groups of the alkanedicarboxylic acid can be carried out in the same manner as in the α,β-ethylenically unsaturated dicarboxylic acid, particularly the C1-C4 alkyl esters, and in the case of succinic acid, the anhydride.

[0050] Step (a) may be carried out in bulk or in the presence of a solvent. Examples of suitable solvents include hydrocarbons such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene isomer mixtures, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Examples of suitable solvents in the absence of an acid catalyst include ethers such as dioxane or tetrahydrofuran, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.

[0051] The amount of solvent may be at least 0.1% by weight, preferably at least 1% by weight, more preferably at least 10% by weight, based on the mass of the starting materials to be reacted. It is also possible to use an excess amount of solvent, for example 1.01 to 10 times, based on the mass of the starting materials to be reacted used. An amount of solvent exceeding 100 times the mass of the starting materials is not advantageous because if the concentration of the reactants is too low, the reaction rate drops significantly, resulting in uneconomically long reaction times.

[0052] Step (a) may be carried out in the presence of a moisture removal additive, which is added at the beginning of step (a). Suitable examples include molecular sieves, in particular molecular sieves 4Å, MgSO4 and Na2SO4. It is also possible to add additional moisture removal additive during the reaction or to replace the moisture removal additive with fresh moisture removal additive. It is also possible to distill off the water or alcohol produced during the reaction and to use, for example, a Dean-Stark apparatus.

[0053] Step (a) may be carried out in the absence of an acid catalyst. It is preferable to operate in the presence of an acidic inorganic, organometallic or inorganic catalyst, or a mixture of two or more acidic catalysts.

[0054] Examples of the acidic inorganic catalyst in step (a) include sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid H3PO2, aluminum sulfate hydrate, alum, acidic silica gel (pH=6, particularly=5) and acidic alumina. Examples of the acidic inorganic catalyst include, for example, compounds represented by the general formula Al(OR 2 )3 and aluminum compounds of the general formula Ti(OR 2 Titanates of the group R 2 are the same or different, and each independently represents C1 to C 10 Alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, 1,2-dimethylpropyl, isoamyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl, C3 to C6 12 Cycloalkyl is, for example, selected from cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl, with cyclopentyl, cyclohexyl and cycloheptyl being preferred.

[0055] Preferably, Al(OR 1 )3 and Ti(OR 1 ) Group R in 4 1 are each the same and are selected from isopropyl or 2-ethylhexyl.

[0056] Preferred acidic organometallic catalysts are, for example, dialkyltin oxides R 1 2SnO, R 1 is as defined above. A particularly preferred example of an acidic organometallic catalyst is di-n-butyltin oxide, which is commercially available in the form of oxotin. Further examples of organometallic catalysts are selected from dialkyltin dicarboxylates, such as dibutyltin dilaurate.

[0057] Preferred acidic organic catalysts are, for example, acidic organic compounds containing phosphoric acid groups, sulfonic acid groups, sulfuric acid groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as paratoluenesulfonic acid. Acidic ion exchangers can also be used as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups and crosslinked with about 2 mol % divinylbenzene.

[0058] It is also possible to use a combination of two or more of the abovementioned catalysts. Another possibility is to use those organic or organometallic or inorganic catalysts that are in the form of discrete molecules in immobilized form.

[0059] When it is desired to use an acidic inorganic, organometallic or organic catalyst, the amount of catalyst used in accordance with the present invention is from 0.1 to 10% by weight, preferably from 0.2 to 2% by weight.

[0060] Step (a) is preferably carried out under an inert gas atmosphere, such as carbon dioxide, nitrogen or a noble gas, among which mention may be made especially of argon.

[0061] In one embodiment of the present invention, step (a) is carried out at a temperature between 80° C. and 200° C. It is preferred to operate at temperatures between 130° C. and 180° C., in particular between 140° C. and 170° C. or less. Maximum temperatures of up to 165° C., very preferably up to 160° C., are particularly preferred.

[0062] The pressure conditions of step (a) are not critical. It is possible to operate under a significant reduced pressure, for example from 10 to 500 mbar. Step (a) of the present invention can also be carried out at pressures above 500 mbar. For reasons of simplicity, it is preferred to carry out step (a) at atmospheric pressure, but it is also possible to carry it out at slightly higher pressures, for example up to 1200 mbar. A further option is working under greatly increased pressure, for example up to 10 bar. It is preferred to carry out step (a) at atmospheric pressure.

[0063] In one embodiment of the present invention, the duration of step (a) is from 10 minutes to 48 hours, preferably from 30 minutes to 24 hours, more preferably from 1 hour to 20 hours.

[0064] An unsaturated polyester is obtained from step (a). The term "unsaturated" refers to the presence of carbon-carbon double bonds in the polyester obtained in step (a). It is observed that a portion of the C-C double bonds, for example 5-20% of the double bonds, are isomerized during step (a).

[0065] After step (a), the obtained unsaturated polyester can be easily isolated, for example by removing the catalyst by filtration, and concentrating the filtrate, usually under reduced pressure. Further suitable work-up methods include precipitation after adding water, followed by washing and drying. In other embodiments, the obtained unsaturated polyester is used without further purification.

[0066] In one embodiment of the present invention, the unsaturated polyester obtained from step (a) has an average molecular weight M of 500 to 10,000 g / mol, preferably 600 to 5,000 g / mol, more preferably 700 to 2,500, even more preferably 750 to 2,000 g / mol. n (Gel Permeation Chromatography GPC in DMAc). These are usually readily soluble in polar solvents, i.e., clear solutions can be prepared with up to 50% by weight, and in some cases up to 80% by weight, of the polyesters of the invention, without gel particles detectable by the naked eye. Examples of polar solvents are tetrahydrofuran (THF), ethanol, diethylene glycol, and propylene glycol.

[0067] In one embodiment of the present invention, the unsaturated polyester from step (a) has a hydroxyl number in the range of 20 to 150 mg KOH / g according to DIN 53240 (2016).

[0068] In step (b), the unsaturated polyester obtained from step (a) is reacted with an amine, H2N-R 1 (R1 is as defined above).

[0069] In one embodiment of the present invention, the unsaturated polyester obtained from step (a) and the amine H2N-R 1 is the amount of the unsaturated polyester obtained from step (a) and the amine H2N-R 1 In another embodiment, the molar ratio of the carbon-carbon double bonds of the unsaturated polyester and the amine H2N-R 1 is the amount of the unsaturated polyester obtained from step (a) and the amine H2N-R 1 The molar ratio of the carbon-carbon double bonds of the (Z)-configuration is calculated to be in the range of 1.3:1 to 1:1.3, preferably 1.1:1 to 1:1.1.

[0070] Step (b) can be carried out in bulk or in a polar solvent capable of dissolving the unsaturated ester obtained from step (a). Bulk synthesis is preferred.

[0071] In one embodiment of the present invention, step (b) is carried out at a temperature in the range of 20-80°C, preferably 40-70°C.

[0072] The pressure conditions of step (b) are not critical. It is possible to operate under a significant reduced pressure, for example from 10 to 500 mbar. Step (b) of the present invention can also be carried out at pressures above 500 mbar. For reasons of simplicity, it is preferred to carry out step (b) at atmospheric pressure, but it is also possible to carry it out at slightly higher pressures, for example up to 1200 mbar. A further option is working under greatly increased pressure, for example up to 10 bar. It is preferred to carry out step (b) at atmospheric pressure.

[0073] In one embodiment of the present invention, the duration of step (b) is from 10 minutes to 48 hours, preferably from 1 hour to 30 hours.

[0074] After carrying out step (b), the polyester of the present invention is obtained, for example, as a waxy solid. In many embodiments, the polyester of the present invention contains some unreacted amine H2N-R 1 However, the unreacted amine is not critical to the use of the polyesters of the present invention in cleaning compositions.

[0075] In an exemplary step (a) of the process of the present invention, activated maleic acid and a diol (HO-A 2 -OH) and triol (A 3 (OH)3) leads to a branched unsaturated polyester (a few maleic acid units are converted to the trans configuration): [ka]

[0076] In an exemplary process (b), the branched unsaturated polyester from process (a) is reacted with a primary monoamine R via aza-Michael addition. 1 -NH2 modified: [ka]

[0077] Another aspect of the present invention relates to the use of the polyesters of the present invention in cleaning compositions, particularly laundry detergent compositions. Such compositions may also be referred to as laundry detergent compositions of the present invention, or simply as compositions of the present invention. The laundry detergent compositions of the present invention may be in solid or liquid or gel form at ambient temperature, with liquid or gel form being preferred.

[0078] The polyesters of the present invention can be added in cosmetic formulations, as crude oil demulsifiers, in pigment dispersions for inkjet inks, in electroplating formulations, in cement compositions. Preferably, the polyesters of the present invention can be added (used) in washing or cleaning compositions.

[0079] Another subject of the present invention is therefore a cleaning composition, in particular for fabrics, comprising at least one polyester of the present invention, preferably a cleaning composition, and / or a fabric care and home care product comprising at least one polyester of the present invention, in particular a cleaning composition for the removal, dispersion and / or emulsification of soils and / or modification of treated surfaces and / or maintenance of the whiteness of treated surfaces, preferably at least two of these, more preferably at least three of these, even more preferably four or more of these benefits.

[0080] Selected advantages of the cleaning compositions of the present invention are as follows: i) Good clay removal; ii) Good particulate stain removal; iii) good dirt dispersion and / or emulsification; iv) modification of the treated surface to improve removal upon subsequent recontamination; v) Improved whiteness; vi) at least one enzyme selected from lipases, hydrolases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the above mentioned types, for improved removal of additional oily / greasy stains, food stains and / or combination stains; and / or vii) For further oily / greasy stain removal, food stain removal, and / or combination stains in the presence of at least one enzyme according to vii).

[0081] In one embodiment of the present invention, the composition of the present invention contains the polyester of the present invention in a concentration of 0.05 to 20% by weight, preferably 0.1 to 15% by weight, more preferably 0.5 to 5% by weight.

[0082] In one embodiment of the invention, the polyesters of the invention are added to a composition comprising from about 1% to about 70% by weight of a surfactant combination. In such an embodiment, the polyesters of the invention may be present at a concentration of from about 0.1% to about 5% by weight of the composition, or from about 0.5% to about 2% by weight of each of the compositions of the invention.

[0083] Preferably, the compositions of the present invention are laundry detergents, cleaning compositions and / or fabric care and home care products, preferably laundry detergent compositions. Such compositions of the present invention provide improved removal, dispersion and / or emulsification of soils, and / or modification of treated surfaces and / or maintenance of whiteness of treated surfaces.

[0084] In one embodiment of the invention, the compositions of the invention have a dynamic viscosity in the range of 20 to 20,000 mPa·s, measured at 25° C. by Brookfield, for example by Brookfield viscometer LVT-II, spindle 3 at 20 rpm.

[0085] In one embodiment of the present invention, the composition of the present invention has a water content ranging from 50 to 98% by weight, preferably up to 95% by weight.

[0086] The compositions of the present invention are preferably phosphate-free or, in other words, do not contain phosphate. "Phosphate-free" should be understood in the context of the present invention to mean that the phosphate and polyphosphate content is in the range of 10 ppm to 1% by weight, preferably 10 ppm to 0.2% by weight or less in total, based on the total non-volatile content, measured gravimetrically.

[0087] In one embodiment of the present invention, the compositions of the present invention may have a non-volatile content ranging from 10 to 30% by weight, preferably from 15 to 30% by weight, as measured by evaporation to a constant residue at 105° C. under reduced pressure ("vacuum"), but for at least 2 hours.

[0088] In one embodiment of the invention, the compositions of the invention may contain a solvent other than water, such as ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, glycerol, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, and phenoxyethanol, with ethanol, isopropanol or propylene glycol being preferred.

[0089] In one embodiment of the present invention, the compositions of the present invention comprise 0.5-12% by weight of the organic solvent based on the total weight of each composition. In an embodiment in which the compositions of the present invention are provided as a unit dose, for example in the form of a pouch, the content of the organic solvent may range from 8-25% by weight based on the total weight of each composition.

[0090] In one embodiment of the present invention, the composition of the present invention has a pH value in the range of 7-11, preferably 7.5-9.5, more preferably 8-9.

[0091] The compositions of the present invention may contain one or more surfactants selected from nonionic, anionic, cationic and zwitterionic surfactants, with nonionic and anionic surfactants being preferred.

[0092] In one embodiment of the present invention, the laundry detergent composition of the present invention further comprises at least one anionic surfactant selected from linear alkylbenzene sulfonates and alkoxylated sulfonated fatty alcohols.

[0093] In one embodiment, the polyesters of the present invention comprise C as the primary surfactant. 10 ~C 15It may be used in cleaning compositions that include a surfactant system that includes an alkylbenzene sulfonate (LAS) and one or more additional surfactants selected from nonionic, cationic, anionic surfactants other than LAS, and mixtures thereof.

[0094] Preferred examples of alkoxylated sulfonated fatty alcohols have the general formula (II): C n H 2n+1 -O(CH2CH2O) a -SO3M (II) is a compound according to Hereinafter, this is also referred to as surfactant (1) or anionic surfactant (1), The variables are defined as follows: n is a number ranging from 10 to 18, preferably 12 to 14, even more preferably n=12; a is a number ranging from 1 to 5, preferably 2 to 4, and even more preferably 3. M is selected from an alkali metal, preferably potassium, even more preferably sodium, or ethanolammonium.

[0095] In a compound according to formula (II), the variables n and a may be average numbers and therefore they are not necessarily integers, but in an individual molecule according to formula (II), both n and a denote integers.

[0096] In one embodiment of the invention, the composition of the invention contains an additional anionic surfactant, hereinafter also referred to as linear alkylbenzene sulfonate.

[0097] In one embodiment of the present invention, the composition of the present invention contains, as an anionic surfactant, nC 10 ~C 18Alkali metal or amine salts of alkylbenzenesulfonic acids, especially sodium n-dodecylbenzenesulfonate or ethanolammonium n-dodecylbenzenesulfonate, including mixtures derived from the sodium salts of linear 4-dodecylbenzenesulfonic acid and linear 5-dodecylbenzenesulfonic acid, etc. The amount of sodium n-dodecylbenzenesulfonate or ethanolammonium n-dodecylbenzenesulfonate may range from 10 to 40% by weight based on the total non-volatile content of the liquid detergent composition.

[0098] The ethanol ammonium may be selected from monoethanol ammonium, N,N-diethanol ammonium and N,N,N-triethanol ammonium, with monoethanol ammonium being preferred.

[0099] Further examples of anionic surfactants include C8-C 12 Alkyl sulfate, C 12 ~C 18 Fatty Alcohol Ether Sulfates, Ethoxylated C4-C 12 Sulfuric acid half esters of alkylphenols (ethoxylated: 3-50 mol ethylene oxide / mol), C 12 ~C 18 Alkyl sulfonic acid, C 12 ~C 18 Sulfofatty acid alkyl esters, e.g., C 12 ~C 18 Sulfo fatty acid methyl esters, C 10 ~C 18 Alkylarylsulfonic acid, preferably nC 10 ~C 18 Alkylbenzene sulfonic acid, C 10 ~C 18 Alkyl alkoxy carboxylates, and for example C8-C 24 Alkali metal and ammonium salts of soaps such as carboxylic acids. The alkali metal salts of the above mentioned compounds are preferred, with the sodium salts being particularly preferred.

[0100] In one embodiment of the invention, the composition according to the invention contains at least one non-ionic surfactant, such as a polyglycoside, an alkoxylated fatty amine or an alkoxylated fatty alcohol, and more preferably at least one compound according to formula (III), (IV) or (V).

[0101] In one embodiment of the present invention, the polyglycoside has the formula (III) (G) u -OR 3 (III) and R 3 is a linear or branched chain, preferably linear C8-C 18 alkyl, u is in the range of 1.1 to 4; G is selected from monosaccharides having 4 to 6 carbon atoms, preferably glucose and xylose.

[0102] Even more preferred polyglycosides are linear C4-C 16 alkyl polyglycosides, such as compounds of the general average formula (III.1) 14 Alkyl polyglycosides are likewise suitable. [ka] During the ceremony, R 4 is C1-C4 alkyl, in particular ethyl, n-propyl or isopropyl; R 5 is -(CH2)2-R 4 and G 1 is selected from monosaccharides having 4 to 6 carbon atoms, in particular glucose and xylose, u is in the range of 1.1 to 4 and is an average number.

[0103] In one embodiment of the present invention, the alkoxylated fatty amine has the general formula (IV): C m H 2m+1 -N[(AO) rH]2(IV) and m is a number ranging from 10 to 18, r is different or the same and ranges from 1 to 12; AO are different or the same and are selected from ethylene oxide, or a combination of ethylene oxide with at least one of propylene oxide and butylene oxide.

[0104] In one embodiment of the present invention, the polyalkoxylated fatty alcohol has the general formula (V): C m H 2m+1 -O[(AO) r H] (V) and The variables are defined as follows: M is selected from alkali metals, preferably potassium, even more preferably sodium; AO are different or identical and are selected from ethylene oxide, propylene oxide and butylene oxide, and combinations of at least two of the foregoing, and are in particular ethylene oxide CH2CH2O; r is different or the same and is selected from the numbers ranging from 1 to 12, preferably from 5 to 10.

[0105] In the above surfactants, the variables m and y may be average numbers, so that they are not necessarily integers, but in individual molecules according to formula (II), both m and y denote integers.

[0106] In one embodiment of the present invention, the composition of the present invention contains at least one sequestering agent.Phosphate-free sequestering agents are preferred.Examples are citric acid and aminopolycarboxylic acids and their corresponding alkali metal salts, especially sodium salts.Preferred aminocarboxylic acids are methylglycine diacetate (MGDA) and glutamic acid diacetate (GLDA).

[0107] MGDA and its corresponding salts can be selected from racemic mixtures, D- and L-isomers, and non-racemic mixtures of D- and L-isomers. Preferably, MGDA and its corresponding salts are selected from racemic mixtures and mixtures containing 55-85 mol% of L-isomer with the remainder being D-isomer. Particularly preferred are mixtures containing 60-80 mol% of L-isomer with the remainder being D-isomer.

[0108] The distribution of L- and D-enantiomers can be measured by measuring the optical rotation (polarimetry) or, preferably, by chromatography, e.g., HPLC using a chiral column, e.g., HPLC using one or more cyclodextrins as stationary phase. Preferably, the ee is measured by HPLC with immobilized optically active ammonium salts, such as D-penicillamine.

[0109] GLDA and its corresponding salts can be selected from racemic mixtures, D- and L-isomers, and non-racemic mixtures of D- and L-isomers. Preferably, GLDA and its corresponding salts are selected from mixtures containing 75-99 mol% of the L-isomer, the remainder being the D-isomer. Particularly preferred are mixtures containing 80-97.5 mol% of the L-isomer, the remainder being the D-isomer.

[0110] In one embodiment of the present invention, the composition of the present invention does not contain bleaching agent.Bleaching agent in the context of the present invention refers to organic peroxides, inorganic peroxides and chlorine bleaching agents.Examples of organic and inorganic peroxides are sodium perborate, either anhydrous or, for example, as monohydrate or tetrahydrate or so-called dihydrate, sodium percarbonate, either anhydrous or, for example, as monohydrate, hydrogen peroxide, in each case as free acid or alkali metal salt, in particular sodium salt, persulfates, organic peroxyacids, such as peroxylauric acid, peroxystearic acid, peroxy-α-naphthoic acid, 1,12-diperoxydodecanedioic acid, perbenzoic acid, peroxylauric acid, 1,9-diperoxyazelaic acid, diperoxyisophthalic acid, as well as sulfonylperoxyacids and cationic peroxyacids. Chlorine-containing bleaching agents are, for example, 1,3-dichloro-5,5-dimethylhydantoin, N-N-chlorosulfamide, chloramine T, chloramine B, sodium hypochlorite, calcium hypochlorite, magnesium hypochlorite, potassium hypochlorite, potassium dichloroisocyanurate and sodium dichloroisocyanurate.

[0111] "Free" in the context of bleach means less than 0.5% by weight based on total nonvolatile content.

[0112] In one embodiment of the invention, the composition of the invention contains at least one alkali metal or ethanolammonium salt of a fatty acid, preferably at least one potassium or ethanolammonium salt of a fatty acid. Examples are the sodium and especially potassium salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, as well as soap mixtures derived from natural fatty acids, in particular coconut, palm kernel, olive or tallow fatty acids. Preferred examples are potassium coconut soap, potassium stearate, potassium oleate, nC 12 H 25 Even more preferred is potassium coconut soap having the average formula COOK.The amount of potassium salt of a fatty acid may range from 10 to 25% by weight based on the total non-volatile content of the liquid detergent composition.

[0113] The compositions of the present invention are liquid laundry detergent compositions. The liquid laundry detergent compositions may contain ingredients other than those mentioned above. Examples include surfactants other than those mentioned above, especially zwitterionic surfactants, as well as fragrances, dyes, biocides, preservatives, enzymes, hydrotropes, builders, viscosity modifiers, polymers, buffers, defoamers, and anti-corrosion additives.

[0114] Examples of fragrances are benzyl salicylate, 2-(4-tert-butylphenyl) 2-methylpropional, commercially available as Lilial®, and hexyl cinnamaldehyde.

[0115] Examples of dyes are Acid Blue 9, Acid Yellow 3, Acid Yellow 23, Acid Yellow 73, Pigment Yellow 101, Acid Green 1, Solvent Green 7, and Acid Green 25.

[0116] The liquid detergent compositions of the present invention may contain one or more preservatives or biocides. Biocides and preservatives prevent deterioration of the liquid detergent compositions of the present invention due to attack from microorganisms. Examples of biocides and preservatives are BTA (1,2,3-benzotriazole), benzalkonium chloride, 1,2-benzisothiazolin-3-one ("BIT"), 2-methyl-2H-isothiazol-3-one ("MIT") and 5-chloro-2-methyl-2H-isothiazol-3-one ("CIT"), iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH"), and dibromodimethyl. Hydantoin ("DBDMH"), benzoic acid, sorbic acid and their salts, such as sodium benzoate, ammonium benzoate, calcium benzoate, magnesium benzoate, MEA benzoate, potassium benzoate, calcium sorbate, sodium sorbate, iodopropynyl butylcarbamate ("IPBC"), dichlorodimethylhydantoin ("DCDMH"), bromochlorodimethylhydantoin ("BCDMH"), and dibromodimethylhydantoin ("DBDMH").

[0117] Of particular interest are the following antimicrobial and / or antiseptic agents: 4,4'-dichloro 2-hydroxydiphenyl ether, further name: 5-chloro-2-(4-chlorophenoxy)phenol, Diclosan, DCPP (commercially available as a 30% by weight solution of 4,4'-dichloro 2-hydroxydiphenyl ether in 1,2-propylene glycol), 2-phenoxyethanol, further names: phenoxyethanol, methylphenyl glycol, phenoxetol, ethylene glycol phenyl ether, ethylene glycol monophenyl ether); 2-bromo-2-nitropropane-1,3-diol, further name: 2-bromo-2-nitro-1,3-propanediol, glutaraldehyde (CAS number 111-30-8, further names: 1-5-pentanediol, pentane-1,5-dial, glutaral, glutaric dialdehyde, glyoxal (further names: ethanediol, oxylaldehyde, 1,2-ethanediol); 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-methyl-2H-isothiazol-3-one (MIT, EINECS 220-239-6) (mixture of CMIT / MIT); potassium (E,E)-hexa-2,4-dienoate (potassium sorbate); lactic acid and its salts; in particular sodium lactate, especially L-(+)-lactic acid, salicylic acid and its salts, such as calcium salicylate, magnesium salicylate, MEA salicylate, sodium salicylate, potassium salicylate, and TEA salicylate. benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate, didecyldimethylammonium chloride (DDAC); N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (diamine); peracetic acid, and hydrogen peroxide.

[0118] The biocides or preservatives may be added to the compositions of the invention in a concentration of 0.001 to 10% relative to the total weight of the composition.

[0119] Preferably, the composition of the present invention contains 2-phenoxyethanol at a concentration of 0.1 to 2%, or 4,4'-dichloro-2-hydroxydiphenyl ether (DCPP) at a concentration of 0.005 to 0.6%.

[0120] One embodiment of the present invention therefore relates to a method for protecting an aqueous composition according to the invention from microbial contamination or growth, comprising the addition of 2-phenoxyethanol.

[0121] Examples of viscosity modifiers are agar, carrageenan, tragacanth, gum arabic, alginates, pectin, hydroxyethyl cellulose, hydroxypropyl cellulose, starch, gelatin, locust bean gum, crosslinked poly(meth)acrylates, such as polyacrylic acid crosslinked with methylene bis(meth)acrylamide, as well as silicic acid, clays (including but not limited to montmorillonite, zeolite, dextrin, and casein).

[0122] A hydrotrope in the context of the present invention is a compound that promotes the dissolution of compounds that have limited solubility in water. Examples of hydrotropes are, but are not limited to, organic solvents such as ethanol, isopropanol, ethylene glycol, 1,2-propylene glycol, and glycerol, as well as organic solvents that are miscible with water under normal conditions. Further examples of suitable hydrotropes are the sodium salts of toluenesulfonic acid, xylenesulfonic acid, and cumenesulfonic acid.

[0123] Examples of useful enzymes are one or more hydrolases selected from lipases, amylases, proteases, cellulases, hemicellulases, phospholipases, esterases, pectinases, lactases and peroxidases, as well as combinations of at least two of the foregoing classes. Particularly useful enzymes are selected from proteases, amylases and cellulases.

[0124] The preferred amount of enzyme in the composition of the present invention is in the range of 0.001% to 5% by weight of active enzyme in the detergent composition according to the present invention. Along with the enzyme, enzyme stabilizing systems may also be used, such as, for example, calcium ions, boric acid, boronic acid, propylene glycol and short chain carboxylic acids. In the context of the present invention, short chain carboxylic acids are selected from monocarboxylic acids containing 1 to 3 carbon atoms per molecule and dicarboxylic acids containing 2 to 6 carbon atoms per molecule. Preferred examples are formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, glutamic acid (HOOC(CH2)3COOH), adipic acid and mixtures of at least two of the above, as well as the corresponding sodium and potassium salts.

[0125] Examples of polymers are especially polyacrylic acid and the corresponding alkali metal salts thereof, especially the sodium salts thereof. Suitable polymers are especially polyacrylic acids, preferably having average molecular weights M in the range of 2,000 to 40,000 g / mol, preferably 2,000 to 10,000 g / mol, in particular 3,000 to 8,000 g / mol. w Each is partially or completely neutralized with alkali, in particular with sodium. Likewise suitable copolymeric polycarboxylates are in particular copolymers of acrylic acid and methacrylic acid, and copolymers of acrylic acid or methacrylic acid with maleic acid and / or fumaric acid. Polyacrylic acid and its corresponding alkali metal salts can function as soil redeposition inhibitors.

[0126] Another class of useful copolymers are polyvinylpyrrolidone, copolymers of N-vinylpyrrolidone ("NVP") and N-imidazole, copolymers of acrylic acid and NVP or N-imidazole, or copolymers of both NVP and N-imidazole. Such (co)polymers have average molecular weights M in the range of 5,000 to 100,000 g / mol, as measured by gel permeation chromatography. w Polyvinylpyrrolidone, and copolymers of NVP and N-imidazole, and copolymers of acrylic acid and NVP or N-imidazole may function as dye transfer inhibitors.

[0127] Further examples of polymers are polyethylene terephthalate, polyoxyethylene terephthalate, and polyethylene terephthalate endcapped with one or two hydrophilic groups per molecule, the hydrophilic groups being selected from CH2CH2CH2-SONa, CH2CH(CH2-SONa)2, and CH2CH(CH2SONa)CH2-SONa.

[0128] Further examples of the polymer include polyfunctional polyethyleneimines and / or polyfunctional diamines. Such polyfunctional polyethyleneimines have a molecular weight M in the range of 3,000 to 250,000, preferably 5,000 to 200,000, more preferably 8,000 to 100,000, and even more preferably 10,000 to 20,000 g / mol. w Suitable polyfunctional polyethyleneimines have 80% to 99% by weight, preferably 85% to 99% by weight, more preferably 90% to 98% by weight, more preferably 93% to 97% by weight, or 94% to 96% by weight of ethylene oxide side chains, based on the total weight of the material. Ethoxylated polyethyleneimines are typically based on a polyethyleneimine core with polyethylene oxide side chains. Examples of suitable polyethyleneimines have molecular weights M in the range of 500 to 5000 g / mol, preferably 500 to 2000 g / mol. w , and even more preferably an M of 600 to 800 g / mol w In this case, the ethoxylated polyethyleneimine has an average of 5 to 50, preferably 10 to 35, and even more preferably 20 to 35 ethylene oxide (EO) units per NH functional group.

[0129] Suitable polyfunctional diamines are typically ethoxylated C2-C 12The alkylene diamines are preferably hexamethylene diamines, which are further quaternized and optionally sulfated. Typical polyfunctional diamines have molecular weights M in the range of 2,000 to 10,000, preferably 3000 to 8000, more preferably 4000 to 6000 g / mol. w In a preferred embodiment of the present invention, further quaternized and sulfated ethoxylated hexamethylenediamines may be used which contain an average of 10 to 50, preferably 15 to 40, even more preferably 20 to 30 ethylene oxide (EO) groups per NH function, preferably having two cationic ammonium groups and two anionic sulfate groups.

[0130] In a preferred embodiment of the present invention, the cleaning composition of the present invention contains at least one multifunctional polyethyleneimine and / or at least one multifunctional diamine. The multifunctional polyethyleneimine and multifunctional diamine, or mixtures thereof, can be added to the laundry detergent and cleaning composition of the present invention in small amounts, generally 0.05-15% by weight, preferably 0.1-10% by weight, more preferably 0.25-5% by weight, even up to 2% by weight, based on the total of the particular composition including other components and water and / or solvent. Such compositions then exhibit improved cleaning performance, such as improved stain removal ability, most importantly for particulate stains, especially on polyester fabrics.

[0131] Accordingly, one aspect of the present invention is a laundry detergent composition, particularly a liquid laundry detergent, comprising (i) at least one polyester of the present invention and (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof.

[0132] In one embodiment of the present invention, the ratio of at least one polymer of the present invention to (ii) at least one compound selected from multifunctional polyethyleneimines and multifunctional diamines, and mixtures thereof, is 10:1 to 1:10, preferably 5:1 to 1:5, more preferably 3:1 to 1:3.

[0133] Examples of buffers are monoethanolamine / monoethanolammonium and N,N,N-triethanolamine / N,N,N triethanolammonium.

[0134] An example of a defoamer is silicone.

[0135] The compositions of the present invention are advantageous when used as or in cleaning soiled laundry with inorganic soils such as clay or organic fatty soils such as oil, or for removing non-bleachable stains from laundry, such as, but not limited to, stains from red wine, tea, coffee, vegetable and various fruit juices such as berry juice, and the compositions of the present invention do not leave residue on textile fabrics.

[0136] In one embodiment of the invention, 50 to at least 85% by weight of the organic compounds contained in the composition of the invention are biodegradable, preferably as determined according to the 2016 OECD guidelines, as further described below.

[0137] To be suitable as a liquid laundry detergent, the compositions of the present invention may be in bulk form or in unit dose form, such as a sachet or pouch. Suitable materials for pouches are water-soluble polymers such as polyvinyl alcohol.

[0138] Another aspect of the present invention is the use of the composition of the present invention for washing laundry. In particular, an aspect of the present invention is the use of the composition of the present invention for washing laundry, especially laundry made of or containing polyester. Another aspect of the present invention is a process for washing laundry, hereinafter also referred to as the process of the present invention. The process of the present invention relates to washing laundry by applying at least one composition of the present invention, preferably in a washing machine. The process of the present invention can be carried out in an automatic laundry washing machine or manually. The detergent composition of the present invention is preferably diluted with water before application to soiled laundry.

[0139] In one embodiment of the present invention, the inventive process is characterized in that the corresponding inventive composition is applied to the soiled laundry at a temperature in the range of 20-65°C.

[0140] The laundry process of the present invention, as well as the use of the present invention, allows such clays to be removed very efficiently from soiled laundry.

[0141] A further aspect of the present invention is a process for making the liquid detergent composition of the present invention, hereinafter also referred to as the method of the present invention, which comprises mixing the polyester of the present invention and other ingredients such as, but not limited to, a sequestering agent, a surfactant, and optionally further ingredients as outlined above, with water in one or more steps.

[0142] The present invention is further illustrated by examples. EXAMPLES

[0143] I. Overview The hydroxyl numbers (HN) of the linear and branched unsaturated polyesters were determined using the perchloric acid catalyzed method according to the DIN 53240 (2016) standard.

[0144] Gel Permeation Chromatography (GPC) GPC measurements of the unsaturated polyesters and the polyesters of the invention were carried out on a PSS Agilent 1200 Series at room temperature in THF or DMAc (containing 0.5% LiBr). The nominal solvent flow rate was 1 mL / min. Three SEC columns from PSS Polymer Standards were used for fractionation, with pore sizes of 100 Å, 1000 Å and 10000 Å for THF and 30 Å, 2×1000 Å for DMAc. A refractive index detector G136A and a UV / Vis detector G1314B from Agilent Technologies were used. Calibration was performed with polystyrene as standard for samples in THF and poly(methyl methacrylate) for samples in DMAc. The results were evaluated using WinGPC UniChrom V 8.20 software from Polymer Standards Service GmbH.

[0145] Summary: Biodegradation tests are carried out according to OECD guidelines. According to the OECD guidelines, a test is valid if: 1. The reference material reaches 60% within 14 days. 2. The difference in the extreme values ​​of test reproducibility by the end of the test is less than 20%. 3. The oxygen uptake of the inoculum blank should be 20-30 mg O2 / l and should not exceed 60 mg O2 / l. 4. The pH value measured at the end of the test must be between 6 and 8.5.

[0146] Biodegradation in wastewater was tested in triplicate using the manometric respirometry method of OECD 301F, an aerobic test that measures the biodegradation of wastewater samples by measuring the consumption of oxygen. Measured amounts of wastewater were spiked with 100 mg / L of the test substance, nominally the only carbon source, together with an inoculum (aerated sludge taken from the municipal wastewater treatment plant in Mannheim, Germany). The sludge was stirred in a closed flask at constant temperature (25°C) for 28 days. The consumption of oxygen is measured by measuring the change in pressure in a closed flask using an Oxi TopC. The released carbon dioxide is absorbed in a sodium hydroxide solution. A nitrification inhibitor was added to the flask to prevent the consumption of oxygen by nitrification. The amount of oxygen taken up by the microbial population during the biodegradation of the test substance (corrected for the uptake by a parallel blank inoculum) is expressed as a percentage of ThOD (theoretical oxygen demand measured by elemental analysis of the compound). A positive control, glucose / glutamic acid, is run along with the test samples in each cabinet as a reference material. Calculation: Theoretical Oxygen Demand: The amount of O2 required to oxidize a compound to its final oxidation products, e.g., H2O, CO2. This amount is calculated using elemental analysis data. Calculation of % biodegradation: Experimental O2 uptake·100 divided by theoretical O2 demand. Abbreviations: MeHQ: 4-methoxyhydroquinone

[0147] II.Synthesis II.1 Synthesis of the inventive polyester PE.1 Process (a.1)DEM / 1,6-HD / TMP;1.1:0.5:0.5 A 1 liter two-necked round-bottom flask equipped with a mechanical stirrer with PTFE blades was charged with diethyl maleate (385 g, 2.24 mol), 1,6-hexanediol (120.1 g, 1.02 mol), 1,1,1-trimethylolpropane (136.37 g, 1.02 mol) and dibutyltin dilaurate (1.41 g, 2.23 mmol). The flask was fitted with a Liebig condenser equipped with a Claisen head and a dry N2 flow was applied slowly through the head to keep the reaction under an inert atmosphere. The reaction mixture so obtained was heated to 160°C by oil bath for 10 hours. During the first 2 hours the reaction mixture was kept under N2 flow and then the pressure in the flask was gradually reduced to 50 mbar using a vacuum pump. After 10 hours the unsaturated polyester was obtained. The unsaturated polyester was dissolved in MeHQ (660 mg) and used in step (b.1) without further purification.

[0148] Process (b.1): A 250 mL round-bottom flask equipped with a magnetic stir bar was charged with 200.84 g of the unsaturated polyester from step (a.1), corresponding to 0.9 mol of C-C double bonds. The flask was heated to 50 °C under a stream of dry N and the H2N-(EO) 19 (PO)3-H (900 g, 0.9 mol) was slowly added. Upon completion of the addition, the reaction mixture was stirred at 60° C. for 24 hours. The reaction mixture thus obtained was allowed to cool to ambient temperature. The polyester PE.1 of the present invention was obtained.

[0149] II.2 Synthesis of the inventive polyester PE.2 Process (a.2): A 1 liter two-necked round bottom flask equipped with a mechanical stirrer with PTFE blades was charged with diethyl maleate (758 g, 4.4 mol), 1,6-hexanediol (236 g, 2 mol), glycerol (184 g, 2 mol) and dibutyltin dilaurate (2.78 g, 4.4 mmol). The flask was fitted with a Liebig condenser equipped with a Claisen head and a dry N2 flow was applied slowly through the head to keep the reaction under an inert atmosphere. The reaction mixture so obtained was heated to 160°C for 10 hours. During the first 2 hours the reaction mixture was kept under N2 flow. The pressure in the flask was then gradually reduced to 50 mbar using a vacuum pump. After 10 hours the unsaturated polyester was obtained. 1181 mg of MeHQ was dissolved in the unsaturated polyester which was used in step (b.2) without further purification.

[0150] Process (b.2): A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 100 g (0.49 mol double bonds) of the unsaturated polyester from step (a.2). The flask was heated to 50° C. under a stream of dry N2, and the H2N-(EO) 19 (PO)3-H (490 g, 0.49 mol) was slowly added. Upon completion of the addition, the reaction mixture was stirred at 60° C. for 24 hours. The reaction mixture thus obtained was allowed to cool to ambient temperature. The polyester PE.2 of the present invention was obtained.

[0151] II.3. Synthesis of the inventive polyester PE.3 Process (a.3): A 1 liter two-necked round bottom flask equipped with a mechanical stirrer with PTFE blades was charged with diethyl maleate (758 g, 4.4 mol), 1,6-hexanediol (378 g, 3.2 mol), 1,1,1-trimethylolpropane (107 g, 0.8 mol) and dibutyltin dilaurate (2.78 g, 4.4 mmol). The flask was fitted with a Liebig condenser equipped with a Claisen head and a dry N2 flow was applied slowly through the head to keep the reaction under an inert atmosphere. The reaction mixture so obtained was heated to 160°C for 10 hours. During the first 2 hours, the reaction mixture was kept under N2 flow. The pressure in the flask was then gradually reduced to 50 mbar using a vacuum pump. After 10 hours, an unsaturated polyester was obtained. 1243 mg of MeHQ was dissolved in the unsaturated polyester, which was used in step (b.3) without further purification.

[0152] Process (b.3): A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 100 g (0.49 mol double bonds) of the unsaturated polyester from step (a.3). The flask was heated to 50° C. under a stream of dry N2, and the H2N-(EO) 19 (PO)3-H (490 g, 0.49 mol) was slowly added. Upon completion of the addition, the reaction mixture was stirred at 60° C. for 24 hours. The reaction mixture thus obtained was allowed to cool to ambient temperature. The polyester PE.3 of the present invention was obtained.

[0153] II.4. Synthesis of the inventive polyester PE.4 Process (a.4): A 1 liter two-necked round bottom flask equipped with a mechanical stirrer with PTFE blades was charged with diethyl maleate (379 g, 2.2 mol), 1,6-hexanediol (189 g, 1.6 mol), glycerol (37 g, 0.4 mol) and dibutyltin dilaurate (1.39 g, 2.2 mmol). The flask was fitted with a Liebig condenser equipped with a Claisen head and a dry N2 flow was applied slowly through the head to keep the reaction under an inert atmosphere. The reaction mixture so obtained was heated to 160°C for 10 hours. During the first 2 hours, the reaction mixture was kept under N2 flow. The pressure in the flask was then gradually reduced to 50 mbar using a vacuum pump. After 10 hours, an unsaturated polyester was obtained. 436 mg of MeHQ was dissolved in the unsaturated polyester, which was used in step (b.4) without further purification.

[0154] Process (b.4): A 250 mL round bottom flask equipped with a magnetic stir bar was charged with 100 g (0.49 mol double bonds) of the unsaturated polyester from step (a.4). The flask was heated to 50° C. under a stream of dry N2, and the H2N-(EO) 19 (PO)3-H (490 g, 0.49 mol) was added slowly. Upon completion of the addition, the reaction mixture was stirred at 60° C. for 24 hours. The reaction mixture thus obtained was allowed to cool to ambient temperature. The polyester PE.4 of the present invention was obtained.

[0155] The analyses are summarized in Table 1. The synthesized polyaspartates were used without further purification for the studies. The molar mass, viscosity, and glass transition temperature of selected polyaspartates were measured.

[0156] [Table 1]

[0157] The glass transition temperatures of the polyesters of the present invention were measured using a Netzsch DSC 200 F3 (Erich Netzsch GmbH & Co. Holding KG, Selb, Germany). Each sample was heated from -150°C to 150°C at a rate of 10°C / min under nitrogen atmosphere. Two cooling-heating runs were performed for each sample, and the data from the second heating curve was used. The data was analyzed using Netzsch Proteus Thermal Analysis (Version 4.8.1) software.

[0158] III. Preparation and Testing of Liquid Laundry Detergent Compositions III.1 Overview A liquid-based composition MC1 was prepared according to Table 2.

[0159] [Table 2]

[0160] III.2 Primary cleaning power in Linitest The samples were each tested in a liquid model formulation MC1 according to the composition shown in Table 2 above.

[0161] The polyesters of the invention were added to a model composition MC1 (addition of 3% based on the weight of the liquid model detergent (owod)) together with commercial dyed fabrics (from the Center of Test Materials CFT Vlaardingen. P-H108: clayey soil, P-H115: standard clay; P-H144: red china clay; P-H145: tennis court clay) and 5 g of a commercial soil ballast sheet wfk SBL2004 (from wfk Testgewebe GmbH Brueggen). The washing conditions were 3 g / L detergent, 250 mL liquor, 30 min, 40° C., 4 measurements. After washing, the fabrics were rinsed and dried. The fabrics were instrumentally evaluated before and after washing using a ColourConsult MACH5 multi area color measurement device showing laboratory measurements. The results are summarized in Table 3. From these laboratory measurements, the ΔE values ​​between the unwashed and washed stains were calculated. The higher the ΔE value, the better the performance. To better judge the pure cleaning effect of each polymer sample itself, the obtained values ​​are further expressed as ΔΔE values ​​relative to a reference material without polymer (baseline correction to the plain cleaning effect of detergent only). Again, the higher the ΔΔE value, the better the performance.

[0162] [Table 3]

Claims

1. A polyester comprising at least one diacid-based structural unit, at least one diol-based structural unit, and at least one polyol-based structural unit, wherein the diacid-based structural unit contains a group of formula (I), 【Chemical Formula 1】 In the formula, R １ is a group represented by the general formula CH ２ - CH ２ - O(AO) ｘ - X １ where x is a number from 0 to 75, X １ is hydrogen or methyl, and AO is an alkylene oxide selected from ethylene oxide and at least one combination of ethylene oxide with propylene oxide and butylene oxide, The polyol structural unit is derived from a compound having y hydroxyl groups per molecule, and y is at least 3, The asterisk indicates the bond to the diol or polyol structural unit via the ester oxygen atom, A polyester in which the molar ratio of the diacid-based structural unit to the total of the diol structural unit and the polyol structural unit (the latter being multiplied by 2 / y) is in the range of 2:1 to 1:

2.

2. The polyester according to claim 1, wherein x is 0 or in the range of 1 to 30, and most of the AO in R １ is ethylene oxide.

3. Having an average molecular weight M ｎ in the range of 3,000 to 5,000 g / mol as measured by gel permeation chromatography, the polyester according to claim 1.

4. The polyester according to claim 1, further comprising at least one structural unit selected from dicarboxylic acids having no NH - R １ group, C ４ to C ６

5. The polyester according to claim 1, wherein the diol structural unit is based on ethylene glycol, diethylene glycol, triethylene glycol, 1,4 - butanediol, 1,6 - hexanediol, neopentyl glycol, 2,5 - dimethyl - 2,5 - hexanediol or 2 - ethyl - 1,3 - hexanediol, or a mixture of at least two of the foregoing.

6. The polyester according to claim 1, wherein the polyol component is selected from triols and tetrols.

7. The polyester according to claim 1, wherein the polyol structural unit is based on glycerol, butane - 1,2,4 - triol, n - pentane - 1,2,5 - triol, n - pentane - 1,3,5 - triol, n - hexane - 1,2,6 - triol, n - hexane - 1,2,5 - triol, n - hexane - 1,3,6 - triol, 1,1,1 - trimethylolbutane, 1,1,1 - trimethylolpropane, 1,1,1 - trimethylolethane or trimethylolmethane, or a mixture of at least two of the foregoing.

8. The polyester according to claim 1, wherein the molar ratio of the dicarboxylic acid - based structural unit to the total of the diol structural unit and the polyol structural unit is in the range of 1.5:1 to 1:1.

5.

9. A process for producing the polyester according to any one of claims 1 to 8, (a) A step of reacting an activated α,β - ethylenically unsaturated dicarboxylic acid with a mixture of at least one diol and at least one polyol, wherein the activated unsaturated dicarboxylic acid is selected from activated maleic acid, activated itaconic acid and activated fumaric acid, A step characterized in that the molar ratio of the carboxyl group of the activated α,β - ethylenically unsaturated dicarboxylic acid to the total of the hydroxyl groups of the diol and the polyol is in the range of 2:1 to 1:2, (b) The product obtained in step (a) is R １ -NH ２A process comprising a step of reacting with.

10. The process according to claim 9, wherein the molar ratio of the hydroxyl groups of the diol and the polyol is in the range of 1:2 to 2:

1.

11. The activated α,β-ethylenically unsaturated dicarboxylic acid is C １ ~C ４ alkyl diester, dichloride, and maleic acid ester and itaconic acid and C １ ~C ４ The process according to claim 9, which is selected from the anhydrides of alkyl diesters and the dichlorides of fumaric acid.

12. A laundry detergent containing at least one polyester according to any one of claims 1 to 8.

13. The laundry detergent according to claim 12, further comprising at least one anionic surfactant selected from linear alkylbenzene sulfonate and alkoxylated sulfonated fatty alcohol, and / or further comprising at least one enzyme.

14. The laundry detergent composition according to claim 12, wherein the composition is liquid or gel-type at ambient temperature.

15. A method for protecting the laundry detergent according to claim 12 from microbial contamination or growth, the method comprising the addition of 2-phenoxyethanol.

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