WO2025132402A1 - Procédé de préparation de polyesters à l'aide d'acide téréphtalique - Google Patents

Procédé de préparation de polyesters à l'aide d'acide téréphtalique Download PDF

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WO2025132402A1
WO2025132402A1 PCT/EP2024/086864 EP2024086864W WO2025132402A1 WO 2025132402 A1 WO2025132402 A1 WO 2025132402A1 EP 2024086864 W EP2024086864 W EP 2024086864W WO 2025132402 A1 WO2025132402 A1 WO 2025132402A1
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mixtures
formula
linear
group
substances
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Clemens LIEDEL
Hiroe Yamada
Michael Mager
Peter Klug
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Clariant International Ltd
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Clariant International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the invention relates to a process for preparing polyesters, products or polyesters obtainable by the process, the use of the products or polyesters as soil release polymers and laundry detergent compositions comprising the products or polyesters.
  • Polyesters based on dimethyl terephthalate and their use as soil release polymers especially in laundry detergent compositions are already known.
  • GB 1 ,466,639, US 4,132,680, US 4,702,857, EP 0 199403, US 4,711 ,730, US 4,713,194, and US 4,759,876 describe polyesters based on dimethyl terephthalate and their use as soil release polymers and disclose aqueous detergent compositions containing soil release polymers.
  • polyesters which might be used as soil release polymers during which a low amount of side products is generated.
  • (CnH2n) is a linear or branched alkylene group with n being an integer of from 2 to 10 or mixtures thereof, preferably with n being an integer of from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (CsHe), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (CsHe) and mixtures thereof, and
  • R 1 is a linear or branched, preferably a linear, alkyl group comprising from 1 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 2 to 30 carbon atoms or mixtures thereof, preferably is a linear or branched, preferably a linear, alkyl group comprising from 1 to 20 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 2 to 20 carbon atoms or mixtures thereof, a is, based on a molar average, a number of from 1 to 200, preferably of from 2 to 200, more preferably of from 3 to 150, and
  • R 2 is a linear or branched alkylene group (CmH2m) with m being an integer of from 2 to 10 or mixtures thereof, preferably with m being an integer of from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (CsHe), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (CsHe) and mixtures thereof, particularly preferably is (C2H4) or a mixture of (C2H4) and (CsHe), and extraordinarily preferably is (C2H4), characterized in that the preparation of the polyester comprises the steps of: a) heating a mixture comprising terephthalic acid and one or more alkylene glycols of the formula (II) or mixtures thereof and removing water until the acid value of the system is reduced to 50 mg KOH/g or lower, preferably to 30 mg KOH/g or lower, more preferably to 15 mg KOH/g or lower, even more preferably
  • a subject matter of the invention is a process for preparing a polyester by reacting at least
  • (CnH2n) is a linear or branched alkylene group with n being an integer of from 2 to 10 or mixtures thereof, preferably with n being an integer of from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (CsHe), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (CsHe) and mixtures thereof, and
  • R 1 is a linear or branched, preferably a linear, alkyl group comprising from 1 to 30 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 2 to 30 carbon atoms or mixtures thereof, preferably is a linear or branched, preferably a linear, alkyl group comprising from 1 to 20 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 2 to 20 carbon atoms or mixtures thereof, a is, based on a molar average, a number of from 1 to 200, preferably of from 2 to 200, more preferably of from 3 to 150, and
  • R 2 is a linear or branched alkylene group (CmH2m) with m being an integer of from 2 to 10 or mixtures thereof, preferably with m being an integer of from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (CsHe), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (CsHe) and mixtures thereof, particularly preferably is (C2H4) or a mixture of (C2H4) and (CsHe), and extraordinarily preferably is (C2H4), characterized in that the preparation of the polyester comprises the steps of: a) heating a mixture comprising terephthalic acid and one or more alkylene glycols of the formula (II) or mixtures thereof and removing water until the acid value of the system is reduced to 50 mg KOH/g or lower, preferably to 30 mg KOH/g or lower, more preferably to 15 mg KOH/g or lower, even more preferably
  • WO 2016/146429 A1 describes polyesters obtainable from the dicarboxylic acid terephthalic acid and, where appropriate, isophthalic acid, and from ethylene glycol and polyethylene glycol, with average molecular weights ranging between 2000 g/mol and 8000 g/mol.
  • DE 44 17 686 A1 describes a process for preparing polyesters, wherein a dicarboxylic acid HOOC-Ph-COOH or its reactive derivative is reacted with a monomeric diol under esterification conditions, subsequently is reacted with a polymeric diol under transesterification conditions and is reacted with a monocarboxylic acid, hydroxymonocarboxylic acid, and/or dicarboxylic acid monoester under esterification conditions.
  • EP 1 734 171 A1 describes a fiber-treating agent, e.g., comprising a polyester compound produced by carrying out a condensation polymerization of a polyoxyalkylene monol, an alkylene glycol, and at least one member selected from the group consisting of aromatic dicarboxylic acids and their ester-forming derivatives.
  • WO 2021/233987 A1 describes a process for the preparation of a polyester comprising the steps of: heating one or more substances of the formula Q1 -OOC-C6H4-COO-Q2, wherein Q1 and Q2, independently of one another, are selected from the group consisting of H and (Ci-C4)-alkyl and preferably are CH3, and 1 ,2-propyleneglycol , and one or more specific (poly)alkylene glycol mono C7-C30 alkyl or alkenyl ethers or mixtures thereof, with the addition of a catalyst, to temperatures of from 160 to 220 °C, preferably beginning at atmospheric pressure, and then continuing the reaction under reduced pressure at temperatures of from 160 to 240 °C.
  • the inventive process possesses the advantage that low levels of side products such as dioxane, sublimated dimethyl terephthalate, and/or methanol are generated.
  • the process is more sustainable compared to processes from the prior art based on dimethyl terephthalate as the yield per ton of monomers is higher and the mass of side products is lower.
  • the process leads to products which possess good soil release properties.
  • Different grades of terephthalic acid can be used in the inventive process.
  • combinations of purified and nonpurified terephthalic acid can be used, more preferably comprising at least 50 wt.-%, even more preferably comprising at least 80 wt.-%, and particularly preferably comprising 100 wt.-% purified terephthalic acid, in each case based on the total weight of terephthalic acid used in the inventive process.
  • combinations of recycled and nonrecycled terephthalic acid can be used, more preferably comprising at least 50 wt.-%, even more preferably comprising at least 80 wt.-%, and particularly preferably comprising 100 wt.-% recycled terephthalic acid, in each case based on the total weight of terephthalic acid used in the inventive process.
  • combinations of renewable and non-renewable terephthalic acid can be used, more preferably comprising at least 50 wt.-%, even more preferably comprising at least 80 wt.-%, and particularly preferably comprising 100 wt.-% renewable terephthalic acid, in each case based on the total weight of terephthalic acid used in the inventive process.
  • renewable terephthalic acid The process of obtaining renewable terephthalic acid is known to the person skilled in the art.
  • US 2023/0125062 describes systems and methods for producing aromatic compounds such as para-xylene in high yield from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like.
  • Renewable terephthalic acid can be obtained by oxidation of para-xylene.
  • Examples for the one or more alkylene glycols of the formula (II) or mixtures thereof are ethylene glycol, 1 ,2-propyleneglycol, 1 ,3-propyleneglycol, 2-methyl-1 ,3- propanediol, 1 ,4-butanediol, 1 ,3-butanediol, 2,3-butanediol, 1 ,2-butanediol, 2,2-dimethyl-1 ,3-propanediol, 1 ,2-pentanediol, 1 ,5-pentanediol, 1 ,2-hexanediol, 1 ,6-hexanediol or mixtures thereof.
  • n may vary between those alkylene glycols.
  • the one or more alkylene glycols of the formula (II) or mixtures thereof used in step a) are selected from the group consisting of ethylene glycol, propylene glycol, and mixtures of ethylene glycol and propylene glycol, more preferably are selected from the group consisting of propylene glycol and mixtures of ethylene glycol and propylene glycol and even more preferably the alkylene glycol of the formula (II) used in step a) is propylene glycol.
  • combinations of recycled and non-recycled alkylene glycols of the formula (II) or mixtures thereof can be used, more preferably comprising at least 50 wt.-%, even more preferably comprising at least 80 wt.-%, and particularly preferably comprising 100 wt.-% recycled alkylene glycols of the formula (II) or mixtures thereof, in each case based on the total weight of alkylene glycols of the formula (II) or mixtures thereof used in the inventive process.
  • combinations of renewable and non-renewable alkylene glycols of the formula (II) or mixtures thereof can be used, more preferably comprising at least 50 wt.-%, even more preferably comprising at least 80 wt.-%, and particularly preferably comprising 100 wt.-% renewable alkylene glycols of the formula (II) or mixtures thereof, in each case based on the total weight of alkylene glycols of the formula (II) or mixtures thereof used in the inventive process.
  • alkyl and alkenyl groups R 1 in the one or more substances of the formula (III) or mixtures thereof are, for example, methyl, ethyl, linear or branched propyl, butyl, pentyl, hexyl, heptyl, octyl (e.g., capryl), nonyl, decyl, undecyl, dodecyl, tridecyl (e.g.
  • the groups R 1 in the one or more substances of the formula (III) or mixtures thereof may also be mixtures which have been derived or obtained from natural sources and comprise one or more alkyl and/or one or more alkenyl groups and in case these mixtures comprise one or more alkenyl groups, they may also be partially or totally hydrogenated. Examples of such mixtures are cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl or partially or totally hydrogenated variants of talloyl.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 1 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 2 to 18 carbon atoms or mixtures thereof.
  • R 1 in the one or substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or a linear or branched, preferably a linear, alkenyl group comprising one or more double bonds and from 10 to 18 carbon atoms or mixtures thereof.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 1 to 20 and preferably from 1 to18 carbon atoms, or mixtures thereof.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is methyl.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 10 to 20 carbon atoms or mixtures thereof.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 10 to 18 carbon atoms or mixtures thereof.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is a linear or branched, preferably a linear, alkyl group comprising from 10 to 16 carbon atoms or mixtures thereof.
  • R 1 in the one or more substances of the formula (III) or mixtures thereof is selected from the group consisting of linear or branched alkyl groups comprising from 10 to 16 carbon atoms (such as lauryl, myristyl or isotridecyl), cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, more preferably is selected from the group consisting of linear or branched, preferably linear, alkyl groups comprising from 10 to 16 carbon atoms, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof, even more preferably is selected from the group consisting of linear or branched, preferably linear, alkyl groups comprising from 10 to 16 carbon atoms, partially or totally hydrogenated variants of talloyl and mixtures thereof and particularly preferably is selected from the group consisting of lauryl, myristyl, partially or totally hydrogenated variants of tallo
  • At least a part of the groups R 2 are (CH2CH2) groups. More preferably, in the one or more substances of the formula (III) or mixtures thereof, at least 50 mol-%, even more preferably at least 60 mol-% and particularly preferably at least 70 mol-% of the groups R 2 , in each case based on the total amount of the groups R 2 , are (CH2CH2) groups.
  • the groups R 2 extraordinarily preferably are (CH2CH2) groups or a mixture of (CH2CH2) groups and (CsHe) groups, wherein preferably at least 50 mol-%, more preferably at least 60 mol % and even more preferably at least 70 mol-% of the groups R 2 , in each case based on the total amount of the groups R 2 , are (CH2CH2) groups and especially preferably, the groups R 2 are (CH2CH2) groups.
  • At least a part of the groups R 2 are (CH2CH2) groups made from renewable ethylene oxide. More preferably, in the one or more substances of the formula (III) or mixtures thereof, at least 50 mol-%, even more preferably at least 60 mol-% and particularly preferably at least 70 mol-% of the groups R 2 , in each case based on the total amount of the groups R 2 , are (CH2CH2) groups made from renewable ethylene oxide.
  • the groups R 2 extraordinarily preferably are (CH2CH2) groups made from renewable ethylene oxide or a mixture of (CH2CH2) groups made from renewable ethylene oxide and (CsHe) groups, wherein preferably at least 50 mol-%, more preferably at least 60 mol % and even more preferably at least 70 mol-% of the groups R 2 , in each case based on the total amount of the groups R 2 , are (CH2CH2) groups made from renewable ethylene oxide and especially preferably, the groups R 2 are (CH2CH2) groups made from renewable ethylene oxide.
  • [0(CmH2m)] groups for example [O(C2H4)], [O(C3He)], and [O(C4Hs)] groups, exist in the one or more substances of the formula (III) or mixtures thereof, they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically.
  • the [0(CmH2m)] groups and, e.g., the groups [O(C2H4)], [O(C3He)] and [O(C4Hs)], 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 [(OC2H4)] and [O(C3He)] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups [O(C2H4)], [O(C3He)], and [O(C4HS)] exist.
  • any of the groups [0(CmH2m)], e.g., any of the groups [O(C2H4)], [O(C3He)], and [O(C4HS)], can be linked to R 1 - and -OH in a substance of the formula (III).
  • both, R 1 - and -OH in a substance of the formula (III), may be connected to a [O(C2H4)] group, they may both be connected to a [O(C3He)] group, they may both be connected to a [O(C4Hs)] group, or they may be connected to different groups [0(CmH2m)], e.g., selected from [O(C2H4)], [O(C3He)] and [O(C 4 H 8 )].
  • the one or more substances of the formula (III) or mixtures thereof are of the formula (111-1 ) R 1 -(OC2H4)b-(OC 3 H6)c-OH (HI-1 ) or mixtures thereof, wherein
  • R 1 has the meaning as described above for formula (III), the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise, alternating, periodically and/or statistically, preferably blockwise, wherein the block consisting of the -(OCsHe) groups is bound to -OH, b is, based on a molar average, a number of from 1 to 199, preferably of from 2 to 199, more preferably of from 3 to 149, even more preferably of from 12 to 120 and particularly preferably of from 40 to 50, c is, based on a molar average, a number of from 1 to 199, preferably of from 1 to 10 and more preferably of from 1 to 7, and the sum b + c is, based on a molar average, a number less than or equal to 200 and preferably a number less than or equal to 150.
  • the one or more substances of the formula (111-1 ) or mixtures thereof preferably at least 50 mol-%, more preferably at least 60 mol-% and even more preferably at least 70 mol-% of the groups (OC2H4) and (OCsHe), in each case based on the total amount of the groups (OC2H4) and (OCsHe), are (OCH2CH2) groups.
  • the one or more substances of the formula (111-1 ) or mixtures thereof particularly preferably at least 50 mol-%, more preferably at least 60 mol-% and even more preferably at least 70 mol-% of the groups (OC2H4) and (OCsHe), in each case based on the total amount of the groups (OC2H4) and (OCsHe), are (OCH2CH2) groups made from renewable ethylene oxide.
  • Renewable ethylene oxide can be obtained from bio-ethanol, which can be obtained from natural sources like com, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol can be dehydrated to produce bio-ethylene which can be oxidized with oxygen over a silver catalyst to produce renewable ethylene oxide.
  • R 1 , R 2 and “a” may vary between those substances.
  • R 1 , “b” and “c” may vary between those substances.
  • step b) is performed after step a) has been performed and step c) is performed after step b) has been performed.
  • heating in step a) is executed under ambient pressure or reduced pressure, more preferably under ambient pressure, to temperatures of more than 90 °C, more preferably to temperatures of from 100 °C to 300 °C, even more preferably to temperatures of from 120 °C to 280 °C, particularly preferably to temperatures of from 140 °C to 260 °C and extraordinarily preferably to temperatures of from 160 °C to 240 °C.
  • the acid value of a sample taken during step a) may be determined by volumetric titration with phenolphthalein as indicator, preferably as detailed in the following: 0.5 g of a homogeneous sample, which may e.g. be a homogeneous dispersion, melt or solution, is dissolved in 60 mL isopropanol. Up to 60 mL, preferably up to 10 mL, xylene may be added to obtain a clear solution. In case no clear solution is reached, the acid value is considered not measurable, and heating in step a) is continued. Three drops of a solution of phenolphthalein in isopropanol (1.0 wt.-%) are added.
  • the obtained solution is slowly titrated with a fresh solution of potassium hydroxide (KOH) in isopropanol (0.01 mol/L) until a color change from colorless to pink is observed.
  • the acid value in mg KOH/g is calculated from the amount of used KOH, and from the mass of the sample according to wherein AV is the acid value in mg KOH/g, V K0H [mL] is the added volume of the fresh solution of potassium hydroxide until a color change from colorless to pink is observed in mL, c KOH [mol/L] is the concentration of the fresh solution of potassium hydroxide (KOH) in isopropanol (0.01 mol/L), M KOH [g/mol] is 56.11 g/mol, and m sampie [g] is the mass of the sample in g.
  • step b) of the inventive process combining one or more substances of the formula (III) or mixtures thereof with the mixture obtained in step a) can be performed by adding one or more substances of the formula (III) or mixtures thereof and the mixture obtained in step a) in any order.
  • step b) combining one or more substances of the formula (III) or mixtures thereof with the mixture obtained in step a) is achieved by adding one or more substances of the formula (III) or mixtures thereof to the mixture obtained in step a).
  • step b) combining one or more substances of the formula (III) or mixtures thereof with the mixture obtained in step a) is achieved by adding the mixture obtained in step a) to one or more substances of the formula (III) or mixtures thereof.
  • step b) combining one or more substances of the formula (III) or mixtures thereof with the mixture obtained in step a) is achieved by simultaneously adding the mixture obtained in step a) and one or more substances of the formula (III) or mixtures thereof to a vessel.
  • step b) combining the one or more substances of the formula (III) or mixtures thereof with the mixture obtained in step a), preferably adding of the one or more substances of the formula (III) or mixtures thereof to the mixture obtained in step a) is preferably executed at temperatures of from 10 °C to 300 °C, more preferably at temperatures of from 20 °C to 280 °C, even more preferably at temperatures of from of 30 °C to 260 °C, particularly preferably at temperatures of from 40 °C to 240 °C, and extraordinarily preferably at temperatures of from 50 °C to 220 °C.
  • the mixture obtained in step a) may be heated or cooled before combining it with the one or more substances of the formula (III) or mixtures thereof in step b), preferably before adding the one or more substances of the formula (III) or mixtures thereof in step b).
  • Polycondensing in step c) is preferably executed under a pressure of from 0.1 to 900 mbar, more preferably under a pressure of from 0.5 to 500 mbar, and preferably at temperatures of more than 90 °C, more preferably at temperatures of from 100 °C to 300 °C, even more preferably at temperatures of from 150 °C to 280 °C, particularly preferably at temperatures of from 160 °C to 270 °C and extraordinarily preferably at temperatures of from 180 °C to 260 °C.
  • removal of water in step a) and/or removal of alkylene glycols of the formula (II) in step c) is achieved in part or completely by distillation.
  • removal of water in step a) is achieved partly or completely by distillation
  • distillation of water in the presence of one or more alkylene glycols of the formula (II) or mixtures thereof may preferably be achieved by using a fractionating column.
  • removing alkylene glycols of the formula (II) may include but is not limited to (i) removing alkylene glycols which have reacted, e.g., in step a) and/or step c) and are released during polycondensation, and (ii) removing alkylene glycols which have been present as a solvent and have not taken part in a reaction.
  • step a) and/or step b) and/or step c), more preferably step a) and step b) and step c), are performed under protective atmosphere.
  • the protective atmosphere is achieved by replacing parts of the oxygen of the atmosphere by nitrogen, e.g., by alternatingly applying reduced pressure and flooding with nitrogen or by alternatingly increasing the pressure by the addition of nitrogen and releasing the pressure.
  • the molar ratio of the one or more alkylene glycols of the formula (II) or mixtures thereof to terephthalic acid (formula (I)), in step a) is at least 1.2: 1.0, more preferably is at least 1.5: 1.0, even more preferably is at least 1.8: 1.0, particularly preferably is at least 2.0:1.0, and extraordinarily preferably is at least 2.2:1 .0.
  • the molar ratio of the one or more alkylene glycols of the formula (II) or mixtures thereof to terephthalic acid (formula (I)), in step a) preferably is lower than 10.0:1.0, more preferably is lower than 7.0:1.0 and even more preferably is lower than 3.0:1.0.
  • the molar ratio of the terephthalic acid (formula (I)) to the one or more substances of the formula (III) or mixtures thereof is from 1 :1 to 30:1 , more preferably is from 1 :1 to 20:1 , even more preferably is from 1 :1 to 15:1 , particularly preferably is from 1 :1 to 10:1 and extraordinarily preferably is from 1 :1 to 8:1 .
  • the molar ratio of the terephthalic acid (formula (I)) to the one or more substances of the formula (III) or mixtures thereof is from 1 :1 to 8:1 , R 1 is methyl, and “a” is, based on a molar average, a number of from 1 to 150, preferably of from 10 to 100, and more preferably of from 15 to 60.
  • the molar ratio of the terephthalic acid (formula (I)) to the one or more substances of the formula (III) or mixtures thereof is from 2:1 to 8:1
  • R 1 is a linear or branched alkyl group comprising from 10 to 20 carbon atoms or mixtures thereof, preferably is a linear alkyl group comprising from 10 to 16 carbon atoms or mixtures thereof, and more preferably is selected from the group consisting of lauryl, myristyl and mixtures thereof
  • “a” is, based on a molar average, a number of from 60 to 150, and preferably is a number of from 70 to 140.
  • one or more alkylene glycols of the formula (II) or mixtures thereof are additionally combined in step b) with the mixture obtained in step a) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and are preferably additionally added in step b).
  • n may vary between the alkylene glycols of the formula (II) used in step a) and the alkylene glycols of the formula (II) combined in step b) with the mixture obtained in step a) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof, preferably added in step b).
  • one or more substances of the formula (IV) or mixtures thereof are additionally reacted and are preferably contained in the mixture used in step a) and/or are added in step b), and more preferably are added in step b) wherein
  • such further substances of the formula (IV) or mixtures thereof would be used in a molar ratio of the one or more substances of the formula (IV) or mixtures thereof to the terephthalic acid (formula (I)) of less than 1 :2, and preferably of less than 1 :3.
  • R 3 is a linear or branched alkylene group (C P H2 P ), with p being an integer of from 2 to 10 or mixtures thereof, preferably with p being an integer of from 2 to 6 or mixtures thereof, more preferably is selected from the group consisting of (C2H4), (CsHe), (C4H8) and mixtures thereof, even more preferably is selected from the group consisting of (C2H4), (CsHe) and mixtures thereof, and particularly preferably is (C2H4), and d is, based on a molar average, a number of from 2 to 200, preferably of from 4 to 150, more preferably of from 10 to 120 and even more preferably of from 35 to 120.
  • At least a part of the groups R 3 are (CH2CH2) groups. More preferably, in the one or more polyalkyleneglycols of the formula (V) or mixtures thereof, at least 50 mol-%, even more preferably at least 60 mol-% and particularly preferably at least 70 mol-% of the groups R 3 , in each case based on the total amount of the groups R 3 , are (CH2CH2) groups.
  • the groups R 3 extraordinarily preferably are (CH2CH2) groups made from renewable ethylene oxide or a mixture of (CH2CH2) groups made from renewable ethylene oxide and (CsHe) groups, wherein preferably at least 50 mol-%, more preferably at least 60 mol % and even more preferably at least 70 mol-% of the groups R 3 , in each case based on the total amount of the groups R 3 , are (CH2CH2) groups made from renewable ethylene oxide and especially preferably, the groups R 3 are (CH2CH2) groups made from renewable ethylene oxide.
  • [O(C P H2 P )] groups for example [O(C2H4)], [O(C3He)], and [O(C4Hs)] groups, exist in the one or more polyalkyleneglycols of the formula (V) or mixtures thereof, they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically.
  • the [O(C P H2 P )] groups and, e.g., the groups [O(C2H4)], [O(C3He)], and [O(C4Hs)], 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 [O(C2H4)] and [O(C3He)] arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of different [O(C P H2 P )] groups, e.g., the groups [O(C2H4)], [O(C3He)], and [O(C4Hs)], exist.
  • any of the groups [O(C P H2 P )], e.g., any of the groups [O(C2H4)], [O(C3He)] and [O(C4Hs)] can form an end group of the structure element -(OR 3 )d-
  • the two end groups of the structure element -(OR 3 )d- in a polyalkyleneglycol of the formula (V) may be formed by [O(C2H4)] groups, may be formed by [O(C3He)] groups, may be formed by [O(C4Hs)] groups or may be formed by different [O(C P H2 P )] groups, e.g., different groups selected from [O(C2H4)], [O(C3He)] and [O(C4Hs)].
  • such further substances of the formula (V) or mixtures thereof would be used in a molar ratio of the one or more polyalkyleneglycols of the formula (V) or mixtures thereof to the one or more alkylene glycols of the formula (II) or mixtures thereof of less than 1 :2, preferably of less than 1 :3 and more preferably of less than 1 :4.
  • one or more crosslinking compounds, preferably having 3 to 6 functions capable of polycondensation, or mixtures thereof are additionally reacted and are preferably contained in the mixture used in step a) and/or are added in step b).
  • compounds with multiple hydroxyl functions such as triols (e.g., glycerol or 1 ,2,3-hexanetriol), tetraols (e.g, pentaerythritol), or hexaols (e.g., sorbitol or mannitol), compounds with multiple carboxylic acid functions or their salts, their alkylesters, or their anhydrides such as trimellitic acid, trimellitic anhydride, or trimesic acid, or compounds with both hydroxyl functions and carboxylic acid functions or their salts, their alkylesters, or their anhydrides such as citric acid, malic acid, tartaric acid, or gallic acid may be additionally reacted and preferably may be contained in the mixture used in step a) and/or added in step b).
  • triols e.g., glycerol or 1 ,2,3-hexanetriol
  • tetraols e.g, pentaery
  • the one or more crosslinking compounds or mixtures thereof are selected from the group consisting of citric acid, malic acid, tartaric acid, gallic acid, pentaerythritol, glycerol, sorbitol, mannitol, 1 ,2,3-hexanetriol, trimellitic acid, trimellitic anhydride, trimesic acid, and mixtures thereof.
  • crosslinking compounds or mixtures thereof would be used in a molar ratio of the one or more crosslinking compounds or mixtures thereof to the one or more alkylene glycols of the formula (II) or mixtures thereof of less than 1 :10, preferably of less than 1 :15 and more preferably of less than 1 :20.
  • one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof are additionally reacted and are preferably contained in the mixture used in step a) and/or are added in step b), and more preferably are added in step b)
  • such substances of the formula (VI-1 ) or (VI-2) or mixtures thereof would be used in a molar ratio of the one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof to the one or more substances of the formula (III) or mixtures thereof of less than 1 :2, preferably of less than 1 :3 and more preferably of less than 1 :4.
  • one or more further substances which can take part in polycondensation reactions can additionally be reacted and be added separately or be contained in the mixture used in step a) and/or added in step b).
  • phthalic acid isophthalic acid, 3-sulfophthalic acid, 4-sulfophthalic acid, naphthalene-1 ,4- dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, tetrahydrophthalic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, 2,5-furandicarboxylic acid, adipic acid, sebacic acid, decan-1 ,10-dicarboxylic acid, fumaric acid, succinic acid, 1 ,4-cyclohexanedicarboxylic acid, cyclohexanediacetic acid, glutaric acid, azelaic acid, or their salts or their (di)alkyl esters, preferably their (Ci-C4)-(di)alkyl esters and more preferably their (di)alkyl esters, preferably their (Ci-C4)
  • the mixture used in step a) of the inventive process may comprise further substances such as catalyst systems or substances which do not take part in polycondensation reactions, e.g., one or more solvents or one or more additives.
  • one or more catalyst systems are used in step a) and/or in step c) and are contained in the mixture used in step a) and/or are added in step b) or are added to the reaction vessel at any other time before or during the reaction, e.g., are added during heating in step a) and/or are added to the mixture obtained in step b) and/or are added during step c) separately.
  • one or more catalyst systems and even more preferably one or more metal catalyst systems, are used in step a) and/or in step c).
  • Examples for the one or more catalyst systems comprise carboxylic acids, phenols, metal alkoxides, and/or other typical condensation catalyst systems known in the art such as antimony, titanium, germanium, cobalt, zinc, magnesium, manganese, and/or calcium-based catalyst systems.
  • the one or more catalyst systems may further comprise, e.g., additives, stabilizers, and bluing agents.
  • one or more metal catalyst systems are used in the inventive process, and even more preferably, the one or more metal catalyst systems comprise at least one titanium-based catalyst, and particularly preferably comprise titanium tetraisopropylate and/or titanium tetrabutylate.
  • the amount of the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof, or, in case one or more polyalkyleneglycols of the formula (V) or mixtures thereof are additionally reacted preferably is at least 10 wt.-%, more preferably is at least 20 wt.-%, even more preferably is at least 40 wt.-%, particularly preferably is from 40 to 90 wt.-% and extraordinarily preferably is from 50 to 90 wt.-%, in each case based on the combined weight of the terephthalic acid (formula (I)) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and, if used in the inventive process, the one or more substances of the formula (
  • the amount of the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof in the inventive process is at least 40 wt.-%, more preferably is from 40 to 90 wt.-% and even more preferably is from 50 to 90 wt.-%, in each case based on the combined weight of the terephthalic acid (formula (I)) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and, if used in the inventive process, the one or more polyalkyleneglycols of the formula (V) or mixtures thereof and, if used in the inventive process, the one or more crosslinking compounds having 3 to 6 functions capable of polycondensation or mixtures thereof and, if used in the inventive process, the one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof.
  • no substances of the formula (IV) or mixtures thereof are additionally reacted.
  • the amount of the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof in the inventive process is at least 10 wt.-%, more preferably is from 12 to 90 wt.-%, even more preferably is from 15 to 85 wt.-% and particularly preferably is from 50 to 80 wt.-%, in each case based on the combined weight of the terephthalic acid (formula (I)) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and, if used in the inventive process, the one or more substances of the formula (IV) or mixtures thereof and, if used in the inventive process, the one or more polyalkyleneglycols of the formula (V) or mixtures thereof and, if used in the inventive process, the one or more crosslinking compounds having 3 to 6 functions capable of polycondensation or mixtures thereof and, if used in the inventive process, the one or more substances of the formula (VI).
  • the combined amount of the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and the one or more polyalkyleneglycols of the formula (V) or mixtures thereof preferably is at least 35 wt.-%, more preferably is from 40 to 90 wt.-%, even more preferably is from 50 to 90 wt.-%, particularly preferably is from 60 to 90 wt.-% and extraordinarily preferably is from 70 to 90 wt.-%, in each case based on the combined weight of the terephthalic acid (formula (I)) and the one or more substances of the formula (III) (or (111-1 )) or mixtures thereof and the one or more polyalkyleneglycols of the formula (V) or mixtures thereof and, if used in the inventive process, the one or more substances of the formula (IV) or mixtures thereof and,
  • one or more alkylene glycols of the formula (II) or mixtures thereof further reactants contained in the mixture used in step a) are selected from the group consisting of 3), 4), 5) and 6)
  • the mixture may further comprise, e.g., a catalyst system, preferably a metal catalyst system, further additives, and/or one or more solvents.
  • one or more alkylene glycols of the formula (II) or mixtures thereof further reactants contained in the mixture used in step a) are selected from the group consisting of 3) and 4)
  • crosslinking compounds having 3 to 6 functions capable of polycondensation or mixtures thereof.
  • the reactants contained in the mixture used in step a) are
  • the reactants contained in the mixture used in step a) are
  • the mixture used in step a) consists of
  • a catalyst system preferably a metal catalyst system.
  • step b) in addition to the reactants 1) combined in step b) with the mixture obtained in step a), preferably added in step b), 1 ) one or more substances of the formula (III) (or (111-1 )) or mixtures thereof further reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are selected from the group consisting of 2), 3), 4), 5), and 6)
  • step b) one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof.
  • a catalyst system e.g., a metal catalyst system, further additives, and/or one or more solvents may be added.
  • step b) in addition to the reactants 1) combined in step b) with the mixture obtained in step a), preferably added in step b),
  • one or more substances of the formula (III) (or (111-1 )) or mixtures thereof further reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are selected from the group consisting of 2) and 3)
  • step b) one or more substances of the formula (IV) or mixtures thereof.
  • a catalyst system preferably a metal catalyst system, further additives, and/or one or more solvents may be added.
  • step b) e.g., a catalyst system, preferably a metal catalyst system, further additives, and/or one or more solvents may be added.
  • a catalyst system preferably a metal catalyst system
  • further additives, and/or one or more solvents may be added.
  • step b) in addition to the reactants 1) combined in step b) with the mixture obtained in step a), preferably added in step b),
  • one or more substances of the formula (III) (or (111-1 )) or mixtures thereof further reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are selected from the group consisting of 2), 3), 4), and 5)
  • step b) one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof.
  • a catalyst system e.g., a metal catalyst system, further additives, and/or one or more solvents may be added.
  • step b) 1 ) combined in step b) with the mixture obtained in step a), preferably added in step b),
  • one or more substances of the formula (III) (or (111-1 )) or mixtures thereof further reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are selected from the group consisting of 2), 3), and 4)
  • crosslinking compounds having 3 to 6 functions capable of polycondensation or mixtures thereof.
  • step b e.g., a catalyst system, preferably a metal catalyst system, further additives, and/or one or more solvents may be added.
  • a catalyst system preferably a metal catalyst system
  • further additives, and/or one or more solvents may be added.
  • step b) the reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are
  • step b) e.g., a catalyst system, preferably a metal catalyst system, further additives, and/or one or more solvents may be added.
  • the reactants combined in step b) with the mixture obtained in step a), preferably added in step b), are
  • step b) one or more polyalkyleneglycols of the formula (V) or mixtures thereof.
  • a catalyst system e.g., a metal catalyst system, further additives, and/or one or more solvents may be added.
  • step b) 1) a catalyst system, preferably a metal catalyst system are combined in step b) with the mixture obtained in step a), preferably are added in step b).
  • a further subject matter of the invention is a product or polyester obtainable by the inventive process.
  • Products obtainable by the inventive process comprise the polyesters and additionally may comprise unreacted reactants, side products, catalysts, decomposition products, additives, and/or solvents.
  • Polyesters obtainable by the inventive process comprise one or more structural units of the formula (la) and one or more structural units of the formula (Ila)
  • R 1 has the meaning as described above for formula (III), the -(OC2H4) groups and the -(OCsHe) groups are arranged blockwise, alternating, periodically and/or statistically, preferably blockwise, wherein the block consisting of the -(OCsHe) groups is bound, in the polyester, to a COO group, and b and c have the meaning as described above for formula (111-1 ).
  • Polyesters obtainable by the inventive process may also comprise terminal groups derived from crosslinking structural units in case one or more crosslinking compounds, preferably having 3 to 6 functions capable of polycondensation or mixtures thereof, are additionally reacted. Furthermore, and as already stated above, the polyesters obtainable by the inventive process may also comprise one or more terminal groups of the formula (VI-1 a) or (Vl-2a) or mixtures thereof in case one or more substances of the formula (VI-1 ) or (VI-2) or mixtures thereof are additionally reacted.
  • polyesters obtainable by the inventive process preferably are anionic or nonionic and more preferably are nonionic.
  • the groups (C2H4) in the alkylene glycols of the formula (II) or in the structural units of the formula (Ila), in the substances of the formula (III) (or (111-1 )) or in the terminal groups of the formula (Illa) (or (111-1 a)), in the polyalkyleneglycols of the formula (V) or in the structural units of the formula (Va), or in the substances of the formula (VI-1 ) or in the terminal groups of the formula (VI-1 a) preferably are of the formula -CH2-CH2-.
  • the groups (CsHe) in the alkylene glycols of the formula (II) or in the structural units of the formula (Ila), in the substances of the formula (III) (or (111-1 )) or in the terminal groups of the formula (Illa) (or (111-1 a)), or in the polyalkyleneglycols of the formula (V) or in the structural units of the formula (Va) preferably are of the formula -CH(CH3)-CH2- or -CH2-CH(CH3)-, i.e., of the formula:
  • the groups (C4H8) in the alkylene glycols of the formula (II) or in the structural units of the formula (Ila), in the substances of the formula (III) or in the terminal groups of the formula (Illa), or in the polyalkyleneglycols of the formula (V) or in the structural units of the formula (Va) preferably are of the formula -CH(CH3)-CH(CH3)-, i.e., of the formula:
  • the inventive process describes a polycondensation process. Such a process leads to statistically determined mixtures of polyesters in which a mixture of molecular species with a distribution around a molar average is obtained.
  • the terminal group of the formula (Illa) is linked to an acyl group derived from a dicarboxylic acid, preferably to the structural unit of the formula (la) derived from terephthalic acid, which - in the case of structural unit of the formula (la) and terminal group of the formula (Illa) - results in the following structural entity:
  • a further subject matter of the invention is the use of a product or polyester obtainable by the inventive process as soil release polymer.
  • Soil release polymer as used herein means a product or polymer that enhances soil removal during laundering by modifying the surface of the fabric that is laundered, preferably by increasing surface polarity.
  • the product or polyester preferably is present in a laundry detergent composition.
  • a further subject matter of the present invention is laundry detergent compositions comprising
  • the laundry detergent compositions of the invention comprise the one or more products or polyesters of component Z1 ) preferably in an amount of at least 0.1 wt.-%, more preferably in an amount from 0.1 to 10 wt.-%, even more preferably in an amount from 0.2 to 5 wt.-% and particularly preferably in an amount from 0.2 to
  • the laundry detergent compositions of the invention preferably comprise Z2) one or more surfactants.
  • Surfactants assist in removing soil from textile materials and also assist in maintaining removed soil in solution or suspension in the wash liquor.
  • the one or more surfactants of component Z2) of the laundry detergent compositions of the invention are selected from the group consisting of anionic, nonionic, cationic and zwitterionic surfactants, and more preferably from the group consisting of anionic, nonionic and zwitterionic surfactants.
  • Suitable anionic surfactants that may be used are any of the conventional anionic surfactant types typically used in laundry detergent compositions. 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.
  • 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 laundry detergent compositions of the invention or during the process of formulating the laundry detergent compositions of the invention through excess addition of neutralizing agent.
  • alkyl ether sulfates are alkyl polyethoxylate sulfate anionic surfactants of the formula
  • R 5 is a saturated or unsaturated alkyl chain having preferably from 10 to 22 carbon atoms, and more preferably from 12 to 16 carbon atoms
  • M c + 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 z averages preferably from 1 to 15, more preferably from 1 to 3 and even more preferably is 3.
  • A alkyl sulfates
  • R 6 is a linear or branched alkyl chain having preferably from 8 to 24 carbon atoms, and more preferably from 12 to 18 carbon atoms, and
  • Md + 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.
  • Soaps are preferably fatty acids and more preferably linear saturated or unsaturated fatty acids having from 10 to 18 carbon atoms.
  • 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 and polyhydroxy amides (glucamides) such as N-methyl glucamides. Mixtures of nonionic surfactant may be used.
  • the laundry detergent compositions of the invention contain preferably from 0.2 to 40 wt.-% and more preferably from 1 to 20 wt.-% of a nonionic surfactant, such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“glucamides”), in each case based on the total weight of the laundry detergent composition.
  • a nonionic surfactant such as alcohol ethoxylate, nonylphenol ethoxylate, alkylpolyglycoside, alkyldimethylamineoxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide, polyhydroxy alkyl fatty acid amide, or N-acyl N-alkyl derivatives of glucosamine (“
  • the laundry detergent compositions of the invention may comprise up to 10 wt.-% of a zwitterionic surfactant, e.g., amine oxide or betaine, based on the total weight of the laundry detergent composition.
  • a zwitterionic surfactant e.g., amine oxide or betaine
  • Typical amine oxides used are of the formula
  • R 7 is a long chain moiety, and each CH2R 8 are short chain moieties, and
  • R 8 is preferably selected from the group consisting of H, CH3 and -CH2OH.
  • R 7 is a primary or branched hydrocarbyl moiety with a chain length of from 8 to 18, which can be saturated or unsaturated.
  • R 7 is a primary alkyl moiety with a chain length of 8 to 18 carbon atoms.
  • Preferred amine oxides have compositions wherein R 7 is a Cs-Cis alkyl and R 8 is H. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide, hexadecyl dimethylamine oxide, octadecylamine oxide.
  • a preferred amine oxide material is lauryl dimethylamine oxide, also known as dodecyldimethylamine oxide or DDAO.
  • Betaines may be alkyldimethyl betaines or alkylamido betaines, wherein the alkyl groups have C12-18 chains.
  • the one or more surfactants of component Z2) of the laundry detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps, nonionic surfactants, amine oxides and betaines, and preferably the one or more surfactants of component Z2) of the laundry detergent compositions of the invention are selected from the group consisting of linear alkyl benzene sulfonates, alkyl ether sulfates, alkyl sulfates, soaps and nonionic surfactants.
  • surfactants than the preferred LAS, AES, AS, soaps and nonionic surfactants may be added to the mixture of surfactants.
  • the laundry detergent compositions of the invention may comprise one or more further optional ingredients, e.g., they may comprise conventional ingredients commonly used in laundry detergent compositions.
  • 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, antiredeposition agents, dispersing agents, fabric softening and antistatic agents, fluorescent whitening agents, enzymes, enzyme stabilizing agents, foam regulators, defoamers, malodor 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 laundry detergent compositions.
  • 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.
  • 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.
  • one or more enzymes selected from protease, mannanase, pectate lyase, cutinase, lipase, amylase, and cellulase may be present in the 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 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 laundry detergent composition.
  • buffers are one or more ethanolamines, e.g., monoethanolamine (MEA) or triethanolamine (TEA). They are preferably used in the laundry detergent compositions of the invention at levels of from 1 to 15 wt.-%, based on the total weight of the 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.
  • amino ethanol buffers are alkali hydroxides such as sodium hydroxide or potassium hydroxide.
  • Further washing and cleaning ingredients which may be present in the 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 laundry detergent compositions of the invention in amounts of from about 5 to about 80 wt.-%, based on the total weight of the laundry detergent compositions.
  • Inorganic builders include, for example, alkali metal, ammonium and alkanolammonium salts of polyphosphates, silicates, carbonates, sulfates and aluminosilicates.
  • citrates for example citric acid and its soluble salts, in particular the sodium salt
  • polycarboxylic acid builders which can also be used in granulated compositions, in particular together with zeolites and/or sheet silicates.
  • the 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, anti-static agents, and ironing aids.
  • the laundry detergent compositions of the invention may further comprise pearlisers and/or opacifiers or other visual cues and shading dye.
  • the laundry detergent compositions of the invention may be in solid or in liquid form, including a gel form.
  • the laundry detergent compositions of the invention may be packaged as unit doses in a polymeric film soluble in the wash water.
  • the 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.
  • the laundry detergent composition is solid.
  • the laundry detergent composition is liquid.
  • 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 a laundry detergent composition according to the invention, 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.
  • the concentration of the one or more products or polyesters obtainable by the inventive process in the aqueous solution is typically in the range of from 0.001 g/l to 0.5 g/l, from 0.002 g/l to 0.5 g/l, from 0.01 g/l to 0.5 g/l, from 0.02 g/l to 0.5 g/l, from 0.1 g/l to 0.5 g/l, or from 0.2 g/l to 0.4 g/l, or from 0.001 g/l to 0.2 g/l, from 0.002 g/l to 0.2 g/l, from 0.01 g/l to 0.2 g/l, from 0.02 g/l to 0.2 g/l, or from 0.1 g/l to 0.2 g/l.
  • step a) Products of step a) were prepared. Terephthalic acid and propylene glycol were introduced into reaction vessels at room temperature under a nitrogen atmosphere and stirred. The reaction mixtures were heated up to 100 °C. At this temperature, catalysts were added, and the mixtures were further slowly heated up to 190 °C. Water was distilled out of the systems using heated distillation columns. In each example, the temperature was slowly increased up to 220 °C to keep distillation going on, subsequently held at this temperature, and further stirred. One or more samples were taken during the heating period, and their acid value was determined. Once the desired acid value was reached, approximately 5 to 15 hours after distillation commenced, the reaction mixtures were cooled and stored for further reaction steps.
  • Polyesters were prepared.
  • a product as obtained in Examples I or II and a terminal capped polyalkylene glycol were introduced into reaction vessels at room temperature under a nitrogen atmosphere and stirred.
  • the reaction mixtures were heated up to 100 °C.
  • optionally catalysts were added, and the mixtures were further slowly heated up to 230 °C.
  • the pressure was slowly reduced to 1 mbar.
  • Propylene glycol and impurities were distilled out of the systems.
  • the mixtures were stirred for 4 hours at 230 °C and a pressure of 1 mbar. After the end of this time period, the inner pressure of the reaction vessels was increased to 1 bar using nitrogen, and the molten products were subsequently removed from the reactors and allowed to solidify.
  • a polyester was prepared.
  • a product as obtained in Example III, mPEG200, 5-SIM, and EG were introduced into a reaction vessel at room temperature under a nitrogen atmosphere and stirred.
  • the reaction mixture was heated up to 100 °C.
  • TTB was added, and the mixture was further slowly heated up to 210 °C and stirred for 3 hours at 210 °C.
  • the temperature was reduced to 195 °C, and the pressure was slowly reduced to 1 mbar.
  • Alkylene glycols and impurities were distilled out of the system.
  • the mixture was stirred for 4 hours at 195 °C and a pressure of 1 mbar. After the end of this time period, the inner pressure of the reaction vessel was increased to 1 bar using nitrogen, and the molten product was subsequently removed from the reactor and allowed to solidify.
  • Polyesters were prepared. Terephthalic acid and propylene glycol were introduced into reaction vessels at room temperature under a nitrogen atmosphere and stirred. The reaction mixtures were heated up to 100 °C. At this temperature, catalysts were added, and the mixtures were further slowly heated up to 190 °C. Water was distilled out of the systems using heated distillation columns. In each example, the temperature was slowly increased up to 220 °C to keep distillation going on, subsequently held at this temperature, and further stirred. One or more samples were taken during the heating period, and their acid value was determined. Once the desired acid value was reached, approximately 5 to 7 hours after distillation commenced, the reaction mixtures were cooled to 100 °C under stirring. To each of them, mPEG750 was added.
  • the mixtures were heated to 230 °C, and in each example, the pressure was slowly reduced to 1 mbar. Propylene glycol and impurities were distilled out of the system. The mixtures were stirred for 4 hours at 230 °C and a pressure of 1 mbar. After the end of this time period, the inner pressure of the reaction vessels was increased to 1 bar using nitrogen, and the molten products were subsequently removed from the reactors and allowed to solidify.
  • a polyester was prepared. 780.00 g terephthalic acid and 714.54 g propylene glycol were introduced into a reaction vessel at room temperature under a nitrogen atmosphere and stirred. The reaction mixture was heated up to 110 °C. At this temperature, 6.01 g TTB was added, and the mixture was further slowly heated until distillation started (approximately 183 °C). Water was distilled out of the system using a heated distillation column. The temperature slowly increased during distillation towards 220 °C. Samples were taken during the heating period, and their acid value was determined. At an acid value of 1 .2, approximately 10 hours after distillation commenced, the reaction mixture was cooled to room temperature and stored for further reaction steps. 1307 g reaction mixture were obtained.
  • a polyester was prepared. 46.75 g terephthalic acid, 42.83 g propylene glycol, and 183.54 g mPEG750 were introduced into a reaction vessel at room temperature under a nitrogen atmosphere and stirred. The reaction mixture was heated up to 100 °C. At this temperature, 0.72 g TTB was added, and the mixture was further slowly heated up to 195 °C. Water was distilled out of the system using a heated distillation column. The temperature was slowly increased up to 235 °C to keep distillation going on, subsequently held at this temperature and further stirred. Samples were taken during the heating period, and their acid value was determined.
  • a polyester was prepared. 259.83 g terephthalic acid, 238.02 g propylene glycol, and 1020 g mPEG750 were introduced into a reaction vessel at room temperature under a nitrogen atmosphere and stirred. The reaction mixture was heated up to 110 °C. At this temperature, 2.02 g TTB was added, and the mixture was further slowly heated until distillation started (approximately 194 °C). Water was distilled out of the system using a heated distillation column. The temperature was slowly increased up to 230 °C to keep distillation going on, subsequently held at this temperature and further stirred. Samples were taken during the heating period, and their acid value was determined.
  • SLES 2EO is sodium lauryl ether sulfate with 2 moles EO
  • Nl 7EO is C12-15 alcohol ethoxylate 7EO nonionic

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé spécial de préparation de polyesters à partir d'au moins de l'acide téréphtalique, un ou plusieurs alkylène glycols et une ou plusieurs substances permettant d'obtenir des groupes terminaux. Le procédé présente par exemple l'avantage de générer de faibles niveaux de produits secondaires. Les polyesters peuvent être utilisés en tant que polymères antisalissure, en particulier dans des compositions de détergent à lessive.
PCT/EP2024/086864 2023-12-19 2024-12-17 Procédé de préparation de polyesters à l'aide d'acide téréphtalique Pending WO2025132402A1 (fr)

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EP23218253 2023-12-19
EP23218253.5 2023-12-19
EP24153001.3 2024-01-19
EP24153001 2024-01-19
EP24188162.2 2024-07-11
EP24188162 2024-07-11

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PCT/EP2024/086864 Pending WO2025132402A1 (fr) 2023-12-19 2024-12-17 Procédé de préparation de polyesters à l'aide d'acide téréphtalique
PCT/EP2024/086808 Pending WO2025132368A1 (fr) 2023-12-19 2024-12-17 Procédé de préparation de polyesters à l'aide d'acide téréphtalique

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US4132680A (en) 1976-06-24 1979-01-02 The Procter & Gamble Company Detergent compositions having soil release properties
EP0199403A2 (fr) 1985-04-15 1986-10-29 The Procter & Gamble Company Compositions détergentes liquides stables
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
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EP1734171A1 (fr) 2004-04-07 2006-12-20 Matsumoto Yushi-Seiyaku Co., Ltd. Agent de traitement de fibre, fibre courte de polyester réalisée avec celui-ci et tissu non tissé
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WO2016146429A1 (fr) 2015-03-19 2016-09-22 Henkel Ag & Co. Kgaa Esters polymères d'acides dicarboxyliques aromatiques utilisés comme substances actives à pouvoir détachant
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US4132680A (en) 1976-06-24 1979-01-02 The Procter & Gamble Company Detergent compositions having soil release properties
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
US4759876A (en) 1985-03-19 1988-07-26 Colgate-Palmolive Company Stable soil release promoting enzymatic liquid detergent composition
EP0199403A2 (fr) 1985-04-15 1986-10-29 The Procter & Gamble Company Compositions détergentes liquides stables
US4711730A (en) 1986-04-15 1987-12-08 The Procter & Gamble Company Capped 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters useful as soil release agents
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DE4417686A1 (de) 1994-05-20 1995-11-23 Henkel Kgaa Endgruppenmodifizierte schmutzablösevermögende Polyester
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