Classifications

• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/825—Mixtures of compounds all of which are non-ionic
  • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

• Substances that may be used, e. g. as surfactants, in various compositions such as laundry detergent compositions, hard surface cleaning compositions, automatic dishwashing compositions, or agrochemical compositions, are already known. However, there is still a need for further substances that may be employed in such compositions.
• a subject matter of the invention is a mixture of fatty alcohol alkoxylates of the formula (I) R 1 O-(C m H 2m O) x -H (I) wherein
• the units -(C m H 2m O) in the fatty alcohol alkoxylates of the formula (I) of the inventive mixture have, on average, at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt.-% and particularly preferably 100 wt.-% bio-based carbon content, in each case relative to the total mass of carbon in the units -(C m H 2m O) in the fatty alcohol alkoxylates of the formula (I) of the inventive mixture.
• the inventive mixture of fatty alcohol alkoxylates of the formula (I) can be applied e. g. in laundry detergent compositions, preferably in liquid laundry detergent compositions, hard surface cleaning compositions, automatic dishwashing compositions, and agrochemical compositions. They may be used in these compositions in particular as surfactants, more specifically as wetting agents, emulsifiers / co-emulsifiers or dispersing agents, but also as rheology modifiers, and in agrochemical compositions they may also be used as leaf wetting agents, spray retention agents or agents to enhance foliar uptake of active ingredients.
• the structural unit of the formula -(C m H 2m O) x - in a single fatty alcohol alkoxylate molecule of the formula (I) may consist of one or more (C 2 H 4 O)-groups, may consist of one or more (CsHsO)-groups or may consist of a mixture of (C 2 H 4 O)- and (CsHsO)-groups.
• (C 2 H 4 O)- and (CsHsO)-groups exist in a structural unit of the formula -(C m H 2m O) x -, they may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically.
• the groups (C 2 H 4 O) and (C 3 H 6 O) 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 (C 2 H 4 O) and (C 3 H 6 O) arranged in a statistical manner, or in a form wherein adjacent instances of statistical and blockwise arrangements of the groups (C 2 H 4 O) and (C 3 H 6 O) exist.
• any of the groups (C 2 H 4 O) and (C 3 H 6 O) can be linked to R 1 O- and -H in a fatty alcohol alkoxylate molecule of the formula (I).
• R 1 O- and -H in a fatty alcohol alkoxylate molecule of the formula (I) may be connected to a (C 2 H 4 O)-group, they may both be connected to a (C 3 H 6 O)-group or they may be connected to either group selected from (C 2 H 4 O) and (C 3 H 6 O).
• Fatty alcohol alkoxylates are already known in the prior art.
• Fatty alcohol ethoxylates of the prior art are e. g. described in US 5,600,020 , US 5,840,995 and US 2005/0240064 A1 .
• Fatty alcohol alkoxylates may be produced by the reaction of fatty alcohol with alkylene oxide e.g. using catalysts based on calcium or magnesium. The catalyst may be removed or left in the fatty alcohol alkoxylate.
• Bio-based fatty alcohol alkoxylates of formula (I) can, for example, be prepared from (i) fatty alcohol and (ii) ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide, wherein at least a part of one of the aforementioned alkylene oxides is bio-based.
• Bio-based ethylene oxide can be obtained from bio-ethanol, which can be obtained from natural sources like corn, sugarcane, or cellulosic biomass through fermentation. Bio-ethanol is then dehydrated to produce bio-ethylene. The bio-ethylene is then oxidized with oxygen over a silver catalyst to produce bio-based ethylene oxide.
• Bio-based propylene oxide can be obtained from
• the fatty alcohol may be produced by an alkaline hydrolysis (saponification) of a triglyceride and subsequent reduction of the fatty acid to the corresponding fatty alcohol.
• alkaline hydrolysis saponification
• Common catalysts for these reactions include sodium hydroxide and potassium hydroxide.
• the fatty alcohol may be obtained synthetically or, more conveniently and generally more economically, from natural sources.
• Triglycerides are widely distributed in nature in a variety of animal and vegetable products.
• Distillation and fractionation processes may be used in the production of the fatty alcohol or carboxylic acid (before reduction) to produce the desired carbon chain distribution.
• R 1 is selected from the group consisting of linear or branched, preferably linear, saturated alkyl groups with 7 to 21 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 7 to 21 carbon atoms, and combinations thereof, more preferably consisting of linear or branched, preferably linear, saturated alkyl groups with 11 to 19 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 11 to 19 carbon atoms, and combinations thereof, and even more preferably consisting of linear or branched, preferably linear, saturated alkyl groups with 11 to 17 carbon atoms, linear or branched, preferably linear, mono- or polyunsaturated alkenyl groups with 11 to 17 carbon atoms, and combinations thereof.
• alkyl and alkenyl groups R 1 in the formula (I) are heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetraicosyl, pentaicosyl, hexaicosyl, heptaicosyl, octaicosyl, nonaicosyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, hexadecenyl, octadecenyl, octadecadienyl, octa
• the groups R 1 in the inventive mixture of fatty alcohol alkoxylates of the formula (I) may e. g. be derived from fatty alcohols, such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alycohol, oleyl alcohol, eicosanyl alcohol, or tricosanyl alcohol.
• ester materials from which the groups R 1 in the inventive mixture of fatty alcohol alkoxylates of the formula (I) may be derived are whale oil, beeswax, carnauba wax, animal fat, e.g. tallow fat, palm oil, palm kernel oil, coconut oil, olive oil, cottonseed oil, soybean oil, peanut oil, rapeseed oil, sunflower oil, castor oil, maize oil, sesame oil, non-edible vegetable oils, tall oil and any mixture thereof.
• the oil from trees is called tall oil.
• Used food cooking oils may also be utilised as a source of the groups R 1 in the inventive mixture of fatty alcohol alkoxylates of the formula (I).
• Triglycerides may also be obtained from algae, fungi, yeast or bacteria.
• variable x is an integer number for each single fatty alcohol alkoxylate molecule of the formula (I) in the mixture according to the invention and may be the same or different for the various fatty alcohol alkoxylate molecules in the mixture according to the invention.
• x is selected from integer numbers from 1 to 150, more preferably from 1 to 100, even more preferably from 1 to 75, particularly preferably from 1 to 50, extraordinarily preferably from 1 to 40 and especially preferably from 1 to 30.
• At least 20 wt.-%, more preferably at least 24 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are fatty alcohol alkoxylates with n a units selected from the group consisting of (C 2 H 4 O)-units, (CsHsO)-units and mixtures of (C 2 H 4 O)-units and (CsHsO)-units, where n a is the integer equal to the number n in case the number n itself is an integer or n a is the integer closest to the number n in case the number n itself is not an integer.
• At least 50 wt.-%, more preferably at least 60 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are fatty alcohol alkoxylates with (n a -1), n a or (n a +1) units selected from the group consisting of (C 2 H 4 O)-units, (CsHsO)-units and mixtures of (C 2 H 4 O)-units and (CsHsO)-units, where n a is the integer equal to the number n in case the number n itself is an integer or n a is the integer closest to the number n in case the number n itself is not an integer.
• At least 70 wt.-%, more preferably at least 80 wt.-%, of the total weight of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are fatty alcohol alkoxylates with (n a -2), (n a -1), n a , (n a +1) or (n a +2) units selected from the group consisting of (C 2 H 4 O)-units, (CsHsO)-units and mixtures of (C 2 H 4 O)-units and (CsHsO)-units, where n a is the integer equal to the number n in case the number n itself is an integer or n a is the integer closest to the number n in case the number n itself is not an integer.
• the mixtures of fatty alcohol alkoxylates of the formula (I) according to the invention are characterized in that the fatty alcohol alkoxylates have a narrow homolog distribution (narrow-range alkoxylates).
• the mixture according to the invention may occur together with starting material used for its preparation, in particular fatty alcohol in case the inventive mixture is prepared by alkoxylation of fatty alcohols (in the following referred to as "composition A").
• composition A fatty alcohol
• the fatty alcohol may be present in an amount of 0.01 wt.-% or more, or 0.05 wt.-% or more, or 0.1 wt.-% or more, or 0.2 wt.-% or more, in each case based on the total weight of the composition A.
• the fatty alcohol is present in an amount of preferably less than 15 wt.-%, more preferably less than 5.0 wt.-%, even more preferably less than 3.0 wt.-%, particularly preferably less than 2.0 wt.-% and extraordinarily preferably less than 1.0 wt.-%, in each case based on the total weight of the composition A.
• by-products may be formed.
• the formation of by-products in chemical reactions is quite normal since these reactions usually do not take place with a selectivity of 100 %.
• these by-products are formed in an amount of preferably less than 20.0 wt.-%, more preferably less than 15.0 wt.-%, even more preferably less than 10.0 wt.-%, particularly preferably less than 5.0 wt.-%, extraordinarily preferably less than 3.0 wt.-% and especially preferably less than 2.0 wt.-%, in each case based on the combined total weight of the mixture according to the invention and the by-products, and in particular in case the inventive mixture is prepared by a method according to the invention.
• starting material and in particular fatty alcohol, occurring together with the mixture according to the invention is considered to form part of the by-products.
• the mixture according to the invention may be purified after its preparation and prior to its use, e.g. by distilling, stripping or filtering-off by-products, but in a preferred embodiment, the mixture may be used as obtained without prior purification.
• the mixture according to the invention may advantageously be prepared by alkoxylation of fatty alcohols using a special alkaline earth metal catalyst.
• a further subject matter of the invention is a method for preparing a mixture of fatty alcohol alkoxylates of the formula (I) according to the invention, R 1 O-(C m H 2m O) x -H (I) wherein R 1 , m and x in formula (I), and the average number of (C m H 2m O)-units of the fatty alcohol alkoxylates of the formula (I) in the mixture according to the invention are as defined above, from ethylene oxide, propylene oxide or a mixture of ethylene oxide and propylene oxide and one or more fatty alcohols of the formula (II) R 1 O-H (II) wherein R 1 in formula (II) has the same meaning as in formula (I), and wherein in the method a catalyst (C) based on an alkaline earth metal is used and at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt
• the ethylene oxide, the propylene oxide or the mixture of ethylene oxide and propylene oxide used for the preparation of the mixture of fatty alcohol alkoxylates of the formula (I) has, on average, at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt.-% and particularly preferably 100 wt.-% bio-based carbon content, in each case relative to the total mass of carbon in the ethylene oxide, the propylene oxide or the mixture of ethylene oxide and propylene oxide used for the preparation of the mixture of fatty alcohol alkoxylates of the formula (I).
• the catalyst (C) is obtainable by a reaction involving
• the carboxylic acid (B) mentioned under component (b) above may e. g. be a carboxylic acid, wherein the carboxylic acid function -COOH is connected to a hydrocarbon group but may also e. g. be a carboxylic acid wherein the carboxylic acid function -COOH is connected to a hydrocarbon group that contains or is interrupted by ether functions.
• the alcohol mentioned in component (b) is an alcohol wherein the hydroxyl function -OH is bonded to a hydrocarbyl group.
• the alcohol solvent is an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water.
• the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, magnesium carbonate, magnesium sulfate, magnesium phosphate, calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, calcium phosphate, strontium hydroxide, strontium acetate, strontium carbonate, strontium sulfate, strontium phosphate, barium hydroxide, barium acetate, barium carbonate, barium sulfate, and barium phosphate.
• the alkaline earth metal compound (A) is selected from the group consisting of calcium hydroxide, calcium acetate, calcium carbonate, calcium sulfate, and calcium phosphate.
• the alkaline earth metal compound (A) is selected from the group consisting of magnesium hydroxide, magnesium acetate, calcium hydroxide, calcium acetate, strontium hydroxide, strontium acetate, barium hydroxide, and barium acetate.
• the alkaline earth metal compound (A) is selected from the group consisting of calcium acetate and calcium hydroxide.
• the strong acid (AC) is an acid which has a pK A value of 3 or less, more preferably is selected from the group consisting of acids of sulfur oxides and phosphorus oxides, even more preferably from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids (among the sulfonic acids methane sulfonic acid is preferred), phosphorus acid, phosphorous acid and phosphonic acids (among the phosphonic acids methane phosphonic acid is preferred) and particularly preferably from the group consisting of sulfuric acid, sulfurous acid and methane sulfonic acid.
• the strong acid (AC) is sulfuric acid.
• the molar ratio of the alkaline earth metal compound (A) to the strong acid (AC) is from 1.0:0.1 to 1.0:1.0, more preferably from 1.0:0.2 to 1.0:0.9 and even more preferably from 1.0:0.3 to 1.0:0.8.
• the polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol is a polyethylene glycol having a molecular weight from 100 g/mol to 1500 g/mol.
• the C 1 -C 18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol is a methyl-capped polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol and more preferably is a methyl-capped polyethylene glycol having a molecular weight from 100 g/mol to 1500 g/mol.
• volatile components are removed before the catalyst (C) is used for the preparation of the mixture of fatty alcohol alkoxylates of the formula (I).
• a carboxylic acid (B) is used in the preparation of the catalyst (C).
• the molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) in the preparation of the catalyst (C) is from 1:1 to 1:5.
• the carboxylic acid (B) is represented by formula (III), R 4 -[O] q -[CH 2 CH 2 -O] p -CH 2 COOH (III) wherein
• the carboxylic acid (B) is represented by formula (III), R 4 -[O] q -[CH 2 CH 2 -O] p -CH 2 COOH (III) wherein
• the carboxylic acid (B) is represented by formula (III), R 4 -[O] q -[CH 2 CH 2 -O] p -CH 2 COOH (III) wherein
• the catalyst (C) is obtainable by a reaction involving
• the catalyst (C) is obtainable by a reaction involving
• the catalyst (C) is obtainable by a reaction involving
• the catalyst (C) is obtainable by a reaction involving
• the catalyst (C) is obtainable by a reaction involving
• the molar ratio of the alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to the one or more fatty alcohols of the formula (II) preferably is from 1:1 to 200:1, more preferably from 1:1 to 100:1, even more preferably from 1:1 to 50:1, particularly preferably from 2:1 to 35:1 and extraordinarily preferably from 2.5:1 to 20:1.
• the molar ratio of alkaline earth metal compound (A) to carboxylic acid (B) (molar ratio (A):(B)) in the preparation of the catalyst (C) preferably is from 1:1 to 1:5. More preferably, the molar ratio (A):(B) is from 1:1.5 to 1:4, even more preferably from 1:1.8 to 1:2.2 and particularly preferably from 1:1.9 to 1:2.1. In an extraordinarily preferred embodiment, the molar ratio of (A):(B) in the preparation of the catalyst (C) is approximately 1:2.
• the reaction for the preparation of the catalyst (C) is carried out in the presence of at least one polar solvent, more preferably a polar solvent comprising at least one hydroxyl group, even more preferably at least one alcohol having 1 to 5 carbon atoms or a mixture thereof with water.
• the polar solvent is propan-2-ol or a mixture thereof with water.
• the polar solvent is ethanol or a mixture thereof with water.
• the acid (AC) is selected from the group consisting of acids of sulfur oxides and phosphorus oxides, more preferably from the group consisting of sulfuric acid, sulfurous acid, sulfonic acids (among the sulfonic acids methane sulfonic acid is preferred), phosphorus acid, phosphorous acid and phosphonic acids (among the phosphonic acids methane phosphonic acid is preferred).
• Sulfuric acid, sulfurous acid and methane sulfonic acid are of particular interest.
• the reaction for obtaining the catalyst (C) is performed in the presence of sulfuric acid.
• the alkaline earth metal catalyst (C) by first allowing the alkaline earth metal compound (A) to react with the carboxylic acid (B), preferably in a solvent as described above, after which the reaction mixture is further treated with the acid (AC).
• the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in a polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol or mixtures of such polyalkylene glycols, or in a C 1 -C 18 alkyl-capped polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol, preferably a methyl-capped polyalkylene glycol having a molecular weight from 100 g/mol to 1500 g/mol and more preferably a methyl-capped polyethylene glycol having a molecular weight from 100 g/mol to 1500 g/mol or mixtures of such alkyl-capped polyalkylene glycols, optionally in the presence of water, after which the reaction mixture is further treated with the acid (AC).
• the dispersing step may be performed in the presence of a carboxylic acid (B), which is represented by formula (III), R 4 -[O
• the alkaline earth metal catalyst (C) by first dispersing the alkaline earth metal compound (A) in an alcohol solvent, preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, after which the reaction mixture is further treated with the acid (AC).
• an alcohol solvent preferably an alcohol solvent having 1 to 5 carbon atoms, more preferably propan-2-ol, or a mixture thereof with water, after which the reaction mixture is further treated with the acid (AC).
• any common reactor may be employed, preferably a reactor with an agitating/mixing means, such as, e.g., a magnetic stirrer, a mechanical stirrer, a static mixer, a blender, a batch disperser, or a Rotor-Stator disperser.
• an agitating/mixing means such as, e.g., a magnetic stirrer, a mechanical stirrer, a static mixer, a blender, a batch disperser, or a Rotor-Stator disperser.
• the preparation of the catalyst (C) is preferably carried out under a pressure of from 0.5 to 2 bar, more preferably from 0.8 to 1.5 bar, even more preferably from 0.9 to 1.2 bar. In a preferred embodiment, the catalyst is prepared under atmospheric pressure. Furthermore, the catalyst (C) is preferably prepared at a temperature of from -30 °C to 80 °C, preferably from -10 °C to 60 °C, more preferably from 0 °C to 50 °C. In a preferred embodiment, the catalyst is prepared at a temperature of from 20 to 40 °C, especially at room temperature.
• the thus prepared alkaline earth metal catalyst (C), preferably the calcium catalyst, typically has a content of alkaline earth metal ions, preferably Ca 2+ ions, that is from 0.5 to 10 wt.-%, often from 1 to 7 wt.-%, often from 2.0 to 5.5 wt.-%.
• the catalyst may be purged of volatile components, such as the solvent, water and other volatile byproducts by employing commonly used methods.
• volatile components such as the solvent, water and other volatile byproducts by employing commonly used methods.
• the volatile components are removed in vacuo, e.g. under a pressure below 0.8 bar, preferably below 0.3 bar, more preferably below 0.1 bar, and/or at elevated temperatures, e.g. 50 to 180 °C, preferably 70 to 150 °C, more preferably 80 to 140 °C.
• the volatile compounds are removed on a rotary evaporator at a pressure below 0.1 bar and a temperature of from 80 °C to 140 °C.
• the method of the invention for preparing a mixture of fatty alcohol alkoxylates of the formula (I) according to the invention comprises the steps of
• the catalyst (C) may be introduced as obtained from the reaction of its preparation described above directly, or in its form that has been purged of volatile compounds, but preferably as obtained from the reaction of its preparation described above directly.
• the fatty alcohols of formula (II) may be introduced in their raw form or may be purified prior to use.
• the catalyst (C) is preferably introduced into the reactor in an amount from 0.01 to 5 wt.-%, preferably from 0.05 to 3 wt.-%, more preferably from 0.1 to 1 wt.-% based on the total weight of the mixture of fatty alcohols of formula (II) and alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide.
• the pressure-resistant reactor is not particularly limited but is designed to withstand the pressures employed in the process, thus that it is not damaged during the process.
• the reactor is designed to withstand pressures both above 10 bar, more preferably above 15 bar, and below 0.01 bar, more preferably below 0.001 bar.
• the pressure-resistant reactor is an autoclave, more preferably an autoclave equipped with an agitating means such as a magnetic or a mechanical stirrer.
• step ii) of the method of the invention it is advisable to carry out step ii) of the method of the invention after step i).
• the step of drying the reactor content is also not necessarily required, because the mixture of fatty alcohol alkoxylates of the formula (I) according to the invention would at least partially be generated in the process.
• the catalyst (C) is introduced into the reactor as obtained from the reaction of its preparation described above directly, it is advisable to carry out the drying step, since the directly obtained catalyst (C) typically contains residues of polar solvents or their mixtures with water.
• the drying step iii) may be omitted.
• step iii) since volatile components may also be present as impurities in the one or more fatty alcohols of formula (II). Therefore, in particularly preferred embodiments, step iii) is carried out.
• the step iii) of drying the reactor content is typically performed at a temperature of from 50 °C to 200 °C, preferably of from 50 °C to 180 °C, more preferably of from 60 °C to 150 °C, even more preferably of from 70 °C to 130 °C, particularly preferably of from 80 °C to 120 °C, and at a pressure below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar.
• the thus generated vacuum is preferably a dynamic vacuum.
• the vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Furthermore, it is advisable to reduce the pressure and increase temperature in the reactor gradually to prevent boiling retardation.
• the step of drying the reactor content is carried out at a temperature of from 80 °C to 120 °C and a pressure below 0.01 bar, preferably over a period of at least 15 minutes, more preferably over a period of at least 30 minutes, even more preferably over a period of at least 1 hour. It is particularly preferred to dry the content of the reactor to constant mass.
• the fluid line between the vacuum pump and the reactor is interrupted, to ensure that the components added to the reactor after the drying remain in the reactor and are not directly withdrawn therefrom. Furthermore, it is preferable to compensate the vacuum in the reactor with nitrogen or other protective gas before carrying out the further steps, to reduce the risk of air entering the reactor.
• Step iv) of heating the content of the reactor is generally performed at a temperature of from 80 °C to 200 °C, preferably from 120 °C to 190 °C, more preferably from 160 °C to 180 °C. This temperature is maintained at least until step vi) is finished, preferably until step vii) is finished.
• the reactor may be optionally pressurized in step v) with nitrogen or other protective gas to a pressure of from 0.3 to 3.5 bar, preferably of from 0.4 to 3.3 bar, more preferably of from 0.5 to 3.0 bar, even more preferably of from 0.7 to 2.5 bar and particularly preferably of from 0.8 to 2.2 bar above atmospheric pressure.
• alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide introduced in the following step is diluted with the protective gas, thus that pressure-controlled dosage of alkylene oxide into the reactor is facilitated.
• step vi) the reactor is further pressurized with alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to a total internal pressure of from 1.5 to 10 bar, preferably from 2 to 8 bar, more preferably from 3 to 6 bar, even more preferably from 4 to 5 bar, above atmospheric pressure, with the proviso that the pressure in step vi) is above the pressure before step vi).
• alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide to a total internal pressure of from 1.5 to 10 bar, preferably from 2 to 8 bar, more preferably from 3 to 6 bar, even more preferably from 4 to 5 bar, above atmospheric pressure, with the proviso that the pressure in step vi) is above the pressure before step vi).
• step vii) after introduction of the intended amount of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide, the alkylene oxide inlet is closed and the reaction is allowed to proceed until the pressure in the reactor is constant.
• alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide
• the pressure is considered constant, if it does not change by more than 0.05 bar over a period of 15 minutes, preferably 30 minutes, more preferably 1 hour. It is particularly preferred that the pressure in the reactor does not change by more than 0.01 bar over a period of 1 hour.
• step vii) it is advisable to remove residual alkylene oxide from the reactor before isolating the mixture of fatty alcohol alkoxylates of the formula (I) according to the invention, in order to prevent any unwanted reactions with alkylene oxide from taking place after isolation of the product.
• residual alkylene oxide is removed from the reactor by cooling the reactor content to a temperature of from 50 to 120 °C, more preferably from 70 to 100 °C and even more preferably from 85 to 95 °C, and employing a pressure of below 0.8 bar, preferably below 0.1 bar, more preferably below 0.05 bar.
• the thus generated vacuum is preferably a dynamic vacuum.
• the vacuum pump for generating the vacuum is not particularly limited; it is, however, preferable to use an aspirator for generating the vacuum. Removal of residual alkylene oxide under these conditions is preferably carried out for at least 10 minutes, more preferably at least 30 minutes, even more preferably at least 1 hour.
• the method of isolation of the mixture of fatty alcohol alkoxylates of the formula (I) according to the invention is not particularly limited. However, it is preferable to isolate the product at elevated temperatures, specifically at temperatures of from 30 to 120 °C, preferably from 40 to 100 °C, more preferably from 50 to 90 °C. At these temperatures the mixture of fatty alcohol alkoxylates of the formula (I) according to the invention is typically in a liquid state and has a sufficiently low viscosity, and therefore may be transferred out of the reactor more easily than in the solid state, e.g. by pouring the product out of the reactor or via a bottom valve, thereby minimizing the amount of residues in the reactor. Thus, the subsequent cleaning and maintenance of the reactor is also facilitated.
• the method for preparing a mixture of fatty alcohol alkoxylates of the formula (I) according to the invention using the catalyst (C) described above may be interrupted at any stage, and continued at a later point in time, without the reaction time being significantly increased.
• a further subject matter of the invention is an alkoxylation product obtainable by the inventive method described above for preparing a mixture according to the invention.
• the alkoxylation product comprises a mixture of fatty alcohol alkoxylates of the formula (I) according to the invention and may optionally comprise further substances such as starting materials or reactants, in particular fatty alcohols, and/or by-products.
• the materials used to prepare the inventive mixture of fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product are bio-based under the description above and derived from natural sources. More preferably, the inventive mixture of fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product has at least 25 wt.-%, preferably at least 50 wt.-%, more preferably at least 75 wt.-%, even more preferably at least 90 wt.-% and particularly preferably 100 wt.-% bio-based carbon content, in each case relative to the total mass of carbon in the mixture of fatty alcohol alkoxylates of the formula (I) or relative to the total mass of carbon in the alkoxylation product, respectively.
• reactants with a respective bio-based carbon content may be used for their preparation.
• the bio-based carbon content as used herein is measured according to standard ASTM D6866-12, Method B.
• the bio-based carbon content of the mixture of fatty alcohol alkoxylates of formula (I) as used herein is measured according to standard ASTM D6866-12, Method B.
• the bio-based carbon content of the alkoxylation product as used herein is measured according to standard ASTM D6866-12, Method B.
• the bio-based carbon content of ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide as used herein is measured according to standard ASTM D6866-12, Method B.
• the bio-based carbon content of the mixture of fatty alcohols of the formula (II) as used herein is measured according to standard ASTM D6866-12, Method B.
• bio-based content is reported in ASTM D6866-12, Method B (see section 3.3.9 of ASTM D6866-12).
• Biobased carbon content “bio-based carbon content”
• biobased content “bio-based content”
• biogenic carbon content “biomass-derived carbon” herein refer to the same thing and are all measured in wt.-%.
• bio-based carbon content is used.
• ASTM D6866-12, Method B lab results report the percentage of bio-based carbon content relative to total carbon, and not to total mass of the sample or molecular weight.
• bio-based carbon content pMC * 0.95 (%)
• the bio-based carbon content as used herein is measured according to standard ASTM D6866-21, Method B.
• the bio-based carbon content of the mixture of fatty alcohol alkoxylates of formula (I) as used herein is measured according to standard ASTM D6866-21, Method B.
• the bio-based carbon content of the alkoxylation product as used herein is measured according to standard ASTM D6866-21, Method B.
• the bio-based carbon content of ethylene oxide, propylene oxide or mixtures of ethylene oxide and propylene oxide as used herein is measured according to standard ASTM D6866-21, Method B.
• the bio-based carbon content of the mixture of fatty alcohols of the formula (II) as used herein is measured according to standard ASTM D6866-21, Method B.
• bio-based content is reported in ASTM D6866-21, Method B.
• Biobased carbon content refers to the same thing and are all measured in wt.-%.
• bio-based carbon content refers to the same thing and are all measured in wt.-%.
• ASTM D6866-21, Method B lab results report the percentage of bio-based carbon content relative to total carbon, and not to total mass of the sample or molecular weight.
• Bio-based products are part of the natural carbon cycle. If these products are incinerated or biodegraded, the quantity of carbon dioxide that is emitted corresponds to the quantity fixed by photosynthesis during biomass growth.
• the provided sample material does not undergo any pre-treatment procedure and is converted to graphite as is using the following procedure.
• EA Elemental Analyzer
• the remaining CO 2 is transferred into a graphitization system, preferably custom-made, converted into carbon (graphite) catalytically using H 2 and an iron-powder catalyst.
• the carbon-14 determination of the graphite can be performed at the Klaus-Tschira-Archaeometrie-Center using an accelerator mass-spectrometer (AMS) of the type MICADAS (developed at the ETH Zurich, Switzerland).
• AMS accelerator mass-spectrometer
• inventive mixture of fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product are at least partly prepared from renewable resources and thus are advantageous from an ecological point of view.
• inventive mixture of fatty alcohol alkoxylates of the formula (I) can e. g. be applied in laundry detergent compositions, preferably in liquid laundry detergent compositions, hard surface cleaning compositions, automatic dishwashing compositions, and agrochemical compositions.
• a further subject matter of the invention is a laundry detergent composition, preferably a liquid laundry detergent composition, a hard surface cleaning composition, an automatic dishwashing composition, or an agrochemical composition comprising the inventive mixture of fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product.
• the amount of the inventive mixture of fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product in the laundry detergent composition, hard surface cleaning composition, automatic dishwashing composition, or agrochemical composition of the invention is preferably from 0.1 to 20% by weight, more preferably from 0.1 to 10.0% by weight and even more preferably from 0.3 to 8% by weight, in each case based on the total weight of the composition of the invention.
• laundry detergent compositions including liquid laundry detergent compositions, their preparation and application are well-known in the art.
• laundry detergent compositions may comprise one or more optional ingredients, e. g. they may comprise conventional ingredients commonly used in laundry detergent compositions.
• optional ingredients include, but are not limited to soil release polymers, preferably soil release polyesters and more preferably soil release polyesters comprising or consisting of structure elements derived from dimethyl terephthalate, and structure elements derived from alkylene glycol, e. g. from ethylene glycol and/or from propylene glycol, and terminal groups derived from alkyl polyalkylene glycol, e. g.
• Optional ingredients that may be contained in the laundry detergent compositions are e. g. described in WO 2021/233987 A1 .
• hard surface cleaning compositions may comprise one or more optional ingredients, e. g. they may comprise conventional ingredients commonly used in hard surface cleaning compositions.
• optional ingredients include, but are not limited to polymers, copolymers, surfactants, water, pH regulators, complexing agents, solvents other than water, viscosity regulators, enzymes, bleaches, preservatives, fragrances, dyes, disinfectants, buffers, corrosion inhibitors, organic and inorganic salts, optical brighteners, antioxidants, opacifiers, hydrotropes, abrasives, oxidizing agents, and/or biocides.
• Optional ingredients that may be contained in the hard surface cleaning compositions are e. g. described in WO 2021/165188 A1 or in WO 2018/095915 A1 .
• automatic dishwashing compositions their preparation and application are well-known in the art.
• automatic dishwashing compositions may comprise one or more optional ingredients, e. g. they may comprise conventional ingredients commonly used in automatic dishwashing compositions.
• optional ingredients include, but are not limited to surface-active agents, enzymes, builders, bleaching agents, surfactants, polymers, chelating agents, glass corrosion inhibitors, water, solvents other than water, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulators.
• surface-active agents include, but are not limited to surface-active agents, enzymes, builders, bleaching agents, surfactants, polymers, chelating agents, glass corrosion inhibitors, water, solvents other than water, thickeners, foaming inhibitors, color particles, silver protecting agents, agents for preventing the tarnishing of silver, corrosion inhibitors, colorants, fillers, germicidal agents, hydrotropic agents, antioxidants, enzyme stabilizers, perfumes, solubilizers, carriers, processing aids, pigments and pH regulator
• Optional ingredients that may be contained in the automatic dishwashing compositions are e. g. described in WO 2023/052542 A1 or in WO 2023/057335 A1 .
• agrochemical compositions their preparation and application are well-known in the art.
• agrochemical compositions may comprise one or more optional ingredients, e. g. they may comprise conventional ingredients commonly used in agrochemical compositions.
• optional ingredients include, but are not limited to water, solvents other than water, co-solvents, acidifiers, adjuvants such as spreaders, retention promoters, humectants, penetrants and stickers, dispersing agents, emulsifiers, photodegradation stabilizers, spontaneity agents, wetting agents, functional polymers, cold stabilizers (antifreezes), preservatives, antioxidants, light stabilizers, foam generators or defoamers, fragrances, protective colloids, binders, adhesives, thickeners, thixotropic agents, sequestrants, complexing agents, mineral and vegetable oils, and active ingredients, e. g. pesticides such as herbicides, fungicides, insecticides, acaricides, nematicides, and plant growth regulators; biocides such as bactericides; plant nutrients; repellents, and safeners.
• pesticides such as herbicides, fungicides, insecticides, acaricides,
• Optional ingredients that may be contained in the agrochemical compositions are e. g. described in WO 2021/099079 A1 .
• inventive mixture of fatty alcohol alkoxylates of the formula (I) or the inventive alkoxylation product may be used, e.g. in the inventive compositions, in particular as surfactants, more specifically as wetting agents, emulsifiers / co-emulsifiers or dispersing agents, but also as rheology modifiers, and in agrochemical compositions they may also be used as leaf wetting agents, spray retention agents or agents to enhance foliar uptake of active ingredients.
• a further subject matter of the invention is the use of the inventive mixture of fatty alcohol alkoxylates of the formula (I) or of the inventive alkoxylation product, preferably in the inventive compositions, as surfactant, more specifically as wetting agent, emulsifier / co-emulsifier or dispersing agent, but also as rheology modifier, and in agrochemical compositions also as leaf wetting agent, spray retention agent or agent to enhance foliar uptake of active ingredients.
• surfactant more specifically as wetting agent, emulsifier / co-emulsifier or dispersing agent, but also as rheology modifier, and in agrochemical compositions also as leaf wetting agent, spray retention agent or agent to enhance foliar uptake of active ingredients.
• surfactant more specifically as wetting agent, emulsifier / co-emulsifier or dispersing agent, but also as rheology modifier, and in agrochemical compositions also as leaf wetting agent, spray retention agent or agent to enhance foli
• the present invention relates
• bio-based mixtures mixtures, preparation methods, alkoxylation products, compositions, and uses are hereinafter referred to as "bio-based mixtures", “bio-based preparation methods”, “bio-based alkoxylation products”, “bio-based compositions”, and “bio-based uses”.
• Dispersogen TM PSL 100 Polyacrylate copolymer EO Ethylene oxide or a unit -(CH 2 CH 2 O) Fatty Acid is a C 12-18 stripped palm kernel fatty acid HEDP 1-Hydroxyethane-1,1-diphosphonic acid LAS is C 12-14 linear alkylbenzene sulfonate, sodium salt MGDA Methylglycine-diacetic acid PO Propylene oxide or a unit -(CH(CHs)-CHz-O) or -(CH 2 -CH(CH 3 )-O-) Polyglykol 1000 Polyethylene glycol with an average molecular weight of 1000 g/mol SLES 2EO is Sodium lauryl ether sulfate with 2 moles EO Synergen TM GL 5 Copolymer of glycerol / coconut fatty acid / phthalic acid anhydride TAED Tetraacetylethylenediamine Texcare TM S
• Emulsogen TM COL 050 is a commercial product carboxylic acid (B) comprising, as main component, a carboxylic acid represented by formula (III) wherein R 4 is oleyl, q is 1, and p is, based on molar average, 5.
• B carboxylic acid
• R 4 is oleyl
• q is 1
• p is, based on molar average, 5.
• a mixture of 622.0 g iso-nonanoic acid, 1922.4 g of propan-2-ol and 147.6 g water is dispersed for 1 minute with a Rotor-Stator disperser. 148.2 g of calcium hydroxide are added within 30 minutes.
• Method of preparation of catalyst (C) with a methyl-capped polyalkylene glycol and a carboxylic acid (B) f) A mixture of 350 g of methyl-capped polyethylene glycol with an average molecular weight of 350 g/mol, 240 g of calcium acetate monohydrate, and 350 g of oleic acid is agitated with a lab disperser. After this, 60 g of concentrated sulfuric acid (98%) is added and the mixture is again agitated with the lab disperser to yield the final catalyst with a Ca 2+ content of 5.5 wt.-%.
• the alkoxylation is carried out in a semi-batch process with automated dosage of alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide and mixtures of ethylene oxide and propylene oxide within a given temperature window and up to the specified maximum pressure.
• the pressure is adjusted according to the increased filling volume of the vessel. After introduction of the intended amount of alkylene oxide and closing the alkylene oxide inlet, the reaction is continued until the pressure becomes constant.
• the reactor content is cooled to 90 °C and aspirator vacuum is applied for 30 minutes in order to remove residual alkylene oxide.
• the temperature is reduced to 80 °C and the final product is transferred into storage vessels and analyzed.
• a typical batch scale is 400 g to 2000 g.
• the uptake of the intended amount of alkylene oxide can be assured by gravimetry and by determination of the hydroxyl value according to DIN EN ISO 4629-2.
• compositions Composition A1 A2 Component amount [wt.-% a.m.] amount [wt.-% a.m.] LAS 5.2 5.2 SLES 2EO 6.5 6.5 C 12-15 alcohol ethoxylate 7 EO nonionic 1) 5.2 5.2 Fatty Acid 2.8 2.8 Glycerol 2.4 2.4 Ethanol 1.2 1.2 Sodium citrate 1.7 1.7 Sodium tetraborate decahydrate 2.0 2.0 Sodium chloride 1.0 1.0 Texcare TM SRN 260 - 1.0 Demineralized water and NaOH to adjust pH ad 100 ad 100 pH value 8.4 8.4 a.m.
• compositions A-G comprise no further additive Compositions A1, B1, C1, D1, E1 and
• n in the C 11 alcohol ethoxylate is either 7 or 10.
• the copolymers 1 to 6 correspond to copolymers 1 to 6 disclosed in Tables 1 and 1a of WO 2018/095915 A1 , respectively.
• EO and PO 100 wt.-% bio-based carbon content Table D Agrochemical composition (numbers are % by weight based on composition) Composition A1 Azoxystrobin 97% by weight 23.8 Synergen TM GL 5 5.8 C 16/18 fatty alcohol ethoxylated with 15 EO 1) 5.0 Dispersogen TM PSL 100 0.5 Defoamer 0.6 Xanthan gum (2% aqueous solution with 0.1% biocide) 12.9 1 ,2-Propylene glycol 5.5 Demineralized water 45.9 Total 100.0 1) EO: 100 wt.-% bio-based carbon content

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• 2023
  • 2023-11-29 EP EP23212940.3A patent/EP4563681A1/de not_active Withdrawn

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