Ethoxylated glycerides and method for preparing the same

Abstract

The present invention relates to the use of a specific type of calcium catalyst (C) for the preparation of alkoxylated glycerides, the alkoxylated glycerides prepared in the presence of said catalyst, and a process for the preparation of alkoxylated glycerides. It has been found that in the presence of the above-mentioned calcium catalyst (C), the alkoxylation reaction requires significantly less time. In addition, it has been found that ethoxylated glycerides prepared in the presence of calcium catalyst (C) result in a more homogeneous product with significantly lower hydroxyl values, less decomposition, and improved processability.

Description

[0001] The present invention relates to the use of a specific type of calcium catalyst for the preparation of alkoxylated glycerides, alkoxylated glycerides prepared in the presence of such a catalyst, and a method for preparing alkoxylated glycerides.

[0002] Alkoxylated fatty acid esters are known in the literature as surfactants in different fields such as home care, cosmetics, textiles, and other industries. Frequently, the preparation of such alkoxylated esters is carried out in the presence of a catalyst. Commonly used catalysts are, for example, sodium hydroxide / alcohol mixtures or sodium alkoxides.

[0003] DE-A 3 914 131 discloses the use of magnesium / aluminum salts as catalysts in the preparation of alkoxylated fatty acid esters. The use of calcium-based catalysts for the alkoxylation of organic compounds such as fatty alcohols is described in US 4,820,673. US 4,835,321 provides calcium / aluminum-based catalysts for the synthesis of alkoxylated fatty alcohols.

[0004] US 5,386,045 discloses the use of catalysts prepared from alkoxylated alcohols, calcium-containing compounds, Lewis acidic metals, and metal alkoxide inorganic acid compounds, or catalysts prepared from calcium-containing compounds and specific activators, for the preparation of alkoxylated fatty acid esters of monoalcohols, diols, or triols.

[0005] An object of the present invention is to provide ethoxylated glycerides having a particularly low degree of decomposition, which are characterized by a small number of free hydroxyl groups.

[0006] It has now surprisingly been found that a specific type of calcium catalyst is particularly suitable for achieving this object.

[0007] Accordingly, the present invention provides the use of a catalyst (C) obtainable by a reaction comprising:

[0008] (A) calcium hydroxide, and

[0009] (B) a carboxylic acid containing 3 to 40 carbon atoms,

[0010] for the preparation of an ethoxylated glyceride of the general formula (I) from ethylene oxide and one or more triglycerides,

[0011]

[0012] wherein R 1 、R 2 and R 3 are the same or different and independently selected from saturated or unsaturated linear or branched hydrocarbon (alkyl) chains having 3 to 40 carbon atoms; and

[0013] m, n, and o are the same or different and each independently is an integer, provided that the number average of the sum m + n + o is at least 3,

[0014] wherein the molar ratio of calcium hydroxide (A) to carboxylic acid (B) in the preparation of the catalyst (C) is 1:1 - 1:5.

[0015] The present invention also provides an ethoxylated glyceride of general formula (I)

[0016]

[0017] which is prepared from ethylene oxide and one or more triglycerides of formula (II) in the presence of a calcium catalyst (C) as defined above

[0018]

[0019] characterized in that

[0020] R in formula (I) and (II) 1 , R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched C7 - C 24 hydrocarbon chains; m, n, and o in formula (I) are the same or different and each independently is an integer from 1 - 200, provided that the number average of the sum m + n + o is greater than 5.

[0021] Although m, n, and o in the formula are integers, the described products are usually mixtures of various components.

[0022] The present invention also provides a method for preparing an ethoxylated glyceride of formula (I),

[0023]

[0024] comprising the steps of

[0025] i) introducing a catalyst (C) as defined above and a triglyceride of formula (II)

[0026]

[0027] into a pressure-resistant reactor;

[0028] ii) optionally replacing the air in the reactor with nitrogen or other protective gas;

[0029] iii) optionally drying the reactor contents at a temperature of 50 - 200 °C and / or a pressure of less than 0.8 bar;

[0030] iv) heating the contents of the reactor to a temperature of 80 °C - 200 °C;

[0031] v) Optionally, pressurize the reactor with nitrogen or other protective gas to a pressure greater than atmospheric pressure by 0.3 bar - 3.5 bar.

[0032] vi) Pressurize the reactor with ethylene oxide gas to a pressure greater than atmospheric pressure by 1.5 bar - 10 bar, provided that the pressure is greater than the pressure before step vi);

[0033] vii) React the mixture until the pressure in the reactor is constant;

[0034] wherein R in formulas (I) and (II) 1 、R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched C7 - C 24 hydrocarbon chains;

[0035] m, n, and o in formula (I) are the same or different and each is independently an integer from 1 - 200, provided that the number average of the sum of m + n + o is greater than 5.

[0036] Another aspect of the present invention is the use of the ethoxylated glycerol esters as described above in a dishwashing composition.

[0037] Surprisingly, it has been found that in the presence of the above-mentioned calcium catalyst (C), the alkoxylation reaction requires significantly less time than in the presence of catalysts known in the art. In addition, it has been found that, relative to ethoxylated glycerol esters known in the art, the ethoxylated glycerol esters prepared in the presence of calcium catalyst (C) result in a more uniform product with significantly lower hydroxyl values, less decomposition products, and improved processability.

[0038] The calcium catalyst (C) used for the preparation of ethoxylated glycerol esters according to the present invention can be obtained in a reaction comprising:

[0039] (A) Calcium hydroxide Ca(OH)2, and

[0040] (B) A carboxylic acid containing 3 to 40 carbon atoms.

[0041] In this reaction, the molar ratio of calcium hydroxide (A) to the carboxylic acid containing 3 to 40 carbon atoms (B) is 1:1 - 1:5. Preferably, the molar ratio (A):(B) is 1:1.5 - 1:4, more preferably 1:1.8 - 1:2.2, even more preferably 1:1.9 - 1:2.1. In a particularly preferred embodiment, the ratio (A):(B) in the preparation of the catalyst (C) is approximately 1:2.

[0042] The reaction for the preparation of the catalyst (C) is preferably carried out in the presence of at least one polar solvent, more preferably a polar solvent containing at least one hydroxyl group, even more preferably at least one alcohol having 1 to 5 carbon atoms or a mixture thereof with water. In a particularly preferred embodiment, the polar solvent is propan-2-ol or a mixture thereof with water. In another particularly preferred embodiment, the polar solvent is ethanol or a mixture thereof with water.

[0043] The acid used as the carboxylic acid (B) containing 3 to 40 carbon atoms is preferably a carboxylic acid represented by formula (III) or formula (IV).

[0044]

[0045] In formula (III), R 4 is generally selected from saturated or unsaturated linear or branched C1-C 30 hydrocarbyl groups, preferably C5-C 20 hydrocarbyl groups, more preferably C8-C 18 hydrocarbyl groups. R in formula (III) 5 , R 6 , R 7 and R 8 are the same or different and are independently selected from: hydrogen, methyl and ethyl. Preferably, R 5 , R 6 , R 7 and R 8 are hydrogen.

[0046] In addition, p in formula (III) is an integer from 0 - 20, preferably an integer from 1 - 20, preferably an integer from 1 - 11, more preferably an integer from 2 - 5. In a preferred embodiment, in the carboxylic acid of formula (III), R 4 is a saturated or unsaturated linear or branched C8-C 18 hydrocarbyl group, R 5 , R 6 , R 7 and R 8 are hydrogen and p is an integer from 1 - 11.

[0047] In a further preferred embodiment, in the carboxylic acid of formula (III), R 4 is a saturated or unsaturated linear or branched C8-C 18 hydrocarbyl group, R 5 , R 6 , R 7 and R 8 are hydrogen and p is an integer from 2 - 5.

[0048] In formula (IV), R 9 is selected from saturated or unsaturated linear or branched C5-C30 Hydrocarbyl groups, preferably C8-C 18 Hydrocarbyl groups, more preferably C8-C 12 Hydrocarbyl groups. In a particularly preferred embodiment, the carboxylic acid of formula (IV) is isononanoic acid.

[0049] More preferably, the carboxylic acid (B) containing 3 to 40 carbon atoms is the carboxylic acid represented by formula (III), especially where R 4 is a saturated or unsaturated linear or branched C8-C 18 hydrocarbyl group, R 5 , R 6 , R 7 and R 8 is hydrogen and p is an integer from 2 to 5.

[0050] It is desirable to carry out the reaction to obtain the catalyst (C) in the presence of an acid (AC) having a pK A value of 3 or less, preferably 2 or less, preferably 0 or less, and often -3 or less.

[0051] Preferably, the acid (AC) is selected from acids of sulfur oxides and phosphorus oxides, more preferably selected from sulfuric acid, sulfurous acid, sulfonic acids (such as methanesulfonic acid), phosphoric acid, phosphorous acid, and phosphonic acids (such as methylphosphonic acid). Sulfuric acid, sulfurous acid, and methanesulfonic acid are of particular interest.

[0052] In a particularly preferred embodiment, the reaction to obtain the catalyst (C) is carried out in the presence of sulfuric acid.

[0053] Preferably, the acid (AC) is used in the reaction such that the molar ratio of calcium hydroxide (A) to the acid (AC) is 5:1 - 1:1, more preferably 3:1 - 1:1, even more preferably 2:1 - 1:1.

[0054] It is particularly advantageous to prepare the calcium catalyst (C) as follows: First, react calcium hydroxide (A) with the carboxylic acid (B), preferably in the solvent as described above, and then further treat the reaction mixture with the acid (AC).

[0055] For the reaction to obtain the calcium catalyst (C), any common reactor can be used, preferably a reactor having a stirring / mixing device such as a magnetic stirrer, mechanical stirrer, static mixer, blender, or batch disperser. Preferably, a batch disperser is used for mixing the components.

[0056] The preparation of catalyst (C) is preferably carried out under a pressure of 0.5 - 2 bar, more preferably 0.8 - 1.5 bar, even more preferably 0.9 - 1.2 bar. In a preferred embodiment, the catalyst is prepared under atmospheric pressure. Furthermore, the catalyst (C) is preferably prepared at a temperature 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 20 - 40 °C, especially at room temperature.

[0057] The calcium catalyst (C) thus prepared generally has a Ca content between 0.5 wt% and 5 wt%, often 1 - 4 wt%, often 2 - 3 wt%. 2+ Ionic content. Optionally, the catalyst can be freed of volatile components, such as solvents, water and other volatile by-products, by using common methods. Preferably, the volatile components are removed under vacuum, for example at a pressure of less than 0.8 bar, preferably less than 0.3 bar, more preferably less than 0.1 bar and / or at an elevated temperature, for example 50 to 180 °C, preferably 70 to 150 °C, more preferably 80 to 120 °C.

[0058] In a particularly preferred embodiment, the volatile components are removed on a rotary evaporator at a pressure of less than 0.1 bar and a temperature of 80 °C - 120 °C.

[0059] The ethoxylated glycerides of the present invention are in particular the ethoxylated glycerides of formula (I)

[0060]

[0061] and are prepared from ethylene oxide and one or more triglycerides of formula (II) in the presence of a calcium catalyst (C) as defined above

[0062]

[0063]

[0064] R in the ethoxylated glycerides of formula (I) of the present invention and in the one or more triglycerides of formula (II) for preparing the ethoxylated glycerides of the present invention 1 、R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched C7 - C 24 hydrocarbon chains, preferably C9 - C 20 hydrocarbon chains, more preferably C 12 - C 18 hydrocarbon chains.

[0065] In the ethoxylated glycerol esters of the present invention of formula (I), m, n and o are each independently an integer from 1 to 200, preferably from 1 to 80, more preferably from 2 to 70, provided that the number average of the sum m + n + o is greater than 5, preferably greater than 8, more preferably from 8 to 200, even more preferably from 8 to 80, calculated from the saponification value measured according to DIN EN ISO 3681.

[0066] The triglyceride(s) of formula (II) is not particularly limited and may be a natural triglyceride or a synthetic triglyceride. Preferably, the triglyceride does not contain any free hydroxyl groups.

[0067] The hydroxyl value (measured according to DIN EN ISO 4629-2) of the ethoxylated glycerol esters of the present invention prepared in the presence of the catalyst (C) as defined above is generally less than 6 mg KOH / g higher than the hydroxyl value of the triglyceride(s) of formula (II).

[0068] Often, the total hydroxyl value of the ethoxylated glycerol esters of the present invention is less than 7 mg KOH / g, preferably less than 6 mg KOH / g, more preferably less than 5 mg KOH / g. In addition, the ratio of CH2OH groups to hydrocarbon - CH3 groups in the ethoxylated glycerol esters of the present invention is generally less than 0.15, preferably less than 0.12, more preferably less than 0.08, even more preferably less than 0.06, measured as the ratio of the integrals of the corresponding signals in the proton - NMR spectrum. In a particularly preferred embodiment, the hydroxyl value of the ethoxylated glycerol esters of the present invention is less than 7 mg KOH / g and the ratio of CH2OH groups to hydrocarbon - CH3 groups in the ethoxylated glycerol esters of the present invention is less than 0.12. In a more particularly preferred embodiment, the hydroxyl value is less than 5 mg KOH / g and the ratio of CH2OH groups to hydrocarbon - CH3 groups is less than 0.06.

[0069] Preferably, the saponification value of the ethoxylated glycerol esters of the present invention is less than 220 mg KOH / g, more preferably less than 150 mg KOH / g.

[0070] The method of the present invention for preparing the ethoxylated glycerol esters as described above comprises the following steps

[0071] i) introducing the catalyst (C) as defined above and the triglyceride(s) of formula (II) as described above into a pressure - resistant reactor;

[0072] ii) optionally replacing the air in the reactor with nitrogen or other protective gas;

[0073] iii) optionally drying the reactor contents at a temperature of 50 - 180 °C and / or at a pressure of less than 0.8 bar;

[0074] iv) Heat the contents of the reactor to a temperature of 80 °C - 200 °C;

[0075] v) Optionally pressurize the reactor with nitrogen or other protective gas to a pressure of 1.3 - 3.5 bar.

[0076] vi) Pressurize the reactor with ethylene oxide to a pressure of 1.5 bar - 10 bar, provided that the pressure is greater than the pressure before step vi); and

[0077] vii) React the mixture until the pressure in the reactor is constant.

[0078] In step i), the catalyst (C) can be introduced in a form directly obtained from the preparation reaction described above, or in a form from which volatile compounds have been removed. The triglycerides of formula (II) can be introduced in their original form or can be purified before use. Preferably, the triglycerides of formula (II) are purified before use, thereby separating trace amounts of diglycerides, monoglycerides, free glycerol, and other impurities from the starting materials.

[0079] Preferably, the calcium catalyst (C) is introduced into the reactor in an amount of 0.1 - 5% by weight, preferably 0.2 - 3% by weight, more preferably 0.3 - 2% by weight, based on the total weight of the mixture of the triglycerides of formula (II) and ethylene oxide.

[0080] The pressure-resistant reactor is not particularly limited but is designed to withstand the pressures employed in the process so that it will not be damaged during the process. Preferably, the reactor is designed to withstand pressures greater than 10 bar, more preferably greater than 15 bar and less than 0.01 bar, more preferably less than 0.001 bar. Preferably, the pressure-resistant reactor is an autoclave, more preferably an autoclave equipped with a stirring device such as a magnetic or mechanical stirrer.

[0081] Generally, it is not necessarily required to replace the air in the reactor with nitrogen or other protective gas, since the ethoxylated glycerides of the present invention will be produced at least in part in this process. However, the air in the reactor, especially oxygen, can cause safety problems usually during the alkoxylation reaction and decomposition products due to oxidation and / or hydrolysis of the materials used and the products produced, especially at elevated temperatures. Therefore, it is desirable to carry out step ii) of the process of the present invention after step i).

[0082] Generally, the step of drying the reactor contents is not necessarily required either, since the ethoxylated glycerides of the invention will be produced at least in part during the process. However, water and alcohols can promote the hydrolysis and transesterification of the materials used and the products produced under the reaction conditions. In particular, if the calcium catalyst (C) is introduced into the reactor in the form directly obtained from the preparation reaction described above in step i), it is advisable to carry out the drying step, since the catalyst (C) obtained directly usually contains residues of polar solvents or mixtures thereof with water. The drying step iii) can be omitted in the case where the volatile components are removed from the calcium catalyst (C) before it is introduced into the reactor. However, in such a case it is advisable to carry out step iii), since the volatile components can also be present as impurities in one or more triglycerides of formula (ii). Therefore, in a particularly preferred embodiment, step iii) is carried out.

[0083] The step iii) of drying the reactor contents is generally carried out at a temperature of 50 °C - 180 °C, preferably 60 °C - 150 °C, more preferably 70 °C - 130 °C, often 80 °C - 120 °C, and at a pressure of less than 0.8 bar, preferably less than 0.1 bar, more preferably less than 0.05 bar. The vacuum thus produced is preferably a dynamic vacuum.

[0084] The vacuum pump used to produce the vacuum is not particularly limited; however, it is preferred to use a suction pump for producing the vacuum. In addition, it is advisable to gradually increase the temperature in the reactor and reduce the pressure to prevent boiling delay. In a particularly preferred embodiment, the step of drying the reactor contents is carried out at a temperature of 80 °C - 120 °C and a pressure of less than 0.01 bar, preferably for a period of at least 15 minutes, more preferably for a period of at least 30 minutes, even more preferably for a period of at least 1 hour. It is particularly preferred to dry the contents of the reactor to a constant mass.

[0085] After the drying step iii), the fluid line between the vacuum pump and the reactor is interrupted to ensure that the components added to the reactor remain in the reactor after drying and are not drawn out directly therefrom. In addition, it is preferred to compensate for the vacuum in the reactor with nitrogen or other protective gas before carrying out further steps to reduce the risk of air entering the reactor.

[0086] The step iv) of heating the contents of the reactor is generally carried out at a temperature of 80 °C - 200 °C, preferably 120 °C - 190 °C, more preferably 160 °C - 180 °C. This temperature is maintained at least until step vi) is completed, preferably until step vii) is completed.

[0087] After setting the temperature in step iv), the reactor can optionally be pressurized in step v) with nitrogen or other protective gas to a pressure greater than atmospheric pressure by 0.3 - 3.5 bar, preferably 0.5 - 2.0 bar, preferably 0.7 - 1.5 bar, more preferably 0.8 - 1 bar. By performing this step v), the ethylene oxide introduced in the following steps is diluted with the protective gas, thereby facilitating the pressure-controlled dosing of ethylene oxide into the reactor.

[0088] In step vi), the reactor is further pressurized with ethylene oxide to a total internal pressure of 1.5 - 10 bar, preferably 2 - 8 bar, more preferably 3 - 6 bar, more preferably 4 - 5 bar, provided that the pressure in step vi) is greater than the pressure before step vi).

[0089] During step vii), after introducing the desired amount of ethylene oxide, the ethylene oxide is closed and the reaction is allowed to proceed until the pressure in the reactor is constant.

[0090] In the sense of the present invention, if the pressure change is not greater than 0.05 bar within a period of 15 min, preferably 30 min, more preferably 1 hour, the pressure is considered constant. Particularly preferably, the pressure in the reactor changes not greater than 0.01 bar within a period of 1 hour.

[0091] Generally, the total amount of ethylene oxide is added to the reactor and a constant pressure is obtained by the method of the present invention within less than 1000 minutes, often within less than 800 minutes. In a particularly preferred embodiment, a constant pressure is obtained within less than 700 minutes. At this time, the reaction between ethylene oxide and one or more triglycerides of formula (II) is considered complete.

[0092] After completion of step vii), it is desirable to remove the residual ethylene oxide from the reactor before separating the ethoxylated glycerides of the present invention in order to prevent any unwanted reaction with ethylene oxide after product separation. Preferably, the reactor contents are cooled to a temperature of 50 - 120 °C, more preferably 70 - 100 °C, more preferably 85 - 95 °C, and the residual ethylene oxide is removed from the reactor using a pressure of less than 0.8 bar, preferably less than 0.1 bar, more preferably less than 0.05 bar. The vacuum thus produced is preferably a dynamic vacuum. The vacuum pump used to produce the vacuum is not particularly limited; however, a suction pump for producing a vacuum is preferably used. Removal of the residual ethylene oxide under these conditions is preferably carried out for at least 10 minutes, preferably at least 30 minutes, more preferably at least 1 hour.

[0093] The method for separating the ethoxylated glycerol esters of the present invention is not particularly limited. However, it is preferred to separate the product at an elevated temperature, especially at a temperature of 50 - 120°C, preferably 60 - 100°C, more preferably 70 - 90°C. At these temperatures, the ethoxylated glycerol esters of the present invention are generally in a liquid state and have a sufficiently low viscosity, and can thus be more easily transferred from the reactor than in the solid state, for example, by pouring the product out of the reactor or via a bottom valve, thereby minimizing the amount of residue in the reactor. Therefore, the subsequent cleaning and maintenance of the reactor are also facilitated.

[0094] Surprisingly, it has been found that the method for preparing the ethoxylated glycerol esters according to the present invention using the calcium catalyst (C) described above can be interrupted at any stage and continued at a later time point without significantly increasing the reaction time. In contrast, the interruption of the preparation method using catalysts known in the art requires substantially longer reactivation after the interruption, such that the total reaction time is increased by a significant amount.

[0095] Furthermore, it has been observed that the preparation method using catalysts known in the art results in grayish-white solid residues in the reactor, and no such residues are found if a specific type of calcium catalyst (C) is used. The following examples and claims further elaborate the present invention in more detail. Examples

[0096] Comparative Synthesis Example 1 Preparation of the calcium catalyst of US 5,386,045

[0097] Stir a mixture of 125 g of alcohol ethoxylate (from C 10 / C 12 -fatty alcohol and 40 wt% ethylene oxide, e.g., ALFONIC 1012 - 40 from Vista Chemical Company), 2 g of 2-ethylhexanoic acid, and 10.9 g of calcium hydroxide in a nitrogen atmosphere at room temperature in an autoclave, while adding 2 g of concentrated sulfuric acid over a 10-min period. After complete addition of the sulfuric acid, continue stirring for 5 h. Subsequently, heat the mixture to 150°C and remove the volatile components in a nitrogen stream over 15 min. Cool the mixture to 125°C and add 17.5 g of trialkoxy aluminum (containing about 6 wt% Al and having an average alkoxy carbon chain length of 10 carbon atoms).

[0098] Stir the mixture at 125°C for an additional 2 h, after which the temperature is raised to 190°C and the volatile components are removed in a nitrogen stream. After an additional 0.5 h at 190°C, cool the mixture to ambient temperature to provide a catalyst with a Ca 2+ content of approximately 3 wt% and an Al 3+ content of approximately 0.6 wt% (hereinafter referred to as "(C-0)").

[0099] Comparative Synthesis Example 2 for preparing a cocatalyst (glyceryl monooleate)

[0100] A mixture of 9.2 g of glycerol and 28.2 g of oleic acid was heated to 175 °C and stirred at this temperature while removing water using a dean - stark apparatus until the acid value < 2 mg KOH / g.

[0101] Synthesis Example 1

[0102] Preparation of calcium catalyst (C) using the carboxylic acid of formula (III)

[0103] a) At ambient temperature, a mixture of 1047.0 g of the carboxylic acid of formula (III) (sold by Clariant Produkte (Deutschland) GmbH under the trade name "Emulsogen COL 050"), 55.8 g of calcium hydroxide, and 360.6 g of propan - 2 - ol was stirred for 5 min using an Ultra Turrax (from IKA Werke GmbH & Co KG) batch - type disperser. After that, 44.2 g of concentrated sulfuric acid was added within two minutes and the mixture was stirred again for 5 min using the batch - type disperser, providing a catalyst with a Ca 2+ content of 2.00 wt% (hereinafter referred to as "(C - 1)").

[0104] Similar results of a catalyst with a Ca 2+ content of approximately 2.00 wt% can be obtained by using methanesulfonic acid or sulfurous acid instead of sulfuric acid.

[0105] b) At ambient temperature, a mixture of 1047.0 g of the carboxylic acid of formula (III) (sold by Clariant Produkte (Deutschland) GmbH under the trade name "Emulsogen COL 050"), 55.8 g of calcium hydroxide, and 360.6 g of propan - 2 - ol was stirred for 5 min using an Ultra Turrax (from IKA Werke GmbH & Co KG) batch - type disperser. After that, 42.9 g of methanesulfonic acid (99 wt%) was added within two minutes and the mixture was stirred again for 5 min using the batch - type disperser, providing a catalyst with a Ca 2+ content of 2.00 wt% (hereinafter referred to as "(C - 3)").

[0106] c) At ambient temperature, stir a mixture of 1047.0 g of the carboxylic acid of formula (III) (sold by Clariant Produkte (Deutschland) GmbH under the trade name "Emulsogen COL 050"), 55.8 g of calcium hydroxide, and 360.6 g of propan-2-ol for 5 min using an Ultra Turrax (from IKA Werke GmbH & Co KG). After that, add 603.7 g of sulfurous acid (6 wt%) within two minutes and stir the mixture again for 5 min using the Ultra Turrax. Remove the solvent mixture under vacuum to provide a catalyst with a Ca 2+ content of approximately 2 wt% (hereinafter referred to as "(C-4)").

[0107] Emulsogen COL 050 is a commercially available carboxylic acid (B) that contains the carboxylic acid represented by formula (III) as the main component, where R 4 is oleyl, R 5 、R 6 、R 7 and R 8 are hydrogen, and p is 5.

[0108] Synthesis Example 2

[0109] Preparation of calcium catalyst (C) using the carboxylic acid of formula (IV)

[0110] Stir a mixture of 114 g of isononanoic acid, 26.7 g of calcium hydroxide, 346.38 g of propan-2-ol, and 26.7 g of water for 5 min using an Ultra Turrax (from IKA Werke GmbH & Co KG). After that, add 10.62 g of concentrated sulfuric acid all at once and stir the mixture again for 5 min using the Ultra Turrax to provide a catalyst with a Ca 2+ content of 2.75 wt% (hereinafter referred to as "(C-2)").

[0111] Synthesis Example 3

[0112] General alkoxylation procedure

[0113] Place the triglyceride of formula (II), the catalyst, and, if applicable, the cocatalyst in a glass autoclave, and then flush it with nitrogen by alternately applying vacuum and introducing nitrogen (3 cycles). Dry the mixture at 100 °C under pump vacuum for 1 hour. Restore the pressure in the autoclave to ambient with nitrogen and heat to 175 °C. At this temperature, pressurize the autoclave with nitrogen to a pressure greater than atmospheric pressure by 0.8 bar, and then perform pressure-controlled dosing of ethylene oxide until a maximum pressure greater than atmospheric pressure by 4.5 bar is reached.

[0114] Automated dosing of ethylene oxide using a semi-batch method for ethoxylation within a given temperature window up to a specified maximum pressure. The pressure is adjusted according to the increased filling volume of the vessel. After introducing the expected amount of ethylene oxide and closing the ethylene oxide inlet, the reaction is continued until the pressure becomes constant.

[0115] The reactor contents are cooled to 90 °C and a vacuum pump vacuum is applied for 30 min to remove residual ethylene oxide. The temperature is lowered to 80 °C and the final product is transferred to a storage container and analyzed. A typical batch size is from 400 g to 2000 g. The uptake of the expected amount of ethylene oxide is determined by the gravimetric method and by measuring the saponification value according to DIN EN ISO 3681.

[0116] The materials used in Synthesis Example 3 and the reaction time to constant pressure are shown in Table 1 (molar equivalents) below:

[0117]

[0118]

[0119] Interrupting Synthesis Example 3 for 15 hours when using C-0 caused the reaction to re-initiate at a significantly slower rate than the initiation of the reaction at the start. Interrupting when using C-1 or C-2 caused the reaction to resume at substantially the same rate as directly observed before the interruption.

[0120] Furthermore, ethoxylation can also be carried out using the same procedure with catalyst C-1 or C-2 using fatty alcohols, fatty acid alkyl esters, and fatty acid alkylene glycol diesters instead of triglycerides. In addition, the ethoxylation of triglycerides, fatty alcohols, fatty acid alkyl esters, and fatty acid alkylene glycol diesters can also be carried out in the presence of additional glycerol to obtain a product with higher polarity due to the larger amount of hydroxyl groups in the product.

[0121] It is clearly visible from Table 1 that in the examples of the present invention, when using catalyst (C-1) or (C-2), the triglycerides react at a significantly higher rate than in the comparative examples using catalyst (C-0) or KotBu (optionally using glycerol monooleate as a co-catalyst). Faster reaction rates were observed for any amount of ethylene oxide introduced and for any triglyceride used.

[0122] Furthermore, after emptying the autoclave after the reaction using catalyst (C-0), a grayish-white solid adhered to the stirrer and the temperature sensor as well as in the reaction vessel. These solids were not observed when using catalyst (C-1) or catalyst (C-2) in the reaction.

[0123] In Table 2, the appearance of several comparative examples and examples of the present invention under different conditions is described.

[0124] Table 2:

[0125]

[0126]

[0127] In Table 3, the hydroxyl values and the ratio of CH2OH groups to hydrocarbon - CH3 groups of several embodiments of the present invention and comparative examples are shown.

[0128] The hydroxyl value was measured according to DIN EN ISO 4629 - 2. The ratio of CH2OH groups to hydrocarbon - CH3 groups was calculated from the integration ratio of the corresponding proton - NMR signals using a Bruker NMR spectrometer at 400 MHz with CDCl3 as the solvent.

[0129] The off - white solid residue from the comparative example using (C - 0) as the catalyst was insoluble and not analyzed.

[0130] Table 3:

[0131]

[0132]

[0133] It is clearly visible from the OH values of the comparative examples and the embodiments of the present invention that the ethoxylated triglycerides of the embodiments of the present invention using the catalyst (C - 1) undergo less decomposition during the synthesis reaction than the ethoxylated triglycerides of the comparative examples using the catalyst (C - 0) or KOtBu.

[0134] In particular, the saponification of the ester groups after ethoxylation was shown to occur to a lesser extent, as seen from the ratio of CH2OH groups derived from polyethoxy - OH to hydrocarbon - CH3 groups derived from the fatty acid hydrocarbon groups, where the polyethoxy - OH is produced from unwanted side reactions (e.g., due to long reaction times and high reaction temperatures).

[0135] The solubility in water of the ethoxylated triglycerides according to Example 2, Comparative 3, and Comparative 4 (each prepared from 1 molar equivalent of coconut oil and 22.5 molar equivalents of ethylene oxide) was detected by mixing 0.5 parts by weight of the corresponding ethoxylated triglyceride with 99.5 parts by weight of deionized water in a glass test tube at 25 °C, and the transparency of the resulting composition was visually evaluated immediately after mixing and 1 hour after mixing. In each case, the change within the 1 - hour period was not significant. The visual evaluation was carried out according to the following rating:

[0136] Clear, no suspended matter observed

[0137] Almost clear, trace amounts of suspended matter observed

[0138] Slightly turbid, suspended matter observed, dark background still visible

[0139] Turbid, suspended matter obvious, dark background hardly recognizable

[0140] Opaque, suspended matter very obvious, dark background unrecognizable

[0141] The evaluation is shown in Table 4:

[0142] Table 4:

[0143]

[0144]

[0145] As can be seen from the above results, the ethoxylated glycerol esters of the present invention prepared using catalyst C-1 (Example 1) have significantly better solubility in water than the comparative product (Comparative 3) prepared using catalyst C-0 known in the art. This is important for the suitability of the product as a surfactant, for example.

[0146] Despite the small amount of free hydroxyl groups, improved solubility was observed, which is presumably due to the higher polarity promoting dissolution in water.

[0147] The above difference is consistent with the formation of insoluble solid residues during the ethoxylation process using catalyst C-0.

[0148] The increased solubility of the product prepared from KOtBu and the cocatalyst (Comparative 4) is the result of decomposition products carrying a large number of OH groups, which increases the polarity of the mixture and thus the total solubility of the composition in water.

[0149] Application Example 1: Drying capacity and cleaning the interior of a dishwashing machine

[0150] The drying capacity of the machine dishwashing detergent composition F2 containing the ethoxylated glycerol ester of Example 4 was investigated. As a comparative example, the drying capacity of the comparative preparation F1 containing a modified fatty alcohol ethoxylate was tested.

[0151] Test conditions:

[0152] Dishwashing machine: Miele G 1222SC GSL-2

[0153] Test utensils: 10 appetizer spoons

[0154] 10 appetizer forks

[0155] 10 teaspoons

[0156] 2 serving spoons

[0157] 12 drinking glasses

[0158] 10 porcelain cups

[0159] 25 porcelain plates

[0160] 3 SAN (styrene-acrylonitrile copolymer) plates

[0161] 3 PP (polypropylene) plates

[0162] 6 PP bowls

[0163] Tableware cleaning program: P4R0 without pre-rinsing

[0164] Main rinse at 50 °C

[0165] Final rinse at 65 °C

[0166] Water hardness: 21 °dH

[0167] Water softening: None

[0168] Detergent dosage: 18 g, added immediately to the detergent tray after opening the hopper

[0169] Contaminants: 50 g of frozen dirt, added immediately after opening the hopper

[0170] Rinse aid: None

[0171] Cleaning cycle: 4

[0172] All items are treated once with softened water, Neodisher A 8, citric acid, and softened water treatment.

[0173] Evaluation:

[0174] The evaluation of the test utensils starts 30 minutes after the completion of the tableware cleaning cycle. During this time, the tableware cleaning machine door is closed. For each test, evaluate the tableware cleaning cycle 2 to 4. In each case, the evaluation is carried out with a light intensity of 1000 - 1500 lux.

[0175] In a fixed order and set time limit, count the number of adhering drops of residual water for each test utensil item. Depending on the number of drops counted, the following drying capacity rating results are generated for each test utensil item:

[0176] Rating for porcelain, stainless steel, and glass:

[0177] 0 Dry, no water droplets

[0178] 1 1 water droplet

[0179] 2 2 water droplets

[0180] 3 3 water droplets

[0181] 4 4 water droplets

[0182] 5 5 water droplets

[0183] 6 More than 5 water droplets

[0184] Rating of plastic parts:

[0185] 0 Dry, no water droplets

[0186] 1 1 water droplet

[0187] 2 2 water droplets

[0188] 3 3 water droplets

[0189] 4 4 water droplets

[0190] 5 5 water droplets

[0191] 6 6 water droplets

[0192] 7 7 water droplets

[0193] 8 More than 7 water droplets.

[0194] In this rating scheme, for each test utensil cutlery, the best performance score is 0 and the worst performance score is 6. For each cutlery cleaning cycle 2, 3, and 4, the sum of the scores for all test cutlery is formed. To compare formulations F1 and F2, the average rating of all sums for cutlery cleaning cycles 2 to 4 is averaged in each case. This results in a theoretical maximum of 630 for the worst drying performance and a theoretical minimum of 0 for the best drying performance.

[0195] The results are shown in Table 5 below.

[0196] In addition, the fat residues on the plastic parts (filters, rinse aid chambers) of the cutlery cleaning machine are evaluated (on a rating scale of 1 to 7, where 1 indicates a large amount of residue and 7 indicates no residue). These results are also shown in Table 5.

[0197] Composition:

[0198] The compositions of formulations F1 and F2 are shown in Table 5 below.

[0199] Application Example 2: Rinse Aid Performance of Dishwashing Detergent Compositions

[0200] The rinse aid performance of formulation F2 according to the present invention was investigated. As a comparative example, the rinse aid performance of comparative formulation F1 was tested.

[0201] Test conditions:

[0202] Dishwasher: Miele G 1222SC GSL

[0203] Test utensils - tableware: 6 drinking glasses (higher quality)

[0204] (8 material groups) 6 drinking glasses (lower quality)

[0205] 3 PP bowls

[0206] 3 melamine plates

[0207] 3 butter dishes + 4 knives (stainless steel; lower quality)

[0208] 4 knives (stainless steel; higher quality)

[0209] 3 porcelain plates (higher quality)

[0210] 3 porcelain plates (lower quality)

[0211] Dishwashing program: Program 4, R = 2 without pre - rinsing

[0212] Main rinse at 50 °C

[0213] Final rinse at 65 °C

[0214] Water hardness: 21 °dH

[0215] Water softening: None

[0216] Detergent dosage: 18 g, added to the dosing chamber before starting the test

[0217] Contaminants: 100 g of frozen soil, added immediately after opening the dosing chamber

[0218] Rinse aid: None

[0219] Washing cycles: 4

[0220] All test utensils - tableware (except PP bowls) are treated once with softened water, Neodisher A 8, citric acid and again with softened water.

[0221] Evaluation:

[0222] Start the evaluation of the test utensils at least 60 minutes after opening the dishwasher door after the dishwashing cycle is completed. For each test, evaluate dishwashing cycles 2 to 4. The evaluation is carried out according to the following ratings:

[0223] Consider the effect of the rinse aid in the visual rating:

[0224] Stains - Stains of different sizes and intensities

[0225] Contact spots: Stains generated at the contact points between the test utensil tableware and the parts of the tableware cleaning machine

[0226] Stripes: Rinsing aid stripes

[0227] Film formation: A continuous film evenly spread on the test utensil tableware

[0228] Structured film formation: A dispersed and cracked film

[0229] Solid residue: Solid powder or crystalline residue

[0230] Fat residue: Fat droplets or fat film formation

[0231] Iridescence: Glittering iridescence

[0232] Visual rating score:

[0233] 10 Perfect

[0234] 9 Perfect to almost invisible

[0235] 8 Almost invisible

[0236] 7 Almost invisible to visible

[0237] 6 Visible

[0238] 5 Visible to obstructive

[0239] 4 Obstructive

[0240] 3 Obstructive to unacceptable

[0241] 2 Unacceptable

[0242] 1 Absolutely unacceptable

[0243] Based on the above visual rating scores, the combinations of the effects of the eight rinsing aids listed above result in ratings from 1 - 10, where a rating of 1 represents the worst performance and a rating of 10 represents the best performance. For each of the above 8 test utensil material groups in each tableware cleaning cycle, the average rating is determined, then the sum of the ratings of all material groups in each individual tableware cleaning cycle is calculated, and then the overall average rating for tableware cleaning cycles 2 to 4 is determined. The resulting average rating is used as the final rinsing aid performance of formulations F1 and F2. This results in a theoretical maximum of 80 for the best performance and a theoretical minimum of 8 for the worst performance.

[0244] Composition:

[0245] The composition of formulation F2 according to the present invention and the composition of F1 are shown in Table 5 below. The results are also shown in Table 5.

[0246] Table 5: Composition, drying ability, fat residue and rinsing aid performance of formulations F1 and F2

[0247]

[0248]

[0249] * ) The components are added according to their active ingredient content in % by weight.

[0250] ** ) Sodium sulfate is added as a filler to keep the quality of the detergent composition in a constant balance, without acting and without affecting the performance of the detergent composition.

[0251] It is clearly seen from the results in Table 5 above that, compared with composition F1, the use of the machine dishwashing detergent composition F2 results in beneficial values for the drying capacity, the fat residues in the machine compartments and the rinsing aid performance.

[0252] In addition, formulation F2 shows excellent cleaning performance and excellent filter cleaning properties.

Claims

1. Use of a catalyst (C) obtainable by a reaction comprising: (A) calcium hydroxide, and (B) a carboxylic acid having 3 to 40 carbon atoms, for the preparation of an ethoxylated glyceride of formula (I) from ethylene oxide and one or more triglycerides, wherein R 1 、R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched hydrocarbon chains having 3 to 40 carbon atoms; and m, n and o are the same or different and each independently is an integer, provided that the sum of m + n + o is at least 3, characterized in that the molar ratio of calcium hydroxide (A) to carboxylic acid (B) in the preparation of the catalyst (C) is 1:1 - 1:5, the carboxylic acid (B) is represented by formula (III), wherein R 4 is oleyl; R 5 、R 6 、R 7 and R 8 are hydrogen; and p is an integer from 1 - 11, The reaction including (A) and (B) further includes an acid (AC) having a pK A value of 3 or less, the acid (AC) is selected from acids of sulfur oxides and phosphorus oxides and the molar ratio of (A):(AC) is 5:1 - 1:

1.

2. Use according to claim 1, wherein p is an integer from 2 - 11.

3. Use according to claim 2, wherein p is an integer from 2 - 5.

4. Use according to claim 1, characterized in that the reaction comprising components (A) and (B) further comprises an alcohol solvent having 1 to 5 carbon atoms, or a mixture thereof with water.

5. Use according to claim 4, wherein the alcohol solvent is propan - 2 - ol.

6. Use according to claim 1 or claim 4, characterized in that the acid (AC) is selected from sulfuric acid, sulfurous acid, sulfonic acid, phosphoric acid, phosphorous acid and phosphonic acid.

7. Use according to claim 1 or claim 4, characterized in that the acid (AC) is selected from sulfuric acid, sulfurous acid and methanesulfonic acid.

8. Use according to claim 1 or claim 4, characterized in that the acid (AC) is sulfuric acid.

9. Use according to claim 1 or claim 4, characterized in that volatile components are removed before the catalyst (C) is used for the preparation of the ethoxylated glyceride of formula (I).

10. Use according to claim 1 or claim 4, characterized in that the Ca 2+ ion content in the catalyst (C) is between 0.5% by weight and 5% by weight.

11. A method for preparing an ethoxylated glyceride of formula (I), comprising the following steps i) introducing a catalyst (C) as defined in claim 1 or claim 10 and one or more triglycerides of formula (II) into a pressure - resistant reactor; ii) optionally replacing the air in the reactor with nitrogen or other protective gas; iii) optionally drying the reactor contents at a temperature of 50°C - 200°C and / or under a pressure of less than 0.8 bar; iv) heating the contents of the reactor to a temperature of 80°C - 200°C; v) optionally pressurizing the reactor with nitrogen or other protective gas to a pressure greater than atmospheric pressure by 0.3 bar - 3.5 bar; vi) pressurizing the reactor with ethylene oxide gas to a pressure greater than atmospheric pressure by 1.5 bar - 10 bar, provided that the pressure is greater than the pressure before step vi); vii) reacting the mixture until the pressure in the reactor is constant; wherein R in formulas (I) and (II) 1 , R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched C7-C 24 hydrocarbon chains; m, n and o in formula (I) are the same or different and each independently is an integer from 1 - 200, provided that the number average of the sum of m + n + o is greater than 5.

12. The method according to claim 11, characterized in that after carrying out step vii), the mixture is cooled to a temperature of 50 - 120°C and the residual ethylene oxide is removed under a pressure of less than 0.8 bar.

13. The method according to claim 11 or claim 12, characterized in that in step i), catalyst (C) is introduced in an amount of 0.1% to 5% by weight, based on the total weight of the mixture of triglycerides of formula (II) and ethylene oxide.

14. The method according to claim 11 or claim 12, characterized in that steps ii), iii) and v) are carried out.

15. A mixture of ethoxylated glycerides of formula (I) which is prepared by the method according to any one of claims 11 - 14 from ethylene oxide and one or more triglycerides of formula (II), characterized in that R in formulas (I) and (II) 1 , R 2 and R 3 are the same or different and are independently selected from saturated or unsaturated linear or branched C7-C 24 hydrocarbon chains; m, n and o in formula (I) are the same or different and each independently is an integer from 1 to 200, provided that the number average of the sum of m + n + o is greater than 5.

16. The mixture of ethoxylated glycerides according to claim 15, characterized in that m, n and o are the same or different and each independently is a number from 1 to 80.

17. The mixture of ethoxylated glycerides according to claim 16, wherein m, n and o are the same or different and each independently is a number from 2 to 70.

18. The mixture of ethoxylated glycerides according to claim 15 or claim 16, characterized in that the hydroxyl value is less than 6 mg KOH / g.

19. Use of the mixture of ethoxylated glycerides of formula (I) according to claim 15 in a dishwashing composition.

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