PL147701B1 - Method of obtaining n,n-di/polyoxyethylene/alkylamine n-oxides - Google Patents

Description

The subject of the invention is a method of obtaining S-oxides of N, N-di (polyoxyethylene) alkylamines with 12-22 carbon atoms in a saturated or unsaturated hydrocarbon chain and the content of 5-22 oxyethylene groups, which are a new type of amine surface-active compounds. They can be used in many fields of the economy, especially in the production of household and cosmetic chemicals. Basic types of the so far known long-chain alkylamine oxides, total N-oxides, NfN-di (2-hydroxyethyl) -alkylamines of the formula RN / CH2CH2OH / 2.0, N, N-dimethylalkylamine N-oxides of the formula RN / CH2 / 2 O and alkylamido-propylene diamethylamine N-oxides of the formula RC0NH / CH2 / 3'-CHy2.0, where R is an alkyl radical.

The synthesis of the above types of amine oxides consists in the oxidation of a suitable tertiary alkylamine with 30-35% aqueous hydrogen peroxide solution at a temperature of 323-343K for 3-6 hours with a molar ratio of amine to hydrogen peroxide of 1.1-1.5.

The synthesis of these amine oxides is carried out using an alcohol or an alcohol-water mixture as solvent. there is no information in the literature on the synthesis and properties of NfN-di / polyoxyethylene / alkylamines N-oxides containing more than 5 oxyethylene groups in a molecule of formula RH / CH2CH20 / xH / CH2CH20 / yH /. 0; This is due to the fact that the known methods for the oxidation of tertiary alkylamines to their N-oxides could not be applied to the preparation of this type of amine oxides. In this case, low degrees of conversion of the amines to their N-oxides are obtained, even with the use of significant excesses of hydrogen peroxide. The presence of a large amount of unreacted amines (over 10% by weight) in a commercial product containing amine oxides disqualifies their use in various household and cosmetic chemistry products. • The raw material for the synthesis of NtN-di / polyoxyethylene / alkyl amine N-oxides, which is the subject of this invention NtN-di (polyoxyethylene) -alkylamine obtained by the ethoxylation of an alkylamine with ethylene oxide in the presence of catalytic amounts of sodium or potassium hydroxide. The use of the so obtained oxyethylene alkylamine147 701 2 for the synthesis of N, N-di (polyoxyethylene) alkylamine N-oxides by known methods leads to a low conversion of amines to their N-oxides (maximum 50%), even when the ratio is used molar amine to H ^ Like 1: 1.5. This is due to the rapid decomposition of hydrogen peroxide under the influence of strong bases (sodium and potassium hydroxide) which are catalysts for the ethoxylation of primary to tertiary amines.

The Polish patent specification No. 112243 describes a method for the preparation of N, N-di (polyoxyethylene) alkylamine, consisting in the okayethylenation of an alkylamine in the presence of water as a catalyst. The synthesis of amine N-oxides from the thus obtained alkylamines also proceeds with a low yield, in the order of 40-50%.

The aim of the invention is to develop such a method for the oxidation of N, N-di / polyoxyethylene / alkylamine containing 5-22 oxyethylene groups and 12-22 carbon atoms in the alkyl chain, to obtain N, N-di / polyokeyethylene / alkylamine N-oxides with high performance.

The process according to the invention consists in heating the N, N-di (polyoxyethylene / alkylamine) catalyst obtained in the ethoxylation reaction to the temperature of 403-523K, preferably 413-473K, and kept at this temperature for a period of 0.5 -3 hours.

Then, after cooling to 313-343K, oxidation reactions are carried out with 20-354 hydrogen peroxide solution, optionally in the presence of alcohol and / or water as solvent.

This procedure provides an unexpectedly high degree of conversion of N, N-di / polyoxyethylene / alkylaaines to their N-oxides, ie about 90-100% with respect to the amine used. During the heating, the decomposition of ammonium hydroxides takes place, which presumably affects the conversion of the amines into N-oxides.

The synthesis of amine oxides, the type of amine oxyethylation catalyst used, the annealing processes of tertiary amines and the degree of conversion thereof to amine oxides, according to the invention, are not known in the literature.

The amine oxides obtained by the process according to the invention, containing 5-22 oxyethylene groups in the molecule, are hydrophilic in nature. Known oxides of ethoxylated amines, i.e. N-oxides, N, N-di (2-hydroxyethyl) alkylamines, e.g. obtained from dodecylamine / C12 / at a concentration of more than 5% in aqueous solutions at room temperature, form a thin solution, while N-oxides N, N-di (polyoxyethylene) dodecylamine, even when cooled to 268K, are clear solutions. The new amine oxides are therefore very soluble in water. They can be 30-60%, and even 70% liquid water solutions. Hitherto known amine oxides, such as N, N-di (2-hydrocayethyl) alkylamine N-oxides and N, N-dimethylalkylamine N-oxides, had to contain considerable amounts in order to keep the liquid form at 25-50% concentration. % of alcohol, usually isopropanol or ethanol. Obtaining highly ethoxylated amine oxides enables lower consumption of perhydrol per weight unit of the product. The above factors, that is the elimination of alcohol, lower consumption of perhydrol significantly reduce the unit price of the product, calculated as active substance, compared to the known and produced so far. The obtained new type of ethane amine oxides gives a new group of surfactants with universal softening, bacteriostatic, anti-corrosive, etc. properties depending on the degree of amine ethoxylation. It makes it possible to use them in various areas of the chemical industry.

Comparative example.

1 mol / 358 g / N, N-di / ethanol / octadecylamine with 9 mol / 396 g / ethylene oxide was ethoxylated in a pressure autoclave with a capacity of 1 day. The reactions were carried out at the temperature of 353-393K in the presence of 0.038 mol (0.17 g) of water as a catalyst. Then 100 g of the obtained N, N-di (polyoxyethylene) octadecylamine, 50 g of water and 50 g of ethanol were introduced into the reactor equipped with a mechanical stirrer, thermometer, liquid dispenser and reflux coolers, and 30% aqueous hydrogen peroxide solution was added dropwise at a temperature of 323-333K. for 0.5 hour in the amount of 21g. After the hydrogen peroxide was added, the reaction mixture was heated to 343K and the reaction was carried out at this temperature for a further 4 hours.

A product was obtained containing i - 4% of N-oxide, N »N-di / polyoxyethylene / octadecylamine, - 37% of unreacted N9N-di / polyoxyethylene / octadecylamine. 147 701 Example I. Prepared as in comparative example I, N-di / polyokeyethylene / octadecylamine was heated for 1.5 hours at 403-423K, and then the product was oxidized with 30% hydrogen peroxide solution * Reactions were carried out in the same conditions as in the comparative example, and the product was obtained with 41% by weight H, N-di H-oxide (polyoxyethylene / octadecylamine / 11 moles of ethylene oxide per mole of amine); - 1% by weight of unreacted starting amine; - 0.25% by weight of hydrogen peroxide; - the supplement to 100% by weight is an ethanol-water mixture.

The physicochemical data of the obtained product are as follows: density 975 Kg / m, boiling point 361.3K, freezing point -256.6K, PH of a 10% aqueous solution of the product was 6.5 * Example II. In a pressure autoclave with a capacity of 1 dm amine laury- new in the amount of 0.5 mol / 92.5 g / was reacted with 11 mol / 484 g / of ethylene oxide in the presence of 0.04 mol / 0.7 g / water at the temperature of 353-373K and a pressure of 0.3-0.4 MPa. The obtained V, tf-di (polyoxyethylene) lauryl amine containing 22 oxyethylene groups was heated at 403 K for 3 hours. The product obtained was then subjected to an oxidation reaction. For this purpose, 100 g of the obtained M, N-di (polyoxyethylene) lauryl amine were introduced into a reactor equipped with a stirrer, a thermometer, a liquid dispenser and a reflux cooler. 100 g of isopropanol and 14 g of 30% hydrogen peroxide solution was added dropwise at 323-333 K over the period of 0.5 hours. Reactions continued for 4 hours.

A product was obtained containing 44% by weight of H-H-di u-oxide (polyoxyethylene / laurylamine / 22 moles of ethylene oxide per 1 mole of amine); - 1% by weight of unreacted amine; - 0.28% by weight of hydrogen peroxide.

The physical and chemical data of the obtained product are as follows: the density of 967 kg / m3, the boiling point 363K, the freezing point 247.6K, the pH of a 10% aqueous solution of the product was 6.8. example III. In a pressure autoclave with a capacity of 1 dm, 1 mol / 325 g / of an amine obtained from rapeseed oil acids, containing an alkyl radical of 22 carbon atoms with 5 mol / 220 g / ethylene oxide in the presence of 0.03 mol / 0.5 g / water as a catalyst. The reactions were carried out at the temperature of 363-383K and the pressure of 0.2-0.3 MPa.

The obtained N, N-di / polyoxyethylene / docosanamine containing 5 oxyethylene groups in the amount of 100 g was heated at 523K for 0.5 hour, and then, after cooling, the product was oxidized with 30% hydrogen peroxide solution, used in the amount of 25 g in the presence of 100g of ethanol.

The product was obtained containing - 39% by weight of N-di N-oxide / polyoxyethylene / docosanamine / 5 moles of ethylene oxide per 1 mole of amine /; - 5% by weight of unreacted amine; - 0.30% by weight of hydrogen peroxide.

The physical and chemical data of the obtained product are as follows: density 956 kg / m 2, boiling point 359.7 K, freezing point 268 K, pH of a 10% aqueous solution of the product was 6.5. Example IV. In the apparatus and under the conditions described in Example III, 260 g of R-C C-C ^ stearate amine were ethoxylated in the presence of 15.6 g of water, introducing 360 g of ethylene oxide under 0.3-0.4 MPa. The yield was 652 g of the product combining 8 moles of ethylene oxide with 1 mole of amine. The product was kept at the temperature of 413-443K for 1 hour. Next, 100 g of the obtained H, M-di (polyokeyethyl) stearylamine, 50 g of ethanol, 50 g of water and 26 g of hydrogen peroxide were introduced into the reactor and oxidation reactions were carried out as in example II * 147 701 4 The product was obtained containing 38% by weight of NN- N-oxide. di (polyethyethylene / stearylamine / 8 moles of ethylene oxide per mole of amine); - 3.0% by weight of unreacted alkylamine; - 0.15% by weight of hydrogen peroxide.

The physicochemical data of the obtained product are as follows: density 972 kg / m3, boiling point 303 K, freezing point 257K, pH of a 10% aqueous solution of the product was 6.9 "Patent shot. Method for obtaining H, N-di / polyokeyethylene / -alkylamines N-oxides with 12-22 carbon atoms in a saturated or unsaturated hydrocarbon chain and with a content of 3 * 22 oxyethylene groups eh 9 consisting in ethoxylation of alkylamine in the presence of water as a catalyst and oxidation of the obtained N, N-di / polyoxyethylene / alkylamine with a solution of hydrogen peroxide characterized in that the H, N-di / polyoxyethylene / alkylamine obtained in the ethoxylation reaction is heated to a temperature of 403-523K, preferably to 413-473K, and kept at this temperature for a period of 0.5-3 hours, and then after cooling, it is oxidized with 20-35% hydrogen peroxide solution, possibly in the presence of alcohol and / or water as a solvent * Pracownia Poligraficzna UP PRL. Mintage 100 copies

Price PLN 400