PROCESS FOR THE PREPARATION OF ETHERCARBOXYLATES

Abstract: A process is disclosed for the preparation of ethercarb­ oxylates by oxidation of etheralcohols, having the general formula of R-O-CH₂CH₂O) n H, where R represents an alkyl group having 8-22 carbon atoms, a phenyl group or an alkylphenyl group and n a whole number from 1-100, or mixtures of these etheralcohols, or by oxidation of oxyethy­ lene-oxypropylene block copolymers having an average molecular weight of 1000-12000 and a content of 10-80% by weight ethylene oxide units, or mixtures of these copoly­ mers. In this process a catalyst is used which, in adition to palladium, also contains platinum in a platinum : palladium weight ratio of between 0.1:1 and 5:1.

Description: PROCESS FOR THE PREPARATION OF ETHERCARBOXYLATES The invention relates to a process for the preparation of ethercarboxylates by oxidation of etheralcohols, having the general formula of R-O-(CE2CH20)nH, where R represents an alkyl group having 8-22 carbon atoms, a phenyigroup or an alkylphenyl group and n a whole number from 1of00, or mixtures of these etheralcohols, or by oxidation of oxyethylene-oxypropylene block copolymers having an average molecular weight of 1000-12000 and a content of 10-80 % by weight ethylene oxide units, or mixtures of these copolymers. This process, known from the United States patent specification 4,214,101, is performed at a pH of 8-13 with a molecular oxygencontaining gas and a palladium catalyst on activated carbon as carrier. It has now been found that catalysts also containing platinum, in addition to palladium, are substantially more active in this known oxidation. The process according to the invention for the preparation of ethercarboxylates by oxidation of the said products with a molecular oxygen-containing gas at a pH of 8-13 while using a palladium catalyst on activated carbon as carrier is characterized in that a catalyst is used which, in addition to palladium, also contains platinum in a platinum: palladium weight ratio of between 0.1 : 1 and 5 : 1. Preference is given to performing the process according to the invention while applying a platinum: palladium weight ratio of between 0.4 : 1 and 2.5 : 1. The total quantity of platinum and palladium in the catalyst may be varied, for instance between 1 and 15 % by weight, preferably between 2 and 12 % by weight. Very suitable are catalysts having the platinum and palladium applied to the same quantity of activated carbon. The process according to the invention can be performed very suitable by performing the oxidation in an aqueous medium and, by addition of, for instance, an alkalinemetalhydroxide, keeping the pH within the desired limits. In this process the chosen concentration of the starting product in the aqueous medium may vary, for instance between 5 and 50 percent by weight. Preference is given to applying a con centration of between 10 and 35 percent by weight. The reaction mixture will then be of a suitable viscosity without being diluted too much. In the process according to the invention preference is given to the use of oxygen having a purity of at least 95 % as molecular oxygen-containing gas. As the oxygen is purer the need to discharge for removing the impurities in the oxygen will be smaller and the foam formation going with this discharge will be avoided. The partial oxygen pressure may vary, for instance, between 1 and 50 bar. A partial oxygen pressure of between 1.5 and 10 bar is very suitable. The process according to the invention may be performed at various temperatures, for instance a temperature of 50-120 CC. Preferably a temperature of between 65 and I00 CC is applied. The reaction mixture obtained in the oxidation process according to the invention can be worked up in different ways, for instance by separating off the catalyst, subsequently acidifying the reaction mixture with concentrated hydrochloric acid and recovering the desired product by extraction with, for instance, chloroform or by heating the acidified reaction mixture to, for instance, 80 CC with formation of two liquid layers and separating off the aqueous layer formed. If the ethercarboxylates are desired in the form of salts, the reaction mixture obtained can be worked up by just separating off the catalyst. An aqueous solution of the desired product will then be left, which solution can be concentrated, if so desired, by evaporation. The process according to the invention is particularly suitable for the oxidation of etheralcohols or mixtures of etheralcohols having the said general formula, where R represents an alkyl group having 10-18 carbon atoms and n a whole number from 4-13. The products obtained by applying the process according to the invention can be used in practice as surface-active substances, for instance in detergents. In the following examples the invention will be further elucidated. Examples I-V An autoclave having a capacity of 1 litre, provided with a stirrer, was filled with 5 g catalyst, 500 g distilled water and 100 g of a mixture of laurylalcoholpolyglycolethers with an average of 5.5 ethyleneoxide groups, which mixture is commercially available under the name of Akyporox RLM 55 (registered trademark). Subsequently the air in the autoclave was replaced by oxygen (purity higher than 99 Z), the temperature of the mixture in the autoclave raised, during stirring, to 85 "C and the pressure of the oxygen in the autoclave set at 1.5 bar. By adding aqueous sodium hydroxide (20 % by weight) the pH of the reaction mixture was kept between 8 and 13, while by addition of oxygen (through a small tube having its mouth under the stirrer) the pressure in the autoclave was maintained at 1.5 bar. Once the adsorption of oxygen by the reaction mixture had virtually ceased, the catalyst was filtered off, the reaction mixture acidified with concentrated hydrochloric acid to pH = 2 and the mixture obtained extracted three times with 100 cm3 chloroform. The chloroform of the extract obtained was evaporated, and of the remaining residue the ethercarboxylic acid content (EPTON number) and the etheralcohol content (hydroxyl number) were determined. The results of these determinations were used for calculating the conversion of the starting product. The following table mentions a few data and the conversions calculated. The catalysts used, with activated carbon as carrier, had been prepared in the way described in the United States patent specification 4,052,336, which specification is hereby incorporated by reference. For the purpose of comparison, comparative examples 1-6 are mentioned in the table. The catalyst used in example V was a mixture of the catalysts used in comparative examples 2 and 5. In the other examples the catalyst had been prepared by precipitating the platinum and palladium jointly on the activated carbon (Norit-SX-2). It is true that in comparative examples 5 and 6 a reasonable conversion is yet achieved, but the colour of the final product is less suitable. number Pt and/or Pd duration conversion colour example or content ( wt.) oxidation in % product comparative in catalyst in hours obtained example I 2.5 % Pt 2.5 7 Pd 6 88 yellow II 5 % Pt 5 % Pd 6 89 light yellow III 3 % Pt 7 Z Pd 6 74 yellow IV 7 % Pt 3 % Pd 6 99 light yellow V 5 Z Pt 5 % Pd 6 62 yellow 1 2 % Pd 12 11 yellow 2 5 % Pd 12 3 yellow 3 10 % Pd 24 4 yellow 4 2 Z Pt 6 40 brown 5 5 Z Pt 6 61 reddish brown 6 8 % Pt 6 64 dark brown Example VI In the way described for examples I-V a mixture of nonylphenolpolyglycolethers having 9.5 ethylene oxide groups on average, which mixture is commercially available under the name of Akyporox NP 95 (registered trademark), was oxidized, using the catalyst according to example IV. After a period of 6 hours a dark yellow product was obtained and the conversion was 100 %. Example VII Example IV was repeated, using as starting product a mixture of laurylalcoholpolyglycolethers having 10 ethylene oxide groups on average, which mixture is commercially available under the name of Akyporox RLM 100 (registered trademark). After a period of 6 hours a light yellow product was obtained and the conversion was 99 %.

Claims: CLAIMS 1. Process for the preparation of ethercarboxylates by oxidation of etheralcohols, having the general formula of R-O-(CH2DH20)nH, where R represents an alkyl group having 8-22 carbon atoms, a phenyl group or an alkylphenyl group and n a whole number from 1-100, or mixtures of these etheralcohols', 'or by oxidation of oxyethylene-oxypropylene block copolymers having an average molecular weight of 1000-12000 and a content of 10-80 % by weight ethylene oxide units, or mixtures of these copolymers, characterized in that a catalyst is used which, in addition to palladium, also contains platinum in a platinum : palladium weight ratio of between 0.1 : I and 5 : 1. 2. Process according to claim 1,characterized in that a catalyst-is used with a platinum : palladium weight ratio of between 0.4 : 1 and 2.5 : 1. 3. Process according to claim I or 2, characterized in that a catalyst is used containing 2-12 % by weight of platinum and palladium jointly. 4. Process according to any one of claims 1-3, characterized in that a catalyst is used having the platinum and palladium applied to the same quantity of activated carbon. 5. Process according to any one of claims 1-4, characterized in that the product to be oxidized is started from while being contained in an aqueous medium in a concentration of 10-35 % by weight. 6. Process according to any one of claims 1-5, characterized in that the oxidation process is performed using oxygen with a partial pressure of 1.5-10 bar. 7. Process according to any one of claims 1-6, characterized in that the oxidation process is performed at a temperature of 65-100 CC. 8. Process according to any one of claims 1-7, characterized in that etheralcohols or mixtures of etheralcohols having the said general formula, where R represents an alkyl group having 10-18 carbon atoms and n a whole number from 4-13, are started from.

Inventors: DE MAN, HENDRIKUS CORNELIS J., SPRONKEN, JOSEPHUS MARIE HUBERTUS
Applicants: STAMICARBON B.V.
Application year: 1982
Main classification: C07C59
IPC codes: C07C51, B01J23, C07C67, C07C59, C08G65, C07B61