Surface-active agents derived from sulfosuccinic esters

Abstract: Sulfosuccinic surface-agents having the formula: wherein M = Na, K, NH₄; R₁ = monoalkyl (C₈-C₂₀) ether of a polyhexose, polypentose or sorbitol, optionally hydroxylated and/or ethoxylated; R₂ = M, alkyl (C₈-C₂₀); are prepared by the sulfonation of the corresponding maleic esters.

Description: Description for the following Contracting States : BE, DK, GR, IT, LU, SE The present invention relates to surface-active agents derived from sulfosuccinic di-esters and semiesters. Sulfosuccinic surface-active agents derived from fatty alcohols possibly ethoxylated are already known. These surface-active agents have excellent skin tolerability, biodegradability, non-toxicity together with a fair foaming, emulsifying and wetting power. They are consequently suitable for use in a wide field of applications, such as detergents in general, the food industry, textile industry, emulsion polymerization , etc. The non-ethoxylated kinds however, are not soluble in water. The ethoxylated kinds must have an ethoxylation degree of at least 3 to 4 to show an acceptable solubility for detergent uses. Ethoxylation, on the other hand, involves the use of ethylene oxide, which is dangerous for the operators, and also gives rise to the formation of reaction by-products which could be harmful even in small quantities, especially for the skin. Surface-active agents have been found composed of sulfosuccinic diesters and semiesters which have excellent solubility in water even without oxyethylene units in their structure. The present invention therefore relates to sulfosuccinic esters having the formula: wherein: M is Na, K, Mg NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 to 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the sorbitol residue, m=1, n=0 and p=1. The cation M is preferably selected from sodium and the ammonium group. The radical R is preferably selected from linear or branched alkyls containing from 8 to 14 carbon atoms. In particular, when m=1, the radical R is preferably an alkyl containing 8 carbon atoms. A preferred group of compounds is that where in the R 1 group, Z represents the residue of glucose, m and n are equal to 0 and p is between 1 and 5. Another group of preferred compounds is that wherein the R 1 group represents the residue of hydroxydecylsorbitol. Sulfosuccinic esters having formula (I) are prepared by a process including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. The reaction can be represented by the following equation: The maleic diesters and semiesters having formula (I) are well-known products and can be prepared by reacting maleic acid with alcohols having formulae R 1 OH and R 2 OH, wherein R 1 and R 2 have the meaning specified above. The alcohols having formula R 1 OH can be prepared by reacting a R 3 OH alcohol with a hexose or pentose, wherein R 3 has the same meaning as R 1 except that p is equal to 0. In the case of sorbitol, the alcohol R 1 OH is prepared starting from alpha-epoxide in accordance with the following equation: where R has the above-defined meaning. In accordance with a specific aspect of the present invention, the alcohols having formula R 1 OH can be mixed with even high quantities (up to 50% by weight and more) of unreacted alcohols having the formula R 3 OH, preferably from 5 to 90%, more preferably from 70 to 80% when R 3 is an alkyl having a long chain; and from 10 to 20% when the alkyl has a short chain; from 20 to 70% when the chain of the alkyl has about intermediate values of the preferred R 1 . Alcohols having formula R 3 OH, by reaction with maleic acid and subsequent sulfonation, produce sulfosuccinates having the formula: Both the esters corresponding to formula (I) of the present invention, and those correpsonding to formula (III), are very effective surface-active agents which, even if used in quite low percentages, allow a considerable decrease in surface tension and can therefore be used as emulsifiers, dispersers and detergents in general. The solubility in water of the esters of the present invention is high, even in non-ethoxylated compounds, and is however higher with an equal degree of ethoxylation to the known sulfosuccinates, as is the surface tension, the foaming and imbibing power. Besides their excellent detergent properties, they have no toxic or irritating effect on the skin or eyes and there is no acute toxicity if swallowed orally. In addition, they are highly biodegradable. The sulfosuccinates of the present invention have proved to be compatible with most of the known anionic, amphoteric and non-ionic surface-active agents, and can consequently be formulated with these. The esters of the present invention, because of their combination of characteristics, have proved to be very flexible in the various applications of surface-active agents. Owing to their high detergent power together with a lack of toxic effects on the skin, hair and eyes, they are particularly suitable for cosmetic applications such as the preparation of liquid and cream detergents for the skin, shampoo and bath foam. The following examples provide a better illustration of the present invention but do not limit it in any way. EXAMPLE 1 Preparation of a sulfosuccinic semiester with a monoalkylpolyglucoside . 916 g (1 mole) of a maleic semiester of mixtures of polyglucosidated decyl and dodecyl alcohols, wherein the polyglucose has a polymerization degree of 3 to 4, 138.6 g (1.1 mole) of sodium sulfite and 158.9 g of distilled water are charged into a reactor equipped with a heating system, stirrer, thermometer and reagent inlet system. The temperature is brought to 100°C under stirring and the reaction mixture is kept at this temperature for three hours. The mixture is cooled to room temperature and is discharged from the reactor. 2636.5 g of a yellowish-white pasty product is obtained, containing 60% of water, having a 5% solution of clear active substance with a pH equal to 6.8 and organic SO 3 content of 2.9%. EXAMPLE 2 Preparation of a sulfosuccinic semiester with a monoalkylpolyglucoside . Using the same procedure as Example 1, 646 g (1 mole) of a maleic semiester prepared from a polyglucose with a polymerization degree of 3 and 4 etherified with a mixture of dodecyl alcohol and tetradecyl alcohol, are reacted with 138.6 g (1.1 moles) of sodium sulfite and 1626.9 g of distilled water. 2711.5 g of a white pasty solid product are obtained, containing 60% of water, having a 5% solution of active substance with a pH equal to 6.9 and organic SO 3 content of 3.0%. EXAMPLE 3 Preparation of a sulfosuccinic semiester with a hydroxyalkylsorbitol . Using the same procedure as Example 1, 436 g (1.0 moles) of a maleic semiester prepared from hydroxydecylsorbitol, are reacted with 138.6 g (1.1 moles) of sodium sulfite and 861.9 g of distilled water. 1436.5 g of a white, pasty fluid product are obtained, containing 60% of water, having a 5% solution of active substance with a pH equal to 6.8 and organic SO 3 content of 5.5%. EXAMPLE 4 Preparation of a sulfosuccinic semiester with a monoalkylpolyglucoside . 500 g of a maleic ester, at 50% in water, prepared from a polyglucoside having a polymerization degree of 2.6 etherified with a mixture of decyl alcohol and dodecyl alcohol containing 29% by weight of the above mixture of alcohols in free form, 87.8 g of sodium sulfite and 256.7 g of distilled water are loaded into a reactor equipped with a heating system, stirrer, thermometer and reagent inlet system. The temperature is brought to 100°C under stirring and the reaction mixture is kept at this temperature for three hours. The mass is already very clear after thirty minutes of reaction. The mixture is cooled to room temperature and is discharged from the reactor. 844.5 g of a yellow clear liquid product are obtained, containing 60% of water, having a 5% solution of clear active substance with a pH equal to 7.0 and organic SO 3 content of 6.3%. EXAMPLE 5 Preparation of a sulfosuccinic semiester with a monoalkylpolyglucoside . Using the same procedure as Example 4, 450.0 g of a maleic ester, at 50% in water, prepared from a polyglucose having a polymerization degree of 3.9 etherified with a mixture of dodecyl and tetradecyl alcohols, containing 38% by weight of the above mixture of alcohols in free form, are reacted with 87.1 g of sodium sulfite and 243.1 g of distilled water. 780.2 g of a white, pasty solid product are obtained, containing 60% of water, having a 5% solution of clear active substance with a pH equal to 7.1 and organic SO 3 content of 5.9%. APPLICATIVE TESTS The following tests were carried out on the products obtained in Examples 1-5 and on the sulfosuccinic semiester of C 12 -C 14 fatty alcohols, sodium salt, (Example A as a comparison): Surface tension The surface tension of solutions at 0.1% of active substance was measured at 20°C using the du-Nouy method. The results, measured in N/m (dine/cm) at a concentration of 1 g/l, are shown in the Table. Foaming power The capacity of producing foam was evaluated using the Ross-Miles method at 25°C. Measurements were made in distilled water at concentrations of 0.5 g/1 after 0 minutes (I) and after 5 minutes (II), and at concentrations of 1 g/1 after 0 minutes (III) and after 5 minutes (IV). The same measurements were repeated in hard water 5 mg/l Ca (30°F) (V-VIII). The results are shown in the Table. Imbibing power The imbibing power was evaluated by measuring the time taken by a special cotton planchet, completely immersed in a solution at 0.2% of active substance of the product being tested, to fall to the bottom of the container. The results are shown in the Table. Solubility 5% aqueous solutions of the compounds obtained in Examples 1, 2 and 3 are very clear, whereas in the case of comparative Example A, the appearance is decidedly cloudy. Example Surface tension Foaming power Imbibing power I II III IV V VI VII VIII 1 0.0275 40 40 55 55 40 30 45 40 100 2 0.0276 60 55 100 95 45 40 100 95 60 3 0.0265 65 60 110 100 25 20 45 35 98 4 0.0290 40 30 55 50 45 40 145 140 96 5 0.0305 60 55 90 85 110 105 130 125 55 A 0.0341 20 15 20 15 15 15 15 15 155 Description for the following Contracting States : AT, CH, DE, ES, FR, GB, LI, NL The present invention relates to surface-active agents derived from sulfosuccinic di-esters and semiesters. Sulfosuccinic surface-active agents derived from fatty alcohols possibly ethoxylated are already known. These surface-active agents have excellent skin tolerability, biodegradability, non-toxicity together with a fair foaming, emulsifying and wetting power. They are consequently suitable for use in a wide field of applications, such as detergents in general, the food industry, textile industry, emulsion polymerization , etc. The non-ethoxylated kinds however, are not soluble in water. The ethoxylated kinds must have an ethoxylation degree of at least 3 to 4 to show an acceptable solubility for detergent uses. Ethoxylation, on the other hand, involves the use of ethylene oxide, which is dangerous for the operators, and also gives rise to the formation of reaction by-products which could be harmful even in small quantities, especially for the skin. EP-A-0 454 321, unpublished at the filing date of the present application, discloses glycoside esters of solfosuccinic acid. Surface-active agents have been found composed of sulfosuccinic diesters and semiesters which have excellent solubility in water even without oxyethylene units in their structure. The present invention therefore relates to sulfosuccinic esters having the formula: wherein: M is Na, K, Mg NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 to 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the sorbitol residue, m=1, n=0 and p=1. The cation M is preferably selected from sodium and the ammonium group. The radical R is preferably selected from linear or branched alkyls containing from 8 to 14 carbon atoms. In particular, when m=1, the radical R is preferably an alkyl containing 8 carbon atoms. A preferred group of compounds is that where in the R 1 group, Z represents the residue of glucose, m and n are equal to 0 and p is between 1 and 5. Another group of preferred compounds is that wherein the R 1 group represents the residue of hydroxydecylsorbitol. Sulfosuccinic esters having formula (I) are prepared by a process including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. The reaction can be represented by the following equation: The maleic diesters and semiesters having formula (I) are well-known products and can be prepared by reacting maleic acid with alcohols having formulae R 1 OH and R 2 OH, wherein R 1 and R 2 have the meaning specified above. The alcohols having formula R 1 OH can be prepared by reacting a R 3 OH alcohol with a hexose or pentose, wherein R 3 has the same meaning as R 1 except that p is equal to 0. In the case of sorbitol, the alcohol R 1 OH is prepared starting from alpha-epoxide in accordance with the following equation: where R has the above-defined meaning. In accordance with a specific aspect of the present invention, the alcohols having formula R 1 OH can be mixed with even high quantities (up to 50% by weight and more) of unreacted alcohols having the formula R 3 OH, preferably from 5 to 90%, more preferably from 70 to 80% when R 3 is an alkyl having a long chain; and from 10 to 20% when the alkyl has a short chain; from 20 to 70% when the chain of the alkyl has about intermediate values of the preferred R 1 . Alcohols having formula R 3 OH, by reaction with maleic acid and subsequent sulfonation, produce sulfosuccinates having the formula: Both the esters corresponding to formula (I) of the present invention, and those correpsonding to formula (III), are very effective surface-active agents which, even if used in quite low percentages, allow a considerable decrease in surface tension and can therefore be used as emulsifiers, dispersers and detergents in general. The solubility in water of the esters of the present invention is high, even in non-ethoxylated compounds, and is however higher with an equal degree of ethoxylation to the known sulfosuccinates, as is the surface tension, the foaming and imbibing power. Besides their excellent detergent properties, they have no toxic or irritating effect on the skin or eyes and there is no acute toxicity if swallowed orally. In addition, they are highly biodegradable. The sulfosuccinates of the present invention have proved to be compatible with most of the known anionic, amphoteric and non-ionic surface-active agents, and can consequently be formulated with these. The esters of the present invention, because of their combination of characteristics, have proved to be very flexible in the various applications of surface-active agents. Owing to their high detergent power together with a lack of toxic effects on the skin, hair and eyes, they are particularly suitable for cosmetic applications such as the preparation of liquid and cream detergents for the skin, shampoo and bath foam. The following examples provide a better illustration of the present invention but do not limit it in any way. EXAMPLE Preparation of a sulfosuccinic semiester with a hydroxyalkylsorbitol . Using the same procedure as Example 1, 436 g (1.0 moles) of a maleic semiester prepared from hydroxydecylsorbitol, are reacted with 138.6 g (1.1 moles) of sodium sulfite and 861.9 g of distilled water. 1436.5 g of a white, pasty fluid product are obtained, containing 60% of water, having a 5% solution of active substance with a pH equal to 6.8 and organic SO 3 content of 5.5%. APPLICATIVE TESTS The following tests were carried out on the products obtained in the Example and on the sulfosuccinic semiester of C 12 -C 14 fatty alcohols, sodium salt, (Example A as a comparison): Surface tension The surface tension of solutions at 0.1% of active substance was measured at 20°C using the du-Nouy method. The results, measured in N/m (dine/cm) at a concentration of 1 g/l, are shown in the Table. Foaming power The capacity of producing foam was evaluated using the Ross-Miles method at 25°C. Measurements were made in distilled water at concentrations of 0.5 g/1 after 0 minutes (I) and after 5 minutes (II), and at concentrations of 1 g/1 after 0 minutes (III) and after 5 minutes (IV). The same measurements were repeated in hard water 5 mg/l Ca (30°F) (V-VIII). The results are shown in the Table. Imbibing power The imbibing power was evaluated by measuring the time taken by a special cotton planchet, completely immersed in a solution at 0.2% of active substance of the product being tested, to fall to the bottom of the container. The results are shown in the Table. Solubility 5% aqueous solution of the compound obtained in Example is very clear, whereas in the case of comparative Example A, the appearance is decidedly cloudy. Example Surface tension Foaming power Imbibing power I II III IV V VI VII VIII 3 0.0265 65 60 110 100 25 20 45 35 98 A 0.0341 20 15 20 15 15 15 15 15 155

Claims: Claims for the following Contracting States : BE, DK, IT, LU, SE Sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1. Esters in accordance with Claim 1, wherein Z represents the residue of glucose, m and n are equal to 0 and p is between 1 and 5. Esters in accordance with Claim 1, mixed with sulfosuccinic esters having the formula: where R 3 has the same meaning as R 1 except that p is equal to 0. Sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is H or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1; and the condition that when Z is an hexose or a pentose and R 2 is M then m is 1, or n is 1-20 and X is CH 3 . Cosmetic and/or detergent compositions containing one or more sulfosuccinic esters in accordance with Claim 1 to 4. Detergent compositions in accordance with Claim 5, wherein the sulfosuccinic esters are mixed with other surface-active agents. Claims for the following Contracting States : AT, CH, DE, FR, GB, LI, NL Sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1 and that when Z is a hexose or a pentose and R 2 is M, m is 1. Esters in accordance with Claim 1, except that, when Z is a hexose or a pentose, m is both 0 and 1, mixed with sulfosuccinic esters having the formula: where R 3 has the same meaning as R 1 except that p is equal to 0. Sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is H or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1; and the condition that when Z is an hexose or a pentose and R 2 is M then m is 1, or n is 1-20 and X is CH 3 . Cosmetic and/or detergent compositions containing one or more sulfosuccinic esters in accordance with Claim 1 to 3. Detergent compositions in accordance with Claim 4, wherein the sulfosuccinic esters are mixed with other surface-active agents. Claims for the following Contracting State : ES A process for the preparation of sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1 and that when Z is a hexose or a pentose and R 2 is M, m is 1, including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. A process for the preparation of esters in accordance with claim 1, except that, when Z is a hexose or a pentose m is both 0 and 1, which further comprises mixing the resulting esters with sulfosuccinic esters having the formula: where R 3 has the same meaning as R 1 except that p is equal to 0. A process for the preparation of sulfosuccinic esters having the formula: wherein is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1; and the condition that when Z is an hexose or a pentose and R 2 is M then m is 1, or n is 1-20 and X is CH 3 , including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. A process for the preparation of cosmetic and/or detergent compositions containing one or more sulfosuccinic esters in accordance with claim 1 to 3 which comprises mixing at least one of said esters with at least one suitable vehicle. A process for the preparation of detergent compositions in accordance with claim 4, wherein the sulfosuccinic esters are mixed with other surface-active agents. Claims for the following Contracting State : GR A process for the preparation of sulfosuccinic esters having the formula: wherein: M is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1, including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. A process for the preparation of esters in accordance with claim 1, wherein Z represents the residue of glucose, m and n are equal to O and p is between 1 and 5. A process for the preparation of esters in accordance with claim 1, which further comprises mixing the resulting esters with sulfosuccinic esters having the formula: where R 3 has the same meaning as R 1 except that p is equal to 0. A process for the preparation of esters having the formula: wherein is Na, K, Mg, NH 4 or their mixtures; R 1 represents the group: wherein: R is an alkyl containing from 8 to 20 carbon atoms, X is H or CH 3 , Z represents the residue of a hexose, pentose or sorbitol, with m which can be 0 or 1, n which can vary from 0 to 20, and p which can vary from 1 to 10, R 2 is M or R, on the condition that when Z is the residue of sorbitol, m=1, n=0 and p=1; and the condition that when Z is an hexose or a pentose and R 2 is M then m is 1, or n is 1-20 and X is CH 3 , including the sulfonation of the respective maleic di-esters and semiesters having the formula: with the required sulfite or bisulfite of the cation M, wherein R 1 , R 2 and M have the meaning specified above. A process for the preparation of cosmetic and/or detergent compositions containing one or more sulfosuccinic esters in accordance with claim 1 to 4 which comprises mixing at least one of said esters with at least one suitable vehicle. A process for the preparation of detergent compositions in accordance with claim 5, wherein the sulfosuccinic esters are mixed with other surface-active agents.

Inventors: BERNARDI PAOLO, FORNARA DARIO, GARLISI SALVATORE, BERNARDI, PAOLO, FORNARA, DARIO, GARLISI, SALVATORE
Applicants: AUSCHEM S P A IN FALLIMENTO, AUSCHEM S.P.A. IN FALLIMENTO
Application year: 1992
Main classification: C07H15
IPC codes: A61K8, C11D1, A61Q5, C07H15, C07C309, B01F17, A61Q19