US3086986A - Surface-active urethanes and a process for preparing them - Google Patents
Surface-active urethanes and a process for preparing them Download PDFInfo
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- US3086986A US3086986A US814170A US81417059A US3086986A US 3086986 A US3086986 A US 3086986A US 814170 A US814170 A US 814170A US 81417059 A US81417059 A US 81417059A US 3086986 A US3086986 A US 3086986A
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- acid ester
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
Definitions
- R represents an alkyl group which contains 8-12 carbon atoms and forms either a straight chain or is branched with l-4 side chains, preferably l-3 side chains, containing each 2-6, especially 2-4, carbon atoms
- R represents an alkyl group which contains 8 carbon atoms and constitutes either a straight chain or is branched preferably with one side chain containing 2-4, preferably 2, carbon atoms
- X represents a low molecular weight alkylene radical containing about l-3 carbon atoms
- Y represents a carboxyl or a sulfonic acid group in the free form or in the form of the water-soluble salts thereof, can be obtained by subjecting compounds of the general formula R NH-XY wherein R X and Y have the meanings given above, with chlorocarbonic acid esters of the general formula wherein R has the meaning given above, to a reaction corresponding to the Schotten-
- the compounds of the general formula constitute secondary amines, R having the aforementioned meaning of an alkyl radical which contains 8 carbon atoms and which may either form a straight chain or a branched chain.
- alkyl radicals R of this type there may be mentioned by Way of example:
- chlorocarbonic acid esters of the general formula wherein R represents an alkyl radical containing 8-12 carbon atoms and forming either a straight chain or being branched with side chains each containing 2-6, especially 2-4, carbon atoms there are mentioned by way of example, the following:
- the last mentioned compound imparts to the surfaceactive agents prepared therefrom a surprisingly high wetting power which is particularly effective even at elevated temperatures.
- the surfaceactive compounds are prepared according to this inven-tion by subjecting thecomponent preferably in the form of its salts and, if necessary, in solvents, for example, water or low molecular weight alcohols, e.g. methanol, ethanol, propanol, or mixtures of these alcohols with one another or with water, to the reaction with the chlorocarbonic acid esters of the formula R-O-CO-Cl in the manner as such known of the Schotten-Baumann reaction.
- solvents for example, water or low molecular weight alcohols, e.g. methanol, ethanol, propanol, or mixtures of these alcohols with one another or with water
- chlorocarbonic acid esters of the formula R-O-CO-Cl in the manner as such known of the Schotten-Baumann reaction.
- the salt formation with the carboxylic acid groups or sulfonic acid groups there enter into consideration particularly the alkali metal or alkaline earth metal ions, or the ion of ammonia
- the solution of the amine component is reacted with the chlorocarbonic acid ester advantageously in the presence of a substance capable of binding the hydrochloric acid formed during the reaction.
- the solution of the component R -NH-XY can be preliminarily mixed with an equivalent amount of acid-binding agenteither in solid form or in the form of a solutionand then the chlorocarbonic acid ester may be added slowly,
- Particularly suitable is a process in which the acid-binding substance is added in an equivalent quantity or in an excess quantity gradually at the rate of which the component R -NHXY reacts with the chlorocarbonic acid ester slowly added while regulating the rate of addition so as to ensure maintenance of a pH value of about 6 to about 12, preferably 8-10, in the reaction mixture.
- the reaction can be carried out at a temperature in the range of about C. and about 120 C., preferably about C. and about 80 C.
- the reaction may be carried out without additional cooling or heating. It is often advantageous to maintain the reaction temperature, at first by cooling, at between 0 C. and 30 C., and then to finish the reaction, if necessary under pressure, at an elevated temperature, for example, up to 120 C. In some individual cases it is possible to carry out the reaction without the use of a.solvent.
- acid-binding agents that are suitable to bind the hydrogen chloride formed during the reaction, there enter into consideration, for example, inorganic hydroxides, carbonates or bicarbonates, especially of the alkali metals and alkaline earth metals and organic bases, preferably tertiary bases, for example, pyridine, N-ethylpiperidine, trimethylamine, triethylamine and triethanolamine.
- the urethanes' obtained by the process of the present invention possess an unequalled wetting power as compared with known products. This results clearly from a Comparison of the wetting values of the compounds given in Tables I and H. Furthermore, the products of the present invention possess an increased fastness to saponification so that they may also be used in acid and alkaline liquors, even at elevated temperatures. Some of the novel products are distingiished by an excellent wetting power in the heat.
- the urethanes obtained by the process of the present invention may be used as rapid wetting agents in the textile industry, for example, for dyeing, printing, bleaching, mercerising, fulling, carbonisin kier-boiling, finishing, and in other industries where rapid wetting is desired, for example, in the leather industry, in galvanizations, in the production of construction auxiliaries and of cos- In order to increase the wetting speed, they may also be added to other surface-active substances or mixtures of substances, for example, emulsifiers, emulsions, detergents, swelling agents, unsoluble suspension auxiliaries or even mixtures of organic solvents.
- the thickly pasty mixture is further stirred for 1 hour at 45 C., then cooled to 20 C., and neutralized by adding in small portions about 80 kg. of hydrochloric acid of about 10% strength.
- the thickly pasty reaction mixture is then kneaded for 10 minutes at about 20 C. with about 100 kg. of common salt until the reaction product separates in the form of a jelly.
- the solution of salt is withdrawn by the bottom outlet.
- the remaining jelly-like reaction product is fused at 98 C. during the night and then drawn off" at this temperature.
- the compound has a wet-ting time of 100 seconds, measured with a standardized circular cotton fabric put on the surface of the solution (funnel method).
- a circular cotton fabric (diameter 3 cm.) of 0.4 gram in weight is put on 1 litre of distilled water having a temperature of 20 C. and pressed by means of a glass funnel below the surface of the liquid, and the amount of wetting agent is determined which is necessary for causing the fabric to sink within 100 seconds (cf. K. Lindner, Textilosstoff und Waschrohstoffe (1954), page 829).
- the wetting values of other urethanes prepared by the process of the present invention are given in the following Table I.
- the corresponding potassium or calcium salts in which case the corresponding hydroxides, such as potassium hydroxide or calcium hydroxide, respectively, may then be used, if necessary, as hydrogen chloride binding substances.
- the thickly pasty mixture is further stirred for one hour at 45 C., then cooled to 20 C., and finally neutralized by adding in small portions about kg. of hydrochloric acid of about 10% strength.
- the thickly pasty reaction mixture is then kneaded for 10 minutes at about 20 C. with about kg. of common salt until the reaction product separates in the form of a jelly.
- the solution of salt that has separated is withdrawn by the bottom outlet.
- the remaining jelly-like reaction mixture is fused over night at about 98 C. and then drawn off at this temperature.
- R is di-isobutylcarbino and R is 2-ethy1-hexyl.
Description
United States Patent M There have already been described surface-active compounds carrying carboxyl or sulfonic acid groups which are obtained by the reaction of aminoacetic or aminoethanesulfonic acids that are either unsubstituted at the nitrogen or substituted with low molecular Weight alkyl radicals or the phenyl radical, with chlorocarbonic acid esters obtained from alcohols containing 9 or more carbon atoms. There have also already been described surface-active compounds which are prepared by the reaction of chloroformic acid esters obtained from alcoholscontaining 6-8 carbon atoms and derived fromthe oxosynthesis and which, in addition, contain methyl groups Bfihhfidh Patented Apr. 23, 1963 which are linked via the amino group with the low mo lecular weight alkyl radical X which contains about 1-3 carbon atoms and is substituted at the terminal group by an acid group Y such as -COOH or -SO H, and form the mentioned compounds of the formula As such compounds, there enter into consideration for 0 the process of the present invention especailly the aminoas side chains, with primary or secondary aminocarboxylic acids, aminosulfonic acids or amino-sulfuric acid esters.
The wetting power of these known products is still insufficient for many purposes.
Now we have found that surface-active compounds which display a substantially greater wetting power and correspond to the general formula wherein R represents an alkyl group which contains 8-12 carbon atoms and forms either a straight chain or is branched with l-4 side chains, preferably l-3 side chains, containing each 2-6, especially 2-4, carbon atoms, R represents an alkyl group which contains 8 carbon atoms and constitutes either a straight chain or is branched preferably with one side chain containing 2-4, preferably 2, carbon atoms, X represents a low molecular weight alkylene radical containing about l-3 carbon atoms, and Y represents a carboxyl or a sulfonic acid group in the free form or in the form of the water-soluble salts thereof, can be obtained by subjecting compounds of the general formula R NH-XY wherein R X and Y have the meanings given above, with chlorocarbonic acid esters of the general formula wherein R has the meaning given above, to a reaction corresponding to the Schotten-Baumann reaction (cf. L. Gattermann, Die Praxis des organischen Chemikers, 32nd edition, page 118 (1947)).
The compounds of the general formula constitute secondary amines, R having the aforementioned meaning of an alkyl radical which contains 8 carbon atoms and which may either form a straight chain or a branched chain. As branched hydrocarbons enter into consideration preferably those having a side chain containing 2-4 carbon atoms. As alkyl radicals R of this type, there may be mentioned by Way of example:
acetic acid, the S-aminopropane-sulfonic acid-(l), and the 2-aminopropane-sulfonic acid-(l) and particularly the Z-amiuo-ethane-sulfonic acid-(1), each of which carries the above defined radical R at the nitrogen atom. fi- Aminopropionic acid, which is substituted with R is also suitable.
As chlorocarbonic acid esters of the general formula wherein R represents an alkyl radical containing 8-12 carbon atoms and forming either a straight chain or being branched with side chains each containing 2-6, especially 2-4, carbon atoms, there are mentioned by way of example, the following:
Particularly suitable are the compounds and such compounds as have terminal branchings and chlorocarbonic acid ester groups at the secondary hydroxyl groups, for example,
The last mentioned compound imparts to the surfaceactive agents prepared therefrom a surprisingly high wetting power which is particularly effective even at elevated temperatures.
The surfaceactive compounds are prepared according to this inven-tion by subjecting thecomponent preferably in the form of its salts and, if necessary, in solvents, for example, water or low molecular weight alcohols, e.g. methanol, ethanol, propanol, or mixtures of these alcohols with one another or with water, to the reaction with the chlorocarbonic acid esters of the formula R-O-CO-Cl in the manner as such known of the Schotten-Baumann reaction. For the salt formation with the carboxylic acid groups or sulfonic acid groups, there enter into consideration particularly the alkali metal or alkaline earth metal ions, or the ion of ammonia. Sodium, potassium or ammonium salts are preferably used.
The solution of the amine component is reacted with the chlorocarbonic acid ester advantageously in the presence of a substance capable of binding the hydrochloric acid formed during the reaction. The solution of the component R -NH-XY can be preliminarily mixed with an equivalent amount of acid-binding agenteither in solid form or in the form of a solutionand then the chlorocarbonic acid ester may be added slowly,
metic and pharmaeeutic preparations.
preferably while stirring. Particularly suitable is a process in which the acid-binding substance is added in an equivalent quantity or in an excess quantity gradually at the rate of which the component R -NHXY reacts with the chlorocarbonic acid ester slowly added while regulating the rate of addition so as to ensure maintenance of a pH value of about 6 to about 12, preferably 8-10, in the reaction mixture.
The reaction can be carried out at a temperature in the range of about C. and about 120 C., preferably about C. and about 80 C. In general, the reaction may be carried out without additional cooling or heating. It is often advantageous to maintain the reaction temperature, at first by cooling, at between 0 C. and 30 C., and then to finish the reaction, if necessary under pressure, at an elevated temperature, for example, up to 120 C. In some individual cases it is possible to carry out the reaction without the use of a.solvent.
As acid-binding agents, that are suitable to bind the hydrogen chloride formed during the reaction, there enter into consideration, for example, inorganic hydroxides, carbonates or bicarbonates, especially of the alkali metals and alkaline earth metals and organic bases, preferably tertiary bases, for example, pyridine, N-ethylpiperidine, trimethylamine, triethylamine and triethanolamine.
There may also be used mixtures of various compounds of the general formula R --NHXY and/ or mixtures of the chlorocarbonic acid esters concerned. Thereby are often obtained products that have a particularly favorable solubility.
The urethanes' obtained by the process of the present invention possess an unequalled wetting power as compared with known products. This results clearly from a Comparison of the wetting values of the compounds given in Tables I and H. Furthermore, the products of the present invention possess an increased fastness to saponification so that they may also be used in acid and alkaline liquors, even at elevated temperatures. Some of the novel products are distingiished by an excellent wetting power in the heat.
The urethanes obtained by the process of the present invention may be used as rapid wetting agents in the textile industry, for example, for dyeing, printing, bleaching, mercerising, fulling, carbonisin kier-boiling, finishing, and in other industries where rapid wetting is desired, for example, in the leather industry, in galvanizations, in the production of construction auxiliaries and of cos- In order to increase the wetting speed, they may also be added to other surface-active substances or mixtures of substances, for example, emulsifiers, emulsions, detergents, swelling agents, unsoluble suspension auxiliaries or even mixtures of organic solvents.
The following examples serve to illustrate the invention'but they are not intended to limit it thereto:
EXAMPLE 1 259 kg. of the sodium salt of Z-ethylhexyl-aminoethanesulfonic acid in form of an aqueous solution of strength are introduced into a vessel with stirrer, holding 2 m. and provided with devices for heating and cooling and a heatable bottom outlet. To this solution are added in the course of about 2 hours at about 20 C. and while slowly stirring (about 60 r.-p.m.), 192.5 kg. of 2-ethyl-hexyl-chloro-carbonic acid ester, and the mixture is constantly maintained alkaline with respect to phenolphthalein by adding about 1 mol (=41 kg.) of NaOH in the form of a concentrated lye. The thickly pasty mixture is further stirred for 1 hour at 45 C., then cooled to 20 C., and neutralized by adding in small portions about 80 kg. of hydrochloric acid of about 10% strength. The thickly pasty reaction mixture is then kneaded for 10 minutes at about 20 C. with about 100 kg. of common salt until the reaction product separates in the form of a jelly. The solution of salt is withdrawn by the bottom outlet. The remaining jelly-like reaction product is fused at 98 C. during the night and then drawn off" at this temperature.
Yield: 380 kilograms of product in the form of a paste of 45% strength.
Already in a concentration or" 0.15 gram of washingactive substance per litre of neutral water having a temperature of 20 C., the compound has a wet-ting time of 100 seconds, measured with a standardized circular cotton fabric put on the surface of the solution (funnel method). According to this method, a circular cotton fabric (diameter 3 cm.) of 0.4 gram in weight is put on 1 litre of distilled water having a temperature of 20 C. and pressed by means of a glass funnel below the surface of the liquid, and the amount of wetting agent is determined which is necessary for causing the fabric to sink within 100 seconds (cf. K. Lindner, Textilhilfsmittel und Waschrohstoffe (1954), page 829). The wetting values of other urethanes prepared by the process of the present invention are given in the following Table I.
Instead of the sodium salts of the above-mentioned sulfonic acids, there may also be used the corresponding potassium or calcium salts, in which case the corresponding hydroxides, such as potassium hydroxide or calcium hydroxide, respectively, may then be used, if necessary, as hydrogen chloride binding substances.
EXAMPLE 2 209 kg. of the sodium salt of 2-ethylhexyl-amino-acetic acid in the form of an aqueous solution of 20% strength are introduced into a vessel with stirrer, having a capacity of 2 m. and being'provided with devices for cooling and heating and a heatable bottom outlet. To this solution are added at about 20 C. in the course of 2 hours and while slowly stirring (about 65 r.p.-m.), 192.5 kg. of Z-ethylhexyl-chlorocarbonic acid ester, and the mixture is constantly maintained alkaline with respect to phenolphthalein by adding about 1 mol (=about 41 kg.) of NaOH in the form of a concentrated lye. The thickly pasty mixture is further stirred for one hour at 45 C., then cooled to 20 C., and finally neutralized by adding in small portions about kg. of hydrochloric acid of about 10% strength. The thickly pasty reaction mixture is then kneaded for 10 minutes at about 20 C. with about kg. of common salt until the reaction product separates in the form of a jelly. The solution of salt that has separated is withdrawn by the bottom outlet. The remaining jelly-like reaction mixture is fused over night at about 98 C. and then drawn off at this temperature.
Yield: 335 kg. of reaction product in the form of a paste of about 45% strength. I
The wetting values of known urethanes are given in the following Table II.
Already in a concentration of 0.20 gram of washingactive substance per liter of neutral water (pH 7) having a temperature of 20 C., the compound shows a wetting time of 100 seconds, measured on standardized circular cotton fabric put on the solution (funnel method, cf. Ex-
ample 1).
Table II Alkyl-chloroformic acid Wetting Amino component ester value (g./1.)
(a) 2+:thy1hexyltaurine 3-methyl-hexyl-chloroiormic 0.27
acid ester.
(b) 2-ethylhexyltaurine oleylchloroformic acid ester.. 5
() 2-ethylhexyltaurine Z-ethylbutylchloroiormic 0.52
acid ester.
(11) N-butyl-taurine Z-ethylhexyl-chloroformic 1.28
acid ester.
(0) N-butyl-taurine dodrzcyl-chlorotormic acid 1.55
es er.
(1)1sobutyl-taurine 2-ethylhexy1-ehloroformic 1.02
acid ester.
(0) isobutyl-taurine dodtzcyl-chloroformic acid 0.6
es er.
(h) isobutyl-taurine trimethylnonyl-chiorofonnic 0.46
acid ester.
(i) isobutyl-taurine 2-butyIoctyl-chloroiormic 0.62
acid ester.
(j) isobutyl-taurinediisobutylcarbionol-chioro- 1.5
formic acid ester.
(k) cyclohexyi-taurine 2-ethylhexyl-chloroformic 1.15
acid ester.
(1) methyl-taurmeu 1.5
(m) methyl-taurine. oleyl-chloroformic acid ester 3. 75
('n) dodecyl-taurlne. 2ethylhexyl-chloroformic 0.96
acid ester.
(0) Z-ethylhexyl-glycocoll. Z-ethylbutyl-chloroformic 0.52
acid ester.
(1)) 2-ethyihexyl-glycocoll...... oleyl-chloroformie acid ester- We claim: 1. Surface-active compounds of the formula R0 mmomomsmm wherein R is an alkyl radical having 812 carbon atoms and R is a member selected from the group consisting of 2-ethyl-hexyl and n-octyl.
2. A surface-active compound as in claim 1 wherein R is n-octyl and R is n-octyl.
3. A surface-active compound as in claim 1 wherein R is Z-ethyl-hexyl and R is Z-ethyI-hexyl.
4. A surface-active compound as in claim 1 wherein R is di-isobutylcarbino and R is 2-ethy1-hexyl.
5. A surface-active compound as in claim 1 wherein R is n-octyl and R is 2-ethyl-hexyl.
6. A surface-active compound as in claim 1 wherein R is dodecyl and R is 2ethy1-hexyl.
References Cited in the file of this patent UNITED STATES PATENTS 1,933,945 Uln'ch et al. Nov. 7, 1933 2,157,362 Ulrich et al. May 9, 1939 2,722,551 Snell et a1. Nov. 1, 1955 FOREIGN PATENTS 599,692 Germany July 7, 1934 854,796 Germany Nov. 6, 1952 31,851 Netherlands Jan. 15, 1934 112,827 Sweden Jan. 2, 1945
Claims (1)
1. SURFACE-ACTIVE COMPOUNDS OF THE FORMULA
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3086986X | 1958-05-24 |
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| Publication Number | Publication Date |
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| US3086986A true US3086986A (en) | 1963-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
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| US814170A Expired - Lifetime US3086986A (en) | 1958-05-24 | 1959-05-19 | Surface-active urethanes and a process for preparing them |
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| Country | Link |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454624A (en) * | 1966-10-05 | 1969-07-08 | Gaf Corp | Anionic detergents of sulfoalkyl-carbamate esters |
| US3906027A (en) * | 1972-08-05 | 1975-09-16 | Bayer Ag | N-(perfluoroalkyl-sulphonyl)-carbamic acid esters of polyalkylene oxides |
| US4245110A (en) * | 1974-03-14 | 1981-01-13 | Bayer Aktiengesellschaft | Polyalkylene oxide-containing urethane polyols with sulphonic acid groups |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL31851C (en) * | ||||
| US1933945A (en) * | 1931-02-16 | 1933-11-07 | Ig Farbenindustrie Ag | Production of urethane substances |
| DE599692C (en) * | 1931-03-27 | 1934-07-07 | I G Farbenindustrie Akt Ges | Process for the production of wetting, cleaning and dispersing agents |
| US2157362A (en) * | 1935-11-08 | 1939-05-09 | Ig Farbenindustrie Ag | Process of producing urethane substances containing carboxyl or sulphonic acid groups |
| DE854796C (en) * | 1942-11-07 | 1952-11-06 | Hoechst Ag | Process for the production of water-soluble urethanes |
| US2722551A (en) * | 1952-09-18 | 1955-11-01 | Parke Davis & Co | Alanylaminoethanemercapto compounds and method for obtaining the same |
-
1959
- 1959-05-19 US US814170A patent/US3086986A/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL31851C (en) * | ||||
| US1933945A (en) * | 1931-02-16 | 1933-11-07 | Ig Farbenindustrie Ag | Production of urethane substances |
| DE599692C (en) * | 1931-03-27 | 1934-07-07 | I G Farbenindustrie Akt Ges | Process for the production of wetting, cleaning and dispersing agents |
| US2157362A (en) * | 1935-11-08 | 1939-05-09 | Ig Farbenindustrie Ag | Process of producing urethane substances containing carboxyl or sulphonic acid groups |
| DE854796C (en) * | 1942-11-07 | 1952-11-06 | Hoechst Ag | Process for the production of water-soluble urethanes |
| US2722551A (en) * | 1952-09-18 | 1955-11-01 | Parke Davis & Co | Alanylaminoethanemercapto compounds and method for obtaining the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3454624A (en) * | 1966-10-05 | 1969-07-08 | Gaf Corp | Anionic detergents of sulfoalkyl-carbamate esters |
| US3906027A (en) * | 1972-08-05 | 1975-09-16 | Bayer Ag | N-(perfluoroalkyl-sulphonyl)-carbamic acid esters of polyalkylene oxides |
| US4245110A (en) * | 1974-03-14 | 1981-01-13 | Bayer Aktiengesellschaft | Polyalkylene oxide-containing urethane polyols with sulphonic acid groups |
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