US3232975A - Process for bleaching sulfonic acids, esters and chlorides - Google Patents

Process for bleaching sulfonic acids, esters and chlorides Download PDF

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Publication number
US3232975A
US3232975A US144063A US14406361A US3232975A US 3232975 A US3232975 A US 3232975A US 144063 A US144063 A US 144063A US 14406361 A US14406361 A US 14406361A US 3232975 A US3232975 A US 3232975A
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acid
sulfonic acid
carbon atoms
sulfonic
acids
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Merkel Karl
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/42—Separation; Purification; Stabilisation; Use of additives

Definitions

  • color number means that the solution has a shade like that of an iodine solution which contains as many milligrams of iodine in 100 ml. of water asis indicated by thecolor number.
  • Another object of the invention is a process in which the decolorizing agent can be readily separated from the solutions which have been bleached therewith.
  • a further object of the invention is a process in which with only a single treatment with a small amount of a decolorizing agent, sulfonic acids or theirfderivatives are obtained which have low color numbers.
  • the process may be used with aliphatic or aromatic sulfonic acids and their salts, the corresponding sulfonic acid chlorides and su'lfonic acid esters.
  • Alkanesulfonic acids with 2 to 20 carbon atoms in the alkyl radical alkenesulfonic acids with 2 to 20 carbon atoms in the alkene radical and arylsulfonic acids with one or two benzene rings in the aryl radical and with a total of 6 to'30 carbon atoms and also the corresponding salts, for example the alkali salts, the corresponding sulfonic acid chlorides and sulfonic acid esters are especially suitable.
  • the alkyl, alkenyl and aryl radicals of the said sulfonic acids and sulfonic acid derivatives may contain groups which are inert under the reaction conditions, as, for example halogen atoms, such as chlorine, bromine, iodine or fluorine atoms, carboxyl groups or carboxylic acid ester groups the alcohol components of which contain 1 to 4 carbon atoms.
  • halogen atoms such as chlorine, bromine, iodine or fluorine atoms
  • carboxyl groups or carboxylic acid ester groups the alcohol components of which contain 1 to 4 carbon atoms.
  • the alcohol of the ester grouping may be derived from aliphatic saturated alcohols with 1 to 20 carbon atoms or from, phenols with 6 to 20 carbon atoms.
  • sulfonic acids and sulfonic acid derivatives which can be bleached according to this invention: ethylsulfonic acid, vinylsulfonic acid, octylsul- 3,232,975 Patented Feb.
  • All these sulfonic acids may also be used in the form of their salts, especially the alkali salts, for example, the sodium salt of ethylsulfonic acid, the potassium salt of octylsulfonic acid, the lithium salt of d-odecylsulfonic acid, the lithiur'n salt of hexadecylsulfonic acid, the sodium salt of benzenesulfonic acid and thepotassium salts of toluenesulfonic acids, the sodium salt of 5-sulfo-is ophthalic acid di methyl ester.
  • the alkali salts for example, the sodium salt of ethylsulfonic acid, the potassium salt of octylsulfonic acid, the lithium salt of d-odecylsulfonic acid, the lithiur'n salt of hexadecylsulfonic acid, the sodium salt of benzenesulfonic acid and
  • sulfonic acid chlorides ethylsulfonic' acid chloride, 2-propene-l-sulfonic acid chloride, octylsulfonic acid chloride, dodecylsulfonic acid chloride, mixtures of sulfochlorides of long-chain alkanes such as are obtained by sulfochlorination of the'co rre sponding hydrocarbons, especially those derived from alkanes with 8 to :12 or 16 to 20 carbon atoms, further benzene sulfochloride, toluene sulfochlorides, naphthalene sulfochlorides,'B-chloroethane sulfochloride, 4-chloro benzene sulfochloride, and tert.-butylbenzene sulfochlorides
  • sulfonic acid esters ethylsulfonic acid esters: ethyl
  • the process is especially suitable for bleaching alkylarylsulfonic acids with 4 to 12 carbon atoms in the alkyl group and one or two benzene rings, the alkali salt of these compounds, alkyl sulfonic acids with l2 to 20 carbon atoms and .the alkali salts of the latter compounds prepared on a technical scale.
  • the treatment of the sulfonic acid orits derivatives is effected by mixing orstirringvat a suitable temperature.
  • the treatment with the chlorinated cyanuric acids may be carried out directly.
  • solutions are used, preferably those of 10 to 50% strength. Any inert solvents are suitable, but water is preferred.
  • lower saturated aliphatic alcohols with 1 to 4 carbonatoms such as methanol, ethanol, propanol and butanol, or lower aliphatic ketones with 3m 8 carbon atoms, such as acetone, are suitable.
  • inert solvents for examplelinear or cyclic ethers with 3 to 10 carbon atoms, for example diethyl ether, di-n-butyl ether, tetrahydrofuran and dioxane, or halogen hydrocarbons with l to 6 carbon atoms, such as carbon tetrachloride, chloroform and ethylene chloride, or nitriles of lower fatty acids with 2 to 6 carbon atoms, as :Eor example acetonitrile or propionitrile.
  • inert solvents for examplelinear or cyclic ethers with 3 to 10 carbon atoms, for example diethyl ether, di-n-butyl ether, tetrahydrofuran and dioxane, or halogen hydrocarbons with l to 6 carbon atoms, such as carbon tetrachloride, chloroform and ethylene chloride, or nitriles of lower fatty acids with 2 to 6 carbon atoms, as
  • Pure dior tri-chlorocyanuric acid, alkali salts of dichlorocyanuric acid, for example, the sodium or potassium salt, or mixtures such as are formed by the chlorination of cyanuric acid, if desired in the form of the alkali salts, are used as bleaching agents.
  • the amount to be used depends inter alia on the contents of active chlorine (for example, determinable iodometrically) in the chlorinated cyanuric acid (trichlorocyanuric acid has a content of active chlorine of 91.4%); when the content of active chlorine is high, for example 90%, a smaller amount is sufficient than with low contents, for example 69%.
  • Bleaching is carried out at below 100 C., preferably at temperatures between and 50 C.
  • the chlorinated cyanuric acids may be used solid or in solution, preferably in water or acetone, for example in the form of up to 2% aqueous solutions of trichlorocyanuric acid, up to 25% aqueous solutions of the sodium salt of dichlorocyanuric acid or up to aqueous so lutions of the potassium salt of dichlorocyanuric acid.
  • a mixture with neutral extraneous substances, for example inorganic salts, detergents, cleansing agents or surfaceactive substances is also possible.
  • cyanuric acid is formed from the chlorinated cyanuric acids in the presence of water.
  • Cyanuric acid is practically insoluble and can readily be separated in the usual way, for example by filtration with or without pressure or centrifuging. Usually, adequate separation can be effected even by decantation. Small amounts (about 0.1% per liter of aqueous solution) remain in the solutions of the sulfonic acids. This slight contamination is as a rule innocuous because cyanuric acid is substantially inert chemically.
  • the invention is illustrated by, but not limited to, the following examples in which parts are parts by weight.
  • the bleaching effect is indicated by the color number (iodine color scale).
  • Example 1 0.20 part of dichlorocyanuric acid is added with efiicient stirring at 20 C. to 100 parts of a 30% aqueous solution of the trisodium salt of sulfo-isophthalic acid (initial color number 150). The Whole is heated to 60 C. in half an hour, kept at this temperature for another half hour, allowed to cool and after another half hour filtered. The solution then has the color number 2 to 3.
  • Example 2 A 30% aqueous sulfo-isophthalic acid solution is bleached in a way analogous to that described in Example 1.
  • the color number of the solution is improved from 200 to 5.
  • Example 3 A 20% solution of tertiary-butyl-benzenesulfonic acid in methanol having the color number 200 is heated for an hour with 0.2 part of dichlorocyanuric acid at 35 C. After cooling and filtering the solution then has the color number 6.
  • Example 4 100 parts of a solution of 10 parts of 4-chlorobenzenesulfonic acid in 90 parts of water is intensely mixed by stirring for 2 hours at 50 C. with 0.05 part of the potas sium salt of dichlorocyanuric acid. The color number of the solution is improved from 210 to 13. In a comparative treatment with 1 part of 30% hydrogen peroxide solution, the color number is improved only to 46.
  • Example 5 100 parts of a solution of 15 parts of the sodium salt of p-dodecylbenzene sulfonic acid:
  • Example 6 100 parts of fi-chloroethanesulfonic acid chloride is stirred with 0.3 part of dichlorocyanuric acid for 2 hours. After filtration, fi-chloroethanesulfochloride with a color number of 15 is obtained, Whereas the initial material has a color number of more than 300. In an analogous treatment with 2 parts of active carbon, the color number is however improved only to 69.
  • Example 7 100 parts of a solution of 15 parts of the sodium salt of 5-sulfo-isophthalic acid dimethyl ester:
  • Example 9 100 parts of a commercial alkylsulfochloride, obtained by sulfochlorination of a hydrocarbon mixture of- C to C -alkanes is kept at 20 to 40 C. for about half an hour while being stirred intensely with parts of a 1.0% aqueous solution of trichlorocyanuric acid. The aqueous phase is then separated. The color number of the alkylsulfochloride mixture is improved from 215 to 6. In a comparative treatment with 2 parts of active carbon, a color number of 66 is achieved.
  • alkylsulfonic acid chloride mixture is saponified with caustic soda solution, a mixture of the sodium salts of the alkylsulfon-ic acids is obtained.
  • a 50% aqueous solution with the color number 49 is bleached to color numher 9 by treatment with 0.5 part of dichlorocyanuric acid for 2 hours.
  • Example 10 1.0 part of Water and 0.08 part of dichlorocyanuric acid are added to a solution or" 50 parts of benzene sulfochloride in 50 parts of butyl acetate with efiicient stirring. The mixture is stirred for an hour at room temperature. After separating the aqueous phase, the color number of the butyl acetate solution is improved from 71 to 5. In a comparative test with 1 part of bleaching earth, an improvement only to color number 18 is achieved.
  • Example 11 0.5 part of water and 0.1 part of dichlorocyanuric acid are introduced into 100 parts of fused 4-c'hlorobenzenesulfochloride at 56 C. while stirring well. After separating the cyanuric acid and the water, the color number of the 4-chlorobenzenesulfonic acid chloride has been improved from 88 to 11. In a comparative test with 2 parts of active carbon, a color number of only 30 is achieved.
  • Example 12 100 parts of an aqueous solution of 50 parts of a mixture of 90% ;3- and 10% a-naphthalenesulfonic acid in 50 parts of a 25% aqueous sulfuric acid is stirred with 0.3 part of the potassium salt of dichlorocyanuric acid for 3 hours at C. After filtration, the color number of the solution has been improved from more than 300 to 22; in a. comparative test with 2 parts of active carbon, a color number of only 90 is achieved.
  • Example 13 100 parts of a benzene solution containing 50 parts of p-chloroethane sulfonic acid p'henyl ester is stirred with 1.0 part of water and 0.5 part of dichlorocyanuric acid at 40 C. for 3 hours. The mixture is then filtered and dried. The color number of the solution is improved by this treatment from more than 300 to 18, whereas by treatment with 2 parts of active carbon a color number of only 39 is achieved.
  • a sulfonic acid compound selected from the group consisting of alkane sulfonic acid with 2-20 carbon atoms, an alkene sulfonic acid with 2- 20 carbon atoms, an aryl sulfonic acid with 1-2 aromatic rings, an alkaryl sulfonic acid with 1-2 aromatic rings and not more than 30 carbon atoms, a sulfonic acid chloride of the aforesaid sulfonic acids, an alkali metal salt of the aforesaid sulfonic acids, a halogen-substituted alkene sulfonic acid with 2-20 carbon atoms, a halogensubstituted alkane sulfonic acid chloride with 2-20 carbon atoms, and an ester of the aforesaid sulfonic acids with an alcohol selected from the group consisting of an alkanol of 1-20 carbon atoms, phenol and an alkyl phenol having

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  • Organic Chemistry (AREA)
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US144063A 1960-10-15 1961-10-10 Process for bleaching sulfonic acids, esters and chlorides Expired - Lifetime US3232975A (en)

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DEB59767A DE1127352B (de) 1960-10-15 1960-10-15 Verfahren zur Aufhellung roher aliphatischer oder aromatischer Sulfonsaeuren, deren Salzen, Chloriden oder Estern

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191170A (en) * 1977-10-21 1980-03-04 Carrell David R Solar panel
US4876048A (en) * 1988-12-12 1989-10-24 Pennwalt Corporation Purification of alkanesulfonyl chlorides
US4895977A (en) * 1988-12-12 1990-01-23 Pennwalt Corporation Purification of alkanesulfonic acids using ozone
US4910335A (en) * 1989-08-01 1990-03-20 Pennwalt Corporation Decolorization of alkanesulfonic and arenesulfonic acids

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2185864A (en) * 1937-10-28 1940-01-02 Pittsburgh Plate Glass Co Stable urea-chlorine compound and process for making same
US2607738A (en) * 1948-06-25 1952-08-19 Monsanto Chemicals Bleaching, sterilizing, disinfecting, and deterging compositions
US2827484A (en) * 1956-02-17 1958-03-18 Allied Chem & Dye Corp Sulfonic acid bleaching process
US2828308A (en) * 1955-09-09 1958-03-25 Purex Corp Ltd Process for purifying trichlorocyanuric acid
US2897154A (en) * 1956-07-30 1959-07-28 Purex Corp Ltd Bleaching and disinfecting compositions
US2913460A (en) * 1956-09-10 1959-11-17 Procter & Gamble Composition having bleaching, sterilizing and disinfecting properties, and method of preparation thereof
US2956056A (en) * 1958-02-14 1960-10-11 Grace W R & Co Process for preparing trichlorocyanuric acid

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2185864A (en) * 1937-10-28 1940-01-02 Pittsburgh Plate Glass Co Stable urea-chlorine compound and process for making same
US2607738A (en) * 1948-06-25 1952-08-19 Monsanto Chemicals Bleaching, sterilizing, disinfecting, and deterging compositions
US2828308A (en) * 1955-09-09 1958-03-25 Purex Corp Ltd Process for purifying trichlorocyanuric acid
US2827484A (en) * 1956-02-17 1958-03-18 Allied Chem & Dye Corp Sulfonic acid bleaching process
US2897154A (en) * 1956-07-30 1959-07-28 Purex Corp Ltd Bleaching and disinfecting compositions
US2913460A (en) * 1956-09-10 1959-11-17 Procter & Gamble Composition having bleaching, sterilizing and disinfecting properties, and method of preparation thereof
US2956056A (en) * 1958-02-14 1960-10-11 Grace W R & Co Process for preparing trichlorocyanuric acid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4191170A (en) * 1977-10-21 1980-03-04 Carrell David R Solar panel
US4876048A (en) * 1988-12-12 1989-10-24 Pennwalt Corporation Purification of alkanesulfonyl chlorides
US4895977A (en) * 1988-12-12 1990-01-23 Pennwalt Corporation Purification of alkanesulfonic acids using ozone
US4910335A (en) * 1989-08-01 1990-03-20 Pennwalt Corporation Decolorization of alkanesulfonic and arenesulfonic acids

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GB928123A (en) 1963-06-06
DE1127352B (de) 1962-04-12
BE609099A (fr) 1962-04-12

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