US3492239A - Light-colored sulfonation products - Google Patents

Light-colored sulfonation products Download PDF

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Publication number
US3492239A
US3492239A US635670A US3492239DA US3492239A US 3492239 A US3492239 A US 3492239A US 635670 A US635670 A US 635670A US 3492239D A US3492239D A US 3492239DA US 3492239 A US3492239 A US 3492239A
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mol
sulfonation
mols
same
olefin
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US635670A
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Horst Baumann
Werner Stein
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing

Definitions

  • the present invention relates to the sulfonation of olefins to produce light-colored olefin sulfonates having a low content of non-surfactant components.
  • the time required for the bleaching process can be shortened or the amount of bleach that is necessary can be considerably reduced by carrying out the sulfonation of the olefins in two stages.
  • a one-stage process is preferred if it does not entail any appreciable losses in the quality or quantity of product thereby obtained.
  • the present invention is directed to a process for the preparation of surface-active olefin sulfonates by the sulfonation of olefins with gaseous sulfur trioxide diluted with air or an inert gas, followed by alkaline hydrolysis, wherein as initial material for the preparation of the technically valuable sulfonation products there are employed aliphatic monoolefins having 8 to 22 carbon atoms in their molecules and wherein the sulfonation is carried out in the presence of a polyglycol ether of the formula wherein R represents alkyl having 8 to 22 carbon atoms, R represents hydrogen or alkyl having 1 to 6 carbon atoms, m has a value of 2 or 3, and n represents a whole number of from 1 to 20.
  • the aliphatic monoolefins serving as starting materials preferably contain 12 to 18 carbon atoms and have either a middle or terminal double bond.
  • R and R represent straight-chain, alkyl radicals having 1 to 18 carbon atoms, R represents hydrogen or a straight-chain alkyl radical having 1 to 18 carbon atoms, at least one of the alkyl radicals containing at least 6 carbon atoms. Mixtures of olefins of different structure and chain lengths can also be used.
  • the starting olefins can be obtained in the known manner from hydrocarbon mixtures or by synthesis from olefins of low molecular weight. They do not need to be entirely pure, but may contain small amounts, though not more than 10%, of paraffins and/or diolefins.
  • Suitable olefins are n-decene-l, n-undecene-l, n-tridecene-l, n-dodecene-l, n-tetra-decene-l, npentadecene-l, n-hexadecene-l, n-heptadecene-l, n-octadecene-l and mixtures thereof, sec. n-decene, sec. n-undecene, sec. n-tridecene, sec. n-tetradecene, sec. n-pentadecene, sec. n-hexadecene, sec. n-heptadecene and sec. noctadecene wherein the double bond is distributed over the chain.
  • the polyglycol ethers of the formula as set out above can be prepared by the conventional methods from primary or secondary alcohols by reaction thereof with ethylene oxide or propylene oxide. Mixtures of ethylene oxide and propylene oxide can also be used, or the two alkoxides can be used successively.
  • the alkoxylation can be followed by an alkylation of the free hydroxyl groups which can be conducted according to the known and conventional methods.
  • the two alkyl radicals R and R can be straightor branch-chained or, alternatively, can be cyclic.
  • Ethoxylation products of straight-chain primary or secondary alcohols, which are preferred for use herein, have from 2 to 12 ethylene glycol ether groups as Well as one free hydroxyl group, the alkyl group R having from 10 to 18 carbon atoms.
  • polyglycol ethers examples include the di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona-, deca-, undeca-, and dodeca-ethylene glycol ether of primary or secondary n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol and n-octadecanol.
  • Said polyglycol ethers may be etherified with 1 to 10 propylene glycol ether groups or with methyl, ethyl, propyl or isopropyl groups.
  • polyglycol ethers obtained by the addition of alkylene oxide onto long-chain alcohols may also contain unetherified alcohols. These do not give rise to any problems and may remain in the mixture. In the subsequent sulfonation reaction, they are converted into their corresponding alkyl sulfates.
  • the ratio of olefin to polygylcol ether in the mixture amounts advantageously to from 9:1 to 1:4 parts by weight. These ratios can be exceeded in either direction, but in that case, the color of the reaction products increasingly deteriorates.
  • the sulfonation is conducted according to the known method. If gaseous sulfur trioxide is used as the sulfonating agent, it is used diluted with air or with an inert gas, the sulfur trioxide concentration amounting to from 0.5 to 10 and preferably from 1 to 5 percent by volume.
  • gaseous sulfur trioxide is used as the sulfonating agent, it is used diluted with air or with an inert gas, the sulfur trioxide concentration amounting to from 0.5 to 10 and preferably from 1 to 5 percent by volume.
  • the inert gases which can be employed as diluent, are, for example, nitrogen, carbon dioxide or sulfur dioxide.
  • the equivalent amount of chlorosulfonic acid can also be advantageously used.
  • the hydrogen chloride that forms in the reaction should be removed, for example, by passing a stream of air or inert gas through the reaction mixture, and continuing this operation for some time after the sulfonation has ended, or by alternatively operating under vacuum.
  • the sulfonation can be carried out discontinuously, or continuously, using a cocurrent or countercurrent fiow. It is recommended, however, that the reactants be intensively mixed during the sulfonation reaction.
  • the sulfonation reaction takes place at temperatures ranging from to 60 C., and preferably at temperatures of from 10 to 40 C. As the reaction is an exothermic one, additional heat input is generally unnecessary. In most cases it is necessary to remove the excess reaction heat, and, accordingly, it is recommended that the optimum temperature be maintained by appropriate cooling of the reaction vessel.
  • the reaction time depends to a great extent on the conditions selected for carrying out the reaction, such as the temperature, the concentration of the sulfonating agent and the type of reaction apparatus used. Short re action times can be achieved particularly when the reaction mixture is intensively agitated by means of appropriate mechanical devices or is sprayed, or when reaction apparatus, which is used, are those operating on the thin layer or annular gap principle. If small quantities are used, the mixing action that is produced by the introduction of the inert gas stream into the reaction mixture will suffice under certain circumstances for achieving the desired degree of sulfonation and nature of sulfonation product.
  • the sulfonation is continued until at least 1.0 and no more than 1.3 mols, and preferably 1.05 to 1.2 mols of sulfur trioxide have been absorbed per mol of sulfonatable material.
  • the olefins and the polyglycol ethers which contain a free hydroxyl group in their molecules are considered as the sulfonatable materials.
  • the sulfonation can also be carried out in two stages. In this case it is preferred to proceed in a first stage wherein the sulfonation is carried out as described above, at a reaction temperature of 10 to 40 C. and with a sulfur trioxide concentration in the sulfonating gas of 1 to 5% by volume. After the mixture to be sulfonated has absorbed 60 to of the total amount of sulfur trioxide to be used, it is advantageous that in the second stage the temperature be reduced by about 5 to 10 C. and the sulfur trioxide concentration in the gas reduced by at least 20%, Le, to a range of from 0.5 to 4% by volume.
  • sulfonating agent to be used per mol of sulfouatable material likewise amount to 1.0 to 1.3 mols, of which 0.5 to 1.0 and preferably 0.6 to 0.9 mol can be sulfur trioxide and 0.2 to 0.6 and preferably 0.3 to 0.5 mol can be chlorosulfonic acid.
  • the sulfonation products as obtained according to the described procedures are then neutralized with alkalies, ammonia, organic ammonium bases or alkaline earths and thereafter hydrolyzed by heating in an aqueous solution to temperatures of 80 to 200 C., using therefor that amount of water whereby the crude sulfonation product is in the form of a 7 to 75% solution.
  • Hydrolysis at temperatures above C. is carried out in pressure vessels. In general, 60 to minutes are required for hydrolysis at temperatures of up to 100 C., and from 5 to 15 minutes are needed for hydrolysis at 200 C.
  • the quantity of the alkaline reacting substance used for the neutralization is calculated so that, after neutralization of the sulfonic acid and any excess sulfonating agent that might be present, enough still remains for the neutralization of the sulfonic acid that is formed in the hydrolysis. It is preferable to work with an excess that can amount to as much as 20% of the theoretically necessary amount of alkali.
  • Particularly suitable neutralization agents are the hydroxides, carbonates and bicarbonates of sodium, potassium and ammonium, as well as organic bases, such as the primary, secondary or tertiary amines or alkylolamines having 1 to 4 and preferably two carbon atoms per alkyl or alkylol radical.
  • organic bases react with the sultones contained in the raw sulfonation product to form surface-active alkylsulfobetaines. It is also possible however, first to neutralize the free sulfonic acids with an alkali metal or alkaline earth metal alkaline reacting agent and then to add one of the abovementioned organic bases in such quantity that in the subsequent hydrolysis the sultones contained in the saponifiable portion are converted into alkylsulfobetaines.
  • a bleaching treatment can be carried out with the conventional oxygen-yielding bleaches.
  • the sulfonation products obtained by the process according to the invention contain few, if any, colored by-products and are characterized by their excellent bleachability and low consumption of bleaching agent.
  • the hydrolysis and the bleaching can be carried out simultaneously.
  • the light-colored mixtures manufactured according to the invention consist almost exclusively of surface-active materials.
  • mixtures of olefin sulfonates, or mixtures thereof with alkylsulfobetaines and alkyl polyglycol ether sulfates, or mixtures thereof with unsulfated alkyl polyglycol ethers or dialkyl polyglycol ethers and fatty alcohol sulfates if the polyglycol ethers used as the starting substances contained free fatty alcohols.
  • the unsulfonated olefin content of the mixtures however, amounts to less than 5%.
  • the products of the process have outstanding cleaning, wetting, emulsifying and dispersing properties and can be used in admixture with other wash-active substances and conventional synthetic agents and additives in the formulation of detergents and washing compounds. Further, they can be used advantageously as additives in textile adjuvants.
  • the properties of the products can be extensively adapted to a particular application. If the starting materials include polyglycol ethers having a free hydroxyl group and the hydrolysis is carried out at temperatures of about 100 C., relatively high-sudsing prodnets are produced which have a high cleaning power, such as is desired in fine laundry detergents, foaming cleaners and bathing and hair washing detergents.
  • the saponification of sulfated polyethylene glycol ethers or the use of dialkylated polyethylene glycol ethers results, if there are at least 4 to 5 glycol ether groups in the molecule, in lowsudsing preparations, suitable particularly for use as washing machine detergents. If the end products contain mainly dialkylated or unsulfated polypropylene glycol ethers or unsulfated glycol ethers having 1 to 3 ethylene glycol ether groups in their molecules, the products are suitable primarily as emulsifiers.
  • mixtures of alkyl polyglycol ethers and other sulfonatable materials, especially alkylbenzenes or fatty acid esters, under the same conditions result in the production of dark-colored sulfonation products having a low degree of sulfonation, it was not to be expected that the mixtures used according to the invention would behave in a fundamentally different manner.
  • the olefins used in the following examples contained about 2% paraffinic hydrocarbons.
  • the color values as recited were determined in a 4" cell in the Lovibond Tintometer employing aqueous solutions which contained 5 wt. percent of hydrolyzed and neutralized sulfonation product.
  • the unsulfonated olefins present in the end product were determined by extracting a sample of the hydrolyzed product three to four times using the same volume of benzine having a boiling point of to C. each time, removing the extractant by distillation, and determining the iodine number of the remaining oil.
  • the amount of olefin thereby computed was added to the paraflins that were introduced with the starting material. The value thus obtained is set out hereinafter as the water-insoluble portion in percent by weight of waterfree end product.
  • the mere weighing out of the benzine extract would produce false results since the polygylcol ethers are partially soluble in the organic phase.
  • Example 13 the use of a two-stage procedure is exemplified; in the first stage, the sulfonating was carried out with sulfur trioxide, and in the second stage chlorosulfonic acid was employed as sulfonating agent.
  • Example Olefin Polyglycol Ether sulfonating Agent percent Yellow Red Blue 2 112 g. (0.5 mol) ofn-hexadecene 141 g. (0.5 mol) prim. 012 014 89 g. S03 (1.11 mols) 3. 5 16 2. 9 0
  • alpha olefins C No. 16.5, Example 2.
  • I No. 114.
  • Example Olefin Polyglycol Ether Sulionating Agent percent Yellow Red Blue 13.... 116 g. (0.5 mol) same as 141 g. (0.5mol) same as (a) 0.7 mol of S03, (1)) 0.5 3.8 16 2
  • Example 4. Example 2. mol of CiSOaH.
  • Example 14 Example 14.
  • Example 14 Example 14.
  • a process for the preparation of surface-active sulfonates which comprises reacting an olefin having 8 to 22 carbon atoms in its molecule with 1.0 to 1.3 mole per mol of said olefin gaseous sulfur trioxide diluted with an inert gas as sulfonating agent, in the presence of a polyglycol ether having the formula:
  • R represents alkyl of 8 to 22 carbon atoms
  • R represents a member selected from the group of hydrogen and 'alkyl having I to 6 carbon atoms
  • In is 2 or 3
  • n is a whole number from 1 to 20 at a temperature of from O to 60 C., hydrolyzing the sulfonated olefin product thereby produced and thereafter neutralizing the resulting mixture with an alkaline neutralizing agent; the ratio of said olefin to said polyglycol ether is from 9:1 to 1:4 parts by weight.
  • a process according to claim 1 wherein said olefin is straight chained, has an internal or terminal double bond and contains from 12 to 18 carbon atoms.
  • a process according to claim 1 wherein said olefin has the formula wherein R and R are each straight-chain alkyl having 1 to 18 carbon atoms and R is a member selected from the group consisting of hydrogen and straight-chain alkyl having 1 to 18 carbon atoms, with the proviso that at resultant mixture to a temperature of from 80 to 200 C.
  • sufiicient water is added to the sulfonation reaction product to form a 7 to 75% solution.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US635670A 1966-07-01 1967-05-03 Light-colored sulfonation products Expired - Lifetime US3492239A (en)

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US (1) US3492239A (de)
AT (1) AT266065B (de)
BE (1) BE700739A (de)
DE (1) DE1568769C3 (de)
GB (1) GB1140164A (de)
NL (1) NL150414B (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3691108A (en) * 1969-08-29 1972-09-12 Sumitomo Chemical Co Olefin sulfonate detergent composition
US3714238A (en) * 1968-12-11 1973-01-30 Lion Fat Oil Co Ltd Method of sulfonating an olefin mixture
US3755203A (en) * 1970-12-17 1973-08-28 Jefferson Chem Co Inc Detergent slurry compositions
US3852221A (en) * 1971-08-19 1974-12-03 Jefferson Chem Co Inc Liquid olefin sulfonate detergent
US3864375A (en) * 1972-04-28 1975-02-04 Lion Fat Oil Co Ltd Thin-film type sulfonation process
US3941834A (en) * 1971-06-09 1976-03-02 Standard Oil Company High molecular weight aliphatic hydrocarbon sulfonic acids, sulfonyl chlorides and sulfonamides

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6059903B2 (ja) * 1977-08-25 1985-12-27 ライオン株式会社 内部オレフインスルホン酸塩の製造法
EP0130753B1 (de) * 1983-07-01 1987-12-09 Lion Corporation Verfahren zur Herstellung von Sulfonaten von ungesättigten Fettsäureestern

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2086115A (en) * 1935-12-13 1937-07-06 Blickman Saul Measuring device
US2174761A (en) * 1935-04-13 1939-10-03 Ig Farbenindustrie Ag Condensation products derived from hydroxy compounds and method of producing them
US2365783A (en) * 1940-07-23 1944-12-26 Procter & Gamble Sulphonation of branched chain olefins
DE1215695B (de) * 1964-03-12 1966-05-05 Henkel & Cie Gmbh Verfahren zur Herstellung hellfarbiger Olefinsulfonierungsprodukte bzw. der entsprechenden Sulfonate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2174761A (en) * 1935-04-13 1939-10-03 Ig Farbenindustrie Ag Condensation products derived from hydroxy compounds and method of producing them
US2086115A (en) * 1935-12-13 1937-07-06 Blickman Saul Measuring device
US2365783A (en) * 1940-07-23 1944-12-26 Procter & Gamble Sulphonation of branched chain olefins
DE1215695B (de) * 1964-03-12 1966-05-05 Henkel & Cie Gmbh Verfahren zur Herstellung hellfarbiger Olefinsulfonierungsprodukte bzw. der entsprechenden Sulfonate

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3714238A (en) * 1968-12-11 1973-01-30 Lion Fat Oil Co Ltd Method of sulfonating an olefin mixture
US3691108A (en) * 1969-08-29 1972-09-12 Sumitomo Chemical Co Olefin sulfonate detergent composition
US3755203A (en) * 1970-12-17 1973-08-28 Jefferson Chem Co Inc Detergent slurry compositions
US3941834A (en) * 1971-06-09 1976-03-02 Standard Oil Company High molecular weight aliphatic hydrocarbon sulfonic acids, sulfonyl chlorides and sulfonamides
US3852221A (en) * 1971-08-19 1974-12-03 Jefferson Chem Co Inc Liquid olefin sulfonate detergent
US3864375A (en) * 1972-04-28 1975-02-04 Lion Fat Oil Co Ltd Thin-film type sulfonation process

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AT266065B (de) 1968-11-11
GB1140164A (en) 1969-01-15
BE700739A (de) 1968-01-02
NL150414B (nl) 1976-08-16
DE1568769B2 (de) 1974-10-24
DE1568769A1 (de) 1970-04-16
NL6705091A (de) 1968-01-02
DE1568769C3 (de) 1975-06-19

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