US3000832A - Detergent compositions - Google Patents

Detergent compositions Download PDF

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Publication number
US3000832A
US3000832A US608707A US60870756A US3000832A US 3000832 A US3000832 A US 3000832A US 608707 A US608707 A US 608707A US 60870756 A US60870756 A US 60870756A US 3000832 A US3000832 A US 3000832A
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US
United States
Prior art keywords
alkyl
carbon atoms
salt
detergent
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US608707A
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English (en)
Inventor
Pieter L Kooijman
Petrus W Slokker
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Shell USA Inc
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Shell Oil Co
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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

  • This invention relates to new compositions having detergent properties. More particularly, it pertains to compositions containing synthetic sulfated and sulfonated organic detergents of certain specific types in controlled proporations which have an-exceptionally lvaluable combination of properties.
  • a special object of the invention is the provision of mixtures of alkyl aryl sulfonate detergents and alkyl su1 fate salt detergents which not only have an especially advantageous combination of desirable surface-active properties but also form concentrated solutions in water which are stable to precipitation and gelling at low temperatures and so are eminently adapted for use as liquid detergent compositions. Because of the special advantages of the new detergent mixtures in solutions suitable for sale in the rapidly increasing market for liquid household detergents, for instance,this form of the newcompositions will be emphasized in the following description of the invention, but it will be understood that the new detergent mixtures are not restricted to such use and can be advantageously employed as solid products in powder, flake, bar or other conventional forms.
  • This cold stability is conveniently measured by clear point determinations, the clear point being the temperature, expressed in degrees centigrade, at which a turbid aqueous solution of the detergent mixture of given concentration clarifies during gradual heating.
  • the detergent mixtures of the invention having these advantageous properties are mixtures of alkyl aryl sulfonates having 8 and/or 9 carbon atoms in the alkyl groups, preferably together with one or morealkyl aryl sulfonates vw'th 10, ll, 12 or 13 carbon atoms in the alkyl groups and substantially free from alkyl aryl sulfonates comprising less than 8 or more than 13 carbon atoms in the alkyl groups in admixture with mixtures substan- States Patent 0 'stantial amount in such component.
  • the mixture contain an alkyl aryl sulfonate having either 8 or 9 car-- bon atomsin the group or of a mixture vof such alkyl-aryl sulfonates as the alkyl aryl sulfona'te detergent component of the new detergent mixture or be present in sub- Alkyl aryl sulfona'te's with longer alkyl groups have been found to promote the detergent effect of the mixture and can therefore be added thereto chiefly for this purpose, but alkyl aryl sulfonates with alkyl groups having more than 13 carbon atoms were found .to have an unfavorable eifect.
  • alkyl aryl sulfonate mixtures with alkyl groups comprising 10 and 11, or 10, 1i and 12, or 1.0, 11, 12 and 13, or 11, 12 and 13, etc., carbon atoms are suitable for use in the present mixtures in addition to the essential C and/or C -alkyl aryl sulfonates.
  • mixtures of alkyl aryl sulfonates in which the number of carbon atoms in the alkyl groups do not form successive series,and thus, for example, comprise 10 and 12, 10 and 13, 10, 11 and 13 or 11 and 13 carbon atoms, may likewise be used with the C and/or C -alkyl aryl sulfonates with good results.
  • Alkyl aryl sulfonates which are particularly suitable for use in the process according to the invention may be prepared by alkylation of benzene or naphthalene, or substitution products thereof such as toluene, methyl naphthalene, etc., using HF or H as alkylation catalyst, with an olefin mixture obtained by the vapor-phase cracking of 'paratiin waxes or by cracking by solvent extraction refined catalystically cracked heavy oil, or by polymerization of alkenes such as propene as used for the preparation of propylene tetramers.
  • the olefins used are those having the number of carbon atoms required to give the above indicated alkyl groups.
  • the alkylate is sulfonated and neutralized in] the customary way.
  • the alkyl sulfates chosen are preferably watersoluble secondary alkyl sulfate salt detergents prepared via sulfation of a mixture substantially consisting of C or C to C olefins obtained in one of the two ways just described.
  • mixtures of compounds to be used for the alkylation and the preparaton of alkyl sulfates will be obtained by distilling mixtures which, in addition, contain compounds with more and/or fewer 's,000,saa
  • ixture of this type is also referred to here as a C or C olefin mixture and the sulfate prepared there- 1 as a C or C to C alkyl sulfate.
  • the alkyl aryl sulfonates so that, example, an alkyl aryl sulfonate mixture referred to he term C or C to C may also contain a small entage of C and C alkyl aryl sulfonates.
  • he preferred alkyl aryl sulfonates are the waterble monoalkylbenzene monosulfonic acid salts, pararly the alkali metal, for instance potassium, or amium or amine salts.
  • Similar salts are preferred in ing the C or C to C alkyl sulfate salt detergent ponent of the new mixtures.
  • These alkyl sulfate are advantageously mixtures predominating in ght or substantially straight chain 2-alkylsulfate salts. greatest improvements in foaming, wetting properties clear point have been obtained by use of ternary rgent mixtures of the previously described polyethylglycol with alkylphenol monoethers with C -C lbenzencmonosodium sulfonates and C -C secondrlkyl sodium sulfates.
  • alkylphenol-polyethylene glycol monor which should be present with the indicated alkyl sulfonate and alkyl sulfate salt detergent mixtures reparing the preferred compositions of the invention depend upon the properties desired in the final prod- Even relatively small amounts of the specified lphenolpolyethylene glycol monoethers in the new positions give marked improvements in the wetting foaming properties as well as in the clear point of alkylbenzene sulfonate-secondary alkyl sulfate salt rgent mixtures.
  • the wetting and foamiroperties of the mixture increase.
  • the proportions of the three detergent ionents are 30% C -C alkylbenzene sodium sulzes, 50% C -C secondary alkyl sodium sulfate and octylphenol polyethylene glycol monoether with i ethylene glycol units
  • the relative wetting and foamalues are 200 and 160, respec- I, and the clear point is below 0 C. even in soluof 34% concentration.
  • the alkyl sulfate salts are preferably formed by adding the corresponding olefins to the alkyl aryl hydrocarbon sulfonation product andcarrying out sulfation of the olefins with excess sulfonatmgagent present therein.
  • the sulfonation 15 carried out with oleum of, for example, 20% free S0 concentration using a mole ratio of S0 to alkyl aryl hydrocarbon of about 5 to 7:1.
  • the alkyl aryl sulfonic acids and alkyl sulfuric acids can be separately prepared and mixed together 1B the required ratio, after which the mixture is neutralized and extracted preferably with a liquid hydrocarbon such as gasoline to remove unconverted organic material and/ or other undesirable impurities.
  • the alkyl aryl sulfonate and alkyl sulfate salt detergents employed in the new compositions will usually contain a. certain amount of inorganic salt, particularly the sulfate corresponding to the base used in the neutralization step in their preparation. It may be desirable to add other builders such as phosphates, silicates, carbonates, foam stabilizers, washing promoters, bleaching agents, and the like, depending upon the intended use of the products.
  • the new compositions can also be used in admixture with other detergents. When the compositions are to be used in solution, for instance sold as liquid detergents, it is desirable that the inorganic salt content be below about 25% and more advantageously not greater than about 15%.
  • the active ingredient content i.e.
  • alkyl aryl sulfonate detergent the total weight of alkyl aryl sulfonate detergent.
  • alkyl sulfate salt detergent and alkylphenol polyethylene glycol monoethers in such cases is preferably between about 10% and about 50%. more preferably about 20% to about 40% by weight of the solution.
  • EXAMPLEII Benzene was alkylated in a stirred reactor with a C. to C olefin mixture obtained by vapor phase cracking of a catalytically cracked refined heavy hydrocarbon oil.
  • the alkylation was started with a mixing ratio of benzene to olefins of 10:1.
  • Hydrogen fluoride was used as catalyst, care being taken to ensure a phase ratio of the total quantity of hydrocarbons to hydrogen fluoride of 1:1 by volume.
  • the residence time in the reactor was 30 minutes at room temperature, stirring being carried out at a rate of 220 r.p.m.
  • the pressure was 4 atmospheres absolute.
  • the mixture thus obtained was neutralized with a caustic soda solution and saponiiied in order to convert the dialkyl sulfates present into monoalkyl sulfates. After adding 25% by weight of isopropyl alcohol liquid phase desalting was then carried out. An extraction was then carried out with gasoline as a result of which unconverted organic material was removed. Finally, the solution was boiled down until the desired concentration was obtained.
  • the concentrate prepared in this way was split into three portions which were diluted with water to 20%, 34%, and 40% concentrations, respectively. The clear points thereof were found to be 2 0., 7 C. and 8 C., respectively.
  • compositions in accordance with the invention which have the previously indicated desirable combination 6 of properties are the following in which the proportior by weight: v
  • a detergent composition forming cold stable aqueous solutions of about 10% to about 50% detergent content, consisting essentially of an alkyl aryl hydrocarbon monosulfonic acid water-soluble salt having an alkyl group of '8 to 9 carbon atoms but essentially free of alkyl aryl sulfonate salts containing alkyl groups of less than 8 and more than 13 carbon atoms, together with a secondary alkyl sulfate salt consisting essentially of a secondary alkyl sulfate water-soluble salt having at least 8 to 9 but not more than 18- carbon-atoms per molecule, said sulfonate and alkyl sulfate'salt being present in a weight ratio of from :40 to 20:80, and an alkyl phenol polyethylene glycol monoether having 7 to 9 carbon atom
  • a detergent composition forming cold stable aqueous solutions of about 10% to about 50% detergent content, consisting essentially of a monoalkylbenzene monosulfonic acid sodium salt'wherein the alkyl group contains 8 to 9 through 13 carbon atoms and a secondary alkyl sulfate sodium salt of 8 to 9 through 18 carbon atoms per molecule which is a predominantly straight chain Z-alkyl sulfate salt, and an alkylphenol polyethylene glycol monoether having 7 to 9 carbon atoms in the alkyl group and 8 to 10- ethylene glycol units, the weight ratio of sulfonate 7 to alkyl sulfate salt being from 60:40 to 20:80 and :ontent of said alkyl phenol ether being about to it 30% of said detergent composition.
  • a detergent composition in accordance with claim 5, ch each alkyl group of the alkylbcnzene sulfonate alkyl sulfate salt is derived from olefinic products of r phase cracking of parafiinic hydrocarbons.
  • a liquid detergent composition consisting essentially 'ater, less than about 25% of inorganic salts, and ixture of an alkyl aryl hydrocarbon monosulfonic water-soluble salt having an alkyl group of 8 to 9 m atoms but essentially free of alkyl aryl sulfonate containing alkyl groups of less than 8 and more than arbon atoms and a secondary alkyl sulfate salt cong essentially of a secondary alkyl sulfate water- )le salt having at least 8 to 9 but not more than arbon atoms per molecule, said sulfonate and alkyl te salt being present in a weight ratio of from D to 20:80, and an alkyl phenol polyethylene glycol )ether having 7 to 9 carbon atoms in the alkyl p and 8 to 10 ethylene glycol units in the molecule, ⁇ mount of said ether being between about 2% and t 30% of the total weight of the mixture, said mixbeing between about 10%
  • a liquid detergent composition consisting essentially ater and a ternary mixture consisting of a monoalkyl :ne monosulfonic acid salt wherein the alkyl group contains 8 to 9 through 13 carbon atoms, a secondary alkyl sulfate sodium salt of 8 to 9 through 18 carbon atoms per molecule which is a predominantly straightchain 2-alky1 sulfate salt, and an alkyl phenol polyethylene glycol monoether having 7 to 9 carbon atoms in the alkyl group and 8 to 10 ethylene glycol units, the weight ratio of sulfonate salt to alkyl sulfate salt being from 60:40 to 20:80, and the content of said alkyl phenol ether being about 10% to about of said ternary mixture, said ternary mixture being between about 20% and about by weight of the liquid detergent composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US608707A 1955-09-16 1956-09-10 Detergent compositions Expired - Lifetime US3000832A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL351697X 1955-09-16
NL260756X 1956-07-26

Publications (1)

Publication Number Publication Date
US3000832A true US3000832A (en) 1961-09-19

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ID=26643570

Family Applications (1)

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US608707A Expired - Lifetime US3000832A (en) 1955-09-16 1956-09-10 Detergent compositions

Country Status (7)

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US (1) US3000832A (en, 2012)
BE (1) BE551039A (en, 2012)
CH (1) CH351697A (en, 2012)
DE (1) DE1109304B (en, 2012)
FR (1) FR1158041A (en, 2012)
GB (1) GB818367A (en, 2012)
NL (1) NL200503A (en, 2012)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242091A (en) * 1961-12-19 1966-03-22 Colgate Palmolive Co Spray dried detergent concentrate
US3256155A (en) * 1962-04-11 1966-06-14 Lever Brothers Ltd Dentifrice composition
US3264242A (en) * 1961-10-03 1966-08-02 Dow Chemical Co Aqueous dispersions containing alkylated diphenyloxidedisulfonic acid and a non-ionic surface active agent
US3350319A (en) * 1966-01-18 1967-10-31 Mo Och Domsjoe Ab Aqueous detergent-inorganic builder concentrates
US3422021A (en) * 1963-03-18 1969-01-14 Procter & Gamble Detergent composition
US3876466A (en) * 1971-10-30 1975-04-08 Norland Louis Claude Suzor Manufacture of sugar

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU528816B2 (en) * 1978-02-14 1983-05-12 Unilever Ltd. Detergent composotions
PL310987A1 (en) * 1993-04-08 1996-01-22 Procter & Gamble Secondary (2,3)-alkyl sulphate as a surfactant and mixture containing surfactant particles
EP0693549A1 (en) 1994-07-19 1996-01-24 The Procter & Gamble Company Solid bleach activator compositions
DE19510099C1 (de) * 1995-03-20 1996-08-22 Henkel Kgaa Wasserfreie Tensidgemische enthaltend lang- und kurzkettige sekundäre 2,3-Alkylsulfate

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2213477A (en) * 1935-12-12 1940-09-03 Gen Aniline & Film Corp Glycol and polyglycol ethers of isocyclic hydroxyl compounds
US2617772A (en) * 1952-11-11 Tack-fr ee alkaryl sulfonate
GB690288A (en) * 1949-07-16 1953-04-15 Monsanto Chemicals Improvements in or relating to surface-active alkylbenzene sulphonate compositions
GB704687A (en) * 1950-06-30 1954-02-24 Unilever Ltd Improvements in liquid detergent compositions
GB727467A (en) * 1951-08-10 1955-04-06 Shell Refining & Marketing Co Improvements in or relating to capillary active compositions containing sodium alkylsulphates or alkylated aryl sulphonates
US2733212A (en) * 1956-01-31 Hair shampoo

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL81051C (en, 2012) * 1950-06-21

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617772A (en) * 1952-11-11 Tack-fr ee alkaryl sulfonate
US2733212A (en) * 1956-01-31 Hair shampoo
US2213477A (en) * 1935-12-12 1940-09-03 Gen Aniline & Film Corp Glycol and polyglycol ethers of isocyclic hydroxyl compounds
GB690288A (en) * 1949-07-16 1953-04-15 Monsanto Chemicals Improvements in or relating to surface-active alkylbenzene sulphonate compositions
GB704687A (en) * 1950-06-30 1954-02-24 Unilever Ltd Improvements in liquid detergent compositions
GB727467A (en) * 1951-08-10 1955-04-06 Shell Refining & Marketing Co Improvements in or relating to capillary active compositions containing sodium alkylsulphates or alkylated aryl sulphonates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264242A (en) * 1961-10-03 1966-08-02 Dow Chemical Co Aqueous dispersions containing alkylated diphenyloxidedisulfonic acid and a non-ionic surface active agent
US3242091A (en) * 1961-12-19 1966-03-22 Colgate Palmolive Co Spray dried detergent concentrate
US3256155A (en) * 1962-04-11 1966-06-14 Lever Brothers Ltd Dentifrice composition
US3422021A (en) * 1963-03-18 1969-01-14 Procter & Gamble Detergent composition
US3350319A (en) * 1966-01-18 1967-10-31 Mo Och Domsjoe Ab Aqueous detergent-inorganic builder concentrates
US3876466A (en) * 1971-10-30 1975-04-08 Norland Louis Claude Suzor Manufacture of sugar

Also Published As

Publication number Publication date
CH351697A (de) 1961-01-31
FR1158041A (fr) 1958-06-06
GB818367A (en) 1959-08-12
DE1109304B (de) 1961-06-22
NL200503A (en, 2012)
BE551039A (en, 2012)

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