US3527707A - Liquid detergent composition - Google Patents

Liquid detergent composition Download PDF

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Publication number
US3527707A
US3527707A US285606A US3527707DA US3527707A US 3527707 A US3527707 A US 3527707A US 285606 A US285606 A US 285606A US 3527707D A US3527707D A US 3527707DA US 3527707 A US3527707 A US 3527707A
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United States
Prior art keywords
sodium
sulfonate
alkane
parts
percent
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US285606A
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English (en)
Inventor
James H Mcateer
Joseph F Nelson
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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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
    • C11D1/02—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
    • C11D1/143—Sulfonic acid esters
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates

Definitions

  • the present invention relates to novel liquid synthetic detergent compositions. More particularly, this invention relates to built liquid alkane sulfonate detergent compositions of improved solubility having attractive biodegradation characteristics.
  • Yet another object of this invention is to provide an inexpensive homogeneous liquid detergent composition of high solids content which utilizes minimal amounts of hydrotropes.
  • a further object of this invention is to provide synthetic liquid detergent compositions having improved biodegradation characteristics.
  • alkane sulfonates as a major organic surfactant component of the built liquid detergent formulation. It has been discovered surprisingly that alkane sulfonates have superior compatibility with conventional builders when com pared with the extensively utilized alkylaryl sulfonates such as dodecylbenzene sulfonate. This superiority is evidenced by the fact that significantly smaller amounts of hydrotrope are required to obtain homogeneous, clear, liquid heavy-duty formulations containing amounts of g sodium alkane sulfonate equivalent to the amounts of The convenience afforded by built heavy-duty deterfactants.
  • alkylaryl sulfonates examples of which have been discussed above, constitute the most extensively utilized active surfactant in modern detergent formulations.
  • the present use of these surfactants for the formulation of detergents introduces the further disadvantages that such detergents as now constituted are resistant to biodegradation due to their branchy structure.
  • the continued increase in use of non-biodegradable synthetic detergents is creating increasing concern on the part of public health authorities and the general public.
  • alkylaryl sulfonates now being employed commercially. This result is completely unexpected in view of the fact that the water solubility of sodium alkane sulfonates and sodium dodecylbenzene sulfonate is very nearly identical at room temperature.
  • Sodium alkane sulfonates may also be utilized in the manufacture of bar soaps and solid detergents in granular flake form.
  • the instant invention is concerned only with the unexpected advanages obtainable from employing the sodium alkane sulfonate in the form of a heavy duty liquid detergent.
  • the alkane sulfonates employed in this invention may be in various salt forms, e.g., their potassium, ammonium or triethanol amine salts. Most preferred are the sodium salts due to their economic advantage.
  • the alkane sulfonates are prepared from C to C and preferably C to C alkanes. These alkanes are preferably unbranched normal paraflins since excellent yields of highly biodegradable detergents are obtained from the straight chain paraffin. One to two methyl side chains per molecule are permissible but a high amount of branching is quite undersirable since it tends to increase the detergents resistance to biodegradation.
  • the alkane sulfonates employed in the detergent compositions of this invention may be prepared by a variety of techniques.
  • the normal paraflin feed may be reacted with sulfur dioxide and chlorine whereby the sulfochloride initially produced is converted to the desired alkane sulfonate by treatment with a base, e.g. NaOH.
  • a base e.g. NaOH.
  • This process produces minor amounts of organic chlorides which tend to remain in the final product as an undesirable impurity.
  • Another method of producing the desired alkane sulfonates is by the reaction of sodium bissulfite with a straight chain alkyl halide or by addition to a normal alpha olefin.
  • a particularly preferred method of preparing the alkane sulfonates is by a self-sustaining sulfoxidation process. This process involves the over-all reaction after initiation, is continuously reacted with 0.2 to 4.0 moles of free sulfur dioxide per mole of parafiin and 0.01 to 2.0 moles of free oxygen per mole of paraflin at temperatures in the range of 30 to 160 F.
  • the alkane sulfonic acid obtained from the radiosulfoxidation or peroxide catalyzed process described above is then neutralized with an appropriate base, such as sodium or potassium hydroxide or carbonate, utilizing well-known techniques to obtain the corresponding alkane sulfonate surfactant.
  • the resulting sulfonate salt will typically contain 25% of inorganic sulfate which results from the formation of sulfuric acid in the sulfoxidation reaction.
  • alkane sulfonic acid and its sodium salt via the radio-sulfoxidation process may be subject to a wide variety of modifications. A more detailed description of the process may be found in copending, commonly assigned application Ser. No. 118,221, filed May 15, 1961 now abandoned.
  • the heavy-duty liquid detergents of this invention may contain any of the various types of builders and other adjuvants which are conventionally found in detergent formulations.
  • useful builders include ethylene diamine tetraacetic acid salts, polyphosphates and pyrophosphates, particularly tetrapotassium pyrophosphate.
  • Anticorrosion agents such as sodium or potassium silicates, may be added to the formulation.
  • anti-redeposition agents such as sodium carboxymethyl cellulose may be present in the formulation.
  • the formulation may also contain viscosity reducers, such as ethanol or isopropanol.
  • Various optical bleaches, perfumes, dyes or other coloring agents may also be added.
  • the formulation may at times contain other detergents in combination with the alkane sulfonate when specific results are desired.
  • sodium alcohol sulfates such as sodium lauryl sulfate, sodium hexadecyl sulfate or sodium sulfates of oxo alcohols may be added to the formulation.
  • a typical detergent formulation may contain from to 20, preferably 5 to 15, and more preferably to parts by weight of the alkane sulfonate per 100 parts of solution of the sulfonate surfactant as well as 0 to 5 parts of the inorganic sulfate produced concurrently with the sulfonate.
  • the formulation man contain from 5 to 25 parts by weight of building agent, such as a condensed phosphate, 1 to 5 parts by weight of an anticorrosion agent, such as a metasilicate, and 0.2 to 1.0 part of an anti-redeposition agent, such as sodium carboxymethyl cellulose.
  • a viscosity reducer such as isopropanol may be present in amounts varying from 0 to 10 parts by weight per 100 parts of solution.
  • the weight ratio of sulfonate surfactant to the other components of the liquid detergent formulation may similarly vary over Wide ranges.
  • the composition may contain 0.5 to 4 and preferably 1 to 3 parts by weight of condensed phosphate builders per part of sulfonate surfactant; 0.2 to 0.5 and preferably 0.3 to 0.4 part per part of an anticorrosion agent, 0.02 to 0.10 part per part of anti-redeposition agent, and 0 to 1 part per part of a viscosity reducing agent.
  • a particularly preferred detergent composition based on 100 parts of solution, consists of 10 to 15 parts of sodium alkane sulfonate as well as O to 3 parts of the sodium sulfate.
  • the formulation contains 10 to 30, preferably to 25, parts of tetrapotassium pyrophosphate.
  • a silicate e.g., sodium metasilicate, 0.1 to 0.8 part of carboxymethyl cellulose, and also 2 to 5 parts of isopropyl alcohol.
  • a liquid detergent composition combines a high solids content consisting of both organic surfactant and inorganic builder in a clear, homogeneous solution. It is essential that all of the ingredients in the formulation are fully solubilized since otherwise they will settle out and their utility and appeal as detergents will be lost.
  • the solids content of detergent formulations is conventionally increased by employing coupling or solubilizing agents known as hydrotropes. These materials function to increase the maximum solids content of the formulation but also increase the cost.
  • sodium xylene sulfonate is utilized in limited amounts as a hydrotrope for the sodium alkane sulfonate liquid detergent formulation. It has been discovered that as low as 1 part (by weight) per parts of solution will completely solubilize over 30 parts of solid sodium alkane sulfonate surfactant and builder.
  • the amount of hydrotrope needed for complete solubilization of the alkane sulfonate detergent is a complex function of the ratio of organic surfactant to builders and the total solids content and therefore is not capable of definition with exact certainty, it has been determined that the amount of hydrotrope needed is, at all points, significantly lower than would be expected in view of the vast experience with commercial alkylaryl formulations.
  • the amount of hydrotrope needed per 100 parts of detergent solution will vary from 1 to 8 as the total solids level varies from about 35 to 55 parts per 100 parts of solution.
  • the amount of hydrotrope present in the detergent formulation will be 10 to 50 weight percent of the sodium alkane sulfonate in the formulation. It is to be understood that the amount of hydrotrope needed will increase as the total solids level increases and that therefore the maximum and minimum amounts specified are utilized with the maximum and minimum solids content respectively.
  • EXAMPLE 1 A series of detergent formulations was prepared in order to determine solubility limits of the solid surfactants in liquid compositions. All data are in terms of parts by weight per 100 parts of solution. The formulations are tabulated below.
  • Formula I containing sodium alkane sulfonate, was a clear, homogeneous solution although it contained only 1% of the sodium xylene sulfonate hydrotrope.
  • Formula II which differs from Formula I in that commercial tetrapropylene benzene sulfonate is utilized in similar proportions contained in soluble solids.
  • Formula III is similar to Formula II except for the large increase in the hydrotrope concentration and yet was nonetheless an opaque solution.
  • EXAMPLE 2 A series of detergent formulations was prepared simrlar to Example 1 except that a much higher proportion of SOlldS was employed in the solutions. As before, all
  • compositions are shown as parts by weight per 100 parts by weight of solution.
  • the sodium alkane sulfonate employed had an average carbon number of 15.
  • the formulations are tabulated below.
  • EXAMPLE 4 A C average paraifin feed consisting of a range of C to C was subjected to 'y radiation-initiated sulfoxidation followed by treatment with NaOH to yield sodium octadecane sulfonate and sodium sulfate. The sulfonate product was then mixed in a liquid detergent composition.
  • EXAMPLE 6 Percent dis- Percent disappearance appearance of surfactant surfactant molecules fragments Tetrapropylene benzene sulfonate 0 0 Sodium octadecane sulfonate 100 76 (Substantially linear olefin based) alkyl benzene sulfonate 94 69 The results indicate the complete superiority of the alkane sulfonate detergents. Even when compared with alkyl benzene sulfonates based on fairly linear olefins, the alkane sulfonates show a superiority.
  • alkane sulfonates are compatible with nonionic and anionic surfactants employed for the production of liquid heavy-duty detergents. These include, but are not limited to: alkylphenol polyethenoxy nonionics, alkylphenol polyether sulfates, polyethenoxy nonionics, polyether sulfates, fatty acid soaps, alkylaryl sulfonates and acid amino-alcohol condensation products.
  • a liquid detergent composition consisting essentially of a homogeneous solution of 5 to 20 wt. percent of a C to C sodium alkane sulfonate, 10 to 30 wt. percent of a condensed phosphate selected from the group consisting of polyphosphate salts and pyrophosphate salts, 1 to 8 wt. percent of a hydrotrope selected from the group consisting of sodium xylene sulfonate and sodium toluene sulfonate and 40 to 85 wt. percent water.
  • a liquid detergent composition consisting of a homogeneous solution of 5 to 15 wt. percent of a C to C sodium alkane sulfonate, 10 to 30 Wt. percent of tetrapotassium pyrophosphate, up to 5 wt. percent sodium sulfate, 1 to 8 wt. percent sodium xylene sulfonate and 40 to 80 wt. percent water.
  • a liquid detergent composition consisting of a homogeneous solution of 10 wt. percent of a C to C sodium alkane sulfonate, 20 Wt. percent of tetrapotassium pyrophosphate, 2.5 Wt. percent sodium sulfate, 1 wt. percent sodium Xylene sulfonate, and 66.5 wt. percent water.
  • a liquid detergent composition consisting of a homogeneous solution of 15 wt. percent of a C to C sodium alkane sulfonate, 30 wt. percent of tetrapotassium pyrophosphate, 7 wt. percent sodium Xylene sulfonate and 48 wt. percent water.
  • a heavy duty liquid detergent composition consisting essentially of a phase stable solution of 5 through 20 wt. percent of sodium C to C n-alkane sulfonate wherein the sulfo group is attached to a secondary carbon

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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)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
US285606A 1963-06-05 1963-06-05 Liquid detergent composition Expired - Lifetime US3527707A (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755206A (en) * 1970-03-09 1973-08-28 Colgate Palmolive Co Detergent compositions
US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
US4017409A (en) * 1975-01-02 1977-04-12 The Procter & Gamble Company Liquid household cleaner
US4147673A (en) * 1975-04-11 1979-04-03 S.A. Texaco Belgium N.V. Detergent composition containing sulfinyl dipropionic acids
US4397777A (en) * 1977-02-08 1983-08-09 Colgate Palmolive Company Heavy duty laundry detergent
US4675128A (en) * 1984-12-31 1987-06-23 Henkel Kommanditgesellschaft Auf Aktien Alkane sulfonates as viscosity regulators

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1274780B (de) * 1965-05-19 1968-08-08 Henkel & Cie Gmbh Fluessige Spuel-, Wasch- und Reinigungsmittel
US3565809A (en) * 1967-11-27 1971-02-23 Chevron Res Alpha olefin sulfonate detergent compositions
DE3264512D1 (en) * 1981-04-03 1985-08-08 Procter & Gamble Liquid detergent compositions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2679482A (en) * 1949-10-08 1954-05-25 Colgate Palmolive Co Synthetic detergent compositions
US2956026A (en) * 1955-03-22 1960-10-11 California Research Corp Sulfonate detergent compositions
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US3101324A (en) * 1960-12-12 1963-08-20 Colgate Palmolive Co Liquid detergent composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2679482A (en) * 1949-10-08 1954-05-25 Colgate Palmolive Co Synthetic detergent compositions
US2956026A (en) * 1955-03-22 1960-10-11 California Research Corp Sulfonate detergent compositions
US3085982A (en) * 1959-04-22 1963-04-16 Procter & Gamble Liquid detergent composition
US2999068A (en) * 1959-04-27 1961-09-05 Procter & Gamble Personal use detergent lotion
US3101324A (en) * 1960-12-12 1963-08-20 Colgate Palmolive Co Liquid detergent composition

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3755206A (en) * 1970-03-09 1973-08-28 Colgate Palmolive Co Detergent compositions
US3959165A (en) * 1972-09-15 1976-05-25 Colgate-Palmolive Company Biodegradable, non-polluting, heavy duty synthetic organic detergent composition
US4017409A (en) * 1975-01-02 1977-04-12 The Procter & Gamble Company Liquid household cleaner
US4147673A (en) * 1975-04-11 1979-04-03 S.A. Texaco Belgium N.V. Detergent composition containing sulfinyl dipropionic acids
US4397777A (en) * 1977-02-08 1983-08-09 Colgate Palmolive Company Heavy duty laundry detergent
US4675128A (en) * 1984-12-31 1987-06-23 Henkel Kommanditgesellschaft Auf Aktien Alkane sulfonates as viscosity regulators

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BE648802A (en)) 1964-12-04
NL6405969A (en)) 1964-12-07

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