US3598747A - Alcohol mixtures adapted for use in making detergent sulfates - Google Patents

Alcohol mixtures adapted for use in making detergent sulfates Download PDF

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US3598747A
US3598747A US2670A US3598747DA US3598747A US 3598747 A US3598747 A US 3598747A US 2670 A US2670 A US 2670A US 3598747D A US3598747D A US 3598747DA US 3598747 A US3598747 A US 3598747A
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alcohol
myristyl
alcohols
stearyl
mixture
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US2670A
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William R Axtell
Earl G De Witt
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Ethyl Corp
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Ethyl Corp
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    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C07C29/54—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only starting from compounds containing carbon-to-metal bonds and followed by conversion of the -O- metal to -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00—Esters of sulfuric acids
    • C07C305/02—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton
    • C07C305/04—Esters of sulfuric acids having oxygen atoms of sulfate groups bound to acyclic carbon atoms of a carbon skeleton being acyclic and saturated
    • C07C305/06—Hydrogenosulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/125—Monohydroxylic acyclic alcohols containing five to twenty-two carbon atoms
    • 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
    • C11D1/146—Sulfuric 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/825—Mixtures of compounds all of which are non-ionic
    • C11D1/8255—Mixtures of compounds all of which are non-ionic containing a combination of compounds differently alcoxylised or with differently alkylated chains
    • 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 fatty alcohol compositions. More particularly, the invention relates to a synthetic mixture of fatty alcohol components having particularly beneficial properties and not heretofore made or available by conversion of naturally occurring materials. More particularly, the invention relates to a mixture of alcohols having a substantial proportion of myristyl alcohol, or tetradecanol and being a preferred and more effective substitute for alcohols derived from naturally occurring tallow.
  • alkyl aryl sulfonates derivatives of naturally occurring fats, including, particularly, coconut oil and animal tallow.
  • the alkyl aryl sulfonates are a substantial source of detergent components, but there is indication that these are unsatisfactory for certain reasons, and it is believed that their percentage of the raw material market will decrease in the future.
  • the naturally occurring fats are particularly beneficial in that they are readily susceptible to conversion to surface active agents which have certain benefits, relative to the alkyl aryl sulfonates. These benefits are that such derivatives do not exhibit the branching which is so common among the alkyl radicals of the alkyl aryl sulfonates.
  • alkyl aryl sulfonates having this high degree of branching are believed more resistant to biodegradation in industrial and domestic sewage efiluents, and this resistance has created certain problems to the extent that legislation has been enacted in foreign countries or proposed in the United States, which in effect, limits the use of the alkyl aryl sulfonates.
  • the derivatives from the identified naturally occurring fats are straight chain materials, predominantly, and are more susceptible to biodegradation and also are extremely efiicient detergent components.
  • the type of processing to convert the above-mentioned fats to detergent components is widely varied, but for present purposes, can be summarized by saying that a large fraction of these materials are converted to the corresponding alcohol components or mixtures and are subsequently treated, for example, by sulfation, to form desirable detergent components.
  • Another technique for conversion of the resultant alcohol mixtures involves the reaction with a plurality of moles of alkylene oxide, especially ethylene oxide, and the polyether hydroxy compound resultant, or mixtures of compounds, can be used as components as such, or can also be treated by sulfation or sulfonation.
  • the utility of the naturally occurring fats, employed as above outlined, is limited by several factors.
  • the relative proportions of components in each of these fats, or in the alcohols derived therefrom, are essentially fixed and not variant, as they represent the result of natural synthesis.
  • coconut oil predominates in components having 12 through 16 carbon atoms per molecule, so that the alcohols therefrom predominate in lauryl through palmityl alcohols.
  • the alcohols derived from animal fats are predominantly alcohols of 16 and 18 carbon atoms.
  • the 18 carbon atom alcohol instead of predominating in the saturated compound, includes substantial quantities of the compound having one unsaturated double bond therein.
  • lauryl lauryl myristyl palmityl the predominant component is the 12 carbon atom alcohol, followed by the 14 and 16 in that order.
  • the predominant alcohols are the 18 carbon atom components, followed by the 16, with only very minor quantities of the 14 carbon atom alcohol.
  • the presently available natural fats do not provide a substantial source of mixtures rich in 14 and 16 carbon atom alcohols, viz, myristyl and palmityl alcohols.
  • These two alcohols provide properties such that the resultant detergents partake of the particular benefits of detergents made from coconut oil alcohol, as well as detergents made from the tallow alcohols.
  • the object of the present invention is to provide. a synthesized alcohol mixture which is essentially freed of the limitations on composition heretofore experienced. More particularly, an object of the present invention is to provide a new alcohol product, high in myristyl alcohols, and a particularly beneficial starting material for detergent products. More particularly, an object of the invention is to provide a new composition derived by synthetic techniques as described hereinafter, wherein the preponderance of the mixture consists of the 14-18 canbon atom alcohols, that is, myristyl, palrnityl and stearyl alcohols. Other objects will appear hereinafter.
  • the fatty alcohols of the present process are generated by making a trialkyl aluminum mixture, then oxidizing said trialkyl aluminum components to aluminum alkoxides, and then hydrolyzing said aluminum alkoxides with water or acidified water, whereby a mixture of alcohols according to the present invention and an aluminum salt of an inorganic acid are produced.
  • the product of the invention diifers appreciably from any alcohol mixture obtained from naturally occurring fats or fatty oils and is further significantly desirable in exhibiting high quality standards with respect to a variety of experimental criteria, for example, the acid value, the unsaturation, carbonyl oxygen and ester content and certain other attributes.
  • the product of the present invention can be made by several different specific variants within the above described general procedure.
  • a particularly preferred manufacturing method results in the conjoint production of the product with an alcohol stream corresponding essentially to an alcohol derived from a coconut oil. It is found that the high myristyl alcohol product of the present invention can be thus jointly made with coconut oil, so that the relative proportions are from about 2 to 6 or 7 parts by weight of coconut oil alcohol per part of the high myristyl alcohol product.
  • the initial product mixture includes relatively minor components of alcohols of lower than 12 carbon atoms.
  • a product is derivable which differs greatly in the weight or molecular weight distribution from that which would be predicted or anticipated by any of the prior art.
  • a crude mixture is obtained, from which is separated the synthetic coconut oil alcohol fraction and the desired high myristyl alcohol product.
  • An illustrative, but non-limiting composition of the crude alcohol, made according to the above mentioned preferred route, is as follows:
  • the high myristyl alcohol product has an approximate composition range as given below:
  • the intermediate cut corresponding generally to a coconut oil alcohol, is controlled within the following range of compositions:
  • compositions are on the basis of the alcohol analysis, i.e. exclusive of other impurities, principally hydrocarbons, which may be present in proportions of up to about four percent without seriously affecting the properties of the products.
  • the hydrocarbon impurities are generally alkane and alkene components.
  • Acid value The free fatty acids or acid values of the streams are determined by the A.O.C.S. method Ca 5a- 40. It is expressed in terms of milligrams of potassium hydroxide necessary to neutralize one gram of sample.
  • Iodine value is significant in indicating the degree of unsaturation of a particular product. It is determined by A.O.C.S. method Cd 1-25, and is expressed in terms of centigrams of iodine absorbed per gram of sample.
  • ester value is determined as the difference between the A.O.C.S saponification value (Cd 3-25) and the acid value, as already defined.
  • Moisture value is determined according to A.O.C.S. procedure Ca 2a55.
  • Color.Clarity or color is usually determined using. for example, the American Public Health Association scale (A.P.H.A.).
  • Carbonyl oxygen The total amount of carbonyl oxygen present in the sample is determined using, for example, the method described in Analytical Chemistry 31, 760 (1959).
  • Hydroxyl value The measure of the amount of hydroxyl value of a sample is determined according to A.O.C.S. procedure Cd 13-60. It is defined in terms of milligrams potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
  • Hydrocarbon impurity As previously mentioned. Another quality criterion is the amount of hydrocarbon impurity. This is efficiently determined by gas chromatography.
  • the amount of esters, carbonyl oxygen and the hydroxyl value of the product are probably the most important.
  • the amount of discoloration or degradation of a specimen, when exposed to strong sulfuric acid is frequently determined, particularly for the alcohols of the coconut oil type.
  • the most preferred form of the high myristyl alcohol product of the present invention is obtained in conjunction with about twice its quantity of a product corresponding in general composition to a coconut oil alcohol.
  • the composition of such a preferred high myristyl alcohol product is as given below:
  • compositions such preferred high myristyl alcohol products exhibit additional high quality attributes, including, particularly in that the carbonyl oxygen content does not exceed about 0.05 weight percent, and a hydroxyl value of at least 225, as mg. KOH/g. Further a total non-alcohol impurity concentration of not over about 3 weight percent is experienced. Additional typical quality attributes of less significance include the following:
  • the chemical reactions involved in preparing the alcohols of the present invention include the chain growth of ethylene on a lower alkyl-trialkyl aluminum to obtain higher alkyl-trialkyl aluminum compounds. These are then oxidized to aluminum alkoxide materials which are then hydrolyzed by reaction with an aqueous acid and form thereby alcohols corresponding to the alkyl group and aluminum salts corresponding to the acid of the aqueous acid used.
  • the chain growth of ethylene on a lower alkyl-trialkyl aluminum compound is Well known, generally, but performing this operation in the heretofore known conventional manner will not produce gross trialkyl aluminum mixtures having alkyl groups distributed by chain length as required for the present invention.
  • the alcohols derived thereby will include substantial proportions of lower than desired alcohols than is required for most elficient performance.
  • the alcohol mixture of the present invention is separated by fractionation, resulting in substantial quantities of alcohol components outside the range of the desired product.
  • the most preferred synthesis utilizes a novel process wherein the alkyl groups of the trialkyl aluminum intermediate stream are generated in anti-statistical, or non- Poisson proportions. The characteristics of this highly preferred preparatory process are summarized below.
  • the essential feature of the preferred preparatory process is the use of at least two displacement processes, whereby the distribution of alkyl groups to a non-statistical spectrum is achieved.
  • the operations include the following steps:
  • the ethylene to be utilized in chain growth is divided into two portions, and only a fraction usually of about one-half to three-fourths is reacted with the initial lower alkyl-trialkyl aluminum, preferably triethyl aluminum, in a first chain growth reaction.
  • the chain grown trialkyl aluminum effluent from the first chain growth reaction is then subjected to a displacement reaction with a mixture of olefins predominating in olefins of less than 12 carbon atoms, whereby a displacement product mixture from this first displacement reaction is obtained which includes olefins enriched in higher olefins of above 12 carbon atoms and trialkyl aluminum mixture enriched in alkyl groups of less than 12 carbon atoms.
  • the trialkyl aluminum mixture from the first displacement reaction is then subjected to a second chain growth reaction with the remainder of the ethylene to be reacted.
  • the trialkyl aluminum from the second chain growth reaction is then processed in a second displacement reaction, wherein reaction is carried out with olefins, concen trated in olefins of 12 and higher carbon atoms, as a result of which the trialkyl aluminum fed is converted to trialkyl aluminum mixtures appreciably enriched in alkyl aluminum groups of 12 and higher carbon atoms.
  • the trialkyl aluminum thus obtained exhibits a unique non-Poisson distribution of alkyl group lengths.
  • This mixture is then oxidized with an oxygen containing gas to convert a substantial proportion of the alkyl aluminum bonds to the corresponding alkoxide aluminum bonds, and the oxidized mixture is then hydrolyzed or reacted with a dilute aqueous added acid to form the desired alcohol mixture.
  • Upon separation of certain impurities from the resultant alcohol mixture it is then ready for fractionation and separation of a cut corresponding to a coconut oil alcohol, and the desired myristyl alcohol fraction of the present invention.
  • a variation of the process utilizes a single chain growth reaction, but processes a mixture of fresh low alkyl trialkyl aluminum and trialkyl aluminum, which is generated in a first displacement reaction.
  • at least two displacement reactions are carried out, utilizing circulating olefin streams to continually adjust the identity and proportions of the alkyl groups of the trialkyl aluminum stream.
  • the crude alcohol mixture from which the preferred myristyl-rich alcohol product is derived, has the following composition:
  • Alcohol Weight percent Lower than lauryl max 3 Lauryl 65 :2 Myristyl 25 +4 Palmityl 71-3 Stearyl and higher max 1 Alcohol: Weight percent Lower than myristyl 0.3 Myristyl 2.5 Palmityl 27.2 Stearyl 69.2 Higher than stearyl 0.8
  • compositions of the present invention are readily reacted at F. with chlorosulfonic acid to produce alkyl sulfates for use in detergents.
  • the reaction proceeds according to the following equation and the equilibrium is favored for the desired product by low temperatures of the order of 100 F.
  • Sodium alkyl sulfate detergents are obtained by reacting the alkyl sulfate with caustic. Samples of such material are tested and rated for various properties using standard techniques. One technique is a foam test identified as the Ross-Miles test. This compares the amount of foam obtained from different materials at selected temperatures and concentrations. An important temperature for this is 40 C. which is representative of temperatures used in hand dishwashing operations. A 0.2 wt. percent concentration represents the start of a dishwashing while the 0.1 wt. percent represents the end of effective dishwashing before adding new cleaning agent. When the test is made according to a conventional procedure, foam heights are as follows.
  • the 0.1 percent data for the blend shows a foam height improvement of 13.3 percent over that predictable from the components.
  • the 0.1 percent data shows a foam height improvement of 18.4 percent over that predictable from the components.
  • compositions in preparing detergent bars for personal use Similar desirable characteristics are found with the compositions in preparing detergent bars for personal use. Profuse foam and good cleaning properties are obtained in hand washing and bathing.
  • Palmityl and stearyl in effect require a solubilizing action to make them useful in applications such as the above.
  • Myristyl alcohol provides this effect in the present compositions.
  • unsaturated alcohols particularly C
  • unsaturated alcohols particularly C
  • EXAMPLE I A typical composition of 40 percent myristyl alcohol, 40 percent palmityl alcohol and 20 percent stearyl alco 1101 (by weight) was made and tested using 0.2 weight percent concentration of the sodium alkyl sulfate pastes of the alcohols in a standard water solution of ppm. (parts per million) hardness as equivalent calcium carbonate. The hardness was achieved by use of a mixture of calcium chloride and magnesium sulfate to provide a calcium cation/ magnesium cation weight ratio of 3/2. The temperature of each solution during the test was 95 F.
  • the activity of a sodium alkyl sulfate paste is related to the height of the foam it produces. In other words, the higher the foam, the more active the substance under test. In addition, it is desirable that the foam exhibit stability and therefore the height of the foam is measured not only as soon as it has beefi formed but also after standing for 5 minutes.
  • Example II was repeated in another comparative example using a sodium alkyl sulfate paste derived from another starting alcohol mixture.
  • a synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
  • Alcohol Weight percent Lower than myristyl Not over about 2. Myristyl to 50. Palmityl to 45.
  • a synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
  • a synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
  • a synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
  • Alcohol Weight percent Lower than myristyl Not over about 2. Myristyl 25 to 50. Palmityl 30 to 45.
  • a synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
  • Iodine value Max. 1.0 cg. I gram.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Abstract

HIGHER ALCOHOL COMPOSITIONS ARE DISCLOSED WHICH ARE PRIMARILY MIXTURES OF MYRISTYL, PALMITYL AND STEARYL ALCOHOLS CONTAINING SMALL QUANTITIES OF ALCOHOLS OF LOWER MOLECULAR WEIGHT. THESE COMPOSITIONS CAN BE USED IN MAKING HIGH FOAMING MIXTURES OF ALKYL SULFATES.

Description

United. States Patent Office 3,598,747 Patented Aug. 10, 1971 US. Cl. 252-182 5 Claims ABSTRACT OF THE DISCLOSURE Higher alcohol compositions are disclosed which are primarily mixtures of myristyl, palmityl and stearyl alcohols containing small quantities of alcohols of lower molecular weight. These compositions can be used in making high foaming mixtures of alkyl sulfates.
CROSS REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of our copending application Ser. No. 558,237, filed June 17, 1966, now abandoned, which is a continuation-in-part of application Ser. No. 277,078, filed May 1, 1963, now abandoned.
This invention relates to fatty alcohol compositions. More particularly, the invention relates to a synthetic mixture of fatty alcohol components having particularly beneficial properties and not heretofore made or available by conversion of naturally occurring materials. More particularly, the invention relates to a mixture of alcohols having a substantial proportion of myristyl alcohol, or tetradecanol and being a preferred and more effective substitute for alcohols derived from naturally occurring tallow.
Heretofore, the synthetic detergent industry in the United States has been predominantly based upon surface active agents derived from several particular sources, viz,
alkyl aryl sulfonates derivatives of naturally occurring fats, including, particularly, coconut oil and animal tallow.
The alkyl aryl sulfonates are a substantial source of detergent components, but there is indication that these are unsatisfactory for certain reasons, and it is believed that their percentage of the raw material market will decrease in the future. The naturally occurring fats; however, are particularly beneficial in that they are readily susceptible to conversion to surface active agents which have certain benefits, relative to the alkyl aryl sulfonates. These benefits are that such derivatives do not exhibit the branching which is so common among the alkyl radicals of the alkyl aryl sulfonates. The alkyl aryl sulfonates having this high degree of branching are believed more resistant to biodegradation in industrial and domestic sewage efiluents, and this resistance has created certain problems to the extent that legislation has been enacted in foreign countries or proposed in the United States, which in effect, limits the use of the alkyl aryl sulfonates. On the other hand, the derivatives from the identified naturally occurring fats are straight chain materials, predominantly, and are more susceptible to biodegradation and also are extremely efiicient detergent components.
The type of processing to convert the above-mentioned fats to detergent components is widely varied, but for present purposes, can be summarized by saying that a large fraction of these materials are converted to the corresponding alcohol components or mixtures and are subsequently treated, for example, by sulfation, to form desirable detergent components. Another technique for conversion of the resultant alcohol mixtures involves the reaction with a plurality of moles of alkylene oxide, especially ethylene oxide, and the polyether hydroxy compound resultant, or mixtures of compounds, can be used as components as such, or can also be treated by sulfation or sulfonation.
Generally, the utility of the naturally occurring fats, employed as above outlined, is limited by several factors. For example, the relative proportions of components in each of these fats, or in the alcohols derived therefrom, are essentially fixed and not variant, as they represent the result of natural synthesis. Thus, coconut oil predominates in components having 12 through 16 carbon atoms per molecule, so that the alcohols therefrom predominate in lauryl through palmityl alcohols. On the other hand, the alcohols derived from animal fats are predominantly alcohols of 16 and 18 carbon atoms. In some prod ucts, the 18 carbon atom alcohol, instead of predominating in the saturated compound, includes substantial quantities of the compound having one unsaturated double bond therein.
Each of the above described naturally occurring fats has particularly desirable attributes with respect to subsequently manufactured detergents. The relatively invariant compositions of these fats, and of the alcohols derived therefrom, does create some limitations with respect to most effective and economical manufacture. Thus, in the case of coconut oil alcohol, the quantities of individual alcohols rank as follows:
lauryl lauryl myristyl palmityl In other words, the predominant component is the 12 carbon atom alcohol, followed by the 14 and 16 in that order. With respect to alcohols derived from tallow, the predominant alcohols are the 18 carbon atom components, followed by the 16, with only very minor quantities of the 14 carbon atom alcohol. Thus, the presently available natural fats do not provide a substantial source of mixtures rich in 14 and 16 carbon atom alcohols, viz, myristyl and palmityl alcohols. These two alcohols provide properties such that the resultant detergents partake of the particular benefits of detergents made from coconut oil alcohol, as well as detergents made from the tallow alcohols. The economics of the industry have dictated that these natural fats be processed as unitary mixtures, as the resolution of resultant alcohol mixtures into individual pure alcohol components would be prohibitive in cost and would also mean that the less desired individual components would not find ready usage. Hence, for practical purposes there has not heretofore been available an efficient and economical source of alcohols which are high in myristyl and palmityl alcohols, because of the relatively invariant compositions of naturally occurring raw materials.
The object of the present invention is to provide. a synthesized alcohol mixture which is essentially freed of the limitations on composition heretofore experienced. More particularly, an object of the present invention is to provide a new alcohol product, high in myristyl alcohols, and a particularly beneficial starting material for detergent products. More particularly, an object of the invention is to provide a new composition derived by synthetic techniques as described hereinafter, wherein the preponderance of the mixture consists of the 14-18 canbon atom alcohols, that is, myristyl, palrnityl and stearyl alcohols. Other objects will appear hereinafter.
The fatty alcohols of the present process are generated by making a trialkyl aluminum mixture, then oxidizing said trialkyl aluminum components to aluminum alkoxides, and then hydrolyzing said aluminum alkoxides with water or acidified water, whereby a mixture of alcohols according to the present invention and an aluminum salt of an inorganic acid are produced. The product of the invention diifers appreciably from any alcohol mixture obtained from naturally occurring fats or fatty oils and is further significantly desirable in exhibiting high quality standards with respect to a variety of experimental criteria, for example, the acid value, the unsaturation, carbonyl oxygen and ester content and certain other attributes.
The product of the present invention can be made by several different specific variants within the above described general procedure. A particularly preferred manufacturing method, as described more fully hereinafter, results in the conjoint production of the product with an alcohol stream corresponding essentially to an alcohol derived from a coconut oil. It is found that the high myristyl alcohol product of the present invention can be thus jointly made with coconut oil, so that the relative proportions are from about 2 to 6 or 7 parts by weight of coconut oil alcohol per part of the high myristyl alcohol product.
In addition to the principal cuts which are actually provided, the initial product mixture includes relatively minor components of alcohols of lower than 12 carbon atoms. However, it is surprisingly discovered that a product is derivable which differs greatly in the weight or molecular weight distribution from that which would be predicted or anticipated by any of the prior art.
In the preferred mode of preparing the present product, as explained above, a crude mixture is obtained, from which is separated the synthetic coconut oil alcohol fraction and the desired high myristyl alcohol product. An illustrative, but non-limiting composition of the crude alcohol, made according to the above mentioned preferred route, is as follows:
Alcohol: Weight percent Ethyl 1 Butyl 1 Hexyl 1.5 Octyl 3.3 Decyl 7.8 Dodecyl or lauryl 34.8 Tetradecyl or myristyl 25.8 Hexadecyl or palrnityl 16.4 Octadecyl or stearyl 8.7 Eicosyl or arachidyl and higher 3 The crude stream, of which the foregoing is an illustrative composition, is fractionated into the desired high myristyl alcohol fraction, a fraction high in lauryl alcohol, generally corresponding to a coconut oil alcohol, and a low alcohol fraction predominating in octyl and decyl alcohols. Small amounts of lower-than-octyl, and higher than stearyl alcohols are also separated.
The high myristyl alcohol product has an approximate composition range as given below:
Alcohol: Weight percent Myristyl 25-50 Palmityl 30-45 Stearyl 1530 This product is generally also limited to not over about 2 weight percent, each, of components lower and higher than those listed.
The intermediate cut, corresponding generally to a coconut oil alcohol, is controlled within the following range of compositions:
Alcohol: Weight percent Lower than lauryl max 3 Lauryl 60-7O Myristyl 20-30 Palmityl ,max 10 Higher alcohols max 2 The foregoing compositions are on the basis of the alcohol analysis, i.e. exclusive of other impurities, principally hydrocarbons, which may be present in proportions of up to about four percent without seriously affecting the properties of the products. The hydrocarbon impurities are generally alkane and alkene components.
In addition to the distribution of the alcohol components in the product, and in the synthetic coconut oil alcohol which is customarily concurrently made, various other recognized quality tests are frequently applied. Generally, such tests or product criteria are determined by procedures of the American Oil Chemists Society, and some of these are referred to below.
Acid value.The free fatty acids or acid values of the streams are determined by the A.O.C.S. method Ca 5a- 40. It is expressed in terms of milligrams of potassium hydroxide necessary to neutralize one gram of sample.
Iodine value.The iodine value is significant in indicating the degree of unsaturation of a particular product. It is determined by A.O.C.S. method Cd 1-25, and is expressed in terms of centigrams of iodine absorbed per gram of sample.
Ester value.The ester content is determined as the difference between the A.O.C.S saponification value (Cd 3-25) and the acid value, as already defined.
Moisture value.The moisture value is determined according to A.O.C.S. procedure Ca 2a55.
Color.Clarity or color is usually determined using. for example, the American Public Health Association scale (A.P.H.A.).
Carbonyl oxygen.The total amount of carbonyl oxygen present in the sample is determined using, for example, the method described in Analytical Chemistry 31, 760 (1959).
Hydroxyl value.The measure of the amount of hydroxyl value of a sample is determined according to A.O.C.S. procedure Cd 13-60. It is defined in terms of milligrams potassium hydroxide equivalent to the hydroxyl content of one gram of sample.
Hydrocarbon impurity,As previously mentioned. another quality criterion is the amount of hydrocarbon impurity. This is efficiently determined by gas chromatography.
Among the foregoing quality or identifying tests, the amount of esters, carbonyl oxygen and the hydroxyl value of the product are probably the most important. The amount of discoloration or degradation of a specimen, when exposed to strong sulfuric acid is frequently determined, particularly for the alcohols of the coconut oil type.
The most preferred form of the high myristyl alcohol product of the present invention is obtained in conjunction with about twice its quantity of a product corresponding in general composition to a coconut oil alcohol. The composition of such a preferred high myristyl alcohol product is as given below:
Alcohol: Weight percent Lower than myristyl Not over about 1.5. Myristyl 42:4. Palmityl 36:4. Stearyl 19:3. Higher than stearyl 2 max.
In addition to the foregoing compositions such preferred high myristyl alcohol products exhibit additional high quality attributes, including, particularly in that the carbonyl oxygen content does not exceed about 0.05 weight percent, and a hydroxyl value of at least 225, as mg. KOH/g. Further a total non-alcohol impurity concentration of not over about 3 weight percent is experienced. Additional typical quality attributes of less significance include the following:
Acid value Max. 1.0 mg. KOH/g. Iodine value Max. 1.0 cg. I /g.
Ester value Max. 1.5 mg. KOH/ g. Moisture Max. about 0.15 percent.
As already described the chemical reactions involved in preparing the alcohols of the present invention include the chain growth of ethylene on a lower alkyl-trialkyl aluminum to obtain higher alkyl-trialkyl aluminum compounds. These are then oxidized to aluminum alkoxide materials which are then hydrolyzed by reaction with an aqueous acid and form thereby alcohols corresponding to the alkyl group and aluminum salts corresponding to the acid of the aqueous acid used. The chain growth of ethylene on a lower alkyl-trialkyl aluminum compound is Well known, generally, but performing this operation in the heretofore known conventional manner will not produce gross trialkyl aluminum mixtures having alkyl groups distributed by chain length as required for the present invention. Hence, if the conventional process sequence is obtained, the alcohols derived thereby will include substantial proportions of lower than desired alcohols than is required for most elficient performance. When the above general or conventional procedure is followed, the alcohol mixture of the present invention is separated by fractionation, resulting in substantial quantities of alcohol components outside the range of the desired product. The most preferred synthesis, however, utilizes a novel process wherein the alkyl groups of the trialkyl aluminum intermediate stream are generated in anti-statistical, or non- Poisson proportions. The characteristics of this highly preferred preparatory process are summarized below.
The essential feature of the preferred preparatory process is the use of at least two displacement processes, whereby the distribution of alkyl groups to a non-statistical spectrum is achieved. In carrying out an embodiment of such a process, the operations include the following steps:
The ethylene to be utilized in chain growth is divided into two portions, and only a fraction usually of about one-half to three-fourths is reacted with the initial lower alkyl-trialkyl aluminum, preferably triethyl aluminum, in a first chain growth reaction.
The chain grown trialkyl aluminum effluent from the first chain growth reaction is then subjected to a displacement reaction with a mixture of olefins predominating in olefins of less than 12 carbon atoms, whereby a displacement product mixture from this first displacement reaction is obtained which includes olefins enriched in higher olefins of above 12 carbon atoms and trialkyl aluminum mixture enriched in alkyl groups of less than 12 carbon atoms.
The trialkyl aluminum mixture from the first displacement reaction is then subjected to a second chain growth reaction with the remainder of the ethylene to be reacted.
The trialkyl aluminum from the second chain growth reaction is then processed in a second displacement reaction, wherein reaction is carried out with olefins, concen trated in olefins of 12 and higher carbon atoms, as a result of which the trialkyl aluminum fed is converted to trialkyl aluminum mixtures appreciably enriched in alkyl aluminum groups of 12 and higher carbon atoms.
The trialkyl aluminum thus obtained exhibits a unique non-Poisson distribution of alkyl group lengths. This mixture is then oxidized with an oxygen containing gas to convert a substantial proportion of the alkyl aluminum bonds to the corresponding alkoxide aluminum bonds, and the oxidized mixture is then hydrolyzed or reacted with a dilute aqueous added acid to form the desired alcohol mixture. Upon separation of certain impurities from the resultant alcohol mixture, it is then ready for fractionation and separation of a cut corresponding to a coconut oil alcohol, and the desired myristyl alcohol fraction of the present invention.
Instead of employing two separate chain growth operations, as described above, a variation of the process utilizes a single chain growth reaction, but processes a mixture of fresh low alkyl trialkyl aluminum and trialkyl aluminum, which is generated in a first displacement reaction. In all of these preferred methods of generating the non-Poisson, trialkyl aluminum mixtures from which the desired alcohol product is obtained, at least two displacement reactions are carried out, utilizing circulating olefin streams to continually adjust the identity and proportions of the alkyl groups of the trialkyl aluminum stream.
In a typical operation, according to the preferred process first described above, the crude alcohol mixture, from which the preferred myristyl-rich alcohol product is derived, has the following composition:
Alcohol: Weight percent Ethyl 0.3 Butyl 0.4 Hexyl 1.4 Octyl 3.2 Decyl 6.7 Lauryl 37.2 Myristyl 26.7 Palmityl 15.4 Stearyl 6.4 Higher than stearyl 2.3
In addition to the preferred high myristyl alcohol fractron already described, a mixture corresponding to a coconut oil fraction is separated having the following approximate composition range:
Alcohol: Weight percent Lower than lauryl max 3 Lauryl 65 :2 Myristyl 25 +4 Palmityl 71-3 Stearyl and higher max 1 Alcohol: Weight percent Lower than myristyl 0.3 Myristyl 2.5 Palmityl 27.2 Stearyl 69.2 Higher than stearyl 0.8
From the foregoing it is seen that alcohols from animal fats are virtually devoid of the very desirable myristyl alcohol component whereas the product of the present invention contains from one-fourth to about one-half myristyl alcohol content and in the particularly preferred composition, about 42 percent of this component.
The compositions of the present invention are readily reacted at F. with chlorosulfonic acid to produce alkyl sulfates for use in detergents. The reaction proceeds according to the following equation and the equilibrium is favored for the desired product by low temperatures of the order of 100 F.
The equilibrium is not favorable to this reaction with palmityl and stearyl alcohols per se because of their high melting point.
Sodium alkyl sulfate detergents are obtained by reacting the alkyl sulfate with caustic. Samples of such material are tested and rated for various properties using standard techniques. One technique is a foam test identified as the Ross-Miles test. This compares the amount of foam obtained from different materials at selected temperatures and concentrations. An important temperature for this is 40 C. which is representative of temperatures used in hand dishwashing operations. A 0.2 wt. percent concentration represents the start of a dishwashing while the 0.1 wt. percent represents the end of effective dishwashing before adding new cleaning agent. When the test is made according to a conventional procedure, foam heights are as follows.
The 0.1 percent data for the blend, for example, shows a foam height improvement of 13.3 percent over that predictable from the components.
EFFECTIVENESS CALCULATED FROM COMPONENTS [150 mm. foam height] Percent- Individual age, effec- Fraetion foam tiveness Myristyl, mm 0. 4 185 74.
Palmityl, mm... 0. 4 150 00.0
Stearyl, mm 0. 2 80 16.0
Total, mm 150.0
Actual effectiveness 1 70 Difference Percentage improvein prediction l3. 3
The 0.1 percent data shows a foam height improvement of 18.4 percent over that predictable from the components.
EFFECTIVENESS CALCULATED FROM COMPONENTS [152 mm. foam height] Percent;
Individual age, efiec- Fraction foam tivencss Myristyl, mm 0. 4 185 74. 0
Palmityl 0. 4 175 70.0
Stearyl, nun 0. 2 40 8.0
Total, mm 152.0
Actual efieetiveness 180 Difference f f 28 Percent improvement 28 prediction 100 18. 4
From the foregoing it is evident that myristyl (C alcohol provides the most profuse foaming cleaning agents of this type and that the blend is almost as good as that individual material despite the fact that the individual characteristics of the components, particularly stearyl and to a smaller extent, palmityl, are much lower.
The data also show that stearyl alcohol is of little value per se; however, when used in a composition (mixture) according to the present application, it is almost as good as myristyl alcohol and that the overall value for the mixture is better than that of any of the individual components other than myristyl.
The data show that the present compositions have a superiority of about 15 percent over the percentage-eflectiveness sums for the components. In other words, the effectiveness of the combination based on the claimed alcohol composition exceeded the sum of effectiveness of the components when tested individually.
Another important criteria in this connection is the detersive (cleaning) ability. Again a standard test procedure was used, with a Launder-O-Meter of US. Testing Company using soiled test cloths. This test was made at F. which is a typical home laundering temperature. The detergent sodium alkyl sulfate was used at a 0.1 percent concentration (weight) with 0.05 percent sodium metasilicate as builder.
Increase in reflect- Detergent sodium alkyl sulfate: ance of the wash Alkyl Lauryl (C 17.00
From this it is evident that detergency also peaks at c under the conditions selected and that the composition is practically equal to the peak detergency in cleaning efficiency despite the content of stearyl (C18).
Similar desirable characteristics are found with the compositions in preparing detergent bars for personal use. Profuse foam and good cleaning properties are obtained in hand washing and bathing.
Palmityl and stearyl in effect require a solubilizing action to make them useful in applications such as the above. Myristyl alcohol provides this effect in the present compositions. In prior art compositions based on efficient and economical utilization of starting materials it is necessary to obtain the solubilizing effect through unsaturated alcohols, particularly C The use of unsaturated alcohols has significant adverse effects since they impart undesired properties such as color, odor, rancidity, and instability to heating.
EXAMPLE I A typical composition of 40 percent myristyl alcohol, 40 percent palmityl alcohol and 20 percent stearyl alco 1101 (by weight) was made and tested using 0.2 weight percent concentration of the sodium alkyl sulfate pastes of the alcohols in a standard water solution of ppm. (parts per million) hardness as equivalent calcium carbonate. The hardness was achieved by use of a mixture of calcium chloride and magnesium sulfate to provide a calcium cation/ magnesium cation weight ratio of 3/2. The temperature of each solution during the test was 95 F.
In the test the activity of a sodium alkyl sulfate paste is related to the height of the foam it produces. In other words, the higher the foam, the more active the substance under test. In addition, it is desirable that the foam exhibit stability and therefore the height of the foam is measured not only as soon as it has beefi formed but also after standing for 5 minutes.
The results of the tests are tabulated hereinafter.
Foam height (millimeters) After 5 Initial minutes Composition, 10/10/20 r 1-10 l25 EXAMPLE II In a comparative test, a sodium alkyl sulfate detergent derived from a different starting alcohol mixture was tested as in Example I.
EXAMPLE III Example II was repeated in another comparative example using a sodium alkyl sulfate paste derived from another starting alcohol mixture.
Foam height (millimeters) Mixture, parts by After Comp orient weight Initial minutes g y y g8 ahnity Stearyl 4 45 Total 100 The results of Examples II and III are clearly inferior to those of Example I.
What is claimed is:
11. A synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl Not over about 2. Myristyl to 50. Palmityl to 45.
Stearyl 15 to 30. Higher than stearyl Not over about 2.
2. A synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl max 1.5 Myristyl 42:4 Palmityl 36:4 Stearyl 19:3 Higher than stearyl max 2 said mixture being further defined by having the following attributes:
Carbonyl oxygen Max. 0.05 weight percent.
Hydroxyl Min. 225 as mg. KOH/ gram.
Total impurities Not over about 3 weight percent.
3. A synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
10 Alcohol: Weight percent Lower than myristyl Not over about 2. Myristyl 25 to 50. Palmityl 30 to 45. Stearyl 15 to 30.
Higher than stearyl Total impurities Not over about 2. Not over about 4 Weight percent.
4. A synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl Not over about 2. Myristyl 25 to 50. Palmityl 30 to 45.
Stearyl 15 to 30. Higher than stearyl Not over about 2.
said mixture being further defined by having the following attributes:
Carbonyl oxygen Max. 0.05 weight percent.
Hydroxyl value Min. 225 as mg. KOH/ gram,
Total impurities Not over about 3 Weight percent.
5. A synthetic fatty alcohol mixture having the following composition on a hydrocarbon impurity free basis:
Alcohol: Weight percent Lower than myristyl max 1.5 Myristyl 42:4 Palmityl 36:4 Stearyl 19:3 Higher than stearyl max 2 said mixture being further defined by having the following attributes:
Iodine value Max. 1.0 cg. I gram.
Carbonyl oxygen Max. 0.05 Weight percent.
Hydroxyl value Min. 225 as mg. KOH/ gram.
Ester value Max. 1.5 mg. KOH/ gram.
Total impurities Not over about 3 weight percent.
References Cited UNITED STATES PATENTS 3,412,126 11/ 1968 Gautreaux 260632X 2,865,859 12/1958 LuboWe 25256 2,486,921 11/1949 Byerly 252138 2,166,315 7/1939 Martin.
OTHER REFERENCES Tallow & Coconut Fatty Alcohols From Procter & Gamble, Printed 10/ 1963.
LEON D. ROSDOL, Primary Examiner D. L. ALBRECHT Assistant Examiner US. Cl. X.R.
US2670A 1963-05-01 1970-01-13 Alcohol mixtures adapted for use in making detergent sulfates Expired - Lifetime US3598747A (en)

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DE2105910A DE2105910B2 (en) 1963-05-01 1971-02-09 Mixture of alkali metal or ammonium salts of sulfated alcohols
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342917A2 (en) * 1988-05-17 1989-11-23 Unilever Plc Detergent composition
US6174849B1 (en) * 1996-10-30 2001-01-16 Henkel Kommanditgesellschaft Auf Aktien Water-free surfactant mixtures containing alcohol sulfates

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4322968A1 (en) * 1993-07-09 1995-01-12 Henkel Kgaa Process for the preparation of alkyl sulfates
DE4432365A1 (en) * 1994-09-12 1996-03-14 Henkel Kgaa Anhydrous surfactant mixtures
WO2023051978A1 (en) * 2021-09-29 2023-04-06 Unilever Ip Holdings B.V. Composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0342917A2 (en) * 1988-05-17 1989-11-23 Unilever Plc Detergent composition
EP0342917A3 (en) * 1988-05-17 1990-09-12 Unilever Plc Detergent composition
AU611292B2 (en) * 1988-05-17 1991-06-06 Unilever Plc Detergent composition
US6174849B1 (en) * 1996-10-30 2001-01-16 Henkel Kommanditgesellschaft Auf Aktien Water-free surfactant mixtures containing alcohol sulfates

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