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US3758410A - Vicinal substituted alkanes - Google Patents

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US3758410A
US3758410A US3758410DA US3758410A US 3758410 A US3758410 A US 3758410A US 3758410D A US3758410D A US 3758410DA US 3758410 A US3758410 A US 3758410A
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chain
internal
diol
detergent
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S Liu
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Monsanto Co
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C305/00Esters of sulfuric acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/22Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
    • C07C5/23Rearrangement of carbon-to-carbon unsaturated bonds
    • C07C5/25Migration of carbon-to-carbon double bonds
    • C07C5/2506Catalytic processes
    • C07C5/2562Catalytic processes with hydrides or organic compounds
    • C07C5/2568Catalytic processes with hydrides or organic compounds with ion-exchange resins
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D331/00Heterocyclic compounds containing rings of less than five members, having one sulfur atom as the only ring hetero atom
    • C07D331/02Three-membered rings
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/72Ethers of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL AND VEGETABLE OILS, FATS, FATTY SUBSTANCES AND WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/825Mixtures of compounds all of which are non-ionic

Abstract

MIXTURES OF INTERNAL POSITION ISOMERS OF VICINALLY DISUBSTITUTED LINEAR ALKANES WHEREIN THE ALKYL CHAIN CONTAINS FROM 15 TO 17 CARBON ATOMS AND THE SUBSTITUENTS ARE HYDROXY OR ALKOXY GROUPS, AT LEAST ONE OF THE SUBSTITUENTS BEING ALKOXY GROUPS, ARE EFFECTIVE SURFACTANTS.

Description

United States Patent O 3,758,410 VICINAL SUBSTITUTED ALKANES Shih K. Lin, St. Louis, Mo., assignor to Monsanto Company, St. Louis, M0.

N Drawing. Continuation-in-part of applications Ser. No. 710,644, Mar. 5, 1968, and Ser. No. 852,898, Aug. 25, 1969, both now abandoned. This application Apr. 21, 1971, Ser. No. 136,249

Int. Cl. Clld 3/075 U.S. Cl. 252-89 7 Claims ABSTRACT OF THE DISCLOSURE Mixtures of internal position isomers of vicinally disubstituted linear alkanes wherein the alkyl chain contains from 15 to 17 carbon atoms and the substituents are hydroxy or alkoxy groups, at least one of the substituents being alkoxy groups, are effective surfactants.

BACKGROUND OF THE INVENTION Field of the invention This application is a continuation-in-part of US. patent application, Ser. No. 710,644, filed Mar. 5, 1968 and US. patent application, Ser. No. 852,898, filed Aug. 25, 1969, both of said applications now abandoned.

This invention relates to novel surfactant compositions and to detergent formulations containing such compositions as a surfactant component.

As is well known in the detergent industry, surfactants are compounds or compositions, which in solution, are effective to remove dirt, soil, stains, etc., from fabrics and various other materials. Such surfactants can be used alone or, more commonly, in combination with various adjuvants, re-enforcers, supplements, augmentors, potentiators and/or benefactors usually referred to as detergency builders which in combination with the surfactant provide formulations of enhanced cleansing ability.

An effective surfactant should exhibit substantial cleaning ability not only for natural fabrics or fibers such as cotton but also synthetic fibers such as the polyesters and blends of synthetics with natural fabrics such as the polyester/ cotton blends now utilized extensively in many fabrics.

'In order to avoid contamination of natural water supplies, it is further desirable that a surfactant be biodegradable. Further, from the standpoint of economy and, in some instances, ecological consideration, it is desirable that a surfactant exhibit effective cleaning power in combination with relatively small amounts of builder components. It is additionally desirable that the surfactant have a relatively high flash point in order to permit safe utilization in conventional detergent formulation procedures such as spray drying and low volatility to prevent loss and air pollution. Obviously, it is essential that a surfactant for commercial utilization be economically producible in commercial volumes.

Many surfactants and particularly certain polyglycol ethers are known to the detergent industry as surface active agents. For example, there is disclosed in US. Pat. 2,671,811 a 1,12-octadecanediol/ethylene oxide condensate which is suggested for use as an anti-foaming agent. In British Pat. 1,041,036, there are disclosed various terminal polyglycol ether compounds which are suggested as having utility as cleansing agents. In US. Pat. 3,119,- 848, there is disclosed a 9,10-octadecanediol/ ethylene oxide condensate which is suggested for use as a surface active agent.

Although many surfactants are known, the number suitable for commercialization is quite limited in view of the fact that many surfactants are not efiective on a variety 3,758,410, Patented Sept. 11, 1973 of fabrics, are not suitable for incorporation into detergent formulations by preferred commercial processes, are non-biodegradable, or are not economically producible. It is apparent, therefore, that the provision of novel surfactants possessing the essential commercial requisites discussed above fulfils a recognized need in the detergent industry.

Accordingly, it is an object of the present invention to provide novel surfactants. A further object of the invention is to provide novel surfactants which exhibit acceptable detergency on both natural and synthetic fibers. A further object of the invention is to provide novel surfactants which are biodegradable and exhibit good detergency characteristics even when combined with only relatively low amounts of detergency builders. Still another object of the invention is to provide novel detergent formulations based on such surfactants. I The invention will be better understood from the following description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The novel surfactant compositions of this invention are mixtures of internal position isomers of vicinally disubstituted linear alkanes having alkyl chain lengths of from 15 to 17 carbon atoms. The vicinal substituents may be OH or O(C H O) H wherein x is 2 or 3 (preferably 2) and n is a number from 1 to 16 with the proviso that at least one of the vicinal substituents is The overall degree of alkoxylation will be such that n averages from 3 to 10, preferably 3 to 9, more preferably 5 to 9 and more preferably 5 to 7. The mixture will contain at least 3 position isomers each present in an amount greater than 2 mole percent of the vicinally disubstituted alkane of which it is an isomer as distinguished from a homolog consisting essentially of one isomeric form but containing trace amounts of other isomers. In the specification and claims, the term position isomer is used to indicate compounds of the same alkane chain length having diiferences in positions of substituents on the alkane chain, even in the case where the substituents diifer so that under strict nomenclature the compounds would be designated as different rather than as isomers. Thus, for example, a condensate of 3,4 hexadecanediol with one molecular proportion of ethylene oxide and a condensate of 5,6 hexadecanediol with ten molecular proportions of ethylene oxide are considered herein as position isomers rather than merely different compounds. The term mixture of isomers is not, however, intended to encompass mixtures of homologs each present in only one isomeric form. That is, a composition of 2,3; 3,4; 4,5; etc., disubstituted dodecane is considered a mixture of isomers regardless of the nature of the substituents whereas a composition of 3,4 disubstituted dodecane; 4,5 disubstitued undecane and 2,3 disubstituted tetradecane is not con sidered a mixture of isomers. Of course, the term encompasses a combination of mixed isomers of one homolog with mixed isomers of another homolog.

Such mixtures give superior detergency on both cotton and polyester blend fabrics. In addition, these mixtures have high flash points and low volatility which facilitates their processing in conventional spray drying operations. Likewise, these products have low foaming properties making them useful in heavy duty detergent formulations for automatic washing machines where minimum amounts of foam are desired. Moreover, they are readily prepared at economical cost.

To provide the advantages of this invention, a mixture of isomers, as defined, must be utilized. It is found that such mixtures as compared to single isomers of vicinally disubstituted alkanes of the chain length specified provide unexpected advantages in terms of performance in laundry operations. The alkane chain length is additionally critical in this respect since the unexpected advantage obtained by the use of isomer mixtures is not observed in comparisons of performance of isomer mixtures and single isomers of vicinally disubstituted alkanes having alkyl chain lengths outside the above described range.

As previously pointed out, the surfactants of this invention may be a mixture of isomers of vicinally disubstituted alkanes of a single chain length, that is, a single homolog. For example, the surfactant may be a mixture of 2,3; 3,4; 4,5; etc., disubstituted hexadecane. More commonly and preferably from an economical viewpoint, the surfactant will be a mixture of position isomers of a plurality of homologs having alkyl chain lengths of from 15 to 17--.carbon atoms.

In the interest of the economy and to avoid the need of rigorous separation and isolation of internal isomers and the homolog range specified, the mixtures of this invention may be employed in conjunction with varying amounts of terminal (1,2, substituted) vicinally disubstituted linear alkanes and/or with vicinally disubstituted linear alkanes having alkyl chain lengths greater or less than 15 to 17 carbon atoms. In addition homologs composed of only one isomeric form may be present. The presence of such extraneous material does not destroy the advantages of this invention althoughmaximum performance may not be realized in view of the dilution effect." Accordingly, the presence of such extraneous material is preferably limited to trace amount (less than 2%) or at least to amounts less than 50%, although the advantages of the invention are often apparent in surfactant compositions containing as little as 10% of the isomer mixtures described.

The novel compositions of the present invention may be prepared in a number of ways. For example, an epoxide may be hydrolyzed to a diol, or reacted with ethylene glycol to form a fl-hydroxy ethylene glycol ether, the resulting composition then being combined with the appropriate amount of ethylene oxide. Alternatively, the epoxide can be reacted with the appropriate amount .of polyethylene glycol, making further reaction with the ethylene oxide unnecessary. The epoxides may be obtained from olefins, for example, internal olefins (which may contain minor amounts of alpha olefins) or mixtures of internal olefins and saturated compounds, preferably straight chain internal olefins containing 12 to 20 carbon atoms or a mixture of straight chain internal olefins and paraflins containing about 12 to 20 carbon atoms and mixtures thereof by well known methods such as described in Kirk and Othmer Encyclopedia of Chemical Technology, Second Supplement, pp. 325-346 (1960).

Internal vicinal diols may be obtained from the corresponding epoxides, for example, by hydrolyzing the epoxides to diols using formic acid and hydrogen peroxide. This procedure is described by Swern, Billen and Scanalan, Journal of the American Chemical Society, 68, (15 04- 1507,1946).

Propylene oxide, ethylene oxide or mixtures thereof as mentioned hereinbefore, is condensed in varying amounts with the individual compounds comprising the mixtures of the present invention. The individual condensates making up the mixture may have an amount of alkylene oxide content from about 1 molecular proportion to about 16 molecular proportions. The mixtures of the individual condensates have an overall average alkylene oxide content of about 3 to about 10 molecular proportions, preferably about 5 to about 9 molecular proportions. It is further to be understood that in the products obtained in accordance with the foregoing, the alkylene oxide chain may be distributed equally or unequally on the two hydroxyl groups of the hydrophobe. In this connection, the present invention is not meant to be limited to any specific distribution between the alkylene oxide chain and the internal linear hydrophobe.

Alternatively, ethylene glycol or polyethylene glyco (PEG) having the formula:

HOCH CH OCH CH 'OCH CH OH,

where n is a number from 0 to about 10 may be reacted with internal epoxides, or mixtures of internal epoxides and paratfins having carbon chain lengths of from about 13 to about 18 carbon atoms, to prepare the compositions of the present invention as hereinbefore mentioned.

Generally, the reaction product of'the ethylene glycol and the epoxide is a fl-hydroxy mono-ethylene glycol ether. This ether may then be reacted With ethylene oxide to get the desired products of the present invention. Alternatively, if polyethylene glycol is used as the reactant with the epoxide mixtures, further ethoxylation is not required.

It is noted that preparative procedures based on raw material having alkyl chain lengths of 13 to 18 carbon atoms have been described. It is, of course, essential that such materials contain a substantial amount of the C C17 homologs which provide the advantages of this invention. The use of all C C homologs in preparatory procedures is desirable but is sometimes economically impractical to obtain raw materials so severely limited with respect to chain length.

Generally, when straight chain isomeric internal vicinal diols are condensed with an average of about 3 to about 10 molecular proportions of alkylene oxide, the final product contains some unreacted diol. If desired, this unreacted diol may be removed by distillation. If distillation is employed, some low ethylene oxide condensates are also removed. One advantage of removal is an increase in the flash point of the final product. Flash point is determined by the ASTM, Cleveland Open Cup Method. For example, a straight chain isomeric internal vicinal diol having an average carbon chain length of about 16 to about 17 was condensed with an average of about 3.5 molecular proportions of ethylene oxide and the final product contained about 20% by weight of unreacted diol. This product has a flash point of 415 F. By removing all but about 2.5% by weight of the unreacted diol by distillation, the flash point is increased to about 495 F. This is accomplished by distilling the product at a temperature of about 250 C. at a pressure of 5 mm. of mercury until about 2.5% by weight of diol is left.

The novel detergent formulations of this invention comprise the above-described surfactant mixture of the invention in combination with a detergent builder.

The amount of surfactant present in the detergent formulations, can vary depending on the end product performance desired. However, it is preferred that the range of detergent active to builder weight ratio be from about 1:10 to about 10: 1, and more preferably from about 1:7 to about 1:1. The detergent formulation should contain at least 2% by weight of the surfactant of this invention.

Any of the well known detergency builders employed in combination with conventional surfactants to provide enhanced cleansing performance can be utilized. For example, alkaline water-soluble inorganic salts such as trisodium phosphate and tripotassium phosphate; dialkali metal hydrogen phosphates such as disodium hydrogen phosphate and dipotassium hydrogen phosphate; the alkaline water-soluble molecularly dehydrated alkali metal phosphate salts such as the alkali metal pyrophosphates, for example, tetrasodium pyrophosphate, tetrasodium hydrogen pyrophosphate and tetrapotassium pyrophosphate, also the alkali metal tripolyphosphates such as sodium tripolyphosphate (Na P O and potassium tripolyphosphate; the water-soluble alkali metal metaphosphates such as sodium hexametaphosphate; the water-soluble alkali metal silicates such as sodium silicate having a Na O to SiO mole ratio of 1:1 to 1:3.6, preferably 1:1 to 1:35 and the corresponding potassium silicates; the watersoluble alkali metal borates such as calcined sodium tetraborate or borax; and the water-soluble alkali metal carbonates or bicarbonates such as sodium or potassium carbonates; or sodium sulfate may be utilized.

Examples of organic builders that can advantageously be employed include the amino polycarboxylic acids and salts such as the sodium potassium and ammonium salts of nitrilotriacetic acid (trisodium nitrilotriacetate), the sodium potassium and ammonium salts of amino tri (methylene phosphonic acid), as well as the free acid; and the diphosphonic acids and salts (methylene diphosphonic acid and l-hydroxy, ethylidene diphosphonic acid). There may also be included builders such as the watersoluble salts of polymeric aliphatic polycarboxylic acids such as sodium polymaleate, sodium polyitaconate, sodium (itaconate-aconitrate) copolymer, sodium (itaconateacrylate) copolymer, sodium (ethylene-maleate) copolymer, sodium (ethylene-maleate) copolymer (crosslinked), sodium (vinylmethylether-maleate) copolymer, and sodium (isobutylene-maleate) copolymer as disclosed and described in U.S. Pat. 3,308,067 which is incorporated herein by reference, a synergistic builder combination, as disclosed and described in U.S. Pat. 3,368,978, which is also incorporated herein by reference, and mixtures thereof.

An enzymatically active substance, i.e., a substance composed of a single enzyme or a mixture of enzymes, may also be used in conjunction with the compositions of the present invention. Enzymatically active substances may be obtained from animals, plants or micro-organisms and it is preferred to use enzymatically active substances of a microbial origin as they can be economically produced in appreciable amounts. Suitable micro-organisms produce either a single enzyme or :a mixture of enzymes.

If desired, supplementary surfactants such as well known natural soaps or synthetic anionic, non-ionic, zwitterionic or amphoteric may be utilized. It is preferred, when using the supplemental actives, that there be a weight ratio of novel surface active compositions of this invention to the foregoing described supplementary actives of from about at least 1:1 to about 50:1.

The detergent formulations incorporating or embodying the novel compositions of the present invention may contain any of the usual adjuvants, diluents and additives, for example, perfumes, antitarnishing agents, anti-redeposition agents, bacteria-static agents, dyes, fluorescent agents, suds builders, suds depressors, foam stabilizers and the like.

The detergent formulations of the present invention can be prepared by any of the well known methods in order to yield desirable composition forms such as bar, granular, flake, liquid and tablet forms. It is to be understood that this invention is not limited to any particular method of preparing the detergent formulations containing the organic and/ or inorganic builder and the detergent-active (i.e., both the novel compositions and supplemental detergent-actives). The builder, for example, may be mechanically mixed, or slurried or dissolved in a solution of the other ingredients of the formulations. In addition, the detergent-active (as heretofore defined) may be admixed with the builder in any of the forms in which the builder is present as well as being added simultaneously or separately to an aqueous solution containing the builder and/or other ingredients.

To more fully illustrate the subject invention, the following detailed examples are presented. All parts, percentages and proportions are by weight unless otherwise indicated.

EXAMPLE I Five hundred grams of an alpha olefin having a carbon chain length of carbon atoms and molecular weight of about 196 are charged into a one liter flask equipped with a thermometer, stirring apparatus and condenser. After heating up to 110 C., 100 grams of polystyrene sulfonic acid type cationic exchange resin, commercially available under the trademark Amberlyst 15, is added and the resultant mixture stirred vigorously and kept at the above temperature for about 3 hours. At the end of this period, the alpha olefin is isomerized to a product containing internal olefins as verified by infrared absorption spectrum. The isomeric distribution of the product is given in Table I below. Four hundred and fifty-six grams of this C isomerized product are then charged to a distillation pot and fractionated through a S-plate, l Oldershaw column. The fraction boiling at 118 through 180 C./l0 millimeters of Water pressure is collected to yield a total of substantially internal C olefin product of 405 grams. Into a two liter round bottom flask equipped with a stirring apparatus, thermometer and condenser are charged 124 grams of the isomerized C internal olefin, 845 milliliters of an aqueous solution containing 97% by weight formic acid and 72 grams of an aqueous solution containing 30% by weight hydrogen peroxide. The heterogeneous resultant reaction mixture is heated while stirring vigorously to 40 C. and held at that temperature for 24 hours. After this period, 605 milliliters of formic acid are stripped ofl" under reduced pressure. Six hundred milliliters of 3 N-methanolic potassium hydroxide is then added and the resultant mixture refluxed for one hour. The excess methanol was stripped off under reduced pressure (i.e., 15 mm. of water) and then 900 milliliters of hot (70 C.) distilled water are added to the residue remaining in the pot. After stirring for 10 minutes, the resultant mixture is allowed to cool to room temperature, i.e., 20 C. The lower water layer is then siphoned form the solid diol. A second portion of 900 milliliters of hot (70 C.) distilled water is added and the resultant mixture slurried. The mixture is allowed to cool to room temperature, i.e., 20 C., and the lower water layer siphoned from the solid diol. The solid diol product is filtered and dried under reduced pressure (i.e., 15 mm. of water) in a rotary evaporator, to yield 158 grams of diol product. The diol is first recrystallized from methanolpetroleum ether and then slurried with cold petroleum ether, filtered and dried. A total of grams of an isomeric mixture of substantially pure C vicinal diols having molecular weight of about 230 is obtained. A 0.2 gram sample of the purified diol mixture is dissolved in 25 ml. of ethanol. This is analyzed by the periodic titration as described by S. Sigia Quantitative Organic Analysis Via Functional Groups, John Wiley and Sons, Inc., 1963, p. 39. The analysis shows better than 98% of vicinal diols. The isomeric distribution is determined by a method described in an article, Quantitative Recovery and Programmed Temperature Gas Chromatographic Analysis of Periodate Permanganate Oxidative Cleavage Products, Analytical Chemistry, 35, p. 426 (1964), and is listed in Table I below.

Into a conventional vessel are added 15 grams of the C isomeric internal vicinal diols produced by the procedure set forth above, and 0.2 gram of potassium hydroxide. The resultant mixture was heated to approximately C. under a nitrogen atmosphere. Ethylene oxide is then introduced in a series of stages so that the total pressure is continuously maintained about 15 to 20 cm. above atmospheric pressure, the reaction is stopped after an average of about 5-6 molecular proportions of ethylene oxide is added.

TABLE I [Isomerized olefin and vicinal diol distribution in percent] C15 vicmal Cw vicinal C 1 vicinal 8,9 3 2 2 4. 5 Q in The above procedure is repeated with 500 grams each of C and C Isomeric distribution of the respective olefins and the resulting vicinal diols is given in Table I.

EXAMPLE II Five hundred grams of a mixture of straight chain alpha olefins, of about 20% C 40% C 30% C and 10% C having an average carbon chain length of about 16 to about 17 carbon atoms and an average molecular weight of 231 are isomerized in a manner set forth in Example -I and then converted to the corresponding diol having a molecular weight of 265. One fifteen grams sample is ethoxylated in the same manner as described in Example I with an average of 4-5 molecular proportions of ethylene oxide. The mixtures are tested for their foaming properties, biodegradability properties and detergency characteristics. The forming properties are tested using the Ross-Miles procedure. A commercial alcohol ethoxylate is also tested. The results are listed in Table II below.

The mixture of the present invention and the primary alcohol ethoxylates are tested for biodegradability employing a two step procedure involving the sequential use of two commonly accepted microbiological techniques. The shake flask technique is used as the presumptive step in the procedure. If a detergent-active is 90% or more degraded in the presumptive step, no further testing is needed. If it is not degraded at least 80%, it is considered to be not adequately biodegradable. However, if its biodegradability falls between 80% and 90% by the Presumptive Test, its biodegradability must be determined by the Confirming Test. The confirming step is the semi-contiunous activated sludge test which more closely simulates sewage treatment plant operation. A material must be degraded at least 90% under this procerdure to be considered adequately biodegradable. Both tests are conducted. They are more fully described in Journal of the American Oil Chemists Society, 42, pp. 986-993 (1965). A bismuth iodide method for analysis was employed as described in Z. Anal. Chem. 196, pp. 251-259 (1963).

The results of the Presumptive Tests show that isomeric internal average C C vicinal diol plus an average 4-5 E0. is 95% removed, and the primary alcohol plus 13 E0. is 90%-95% removed. The results of the Confirming Test show that isomeric internal average C -C vicinal diol plus an average 4-5 ED. is 90%-95% removed, and the primary alcohol plus 13 ED. is 95%-100% removed.

The detergency of these mixtures and a C primary alcohol ethoxylate on polyester cotton (65% cotton 35% polyester) and cotton fabrics are determined by employing a test more fully described in an article in the Journal of the American Oil Chemists Society, vol. 42, pp. 723-727, August 1965. The conditions of the wash Water are (a) a hardness of 150 parts per million, (b) a detergency concentration of 0.2%, (c) a temperature of 49 C. and (d) a pH of 9 to 10, the test made using a terg-o-meter machine on standard soiled polyester cotton and cotton fabrics. The following detergent compositions are used in the tests with the percentage being by weight in the aqueous washing solution.

8 Detergent active (a) or (b) .030 Sodium tripolyphosphate .10 Sodium silicate .020

(a) Isomeric internal average C16C17 vicinal diol plus an average of 4-6 10.0.; (b) C13 primary alcohol plus 14 10.0.

The results of using the above detergent formulation are given in Table III.

TABLE III ARd . Polyester Active Cotton cotton Isomeric internal average 015-01.; vicinal diol plus an average of 4-5 E.O 25 22. 2 C13 primary alcohol plus E.O 24. 1 19 A gram sample of a straight chain isomeric internal vicinal diol, having an average carbon chain length of 16 to 17 carbon atoms condensed with an average of 4 to 5 molecular proportions of ethylene oxide products of Ex ample III, having 12 weight percent of unreacted diol, is distilled at a temperature of 225 C. and a pressure of 0.15 mm. of mercury until about 1 weight percent of un reacted diol remained. The flash point determined by the ASTM method before removing the diol is 430 F.; after removal, it is 510 F.

The detergency of the compositions of this invention stripped of unreacted diol versus the unstripped composition and linear alkylbenzene sulfonate is determined using the same washing procedure as in Example III. The water is characterized by having (a) hardness of parts/million, (b) a detergency concentration of 0.15%, (c) a temperature of 49 C. and (d) a pH of 9 to 10. The following detergent compositions are used in the tests with the percentages being by weight in the aqueous washing solution.

Formulations 1) Detergent active (a) or (b) 1 .022 Sodium tripolyphosphate .06 Sodium silicate 015 (2):

Stripped isomeric internal average C -C diol plus an average of 4 13.0. .015 Sodium tripolyphosphate .06 Sodium silicate 015 1 (a) Isomeric internal average Clo-C17 diol plus an average of 45 ELO. unstripped; (h) LAS.

The results of using the above detergent formulations are given in Table IV.

TABLE IV Active: Appearance loss Isomeric internal average C C diol plus an average of 4-5 R0. stripped 5.0 LAS 8.0 Isomeric internal average C -C diol plus an avererage of 4-5 unstripped 8.0

The soil removal is recorded as appearance loss because ten shirts that were cut into swatches for these starches were very different in their initial reflectance and hues. The lower the appearance loss, the better the performance of the formulation. As can be seen, the

EXAMPLE IV A straight chain isomeric internal C vicinal diol condensed with an average of 3 molecular proportions of E0. prepared in the same manner as Example I, a straight chain isomeric internal C vicinal diol condensed with an average of 3 molecular proportions of E0. prepared in the same manner as Example I, a straight chain isomeric internal C vicinal diol condensed with an average of 3 molecular proportions of E0. prepared in the same manner as Example I, and a straight chain isomeric internal'average C -C vicinal diol condensed with an average of 3 molecular proportions of ED. prepared in the same manner as Example I were tested for their detergency on polyester cotton fabrics. The test procedure is the same as set forth in Example H. The water is characterized by having (a) a hardness of 150 parts/million, (b) a detergency concentration of 0.2=by weight based on the total weight of the water, (c) a temperature of 49 C. and (d) a pH of 9 to 10. The following detergent compositions are used in the test with the percentages being by weight in the aqueous washing solution.

Detergent active .03 Sodium tripolyphosphate .08 Sodium nitrilotriacetate .04 Sodium sulfate I .04

The results of using the above detergent formulation are shown in Table V below:

Table V gives the readings taken on a Gardner Color Difierence Meter. As can be seen from the results set forth in Table V, a mixture of different homologs gives better performance than does any one homolog above alone.

EXAMPLE V The following detergent formulations listed in Table VI give good detergency on polyester as well as polyester cotton fabrics.

TABLE VII Active: ARd C diol condensed with 7 molecular proportions of ethylene oxide according to Example I and having similar random isomer distribution 15 C diol condensed with 7 molecular proportions of ethylene oxide according to Example I and having similar random isomer distribution 19.5 C diol condensed with 7 molecular proportions of ethylene oxide according to Example I and having similar random isomer distribution 17 1,2 disubstituted C alkane (7 molecular proportions ethylene oxide) 13.7 7,8 disubstituted C alkane (7 molecular proportions ethylene oxide) 7.5 1,2 disubstituted C alkane (7 molecular proportions ethylene oxide) 13 8,9 disubstituted C alkane (7 molecular proportions ethylene oxide) 14 1,2 disubstituted C alkane (7 molecular proportions ethylene oxide) 11 9,10 disubstituted C alkane (7 molecular proportions ethylene oxide) 12 Direct comparison and routine extrapolation of the data presented in Table VlI indicate that for alkyl chain lengths less than 15 or greater than 17 carbon atoms single isomer (either terminal or internal) provide superior performance as compared to mixtures of isomers. However, unexpectedly, within the alkyl chain length range specified for the compositions of this invention, mixtures of isomers are superior to single isomers.

What is claimed is:

1. A mixture of internal position isomers of a vicinally disubstituted linear alkane having an alkyl chain length of from 15 to 17 carbon atoms, the substituents being selected from the group consisting of --OH and -O(C H O),,H, x being a number from 2 to 3, n being a number from 1 to 16, at least one of the substituents being O(C H O) H, n averaging from 3 to 10 in said mixture and said mixture comprising at least 3 position isomers each present in an amount greater than 2 mole percent of said vicinally disubstituted alkane.

2. The composition of claim 1 wherein x is 2 and n averages from 3 to 9.

3. The composition of claim 2 wherein n averages from 5 to 7.

4. The composition of claim 1 wherein both of said substituents are O(C H O),,H.

TABLE VI [Detergent Formulations of the Present Invention-Percent by Weight] Sodium Sodium polypolyitacon- Active Amount MQNTA 1 STP 1 HEDP 3 maleate ate NaSiOz NaOMC l NazSO Isomeric straight chain internal 015-01 vicinal diol plus an average of 5-6 E.O 10 1 10 Isomeric straight chain internal 01 -0 vicinal dlol plus an average of 8-9 E.0 10 1 10 Isomeric straight chain internal Cis-Cm vicinal diol plus an average of 7-8 15.0 l0 1 10 Cut-C17 (1101 plus H E.() 10 1 19 D 10 1 19 D 10 1 19 1 Trisodium nitrilotriacetate H10. 3 Sodium tripolyphosphate.

3 l-hydroxy-l, l-ethylideue diphosphonic acid. 4 Sodium carboxymethylcellulose.

EXAMPLE VI Detergent formulations containing 10% of the active indicated in Table VII below; 40% sodium tripolyphosphate; 12% sodium silicate (112.4 ratio Na Ozsio and 38% sodium sulfate are prepared.

These formulations are used in 0.15% concentration to wash uniformly soiled swatches of polyester/cotton fabric in water at 120 F., 300 ppm. hardness. Detergency results (ARd) are shown in Table VII.

5. The composition of claim 1 wherein one of said substituents is -OH and the other of said substituents is -O (C H O) H.

6. The composition of claim 1 wherein said composition contains a plurality of homologs having alkyl chain lengths of from 15 to 17 each of said homologs comprising a mixture of position isomers and at least 2 homologs each being present in an amount greater than 2 mole percent of the weight of the mixture.

7. A detergent formulation consisting essentially of, as a surfactant, at least 3% by weight of a mixture of internal positiontisomers of a vicinally disubstituted linear alkane having an alkyl chain length of from 15 to 17 Carbon atoms, vthe substituents being selected from the group consisting of -OH and O(C H O) H, x being a number from 2 to 3, n being a number from 1 to 16 and averaging from '3 to 10 in said mixture, at least one of the substituents being 0 (C H OHH, said mixture comprising at least 3 position isomers each present in an amount greater than 2 mole percent of said vicinally disubstituted alkane and a water' soluble detergency builder, the ratio of surfactant to detergency builder being from about 10:1 to about, 1.10.

t l eferences Cited UNITED STATES PATENTS 10/ 1968-. Bla'ser-etYal. 260-615 I 1/1964 Wrigley et a1. -2 260-404 3/1966 Johnson. a t

FOREIGN PATENTS 1 6/1965 Belgium.

10 LEON D. ROSDQL, Primary Examiner P E. WILLIS, Assistant Examiner U.'S. Cl. X.R.

"W050 UNKTED STATES FATENT @FFECE seamen F eoneeefiioe Patent No. 3,7589% m p 11, 1973 Inventofle) Shin K. Liu

It is certified that error mppeem m the eboveddemcified patent and that eeid Lettema Patent are he'mby marinated ea mm belw:

In column. 7, line 26, after "con-" insert therefor cen In column 10, line 1 delete "1.3.7" and insert therefor l5 5 '"o In column 11, line 15, delete "1 10" and insert therefor 1:10

Signed and sealed this 16th day of April 197).

(SEAL) Attest:

EDWARD TIQFLETQEMELJIL Go l-TAHSHALL DELHJI Attesting Officer Commissioner of Patents

US3758410A 1968-03-05 1971-04-21 Vicinal substituted alkanes Expired - Lifetime US3758410A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936317A (en) * 1972-06-02 1976-02-03 Henkel & Cie G.M.B.H. Dishwashing compositions containing higher 1,2-alkanediol ether monosulfates
US3993605A (en) * 1974-06-05 1976-11-23 Chemische Werke Huls Aktiengesellschaft Foam inhibited or attenuated washing, cleaning and rinsing agents for dishes and utensils
US4172044A (en) * 1976-10-01 1979-10-23 Henkel Kommanditgesellschaft auf Aktien (Hunkel KGaA) Process and concentrates for clear-rinsing in mechanical dishwashing
US4184985A (en) * 1977-07-11 1980-01-22 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Stable, aqueous or aqueous-alcoholic solutions of fat-soluble perfume oils containing hydroxyalkyl ether-ethoxylates
US4332692A (en) * 1979-02-28 1982-06-01 The Procter & Gamble Company Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures
US5432268A (en) * 1992-05-15 1995-07-11 Enichem S.P.A. Process for producing hydroxyalkyl glucosides
US20050126655A1 (en) * 2003-12-10 2005-06-16 Ours David C. Stretch wrap transportable container and method
US20060081500A1 (en) * 2003-02-07 2006-04-20 Basf Aktiengesellschaft Method for processing naphtha
US20090301036A1 (en) * 2008-06-05 2009-12-10 Dave Ours Unitary transporter base and shaper and slip frame former for forming a transportable container
US20090308486A1 (en) * 2008-06-11 2009-12-17 Dave Ours Gentle handling hopper and scrunched bag for filling and forming a transportable container
US8191341B2 (en) 2008-09-03 2012-06-05 Kellogg Company Method for forming a transportable container for bulk goods
US9126705B2 (en) 2010-12-01 2015-09-08 Kellogg Company Transportable container for bulk goods and method for forming the same

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DE69611028D1 (en) * 1996-01-30 2000-12-28 Bp Amoco Corp A process for the isomerization of olefins

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FR2003231A1 (en) * 1968-03-05 1969-11-07 Monsanto Co

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936317A (en) * 1972-06-02 1976-02-03 Henkel & Cie G.M.B.H. Dishwashing compositions containing higher 1,2-alkanediol ether monosulfates
US3993605A (en) * 1974-06-05 1976-11-23 Chemische Werke Huls Aktiengesellschaft Foam inhibited or attenuated washing, cleaning and rinsing agents for dishes and utensils
US4172044A (en) * 1976-10-01 1979-10-23 Henkel Kommanditgesellschaft auf Aktien (Hunkel KGaA) Process and concentrates for clear-rinsing in mechanical dishwashing
US4184985A (en) * 1977-07-11 1980-01-22 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Stable, aqueous or aqueous-alcoholic solutions of fat-soluble perfume oils containing hydroxyalkyl ether-ethoxylates
US4332692A (en) * 1979-02-28 1982-06-01 The Procter & Gamble Company Laundering with a nonionic detergent system at a temperature between the cloud point and the phase coalescence temperatures
US5432268A (en) * 1992-05-15 1995-07-11 Enichem S.P.A. Process for producing hydroxyalkyl glucosides
US7459072B2 (en) * 2003-02-07 2008-12-02 Basf Aktiengesellschaft Method for processing naphtha
US20060081500A1 (en) * 2003-02-07 2006-04-20 Basf Aktiengesellschaft Method for processing naphtha
US6935385B2 (en) 2003-12-10 2005-08-30 Kellogg Company Stretch wrap transportable container and method
US20050126655A1 (en) * 2003-12-10 2005-06-16 Ours David C. Stretch wrap transportable container and method
US20090301036A1 (en) * 2008-06-05 2009-12-10 Dave Ours Unitary transporter base and shaper and slip frame former for forming a transportable container
US7921624B2 (en) 2008-06-05 2011-04-12 Kellogg Company Unitary transporter base and shaper and slip frame former for forming a transportable container
US20090308486A1 (en) * 2008-06-11 2009-12-17 Dave Ours Gentle handling hopper and scrunched bag for filling and forming a transportable container
US8104520B2 (en) 2008-06-11 2012-01-31 Kellogg Company Gentle handling hopper and scrunched bag for filling and forming a transportable container
US8191341B2 (en) 2008-09-03 2012-06-05 Kellogg Company Method for forming a transportable container for bulk goods
US9126705B2 (en) 2010-12-01 2015-09-08 Kellogg Company Transportable container for bulk goods and method for forming the same

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FR2133962A2 (en) 1972-12-01 application

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