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US3427248 - United States Patent Office 3,427,248 Patented...

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Unformatted text preview: United States Patent Office 3,427,248 Patented Feb. 11, 1969 1 3,427,248 DETERGENT Vincent Lamberti, Upper Saddle River, and Henry Le- mair, Leonia, NJ., assignors to Lever Brothers Com- pany, New York, N.Y., a corporation of Maine No Drawing. Filed Oct. 22, 1965, Ser. No. 502,299 US. 'Cl. 252—117 7 Claims Int. Cl. Clld 9/32, 9/30, 9/ 02 ABSTRACT OF THE DISCLOSURE The specification is concerned with certain polyolethers, polyolpolyethers or sulfur analogs thereof which can be used alone as a detergent or in combination with other compounds. This invention relates to a detergent. More particularly, it is concerned with :a detergent which is a polyolether, polyolpolyether or sulfur analog thereof. In the past, a straight chain or branched chain alcohol may be reacted with ethylene oxide to form ethoxylates, such as n-tetradecyl alcohol-7 moles ethylene oxide, dodecyl alcohol—10 moles ethylene oxide and Sterox AJ (tridecyl alcohol-about 9.5 moles ethylene oxide). These ethoxylates have detergent properties. It has now been discovered that certain polyolethers and polyolpolyethers and thioether analogs are surface active agents, e.g., detergent actives, dishwashing deter- gents, lime-soap dispersants and suds-boosters for other detergent actives. The compounds of the invention also have antimicrobial activity and are nontoxic, mild towards skin and completely biodegradable. 5 10 15 20 25 3O 2 method, the compounds of the invention are the reaction products of: (II) with: HZ—(CH2)80H(OH)R’ (III) wherein R, a, b and R’ are as defined heretofore and Z is oxygen or sulfur. If the reaction product is a thioether, it can be oxidized, for example with t-butyl hydroper- oxide in methanol, to form the corresponding sulfoxide. It is also possible to react either a long-chain die] or a monoalkyl ether of glycerol with one molar proportion of ethylene oxide. By this process however, a mixture of products is obtained containing large proportions of un- reacted starting diol or ether, with some mono-ethoxylated compound with which this invention is concerned, and with some poly-ethoxylated compounds such as those rep« resented by the formula RCH(OH)CH20 (CHZCH20)xH wherein x is greater than 1. If .a long—chain epoxyalkane is a reactant, it may be obtained by any suitable method. For example, an alkene may be oxidized directly in the presence of a catalyst or a chlorhydrin may be reacted with sodium hydroxide. Similarly, if a long-chain diol is a reactant, it may be obtained by any suitable method, such as the oxidation and hydration of olefins and the hydrolysis of chlorhydrins. The following short—chain polyhydroxy reactants among others are within the scope of the above structure I: SHORT-CHAIN POLYHYDROXY REACTANT (STRUCTURE III) a R' Z N ame Structure ———_____.—__—_____ 1 H 0 Ethylene glycol .............. HOCHzC H2011 1 0112011 0 Glycerol ________ - HOCH20H(OH)CH20H 1 CH3 0 1,2-propanediol ...... _ HOCHzCHOHCH: 1 H S 2-mercapto ethanol ___________ HSOHzCHzofl 1 CH20H S 3-mereapto-1,2—propanediol - HSCHzCH(0H)CH20H 1 CH3 S 1-mercapto-2—propanol-. _ HSCHzCHOHCHa 2 H 0 1,3—propanediol _________ _ H0—CH2—CHr—CH20H 2 01352011 0 1,2,4-bntane trlol-_-- --_- HOCH20H20H(OH)OH20H 2 CH3 0 1,3-butylene glycol ........... HOCHzCHgCH<OH)CHa 2 H S 3-mercapto-l-propanol ........ HSCHzCHzCHzOH 2 0112011 S 4-mercapto-1,2-butauediol_ _ . . HSCHzCHzCH (OH) OH20H 2 CH3 S 4-mercapto—2—butanol ......... HSCHzCHgCHwH) CH3 —-—-————————___—_________ These new nonionic detergents have the following ge- neric structure: R (%)b H2 Hé—[Z—(Cflz) ECH(OH) R’]m[OH]n H2é~IZ—( CH2) 1: CH(OH) R’]n[OH]m (I) wherein R is an aliphatic hydrocarbon group having 5—12 carbon atoms; each Z is oxygen, sulfur or sulfoxide; a is 1 or2;bisOor 1;mis00r 1;nisOor 1; mi+nis 1; and R’ is H, CHZOH or CH3. As used herein, this structure is intended to include isomeric compounds. Any known method may be employed to prepare the aforementioned polyolethers and polypolyethers and sulfur analogs thereof. However, the preferred method is to react a long chain epoxide or long chain glycidyl ether with a polyhydroxy compound, such as, ethylene glycol or glyc- erol, in the presence of an :acid catalyst, e.g., SnCl4, or a basic catalyst, e.g., NaOCHa. The reaction can also be carried out without a catalyst, but in such cases, longer reaction times are required. In accordance with this 50 55 60 65 70 Preferred compounds in this invention among others include polyolethers, such as 2-hydroxydodecyl 2’-hy‘ droxyethyl ether having the structure: CH3(CH2)90HCH200H20H20H H and 2-hydroxydodecyl glyceryl ether having the structure: CHa(CH2)oCHCH200H20HCH2 H (IJH \OH and polyolpolyethers, such as a-decyl-oc’-hydr0xyethyl glyceryl diether having the structure: CH3(CH2)SCH200H2('}HCH20CH20H20H OH The compounds of the present invention may be used alone as detergents. However, the compounds of the in- vention may also be used in combination with other detergents. Examples of detergent compounds with which the compounds of the invention may be admixed to form superior combinations are the well-known anionic types represented by the water-soluble and water-dispersible organic surface-active agents having in the molecule a hydrophobic group of about 8 to about 22 carbon atoms 3,427,248 3 and a hydrophilic sulfate, sulfonate or carboxylic group having a cation which does not insolubilize the compound. The following anionic detergents among others are suit- able for use with the compounds of the present invention: (1) Alkylbenzenesulfonates, such as the sodium and potassium salts having a branched or straight chain alkyl portion of about 9 to about 15 carbon atoms. ( 2) Alkyl sulfates, such as the sodium and triethanolam— monium salts of Clo—C20 alkyl sulfuric acid, prepared by sulfating the alcohols derived from coconut oil or tallow, or prepared synthetically. (3) The alkali metal and ammonium salts of the sulfated ethoxylates of a long-chain alcohol and 3 to 5 molar pro- portions of ethylene oxide, for example the ammonium salt of an ethoxylate containing an average of 3.1 molar proportions of ethylene oxide and 1 mole of an alcohol mixture known commercially as Alfol 1412, composed of about 2/3 n—tetradecanol and about 1/3 n—dodecanol. (4) The compounds known as “Medialans,” which are amido carboxylic acids formed by condensing fatty acids of C8-C22 chain length with sarcosine, CHgNHCHZCOOH. Generally the alkali metal and basic nitrogen-radical salts are employed. (5) Alkanesulfonates, such as ammonium dodecane- sulfonate. (6) Alkoxyhydroxypropanesulfonates, such as the water—soluble salts of 3-dodecyloxy—2—hydroxy—1—propane- sulfonate. (7) Soaps, the surface-active substances formed usually by the reaction of caustic alkalies with natural glyceridic fats and oils, generally prepared in high purity, and hav- ing the generic molecular formula RCOONa, wherein R is a straight-chain hydrocarbon group having from about 8 to about 22 carbon atoms. The compounds of the invention are also suds-boosters for nonionic detergents. The following nonionic detergents among others are suitable for use with the compounds of the present invention. ( 1) The Pluronics, formed by condensing propylene oxide with propylene glycol to a molecular weight of about 600—2500 to form a base followed by condensing ethylene oxide to this base to the extent of about 10% to about 90%, total molecule basis. US. Pat. Nos. 2,674,619 and 2,677,700 describe operable nonionic compounds. (2) Compounds formed by the simultaneous polymer< ization of propylene oxide and ethylene oxide, and con- taining randomly positioned oxypropylene and oxyethyl- ene groups. These and related compounds are described in US. Pats. Nos. 2,979,528, 3,036,118, 3,022,335, 3,036,130 and 3,048,548. (3) Alkyl phenols having 9—12 carbon atoms in the alkyl portion (straight or branched) ethoxylated with 4—10 molar proportions of ethylene oxide. (4) Ethoxylates of fatty alcohols having 8—18 carbon atoms per molecule and 5 to 30 molar proportions of oxyethylene groups. The compounds of this invention may interact syner- gistically with all suds-producing anionic and nonionic surface-active substances to provide mixtures having im- proved properties beyond those expected on the basis of the properties of the individual components of the mix- ture. With nonsoaps, the synergism may be evident in suds production or stability. With soaps, the synergism may be evident in the form of reduced lime-scum formation. Thus, in accordance with this invention, new com- pounds have been formed. The compounds of the present invention have certain noteworthy features. For example, the synergistic suds—producing properties of the compounds with other detergents and sudsing agents are surprising. The antimicrobial properties of the compounds are also surprising. Furthermore, the compounds of the invention are nonionic surfactants with foaming characteristics su- perior to both well-known anionic and nonionic de- tergents. The ability to formulate a detergent based on the nonionic materials of the invention having high foam- 10 20 25 30 40 60 70 4 , ing or dishwashing characteristics with built-in germicidal properties and which at the same time is biodegradable by sewage or natural water bacteria is certainly surprising and unexpected. The following examples are submitted to illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification and claims are based upon weight. EXAMPLE I A compound, 2,-hydroxy-Cu_15 alkyl glyceryl ether, was prepared :by adding 286 g. (1.3 moles) of 1,2—epoxy-Cn_15 alkane (purity, 89%) dropwise over 30 minutes with stirring at 120°—137° C. to 2401 g. (26 moles) of glycerol containing 2.3 g. of stannic chloride. Heating was con- tinued .for one hour. The upper layer was removed and an additional 286 g. of epoxide was added to the lower, glycerol, layer at 133°—-138° and heating continued for one hour. The first product layer was then returned to the pot and the combined layers neutralized with 5 g. of sodium carbonate. The layers were then separated, and from the top layer olefin, unreacted epoxide, and excess glycerol were removed lby distillation at 0.9 mm. Distilla- tion of the 691 g. residue in a molecular still gave 488 g. (1.67 moles) of distilled product. ' A compound, 2-hydroxydodecyl 2’-hydroxyethyl ether, was prepared as follows. A solution of 1 ml. stannic chloride in 434 g. (7.0 moles) ethylene glycol was stirred at 135°—150° C. while 129 g. (0.63 11101; 90% purity) 1,2-epoxydodecane were added dropwise over a thirty minute period. The solution was held at about 140° C. for an additional hour after which a solution of 8 g. sodium carbonate in 32 g. water was added to neutralize the catalyst. The reaction product therefrom was stripped of excess ethylene glycol (up to 109° C. at 16 mm.). The crude product remaining was filtered and distilled sub- sequently at reduced pressure. These two compounds and one prior art compound were tested for detergency by means of a Terg-O-Tometer Detergency Test. This test gives an empirical measure- ment of the amount of soil removed from fabric under simulated washing conditions. Stated sizes of cotton cloth, soiled in a standard manner with a standard soil, i.e., vacuum cleaner dust, are placed in a miniature washing machine, and they are laundered in the presence of a measured amount of detergent and water of a standard hardness. A Terg-O-Tometer apparatus is described in the Journal of the American Oil Chemists’ Society, vol. 27, pages 153—159, May 1950. After rinsing and drying, the reflectance of the cloths is measured and compared with the reflectance of the soiled cloths before washing. In the detergency tests referred to herein, the Terg-O- Tometer apparatus was maintained in a water bath ad- justed to maintain the temperature of the washing solu- tion at 120° F.:2° F. The paddle oscillation was brought to ninety complete cycles per minute, and the paddle os- cillated through a 320° arc. With agitators in position on the machine, the detergent was added in the desired amount to the washpot of the machine. Subsequently, 1250 ml. of water, having a hard- ness of 180 parts per million as CaCO3 (60 parts magne- sium and 120 parts calcium calculated as calcium carbo- nate), were added. The machine was started and the solu- tion agitated until the detergent was dissolved. Four pieces of soiled cloth heretofore described approximately 4V2 inches x 6 inches were then added and washing was con- tinued for twenty minutes, after which the test swatches were removed from the solution and hand-squeezed. The washpot was refilled with clear rinse water of the same hardness used for washing .at a temperature of 120° F., 1:2" F., and, with the agitators running, the cloths were rinsed for five minutes. The cloths were then removed, hand-squeezed and ironed dry. The detergency units were determined by recording the differences in reflectance readings for washed and unwashed soiled cloths. Table 1 indicates the results of the Terg-O-Tometer tests. 3,427,248 5 TABLE 1 _ Compound:1 Detergency units - 2-hydroxy-Cu-—C15 alkyl glyceryl ether ________ 8.5 2-hydroxydodecy1 2’-hydroxyethyl ether ______ 8.2 ' Sodium mixed C12—015 alkylbenzene sulfo- nate2 _________________________________ 6.9 10.025% compound and 0.05% tetrapotassium pyrophos— phate (TKPP). 3 Derived from tetra— and penta-propylene. This example shows that the compounds of this inven- tion in built formulations have superior detergency as compared with a prior art compound used in household detergent formulations. EXAMPLE II A compound, 2-hydroxydodecyl alkyl glyceryl ether, was prepared by adding 160 g. (0.87 mol) 1,2-epoxy- dodecane dropwise over 50 minutes with stirring at 125° C. to 400 grams (4.35 moles) glycerol (synthetic grade, min. 99.5%) containing 1.7 g. stannic chloride. Shortly after addition had started, the solution became cloudy and two phases developed subsequently. The solution was stirred two additional hours. The catalyst was then neu- tralized by the addition of 4 g. sodium bicarbonate in 200 ml. water and the product was taken up in water and ether. The ether layer was washed and dried, and the solvent was removed therefrom followed by vacuum dis- tillation. The dishwashing properties of this compound and the compound, 2-hydroxydodecyl 2’-hydroxyethyl ether of Example I, were compared with three prior art com- pounds by determining the number of plates washed with 1.5 g. of each compound in 6 quarts of 120 p.p.m. water at 116° F. The results are shown in Table 2. TABLE 2 Number of Compound: plates washed 2-hydroxydodecyl glyceryl ether ______________ 31 2-hydroxydodecyl 2'-hydroxyethyl ether _______ 28 Dodecylphenol-IO ethylene oxide 1 ___________ 5 Sodium dodecylbenzene sulfonate2 __________ 17 Sodium lauryl sulfate ______________________ 5 1Dodecyl chain is derived from propylene tetramer; ethyl- ene oxide chain averages 10 units in length; 012H26¢0 (CH2CH20)10H 9 Dodecyl chain is derived from propylene tetramer. 5 10 20 25 30 35 40 45 6 TABLE 3 Number of Compound: plates washed 2-hydroxydecyl 2’-hydroxyethyl ether ________ 25 2-hydroxydodecyl 2’-hydroxyethyl ether _______ 33 This example demonstrates that compounds of the in- vention have excellent dishwashing properties. EXAMPLE IV The dishwashing properties of the ethylene glycol ether of Example I with (Formulation A) and without (Formu- lation B) a booster were measured by determining the number of dishes washed with 6 g. of each formulation in 6 quarts of 120 p.p.m. water at 116° F. Table 4 has the results. TABLE 4 Formulation Ingredients (parts by wt.) A B 2-hydroxydodecyl 2’-hydroxyethyl ether ........ 30 30 Coconut monoethanolamide ................................ 8 Number of Dishes Washed ...................... 32 41 From this example, it is manifest that compounds with- in the scope of the invention have excellent dishwashing properties alone or in combination with a booster. EXAMPLE V The compound, oc-decyl-u'-hydroxyethyl glyceryl di- ether, was prepared by the addition of 35 g. (0.16 mole) decyl glycidyl ether to 40 g. (0.65 mole) ethylene glycol containing 0.2 m1. of stannic chloride at 125° C. over 0.5 hour. The solution was stirred an additiOnal hour at 135° C. Sodium carbonate was added to destroy the cat- alyst, excess glycol was stripped OE, and the residue was distilled. The ethylene glycol ether of Example I was prepared and a similar ethylene glycol ether was also prepared ex- cept that one of the reactants was 1,2-epoxy-Cn—C15 alkane. These three compounds were tested as suds~boosters for other detergent actives indicated in Table 5. The num- ber of dishes washed for each of the various formulations was determined as described in Example IV. The results are also indicated in Table 5. TABLE 5 '———-————————*__—__—___'___ Formulation (parts by wt.) Ingredients A B C D E F G H I J K L M Ammonium Alfol 1412—31 E0 sulfatel .................... 30 ........ 30 30 ................................ Linear alkylate Sultanate2 .................... 30 . 30 30 ............ Sodium lauryl sulfate 3 _________________ 2-hydroxy 011—15 alkyl 2’-hydroxyethyl eth 2-hydroxydodecyl 2’-hydroxyethyl ether . . - _ ..... - . a-Decyl—a’-hydroxyethyl glyceryl diether ........................ 9 ___- 9 Number of Dishes Washed ............................ 23 8 3 lAnnnonium salt of a sulfated atoms in the hydrocarbon chain. 30 -.-- 30 3532 288 3 42 45 17 10 39 . . reaction product of 3.1 molar proportions of ethylene oxide and 1 mole of a mixture of long chem primary alcohols of which about % has 14 carbon atoms and about )6 has 12 carbon 2Sodium alkylbenzenesulfonate in which the alkyl portion is a linear hydrocarbon chain composed of a mixture of chain lengths of about 11 to about 14 carbon atoms (LAS). 8 Sodium salt of sulfated primary alcohols derived from coconut oil. It is evident from this example that the reaction prod- ucts of 1,2—epoxydodecane have greatly superior dish- washing properties in relation to the standard detergents. EXAMPLE III Two ethylene glycol ethers were formed as described in Example -I with the appropriate 1,2—epoxyalkane re- actant being employed. The dishwashing properties of the two ethers were compared by determining the number of plates washed with 1.8 g. of each ether boosted with 0.49 g. coconut monoethanolamide (CMEA) in 6 quarts of 120 ppm. water at 116° F. The results are shown in Table 3. 65 70 75 It is manifest from the above that the compounds of the present invention are good suds-boosters and have a synergistic efiect. This is shown by the 35 dishes washed with Formulation D whereas 31 total dishes were washed by Formulations A and B, by the 32 dishes washed with Formulation E whereas 26 total dishes were washed by Formulations A and C, by the 42 dishes washed with Formulation I whereas 36 total dishes were washed by Formulations F and G, by the 45 dishes washed with Formulation J whereas 31 total dishes were washed by Formulations F and H and by the 39 dishes washed with Formulation M whereas 27 total dishes were washed by Formulations K and L. Duplicate controls, which were 3,427,248 7 a commercial liquid dishwashing detergent, were run, and 33 and 36 dishes were washed with the two controls. EXAMPLE VI The procedure of Example V was repeated with the formulations shown in Table 6. 5 The results in Table 6 demonstrate that compounds within the purview of the invention are good dishwashing detergents by themselves and are good suds-boosters for other detergent actives. Three runs were made with a com- mercial liquid dishwashing detergent as a control, and 35, 35 and 38 dishes were washed. 10 TABLE 6 8 propriate 1,2-epoxyalkane reactant was used and the ap- propriate glycol or glycerol reactant was used. The lime-soap scum dispersion test consists of agitating 35 cc. of a 1% (soap plus agent) solution at 45° C. in a Wari...
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