Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
  • C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
  • C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
• • 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
  • C11D1/75—Amino oxides

Definitions

• This invention relates to novel tertiary amine oxide detergents and detergent compositions containing them.
• Thermal stability is a highly desirable property which is lacking in many detergents. Such stability is particularly desirable when detergents are subjected to heat during use or processing, as for example, in spray drying granular detergent compositions.
• Another advantageous property for an organic detergent is a low degree of hygroscopicity which results in improved crystallinity.
• detergent surfactants which are hygroscopic are used in bar or granular forms, desirable physical properties are impaired. Bars become soft and slimy and granules tend to cake and lose their free flowing and quick dissolving characteristics.
• trialkylamine oxide have been found to be excellent detergent compounds but are so hygroscopic that they can be effectively used only in liquid detergent compositions.
• the amine oxides of this invention are:
• R is a Z-hydroxyalkyl, 3-hydroxyalkyl or 3alkoxy-2-hydroxypropyl radical in which the alkyl and alkoxy, respectively, range from to 18 carbon atoms in chain length, R; and R are each methyl, ethyl, propyl or isopropyl.
• the class of compounds described above will hereinafter be referred to more simaS R1R2R3N9O.
• Examples of the compounds of this invention are dimethyl 2 hydroxydodecylamine oxide, diethyl-3-hydroxydodecylamine oxide, dimethyl-Z-hydroxytetradecylice amine oxide, dipropyl 3 hydroxyhexadecylamine oxide, propylmethyl 2 hydroxyoctadecylamine oxide, diethyl- 2-hydroxyhexadecylamine oxide, diethyl-Z-hydroxytetradecylamine oxide, diisopropyl 2 hydroxydodecylamine oxide, N,N dimethyl-3-dodecoxy-Z-hydroxypropylamine oxide, N,N diethyl-3-tetradecoxy-2-hydroxypropylamine oxide and methylethyl-3-hydroxydodecylamine oxide.
• Tertiary amine oxides as a broad class of compounds are known. It was surprising to find, however, that the particular trialkylamine oxides containing particularlyplaced hydroxy groups as described above (i.e., a hydroxy group in the 2 or 3 position in R have such highly desirable properties for use as organic detergents, i.e., improved mildness, hygroscopicity and thermal stability characteristics.
• R R and R must be as described above. If the alkyl or alkoxy in R is longer in chain length than 18 carbon atoms or shorter in chain length than 10 carbon atoms, desired detergency is not obtained. Likewise, if R and R contain more than 3 carbon atoms, desired detergency characteristics are not obtained.
• the long chain R radical must contain a hydroxy group in the 2 or 3 position (i.e., the second or third carbon atom from the nitrogen) in order to achieve improved mildness, hygroscopicity and thermo-stability characteristics in accordance with this invention. When the hydroxy group in the R radical is in the l or alpha position, the resultant amine oxide compound has undesirable instability.
• the 3-alkoxy-2-hydroxypropyl R radical has the following general formula:
• R ranges from 10 to 18 carbon atoms in chain length.
• the 2-hydroxyalkyl, 3-hydroxyalkyl and the 3-alkoxy- 2-hydroxypropyl compounds have about the same reduced hygroscopicity characteristics as compared to the corresponding compound containing unsubstituted R alkyl group.
• the 3-hydroxyalkyl compound has about the same water solubility as the corresponding compound containing an unsubstituted R alkyl group whereas the water solubility of the 2-hydroxyalkyl compound is somewhat less than the solubility of the corresponding compound containing an unsubstituted R group.
• R can be derived from naturally occurring fats and oils or from synthetic sources such as olefins. Mixtures of amine oxides are very suitable wherein the alkyl or alkoxy in R varies in chain length in the C to C range, as for example, the alkyl or alkoxy groups derived from coconut fatty alcohol (or distilled coconut fatty alcohol). Those amine oxides in which the alkyl or alkoxy in R ranges from 12 to 14 carbon atoms are preferred.
• the tertiary amine oxides of this invention can be prepared, in general, by oxidizing the corresponding tertiary amine. See, for example, British Patent 437,566.
• the corresponding tertiary amine in general, can be prepared by alkylating, with an appropriate long chain alkyl compound, the appropriate secondary amine. If necessary, the long chain alkyl compound can be such (e.g., ketoalkane) that treatment (e.g., reduction) of the tertiary amine, prior to oxidation, will result in hydroxy substitution at the desired location in the R group.
• treatment e.g., reduction
• alkyl glycidyl ethers a source of the 3-alkoxy-2-hyroxypropyl 3 R is described in Canadian Patent 582,404, issued September 1, 1959 and U.S. Patent 2,989,547, issued June 20, 1961.
• Compounds of this invention are useful per se as detergents and surface active agents. Desirably they are used with other materials to form detergent compositions, particularly solid form compositions as for example, bar, flake, granular or tableted granular compositions.
• the tertiary amine oxides of this invention can also be used to make liquid detergent compositions.
• Such detergent compositions can contain from about 5% to about 80% of the tertiary amine oxides of this invention and from 95% to about 20% of anionic organic detergents, nonionic organic detergents, water-soluble inorganic alkaline builder salts, water-soluble organic alkaline sequestrant builder salts or mixtures thereof.
• Granular or flake detergents preferably contain about 5% to about 50% of the amine oxides of this invention and from about 95% to about 50% normally solid, water-soluble inorganic alkaline builder salts, or watersoluble organic alkaline sequestrant builder salts.
• Bar formulations contain about 5% to about 50% of the amine oxides of this invention when used with anionic detergents, such as a soap base, and, if desired, alkaline inorganic or organic builders or inert fillers.
• Bar formulations can contain about 40% to about 80% of the amine oxides of this invention as the only detergent component, if desired, and the balance inert fillers or builders.
• Anionic organic detergents used alone or in admixture include both the soap and non-soap detergents.
• suitable soaps are the sodium, potassium, ammonium and alkylol-ammonium salts of higher fatty acids (C C
• Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
• anionic organic non-soap detergents are: alkyl glyceryl ether sulfonates; alkyl sulfates; alkyl monoglyceride sulfates or sulfonates; alkyl polyethenoxy ether sulfates; acyl sarcosinates; acyl esters of isethionates; acyl N-methyl taurides; alkyl-benezenesulfonates; alkyl phenol polyethenoxy sulfonates.
• the alkyl and the acyl groups respectively, contain 10 to 20 carbon atoms.
• water-soluble salts the sodium, potassium, ammonium and alkylolammonium salts, for example.
• Specific examples are: sodium lauryl sulfate; potassium N- methyl lauroyl tauride; triethanolammonium dodecylbenzenesulfonate.
• nonionic organic detergents are: polyethylene oxide condensates of alkyl phenols wherein the alkyl group contains from 6 to 12 carbon atoms (e.g., 5- octylphenol) and the ethylene oxide is present in a molar ratio of ethylene oxide to alkyl phenol in the range of 10:1 to 25:1; condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine wherein the molecular weight of the condensation products ranges from 5,000 to 11,000; the condensation product of from about 5 to 30 moles of ethylene oxide with one mole of a straight or branched chain aliphatic alcohol containing from 8 to 18 carbon atoms (e. g., lauryl alcohol).
• Water-soluble inorganic alkaline builder salts used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. (Ammonium or substituted ammonium salts can also be used.) Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, sodium tetraborate, sodium pyrophosphate, sodium bicarbonate, potassium tripolyphosphate, potassium pyrophosphate, sodium heXametaphosphate, sodium sesquicarbonate, sodium monoand diortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the detergency of the subject amine oxides, 4
• water-soluble organic alkaline sequestrant builder salts used alone or in admixture are alkali metal, ammonium or substituted ammonium amino polycarboxylates, e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)- ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium, and triethanolammonium N-(Z-hydroxyethyl)nitrilodiacetates.
• alkali metal, ammonium or substituted ammonium amino polycarboxylates e.g., sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2-hydroxyethyl)- ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium, and triethanolammonium N-(Z-hydroxyethyl)nitrilodiacetates.
• organic alkaline sequestrant builder salts which can be used are: Hydroxyethylethylenediaminetriacetates; 2 hydroxyethyliminodiacetates; diethylenetriamine pentaacetates; 1,2- diaminocyclohexanetetraacetates.
• the alkali metal salts of phytic acid, e.g., sodium phytate are also suitable as alkaline organic sequestrant builder salts (see U.S. Patent 2,739,942).
• Preferred detergent compositions contain about 10% to about 30% of the tertiary amine oxides of the invention and at least an equal amount of sodium tripolyphosphate.
• the amine oxides wherein the alkyl or alkoxy in R contains 12 to 14 carbon atoms are used in such preferred compositions.
• Particularly desirable is dimethyl-2- hydroxydodecylamine oxide which has good sudsing characteristics, being superior in this respect to dimethyldodecylamine oxide. It also is an effective suds enhancing (building) agent for anionic non-soap detergent compounds.
• the detergent compositions of this invention can contain any of the usual adjuvants, diluents or additives, for example, ampholytic or zwitterionic detergents, cationic detergents, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, oxygen or chlorine bleaches, suds builders, suds depressors and the like.
• adjuvants for example, ampholytic or zwitterionic detergents, cationic detergents, perfumes, anti-tarnishing agents, anti-redeposition agents, bacteriostatic agents, dyes, fluorescers, oxygen or chlorine bleaches, suds builders, suds depressors and the like.
• Example I 5 moles of dimethyl amine were liquified under anhydrous conditions using a Dry Ice-acetone condenser. 0.05 mole of anhydrous aluminum chloride was added to the dimethyl amine and a mixture was placed in a cold, glass autoclave liner (3 liter). One mole of C olefin oxide was added to the dimethylamine with mixing and cooling. The liner was placed in a cooled autoclave. After sealing the autoclave, the mixture was heated at 200 C. for three hours. The autogeuic pressure was 300 to 400 p.s.i.g.
• a mixture of dimethyl-2-hydroxyhexadecyl amine oxide and dimethyl-Z-hydroxyoctadecyl amine oxide was obtained from the above process using instead of the C olefin oxide a 60-40 mixture of C olefin oxide.
• the corresponding diethyl and dipropyl compounds can be obtained by using molar equivalent amounts of diethylamine or dipropylamine in the process of Example I.
• dimethyl-2-hydroxydodecyl amine oxide 20 parts are combined with 50 parts of sodium tripolyphosphate and 30 parts of sodium sulfate to form a solid form detergent composition which cleans well in a laundering operation and suds well in a dishwashing operation.
• the dishpan sudsing of dimethyl-Z-hydroxydodecyl amine oxide in such a composition is superior to that of sodium dodecylbenzene sulfonate in a like composition.
• Example II 170 grams of 2-undecanone, 22.5 grams of paraformaldehyde, 40.8 grams of dimethyl amine hydrochloride were mixed with 500 ml. of ethanol and stirred for 24 hours at 78 C. The reaction mixture was acidified and extracted with ethyl ether to remove the unreacted 2- undecanone. The mixture was then made alkaline and extracted again with ethyl ether to obtain 81 grams of 3-ketododecyl dimethyl amine.
• the resulting dimethyl-3-hydroxydodecyl amine oxide was tested for hygroscopicity, being compared with the Z-hydroxydodecyldimethyl amine oxide of Example I and with an unsubstituted dimethyldodecyl amine oxide.
• the hygroscopicity was determined by exposing dry recrystallized material in a constant 50% relative humidity chamber at 70 F.
• the 3-hydroxydodecyl and the 2-hydroxydodecyl compounds are markedly less hygroscopic than the unsubstituted dodecyl compound.
• the thermal stability of the compounds of this invention are indicated by decomposition temperatures of the 3-hydroxydodecyl and the 2-hydroxydodecyl compounds of 145 C. and 130 C. respectively as compared to C. decomposition temperature of unsubstituted dimethyldodecyl amine oxide.
• the dimethyl 3-hydroxydodecyl amine oxide and the dimethyl-Z-hydroxydodecyl amine oxide were tested for detergency properties. These amine oxides were substantially equivalent in detergency to sodium dodecylbenzenesulfonate.
• the determination was made by washing naturally soiled cloth (desized print cloth) swatches in an 0.1% aqueous solution of a mixture of 20% of an organic detergent compound (amine oxide being tested or alkylbenzenesulfonate standard) 50% sodium tripolyphosphate and 30% sodium sulfate.
• the composition had a pH of 10 and the Washing was done at F. for 10 minutes using wash water of 7 grains per gallon hardness.
• the detergency effectiveness was determined by measuring the percentage of lipid soil remaining on a standard size swatch (on a dry basis) after the washing operation. The percentage of lipid soil remaining after washing with the amine oxide test composition was compared with the percentage after washing with the alkyl'benzenesulfonate standard composition. On the basis of the percent residual lipid soil, the lower the percent, the better the detergency performance. A Ter-gotometer was used for the washing Operation. (Tergotometer testing is described in Detergency Evaluation and Testing by J. C. Harris, Interscience Publishers, Inc. (1954), page 60.)
• Diethyl-2-hydroxytetradecylamine oxide, diisopropyl-3- hydroxyphexadecylamine oxide and dimethyl-2-hydroxyalkylamine oxide wherein the alkyl is derived from coconut fatty alcohol can be made by processes similar to those described in Examples I and II. These compounds will have substantially equivalent thermal stability and hygroscopicity characteristics and the detergency efiicacy will be slightly less than that of the hydroxydodecyl compounds.
• Example III 1,818 grams of dodecyl glycidyl ether was charged into a two liter autoclave. Air was purged from the head space with dimethyl amine. The autoclave was then heated to 390 F. A pressure of 450 p.s.i. was obtained in the autoclave by charging dimethyl amine into the autoclave using nitrogen pressure. A dimethyl amine bleed valve was adjusted during the reaction of the ether with the dimethyl amine to keep a constant pressure and temperature. After one hour, the autoclave was cooled. The resultant N,N-dimethyl-3-dodecoxy-2-hydroxypropylamine contained about 25% dissolved dimethylamine which was stripped off at 175 F. at mm. Hg pressure. The amination reaction is represented by the following equation:
• N,N dimethyl 3 dodecoxy-Z-hydroxypropylamine oxide absorbed only 0.3% water after one week of storage in an open vessel at room temperature and conditions. Only 22% water was absorbed upon extreme storage conditions of 90 F. and 80% relative humidity for 7 days. This amine oxide exhibited excellent detergency and sudsing characteristics and has excellent thermal stability.
• N,N diethyl 3 tetradecoxy-2-hydroxypropylamine oxide and N,N-dimethyl-3-hexadecoxy-Z-hydroxypropylamine oxide can be prepared by processes similar to that 25 described in Example II. These compounds have improved characteristics similar to those of the dodecyl compound.
• tertiary amine oxides of this invention can be used in effective detergent compositions having improved hygroscopicity and thermal stability characteristics. They have the following formulas:
• Granular detergent Percent Dimethyl-2-hydroxydodecyl amine oxide 17.5 Sodium sulfate 23 Sodium tripolyphosphate 50 Sodium silicate 6 Water 3.5
• Diethyl-3-hydroxytetradecylamine oxide Ma ma 10 Sodium coconut oil soap 15 Sodium tallow soap 60 8 Milled toilet bar: Percent Triethanolammonium ethylenediaminetetraace-
• dimethyldodecylamine oxide and dimethyl-2-hydroxy-dodecylamine oxide were tested in accordance with the guinea pig immersion test. This test consists of immersing guinea pigs having shaved undersides up to their thorax in a 02% solution of the material being tested at 37 C. for a 4 /2 hour period per day for three consecutive days.
• the animals are graded three days after the last immersion.
• the grades are the average of the results on not less than three animals.
• a 1 to 10 scale is used to rate the effects of the prolonged exposure of the test solution on the :animals skin.
• Grade 10 represents ideal or perfect skin (soft, smooth and flexible) and the effect of a theoretically perfectly mild detergent compound; grade 1 represents severely irritated skin. Other values represent graduations of severity between these extremes.
• Grade 1 in the guinea pig immersion test indicates severely thickened, dry, cracked and bleeding skin, i.e., extreme irritation. (Grade 1 in exaggerated tests on human subjects would indicate severe redness and dryness of the skin.
• Tertiary amine oxides having the formula wherein R is 3-alkoxy-2-hydroxypropyl, in which the alkoxy ranges in chain length from 10 to 18 carbon atoms, and R and R are each selected from the group consisting of methyl, ethyl, propyl and isopropyl.
• N,N-dirnethyl-3-alkoxy-2-hydroxypropyl amine oxide wherein the alkoxy ranges in chain length from 10 to 18 carbon atoms.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Detergent Compositions (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=22561922

Family Applications (1)

Country Status (9)

Cited By (3)

Families Citing this family (1)

Citations (6)

• 1961
  • 1961-12-04 US US156993A patent/US3441611A/en not_active Expired - Lifetime
• 1962
  • 1962-11-26 BE BE625275D patent/BE625275A/xx unknown
  • 1962-11-28 FI FI2145/62A patent/FI41053B/fi active
  • 1962-11-30 FR FR917240A patent/FR1343937A/fr not_active Expired
  • 1962-12-01 DE DE1518087*CA patent/DE1518087C3/de not_active Expired
  • 1962-12-03 NL NL286243D patent/NL286243A/xx unknown
  • 1962-12-04 GB GB45798/62A patent/GB1007342A/en not_active Expired
• 1964
  • 1964-10-05 SE SE11966/64A patent/SE309820B/xx unknown
  • 1964-12-01 DK DK590464AA patent/DK116746B/da unknown

Patent Citations (6)

Also Published As

Similar Documents