BRANCHED TRIALKYLAMINE PRECURSORS, INTERMEDIATES, PRODUCTS MADE THEREFROM AND PROCESSES OF MANUFACTURE

- Eastman Chemical Company

The invention provides branched hydrophobes for the production of surfactants with improved properties over linear hydrophobes. The invention also provides branched C10-12 enals and aldehydes that are oxidized to branched fatty acids or hydrogenated to branched fatty alcohols and further derivatized to surfactants, through ethoxylation or esterification and other or subsequent reactions. The invention further provides surfactants made from the branched trialkylamine intermediates, including amphoteric, cationic and nonionic surfactants.

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Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. 119(e) to U.S. Provisional Application Ser. No. 62/616,502 filed Jan. 12, 2018, which is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The invention generally relates to the field of organic chemistry. It particularly relates to branched trialkylamines, products made therefrom, and related methods of manufacturing. It further relates to surfactants made from branched trialkylamines and end-uses therefor.

BACKGROUND OF THE INVENTION

There is a commercial need for novel surfactants with desirable properties such as low foaming, effective oily soil removal, performance in cold water, compatibility with other ingredients in a cleaning formula, mildness to skin, and a favorable environmental and safety profile.

A common trialkylamine hydrophobe used to make surfactants is dimethyl alkyl amine, made from C12 and C14 fatty alcohols reacted with dimethylamine, sometimes referred to as dimethyl laurylamine, or DIMLA. Neither DIMLA, its trialkylamine intermediate or the surfactants made from it contain branching.

Certain petrochemical detergent alcohols can also be used as surfactant hydrophobes. The most common synthetic detergent alcohols are produced by ethylene oligomerization, for instance, according to the Shell Higher Olefin Process (SHOP) process or the Ziegler alcohol process. Olefins can also be obtained from a Fischer-Tropsch process out of synthesis gas. The processing of producing detergent alcohols adds considerably to energy and facilities usage and consequently to product cost. Also, the resulting hydrophobes are typically over 85% linear.

Certain mixtures of C14 branched hydrophobes have also been described with some of the hydrophobe mixture containing a single branch point. When mixtures of hydrophobes are used to make surfactants, the individual hydrophobes in the mixture are not known to perform as well as the mixtures.

There remains a need in the industry for novel compositions which can be used to produce novel surfactants with desirable properties, for example, low foaming, mildness to skin, effective oily soil and/or stain removal (especially in cold water), high solubility in water, no gelling, ease of formulation, compatibilization or stabilization of other ingredients in a formula, retention of good hydrophobicity compared to linear hydrophobes, tolerance of extreme pH, and/or a favorable environmental and/or safety profile. There also remains a need in the industry for effective reactants and processes to make branched surfactants and corresponding surfactant intermediates with fewer reaction byproducts, fewer reaction steps, and/or reduced reaction solvent(s).

SUMMARY OF THE INVENTION

In view of the above commercial shortcomings in the art, the present disclosure addresses the need for novel compositions, e.g., surfactants, with one or more of the following desirable properties: (1) low foaming, such as according to ASTM E2407, (2) mildness to skin, such as predicted by a zein solubilization test or patch test, (3) effective oily soil and/or stain removal, especially in cold water, such as according to ASTM 4265, (4) compatibility with other ingredients in a cleaning formula, and (5) a favorable environmental profile, (6) high solubility in water; (7) no gelling, (8) ease of formulation, and (9) compatibilization or stabilization of other ingredients in a formula, (10) retains good hydrophobicity compared to linear hydrophobes, (11) tolerance of extreme pH, (12) antimicrobial activity, (13) biodegradability, such as according to OECD 301B and/or (14) an improved safety profile. The compositions of this invention can provide desirable properties for a variety of applications.

The invention is as set forth in the Field of the Invention, the Summary of the Invention, the Description, the Examples, the appended Claims, and the Abstract.

For the ease of reference but not intending to be limiting in any way, certain aspects of this disclosure are numbered consecutively, as follows:

In aspect 1, the invention provides a trialkylamine having the formula:

wherein R1 and R2 are each independently selected from straight or branched chain or cyclic hydrocarbon radicals having 1 to 8 carbon atoms;
wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or combinations thereof; and
wherein R5 and R6 are not H at the same time.

In aspect 2, the invention provides the trialkylamine of aspect 1 wherein (a) R1 and R2 are each independently substituted with groups selected from: —OR3; carboxyl; —NHCOR4; —CONHR4; cyano; —CO2R3; —OCOR3; hydroxy; aryl; heteroaryl; chlorine; or a combination thereof, (b) R3 is selected from C1-C6 alkyl, substituted C1-C6 alkyl or combinations thereof and (c) R4 is selected from C1-C4 alkyl or substituted C1-C15 alkyl.

In aspect 3, the invention provides the trialkylamine of aspects 1 or 2 selected from the group consisting of alkyl dimethyl amines or N,N-dimethylalkylamines.

In aspect 4, the invention provides the trialkylamine of any one of aspects 1-3 wherein R1 can be CH3 or C2H5 and/or R2 can be CH3 or C2H5.

In aspect 5, the invention provides the trialkylamine of aspect 4 wherein R1 is CH3.

In aspect 6, the invention provides the trialkylamine of aspects 4 or 5 wherein R2 is CH3.

In aspect 7, the invention provides the trialkylamine of aspects 4 or 6 wherein R1 can be C2H5.

In aspect 8, the invention provides the trialkylamine of aspects 4, 5, or 7 wherein R2 can be C2H5.

In aspect 9, the invention provides the trialkylamine of any one of aspects 1-4 wherein R1 is CH3 or C2H5 and R2 is a carbohydrate or amino acid.

In aspect 10, the invention provides the trialkylamine of any one of aspects 1-9 wherein R5 and R6 can be one of C3H7, C2H5, CH3, or combinations thereof; and wherein R7 is one of C3H7, C2H5, CH3, H or combinations thereof.

In aspect 11, the invention provides the trialkylamine of aspect 10 wherein R5 is CH3 or C2H5 and/or R6 is CH3 or C2H5.

In aspect 12 the invention provides the trialkylamine of aspects 10 or 11 wherein R5 is CH3.

In aspect 13, the invention provides the trialkylamine of aspects 10-12 wherein R6 is CH3.

In aspect 14, the invention provides the trialkylamine of aspects 11 or 13 wherein R5 can be C2H5.

In aspect 15, the invention provides the trialkylamine of aspects 11, 12, or 14 wherein R6 can be C2H5.

In aspect 16, the invention provides the trialkylamine of any one of aspects 1-2 wherein R1 is CH3 or C2H5 and R2 is a carbohydrate or amino acid.

In aspect 17, the invention provides the trialkylamine of any one of aspects 1-16 having one to three branch points.

In aspect 18, the invention provides the trialkylamine of any one of aspects 1-17 having one to three branch points any of which can be at the R5 and/or R6 positions.

In aspect 19, the invention provides the trialkylamine of any one of aspects 1-18 having two branch points which are at the R5 and R6 positions.

In aspect 20, the invention provides the trialkylamine of any one of aspects 1-19 wherein the number of carbon atoms for the alkyl substituent at the R5 position can be from 1 to 3.

In aspect 21, the invention provides the trialkylamine of any one of aspects 1-20 wherein the number of carbon atoms for the alkyl substituent at the R6 position can be from 1 to 3.

In aspect 22, the invention provides the trialkylamine of any one of aspects 1-21 wherein the number of carbon atoms for the alkyl substituent at the R5 position can be from 1 to 2.

In aspect 23, the invention provides the trialkylamine of any one of aspects 1-22 wherein the number of carbon atoms for the alkyl substituent at the R6 position can be from 1 to 2.

In aspect 24, the invention provides at least one trialkylamine selected from 4-ethyl-N,N,2-trimethyloctan-1-amine, 4-ethyl, 2-methyl, N,N-dimethylhexan-1-amine, or 2,4-diethyl, N,N-dimethyloctan-1-amine.

In aspect 25, the invention provides a composition comprising at least one trialkylamine selected from any one of aspects 1-24 but which does not contain any isomeric compound or mixtures, wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compound(s) can be selected from those of structures:

having from 10 to 18 carbon atoms in the R(R′)CHCH2-moiety in which R has 5 to 9 carbon atoms, and R′ has from 3 to 7 carbon atoms, with most of the compounds having additional methyl or ethyl branches, and in which R′ and R′″ are alkyl or hydroxyalkyl groups or hydrogen and X— is an anion.

In aspect 26, the invention provides a composition comprising at least one trialkylamine which does not contain any isomeric compound or mixture of isomers of aspect 25, wherein said mixtures contain a number of isomeric compounds, wherein said isomeric compound(s) can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 10 to 18 carbon atoms and an alkyl branch at the 2-position containing 3 to 7 carbon atoms, and additional branching in most of the isomers, with most of the additional branches being methyl groups.

In aspect 27, the invention provides a composition comprising at least one trialkylamine which does not contain any isomers or mixtures of isomers of aspect 25, wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compounds can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 12 carbon atoms and an alkyl branch at the 2-position containing 5 carbon atoms or greater, whether or not with additional branching in most of the isomers, whether or not with most of the additional branches are methyl groups and/or ethyl groups.

In aspect 28, the invention provides a composition comprising at least one trialkylamine selected from any one of aspects 1-24 but which does not contain any trialkylamine or mixtures of trialkylamines other than those described herein as being within the aspects of this Summary of the Invention or as otherwise described within the scope of this invention.

In aspect 29, the invention provides a carboxybetaine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 are not H at the same time.

In aspect 30, the invention provides the carboxybetaine of aspect 29 wherein R5 and R6 are C3H7, C2H5, CH3, or combinations thereof; and wherein R7 is one of C3H7, C2H5, CH3, H or combinations thereof.

In aspect 31, the invention provides the carboxybetaine of aspect 30 wherein R5 is CH3 or C2H5 and/or R6 is CH3 or C2H5.

In aspect 32 the invention provides a carboxybetaine of aspects 30 or 31 wherein R5 is CH3.

In aspect 33, the invention provides a carboxybetaine of any one of aspects 30-32 wherein R6 is CH3.

In aspect 34, the invention provides the carboxybetaine of any one of aspects 30, 31 or 33 wherein R5 can be C2H5.

In aspect 35, the invention provides the carboxybetaine of any one of aspects 30-32, or 34 wherein R6 can be C2H5.

In aspect 36, the invention also provides a carboxybetaine having the formula:

In aspect 37, the invention provides a carboxybetaine of aspect 36 comprising 2-(2,4-diethyloctyl)dimethylammonio)acetate.

In aspect 38, the invention provides a hydroxysultaine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 cannot both be H.

In aspect 39, the invention provides at least one hydroxysultaine of aspect 38 wherein R5 is CH3.

In aspect 40, the invention provides at least one hydroxysultaine of aspect 39 wherein R5 is CH3 and R6 is C2H5.

In aspect 41, the invention provides at least one hydroxysultaine of aspects 38 or 39 wherein R6 is C2H5.

In aspect 42, the invention provides at least one hydroxysultaine of aspect 38 wherein R5 and R6 each independently are C2H5.

In aspect 43, the invention provides at least one hydroxysultaine having the formula:

In aspect 44, the invention provides at least one hydroxysultaine of aspect 43 comprising 3-(4-ethyl-2-methyloctyl)dimethylammonio)-2-hydroxypropane-1-sulfonate.

In aspect 45, the invention provides at least one surfactant comprising at least one carboxybetaine of aspects 29-37.

In aspect 46, the invention provides at least one surfactant comprising at least one hydroxysultaine of aspects 38-44.

In aspect 47, the invention provides surfactant(s) comprising or one or more hydroxysultaines of aspects 38-44 and one or more carboxybetaines of aspects 29-37.

In aspect 48, the invention provides a composition comprising one or more carboxybetaines of aspects 29-37.

In aspect 49, the invention provides a composition comprising or one or more hydroxysultaines of aspects 38-44.

In aspect 50, the invention provides a composition comprising or one or more hydroxysultaines of aspects 38-44 and one or more carboxybetaines of aspects 29-37.

In aspect 51, the invention provides a composition which does not contain carboxybetaines made from the mixtures of trialkylamines of any one of aspects 25-27.

In aspect 52, the invention provides a composition which does not contain hydroxysultaines made from the mixtures of trialkylamines of any one of aspects 25-27.

In aspect 53, the invention provides a composition of aspect 48 which does not contain carboxybetaines other than the carboxybetaines of this invention.

In aspect 54, the invention provides a composition of aspect 49 which does not contain hydroxysultaines other than the hydroxysultaines of this invention.

In aspect 55, this invention provides at least one product comprising any one of the following: dish detergent, car wash detergent, shampoo, face wash, body wash; fabric stain remover or fabric cleaner comprising the carboxybetaine of aspects 29-37 or the compositions or surfactants of aspects 45-54, respectively, or combinations thereof.

In aspect 56, this invention at least one product comprising any one of the following: (1) at least one carboxybetaine of aspects 29-37, (2) at least one hydroxysultaine of aspects 38-44, (3) the compositions or surfactants of aspects 45-54, respectively, or (4) any combinations of (1)-(3) of this aspect.

In aspect 57, this invention provides a process for making the alkyl betaines of any one of aspects 29-37 comprising reacting branched C10-12 N,N-dimethylalkylamines with monohalocarboxylic acid or a salt thereof, at least one alkali metal hydroxide or carbonate, and a C1-C4 alcohol and water wherein the amount of the C1-C4 alcohol is greater than that of water, wherein said reaction can occur at a temperature range of from 60° C. to 95° C. or from 70° C. to 85° C.

In aspect 58, this invention provides a process for making the alkyl hydroxysultaines of any one of aspects 38-44 comprising reacting branched C10-12 N,N-dimethylalkylamines with sodium 1-chloro-2-hydroxypropane sulfonate, at least one alkali metal hydroxide or carbonate, a C1-C4 alcohol and water; wherein the amount of the C1-C4 alcohol is greater than that of water; and wherein said reaction can occur at a temperature range of 60° C. to 95° C. or 70° C. to 85° C.

In aspect 59, this invention provides a stain remover of aspects 55 or 56 which demonstrates at least two times the weight loss percentage of a fabric compared to pre-treatable stain removers which contain linear carboxyl betaines after beef fat stains on deposited on said fabric are pre-treated with 3 weight %, based on the total weight of the composition, of said stain remover and then washed through a complete washing machine cycle.

In aspect 60, this invention provides a N-alkyl-N-methylglucamine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3, or H, and Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction;
wherein said reducing sugar is glucose, mannose, fructose, sorbose, arabinose, maltose, isomaltose, maltulose, isomaltulose, trehalulose, lactose, glyceraldehyde, galactose, xylose, ribose, cellobiose, xylobiose, or a combination thereof.

In aspect 61, this invention provides at least one N-alkyl-N-methylglucamine of aspect 60 wherein R5, R6, and R7 and/or the branch points are as defined in any one of aspects 1-8, 10-15, or 17-23 for the trialkylamines of the invention but where the word “trialkylamine” are substituted for these aspects with the words “N-alkyl-N-methylglucamine”.

In aspect 62, the invention provides the N-alkyl-N-methylglucamine of aspect 60 wherein R5 and R6 can be C3H7, C2H5, CH3, or combinations thereof.

In aspect 63, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-62 wherein R6 is CH3 or C2H5.

In aspect 64, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-62 wherein each of R5 and R6 independently are C2H5 or wherein each of R5 and R6 independently are CH3.

In aspect 65, the invention provides the N-alkyl-N-methylglucamine of any one of aspects 60-63 wherein R5 is CH3 or C2H5.

In aspect 66, the invention provides the N-alkyl-N-methylglucamine of any one of aspects 60-65 wherein the N-alkyl-N glucamine has one to three branch points.

In aspect 67, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-66 wherein the N-alkyl-N glucamine has one to two branch points which can be at the R5 and/or R6 positions.

In aspect 68, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-67 having two branch points which are at the R5 and R6 positions.

In aspect 69, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-68 wherein the number of carbon atoms for the alkyl substituent at the R5 position can be from 1 to 3.

In aspect 70, the invention provides the N-alkyl-N-methylglucamines of any one of aspects 60-69 wherein the number of carbon atoms for the alkyl substituent at the R6 position can be from 1 to 3.

In aspect 71, this invention provides an N-alkyl-N-methylglucamine having the formula:

In aspect 72, this invention provides an N-alkyl-N-methylglucamine having the formula:

In aspect 73, this invention provides an N-alkyl-N-methylglucamine having the formula:

In aspect 74, this invention provides an N-alkyl-N-methylglucamine having the formula:

wherein Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction; wherein said reducing sugar is glucose, mannose, fructose, sorbose, arabinose, maltose, isomaltose, maltulose, isomaltulose, trehalulose, lactose, sucrose, galactose, xylose, ribose, cellobiose, xylobiose or a combination thereof.

In aspect 75, this invention provides at least one N-alkyl-N glucamine of aspect 60 which is N-(2-ethylhexyl)-N-methylglucamine.

In aspect 76, this invention provides at least one N-alkyl-N glucamine of any one of aspects 60-75 which is a surfactant.

In aspect 77, this invention provides a product comprising N-alkyl-N glucamines of any one of aspects 60-76 selected from coatings, inks, adhesives, agricultural formulations, fountain solutions, photoresist strippers and developers, shampoos, and detergents and cleaning compositions.

In aspect 78, this invention provides a product comprising the N-alkyl-N glucamines of any one of aspects 60-76 selected from personal care products or skin cleansing formulations.

In aspect 79, this invention provides a process for making the N-alkyl-N glucamines of any of aspects 60-75.

In aspect 80, this invention provides processes for making the trialkylamines of the invention, the N-alkyl-N glucamines, and/or the alkyl-N-sarcosines of the invention using the branched enals and aldehydes useful in the invention.

In aspect 81, the invention provides branched enals and aldehydes useful in making the trialkylamines, the N-alkyl-N glucamines, and/or the alkyl-N-sarcosines useful in the invention.

In aspect 82, aldehydes useful in making the trialkylamines, the N-alkyl-N glucamines, and/or the alkyl-N-sarcosines of the present invention can contain aliphatic hydrocarbon chains, branched, saturated or unsaturated, comprising 2 to 30 carbon atoms.

In aspect 83, aldehydes useful in making the trialkylamines, and/or the N-alkyl-N glucamines, and/or the alkyl-N-sarcosines of the present invention, for example, of any one of aspects 1-82 respectively, can be 2-ethylhexanal, 2-propyl-pentanal, 2-propyl-hexanal, 2-propyl-heptanal, 2-propyl-octanal, 2,4-diethyloctanal, 2-ethyl-4-methyl-nonanal, 2-ethyl-4-methyloctanal, or 2-butyl-4-ethyloctanal or combinations thereof.

In aspect 84, examples of enals or aldehydes useful in making any one of the trialkylamines and/or the N-alkyl-N glucamines and/or the alkyl-N-sarcosines of the present invention, for example, of any one of aspects 1-84 respectively, include but are not limited to as follows: Examples of C10 to C12 enals include but are not limited to: 4-ethyl-2-methyloct-2-enal (C11 enal), 2,4-diethyl-2-octenal (C12 enal), 2-propyl-heptenal (C10 enal), or 2-ethyl-4-methyl heptenal (C10 enal); Examples of C10 to C12 aldehydes include but are not limited to: aldehyde-4-ethyl-2-methyloctanal (C11 aldehyde), 2,4-diethyl-2-octanal (C12 aldehyde); 2-propyl-heptanal (C10 aldehyde), and 2-ethyl-4-methyl heptanal (C10 aldehyde).

In aspect 85, the process of aspect 80 wherein the N-alkyl-N glucamines are made by reacting the C10 through C12 branched enals and branched aldehydes useful in the invention with N-methylglucamine.

In aspect 86, the process of aspects 80 or 85 wherein the N-alkyl-N-methylglucamines can be prepared with branched aliphatic aldehydes.

In aspect 87, the invention provides processes for making the amino based surfactants of the invention by reacting the C10 through C12 branched enals and branched aldehydes useful in the invention with N-methyl amino acids; this invention also includes any products made by this process.

In aspect 88, the invention provides processes for making for making the alkyl-N-sarcosines of the invention by reacting the C10 through C12 branched enals and branched aldehydes useful in the invention with N-methylglycine; this invention also includes any products made by this process.

In aspect 89, the process of any one of aspects 80-86 to make the N-alkyl-N glucamines which includes a reductive amination reaction step wherein the catalysts for the reductive amination reaction can be selected from Raney nickel, palladium, rhodium, ruthenium, platinum, or combinations thereof.

In aspect 90, the process of aspect 89 wherein the catalyst is carried upon a heterogeneous support for ease of removal from the reaction medium. Representative supports can include carbon, alumina, silica, or mixtures thereof, and the like.

In aspect 91, the process of any of aspects 79-86 or 89-90 carried out in an aqueous medium or in an organic solvent.

In aspect 92, the process of any of aspects 80-91, wherein the aldehydes can contain aliphatic hydrocarbon chains, branched, saturated or unsaturated, comprising 2 to 30 carbon atoms.

In aspect 93, the process of any of aspects 80-92 wherein the aldehydes are branched C8-C20 aldehydes, for example, 2-ethylhexanal, 2-propyl-pentanal, 2-propyl-hexanal, 2-propyl-heptanal, 2-propyl-octanal, 2,4-diethyloctanal, 2-ethyl-4-methyl-nonanal, 2-ethyl-4-methyloctanal, or 2-butyl-4-ethyloctanal or combinations thereof.

In aspect 94, the process of any of aspects 80-93 wherein the aldehydes can be limited to the C10-C12 aldehydes of the invention.

In aspect 95, the process of any of aspects 79-86, or 89-94 wherein the reductive amination of sugar, for example, glucose, is achieved at a temperature not exceeding 100° C., or 70° C., or 60° C.

In aspect 96 the process of aspects 80-86 or 89-95 of making the wherein the reaction between N-monoalkylglucamine and aldehydes can be carried out at a temperature from 50 and 170° C., or from 75 and 145° C., or from 100 and 120° C.

In aspect 97, in the process of aspects 80-86 or 89-96, the molar ratio of aldehyde to N-monoalkylglucamine can be at least stoichiometric, or in one embodiment, from 1 to 1.5, or in another embodiment, from 1 to 1.2.

In aspect 98, this invention provides at least one trialkylamine oxide made from any one of the trialkylamines of aspects 1-24.

In aspect 99, this invention provides at least one trialkylamine oxide having the formula:

wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or mixtures thereof; and wherein R5 and R6 are not H at the same time.

In aspect 100, this invention provides at least one trialkylamine oxide of aspect 99 having the formula:

wherein R5 and R6 are C3H7, C2H5, CH3, or mixtures thereof; and wherein R7 is one of C3H7, C2H5, CH3, H or combinations thereof.

In aspect 101, this invention provides at least one trialkylamine oxide of any one of aspects 99 or 100 wherein R6 is CH3 or C2H5.

In aspect 102, this invention provides at least one trialkylamine oxide of aspect 101 wherein R5 and R6 independently are C2H5.

In aspect 103, this invention provides at least one trialkylamine oxide of aspect 102 which is 2,4-diethyl-N,N-dimethyloctan-1-amine oxide.

In aspect 104, this invention provides at least one trialkylamine oxide of any one of aspect 99-101 wherein R5 is CH3 or C2H5.

In aspect 105, this invention provides at least one trialkylamine oxide of aspect 104 wherein R5 is CH3 and R6 is C2H5.

In aspect 106, this invention provides at least one trialkylamine oxide of aspect 105 which is 4-ethyl-N,N-2-trimethyloctan-1-amine oxide.

In aspect 107, this invention provides at least one trialkylamine oxide of any one of aspect 98-106 wherein foaming does not persist for more than 5 minutes when tested according to modified ASTM Method E2407, wherein the method modification is to substitute at least one of said amine oxides for sodium lauryl ether sulfate and to use no defoamer.

In aspect 108, this invention provides at least one trialkylamine oxide of any one of aspects 98-107 having a Zein score of less than 1.0 when normalized to linear alcohol ethoxylate (LAE 10) using the Zein Solubilization Test.

In aspect 109, the invention provides at least one trialkylamine oxide of any one of aspects 98-108 having a Zein score of less than 0.50, or less than 0.40, or less than 0.30, or less than 0.20, or less than 0.10, or less than 0.05, or less than 0.02 when normalized to linear alcohol ethoxylate (LAE 10) using the Zein Solubilization Test.

In aspect 110, the invention provides at least one trialkylamine oxide of any one of aspects 98-109 comprising 0.05 weight % of amine oxide in (1500 ml) deionized water which has a Draves wet-out time (WOT) in seconds of greater than 33 seconds according to Draves Wetting Test or ASTM Method D2281-68.

In aspect 111, the invention provides at least one trialkylamine oxide of aspect 110 having a Draves wet-out time (WOT) in seconds of greater than 300 seconds according to Draves Wetting Test or ASTM D2281-68.

In aspect 112, this invention provides a composition comprising at least one trialkylamine oxide of any one of aspects 98-111.

In aspect 113, this invention provides a composition comprising at least one trialkylamine oxide of any one of aspects 98-112 wherein amines oxides other than those of any one of aspects 98-112 are excluded from the composition.

In aspect 114, this invention provides the composition of any one of aspects 112 or 113 comprising at least one nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or combinations thereof.

In aspect 115, this invention provides the composition of any one of aspects 112-114 comprising 0.01% to 30% by weight of the trialkylamine oxide or the mixture of amine oxides, based on the total weight of the composition equaling 100 weight %.

In aspect 116, the invention provides a composition selected from any one of aspects 112-115 wherein the trialkylamine(s) used to make the amine oxide(s) does not contain any isomeric compound or mixtures, wherein said mixtures can contain a number of isomeric compounds, and wherein said isomeric compound(s) can be selected from those of structures:

having from 10 to 18 carbon atoms in the R(R′)CHCH2-moiety in which R has 5 to 9 carbon atoms, and R′ has from 3 to 7 carbon atoms, with most of the compounds having additional methyl or ethyl branches, and in which R′ and R′″ are alkyl or hydroxyalkyl groups or hydrogen and X— is an anion.

In aspect 117, the invention provides a composition of any one of aspects 112-116 wherein the trialkylamine(s) used to make the amine oxide(s) does not contain any isomeric compound or mixture of isomers of aspect 116, wherein said mixtures can contain a number of isomeric compounds, wherein said isomeric compound(s) can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 10 to 18 carbon atoms and an alkyl branch at the 2-position containing 3 to 7 carbon atoms, and additional branching in most of the isomers, with most of the additional branches being methyl groups.

In aspect 118, the invention provides a composition selected from any one of aspects 112-117 wherein the trialkylamine(s) used to make the trialkylamine oxide(s) of the invention do not contain any isomers or mixtures of isomers of any one of aspects 116 or 117 wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compounds can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 12 carbon atoms and an alkyl branch at the 2-position containing 5 carbon atoms or greater, whether or not with additional branching in most of the isomers, whether or not with most of the additional branches are methyl groups and/or ethyl groups.

In aspect 119, the invention provides a composition comprising at least one trialkylamine oxide selected from any one of aspects 98-111 but which does not contain any amine oxides or mixtures of amine oxides other than those described herein as being within the scope of this invention.

In aspect 120, this invention provides the composition of any one of aspects 112-119 comprising at least one bleach compound, hydrogen peroxide compound, or combinations thereof.

In aspect 121, this invention provides the composition of any one of aspects 112-120 comprising 1.4 weight % of the trialkylamine oxide of any one of aspects 98-111 further comprising 2.5 weight % NaCl, 4.3 weight % sodium lauryl sulfate, 4.3 weight % sodium lauryl ether sulfate in deionized water wherein said composition has a Brookfield viscosity of less than 4000 centipoise at a shear rate of 3/s.

In aspect 122, this invention provides the composition of aspect 121 comprising 3.0 weight percent by volume of NaCl in deionized water wherein said composition has a Brookfield viscosity of less than 3500 centipoise at a shear rate of 3/s.

In aspect 123, this invention provides the composition of aspect 122 comprising 3.5 weight percent by volume of NaCl in deionized water wherein said composition has a Brookfield viscosity of less than 2100 centipoise at a shear rate of 3/s.

In aspect 124, this invention provides the composition of aspect 123 comprising 4.0 weight percent by volume of NaCl in deionized water wherein said composition has a Brookfield viscosity of less than 1500 or less than 1000 or less than 700 centipoise at a shear rate of 3/s.

In aspect 125, this invention provides home care products, industrial cleaners, agrochemical formulations, coatings, fuel treatments, oil cleaners, oil recovery, oil dispersants, disinfectants, water treatments, bleaches, detergents, stain removers, soaps, oily soil cleaners, grease cutters, soft surface cleaners or hard surface cleaners comprising the composition of any one of aspects 112-124 and/or the trialkylamine oxides of any one of aspects 98-111.

In aspect 126, this invention provides dish detergents, kitchen surface cleaners, bathroom surface cleaners, upholstery cleaners, laundry stain removers, carpet cleaners, carpet spot removers, or laundry detergents comprising the composition of any one of aspects 112-124 and/or the trialkylamine oxides of any one of aspects 98-111.

In aspect 127, this invention provides the grease cutters of aspect 125 which are effective at oily soils such as sebum, palm or coconut oil, or animal fat.

In aspect 128, this invention provides a laundry detergent comprising at least one of the trialkylamine oxides of any of 98-111 having at least a 1% or 2% or 3% or 4% or 5% or 6% or 7% or 8% or 9% or 10% or 11% or 12% or 13% or 15% increase in total stain removal index according to ASTM Method D4265, for example, 2% to 11% increase or 3 to 11% increase in total stain removal index according to ASTM Method D4265.

In aspect 129, this invention provides the laundry detergent of aspect 128 comprising a commercial laundry liquid comprising ethoxylated lauryl alcohol, sodium laureth sulfate, sodium carbonate, tetrasodium iminosuccinate, acrylic polymer and stilbene disulfonic acid triazine brightener, but containing no enzymes, dyes or fragrance, for example, the detergent can be ALL FREE CLEAR made by Henkel Corporation, USA.

In aspect 130, this invention provides a process for making any of the trialkylamine oxides of any one of aspects 98-111.

In aspect 131, this invention provides the process of aspect 130 which includes oxidation of branched C10-12 N,N-dimethylalkylamines in a solvent system comprising a polar protic solvent.

In aspect 132, this invention provides the process of aspect 131 wherein the polar protic solvent is an alcohol.

In aspect 133, this invention provides the process of aspect 132 wherein the solvent system comprises alcohol and water.

In aspect 134, this invention provides the process of any one of aspects 132-133 wherein the alcohol is ethanol or isopropanol.

In aspect 135, this invention provides the process of any one of aspects 133-134 wherein the ratio by volume of water to alcohol is from 1:1 to 10:1, or from 2:1 to 5:1, or 3:1, or 4:1

In aspect 136, this invention provides the process of any one of aspects 131-135 wherein the branched N, N-dimethylalkylamines, for example, C10-C12 branched N, N-dimethylalkylamines, are oxidized to trialkylamine oxides using hydrogen peroxide.

In aspect 137, this invention provides the process of aspect 136 wherein the amount of hydrogen peroxide and tertiary amine useful in this invention is present in the range of about 10:1 to about 1:1, or about 5:1 to about 1:1, or about 4:1 to about 1:1, or about 3:1 to about 1:1 of moles of hydrogen peroxide per mole of tertiary amine; or wherein the molar ratio of hydrogen peroxide to tertiary amine is from 10:1, or 9:1, or 8:1, or 7:1, or 6:1, or 5:1, or 4:1, or 3:1, or 2:1 or 1:1.

In aspect 138, this invention provides the process of aspect 137 wherein the amount of hydrogen peroxide and trialkylamine is present in the range of about 3:1 to about 1:1 moles of hydrogen peroxide per mole of tertiary amine

In aspect 139, this invention provides the process of aspect 138 wherein the amount of hydrogen peroxide and trialkylamine is present in the range of about 1-3:1 moles of hydrogen peroxide per mole of tertiary amine.

In aspect 140, this invention provides at least one quaternary ammonium compound made from any one of the trialkylamines of aspects 1-24.

In aspect 141, this invention provides at least one quaternary ammonium compound comprising the following formula:

wherein R8 is methyl, ethyl, butyl, or benzyl, and X is a halide or alkosulfate, wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H; and wherein R5 and R6 are not H at the same time.

In aspect 142, this invention provides the quaternary ammonium compound of aspect 141 comprising the formula:

wherein R5 and R6 are C3H7, C2H5, CH3, or mixtures thereof; and
wherein R7 is one of C3H7, C2H5, CH3, H or mixtures thereof.

In aspect 143, this invention provides the quaternary ammonium compounds of any one of aspects 140-142 wherein R6 is CH3 or C2H5.

In aspect 144, this invention provides the quaternary ammonium compounds of any one of aspects 140-143 wherein R5 and R6 independently are C2H5.

In aspect 145, this invention provides the quaternary ammonium compound of aspect 140-143 wherein R5 is CH3 or CH2H5.

In aspect 146, this invention provides the quaternary ammonium compound of aspect 140-143 or 145 wherein R5 is CH3 and R6 is C2H5.

In aspect 147, this invention provides the quaternary ammonium compound of any one of aspects 140-146 wherein R8 is benzyl or butyl.

In aspect 148, this invention provides the quaternary ammonium compound of any one of aspects 141-147 wherein X— is halide.

In aspect 149, this invention provides the quaternary ammonium compound of aspect 148 wherein the halide is selected from chloride, bromide or iodide.

In aspect 150, this invention provides the quaternary ammonium compound of any one of aspects 148-149 selected from N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride or N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium bromide.

In aspect 151, this invention provides a composition comprising at least one quaternary ammonium compound of any one of aspects 140-150.

In aspect 152, this invention provides a composition comprising at least one quaternary ammonium compound of aspect 151 wherein quaternary ammonium compounds other than those of any one of aspects 140-150 are excluded.

In aspect 153, this invention provides the composition of any one of aspects 151-152 comprising at least one nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or combinations thereof.

In aspect 154, this invention provides the composition of any one of aspects 151-153 comprising 0.01% to 30% by weight of said quaternary ammonium compound based on the total weight of the composition equaling 100 weight %.

In aspect 155, the invention provides a composition selected from any one of aspects 151-154 wherein the trialkylamine(s) used to make the quaternary ammonium compound(s) does not contain any isomeric compound or mixtures, wherein said mixtures can contain a number of isomeric compounds, and wherein said isomeric compound(s) can be selected from those of structures:

having from 10 to 18 carbon atoms in the R(R′)CHCH2-moiety in which R has 5 to 9 carbon atoms, and R′ has from 3 to 7 carbon atoms, with most of the compounds having additional methyl or ethyl branches, and in which R′ and R′″ are alkyl or hydroxyalkyl groups or hydrogen and X− is an anion.

In aspect 156, the invention provides a composition of aspect 155 wherein the trialkylamine(s) used to make the quaternary ammonium compound(s) does not contain any isomeric compound or mixture of isomers of aspect 156, wherein said mixtures can contain a number of isomeric compounds, wherein said isomeric compound(s) can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 10 to 18 carbon atoms and an alkyl branch at the 2-position containing 3 to 7 carbon atoms, and additional branching in most of the isomers, with most of the additional branches being methyl groups.

In aspect 157, the invention provides a composition selected from any one of aspects 151-155 wherein the trialkylamine(s) used to make the quaternary ammonium compound(s) of the invention do not contain any isomers or mixtures of isomers of any one of aspects 155 or 156, wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compounds can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 12 carbon atoms and an alkyl branch at the 2-position containing 5 carbon atoms or greater, whether or not with additional branching in most of the isomers, whether or not with most of the additional branches are methyl groups and/or ethyl groups.

In aspect 158, the invention provides a composition comprising at least one quaternary ammonium compound selected from any one of aspects 151-154 but which does not contain any quaternary ammonium compound or mixtures of quaternary ammonium compounds other than those described in aspects 151-154 or otherwise described within the scope of this invention.

In aspect 159, the invention provides at least one quaternary ammonium compound (for example, the compounds of any one of aspects 140-150 or composition(s) comprising said compound (for example, the compositions of aspects 151-158) which is a disinfecting agent.

In aspect 160, the invention provides at least one quaternary ammonium compound of aspect 159 having a minimum lethal concentration against at least one microbe selected from gram-positive bacteria, gram-negative bacteria, and/or yeast, when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm, or less than 65 ppm.

In aspect 161, the invention provides at least one quaternary ammonium compound of aspect 160 having a minimum lethal concentration against E. coli, S. aureus and/or C-albicans when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm, or less than 65 ppm.

In aspect 162, the invention provides at least one quaternary ammonium compound of aspect 161 having a minimum lethal concentration against E. coli, S. aureus and/or C-albicans when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm wherein the quaternary ammonium compound is N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride.

In aspect 163, the invention provides one or more phase transfer catalysts comprising at least one quaternary ammonium compound of any one of aspects 140-150, or 159-162.

In aspect 164, the invention provides at least one process for using at least one quaternary ammonium compound of any one of aspects 140-160, or 159-162.

In aspect 165, the invention provides at least one process for using at least one quaternary ammonium compound of any one of aspects 140-160, or 159-162 as a phase transfer catalyst.

In aspect 166, the invention provides at least one process of aspect wherein said phase transfer catalyst is used in a process for making a enal or aldehyde, whether branched or not, for example, any enal or aldehyde useful in making any product of this invention, for example, products including but not limited to trialkylamines (including branched or non-branched trialkylamines), amino acids, sarcosine product, N-alkyl-N-methylglucamines, trialkylamine oxides, quaternary ammonium compounds, carboxybetaines, and/or hydroxysultaines of the invention.

In aspect 167, the invention provides at least one process of making a quaternary ammonium compound.

In aspect 168, this invention provides the process of any one of aspects 164-167 wherein the alkylating agent selected to make the quaternary ammonium compound is selected from at least one of C1-C4 alkyl chloride, C1-C4 alkyl bromide or C1-C4 alkyl iodide, benzyl chloride, benzyl bromide or benzyl iodide, or mixtures thereof.

In aspect 169, this invention provides the quaternary ammonium compound of aspect 168 wherein the alkylating agent can be selected from at least one of methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, benzyl chloride, benzyl bromide or mixtures thereof.

In aspect 170 this invention provides the quaternary ammonium compound of aspect 168-169 wherein the halide is C1-C4 alkyl bromide.

In aspect 171, this invention provides the quaternary ammonium compound of aspect 170 wherein the alkyl bromide is butyl bromide or any isomers thereof.

In aspect 172, there is provided a process for the synthesis of C10-C12 enals (for example, enals listed in aspect 84, and for example, 2,4-diethyl-2-octenal), wherein the ratio of phase transfer catalyst, for example, tetrabutyl ammonium bromide, to aldehyde (for example, n-butyraldehyde), can be from 0.05 to 0.10 Mmol, the ratio of base (for example, sodium hydroxide) to aldehyde (for example, n-butyraldehyde) can be from 1.2 to 1.6 Mmol, and the ratio of enal (for example, 2-ethylhexanal) to (aldehyde) n-butyraldehyde can be from 1.8 to 2.2 Mmol.

In aspect 173, there is provided a process for the synthesis of C10-C12 enals, (for example, enals listed in aspect 84, and for example, 2,4-diethyl-2-octenal), wherein the ratio of phase transfer catalyst, for example, tetrabutyl ammonium bromide, to aldehyde (for example, n-butyraldehyde), can be from 0.05 to 0.10 Mmol, the ratio of base (for example, sodium hydroxide) to aldehyde (for example, n-butyraldehyde) can be from 1.2 to 1.6 Mmol, and the ratio of enal (for example, 2-ethylhexanal) to (aldehyde) n-butyraldehyde can be from 1.8 to 2.2 Mmol. In this aspect, the yield of the C10-C12 enals can be 50% or greater, or 55% or greater.

In aspect 174, there is provided a process for the synthesis of C10-C12 enals (for example, enals listed in aspect 84, for example, 2,4-diethyl-2-octenal), wherein the amount of aldehyde (for example, n-butryaldehyde) can be from 450 to 600, or 475 to 565, or 500 to 540, or 510 to 530 Mmol, the base (for example, NaOH), can be present in the amount of 570 to 670 Mmol, and the ratio of base to aldehyde is 1.0 to 1.5, or greater than 1.0 to 1.5, or 1.05 to 1.5, or 1.05 to 1.35, or 1.05 to 1.30.

In aspect 175, there is provided a process of aspect 174 wherein the yield of C10-C12 enals can be 38% or greater, or 39% or greater, or 40% or greater.

In aspect 176, there is provided a continuous process for the synthesis of enals (for example, enals listed in aspect 84, for example, 2,4-diethyl-2-octenal), wherein ratio of base (for example, NaOH) to aldehyde (for example, n-butyraldehyde) can be from 1.30 to 1.80, or from 1.35 to 1.75, or from 1.35 to 1.65, or from 1.35 to 1.60, or from 1.35 to 1.55, or from 1.38 to 1.54 Mmol, the ratio of phase transfer catalyst to aldehyde (for example, n-butyraldehyde) can be from 0.03 to 0.1 or from 0.03 to 0.09, or from 0.03 to 0.08, or from 0.03 to 0.07, or from 0.03 to 0.06, or from 0.04 to 0.1 or from 0.04 to 0.09, or from 0.04 to 0.08, or from 0.04 to 0.07, or from 0.04 to 0.06, or from 0.045 to 0.055 Mmol, wherein the residence time can be from 50 to 120 minutes and wherein the temperature can be from 45 to 80 minutes or from 50 to 75 minutes, wherein the conversion of butyraldehyde can be from 90 to 100% or from 90 to 99%.

In aspect 177, there is provided a process for the hydrogenation of C10-C12 enals (for example, enals listed in aspect 84, for example, 2,4-diethyl-2-octenal), wherein the pressure (kPa) during hydrogenation can be from 6500 or greater, or 6600 or greater, or 6700 or greater, or 6800 or greater or 6850 or greater or 6880 or greater.

In aspect 178, there is provided a process for the hydrogenation of C10-C12 enals wherein at least one enal (for example, enals listed in aspect 84, for example, 2,4-diethyl-2-octenal) and at least one solvent (for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol), can be brought to a pressure of 300 to 400, or from 325 to 375, or from 340 to 350 kPa with hydrogen and heated to 120° C. to 180° C., or 130° C. to 170° C., or 140° C. to 160° C., or 145° C. to 155° C. and wherein the pressure can be then raised to 6500 or greater, or 6600 or greater, or 6700 or greater, or 6800 or greater or 6850 or greater or 6880 or greater kPa.

In aspect 179, there is provided a process of hydrogenation of enals wherein the weight ratio of enal (for example, enals listed in aspect 84, for example, 2,4-diethyl-2-octenal), and at least one solvent for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol) can be 0.80 to 1.2, or 1:1, wherein Pd loading can be from 0.01 to 1.5, or 0.05 to 1.2, or from 0.07 to 1.0, and using carbon support (for example, finely divided carbon).

In aspect 180, there is provided the process of aspect 179 wherein the yield can be greater than 50%, greater than 60%, greater than 70%, greater than 75%, greater than 78%.

In aspect 181, there is provided a process of hydrogenation of enal wherein the weight ratio of enal(s), for example, 2,4-diethyl-2-octenal, and at least one solvent (for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol or ethanol can be 1:1, wherein Pd loading can be from 0.01 to 1.5, or 0.05 to 1.2, or from 0.07 to 1.0, using carbon support (for example, finely divided carbon), wherein the catalyst (for example Noblyst catalyst obtained from Evonik Corporation), and wherein the catalyst can be present at about 4.8% by weight where the total weight of the catalyst, enal and alcohol equals 100 weight %, and wherein the yield can be greater than 50%, greater than 60%, greater than 70%, greater than 75%, greater than 78%.

In aspect 182, there is provided the process of aspect 181 wherein the enal conversion can be 70% or greater, 75% or greater, 80% or greater, 85% or greater, or 90% or greater, or 95% or greater and wherein the enal yield can be 60% or greater, or 65% or greater, or 70% or greater or 75% or greater.

In aspect 183, there is provide the process of aspects 177-182 wherein the solvent can be any non-reactive solvent known to one of ordinary skill in the art.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to the following detailed description of certain embodiments of the invention and the working examples. In accordance with the purpose(s) of this invention, certain embodiments of the invention are described in the Summary of the Invention and are further described herein below. Also, other embodiments of the invention are described herein.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term “about.” Unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Further, the ranges stated in this disclosure and the claims are intended to include the entire range specifications and not just the endpoint(s). For example, a range stated to be 0 to 10 is intended to disclose all whole numbers between 0 and 10 such as, for example 1, 2, 3, 4, etc., all fractional numbers between 0 and 10, for example 1.5, 2.3, 4.57, 6.1113, etc., and the endpoints 0 and 10.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in its respective testing measurements.

As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include their plural referents unless the context clearly dictates otherwise. The terms “containing” or “including” are intended to be synonymous with the term “comprising”, meaning that at least the named compound, element, particle, or method step, etc., is present in the composition or article or method, but does not exclude the presence of other compounds, catalysts, materials, particles, method steps, etc., even if the other such compounds, material, particles, method steps, etc., have the same function as what is named, unless expressly excluded in the claims.

Also, it is to be understood that the mention of one or more process steps does not preclude the presence of additional process steps before or after the combined recited steps or intervening process steps between those steps expressly identified.

In one embodiment, this invention provides novel compositions which can be used to produce novel surfactants. This invention also provides effective reactants and processes to make the branched surfactants and corresponding surfactant intermediates with fewer reaction byproducts, fewer reaction steps, and/or reduced reaction solvent.

As used herein the term “hydrophobe” means a molecule that can serve as the hydrophobic, or non-polar segment of a surface-active compound or surfactant. The branched C10-C12 hydrophobes of this invention and their surfactant derivatives are often liquids at room temperature, the surfactants are typically low foaming and may be mild to skin. Surfactants made from the branched hydrophobes can have improved solubility in water and can interact differently with other ingredients in a formulation. They can also have altered biological activity that can provide beneficial activity (such as antimicrobial, antifungal, and/or antiviral activity) or safety (such as reduced aquatic toxicity, reduced skin irritation, reduced irritation to eyes and mucous membranes, reduced allergenicity or tendency to cause contact dermatitis). As a result, the surfactants derived from branched trialkylamine hydrophobes can have properties well-suited for use in personal and home care applications, which value these traits in formulating, use and disposal of the surfactants.

In one embodiment, this invention provides novel compositions which can be used to produce novel compositions, e.g., surfactants, with one or more of the following desirable properties: (1) low foaming, such as according to ASTM E2407, (2) mildness to skin, such as predicted by a zein solublization test or patch test, (3) effective oily soil and/or stain removal, especially in cold water, such as according to ASTM 4265, (4) compatibility with other ingredients in a cleaning formula, and (5) a favorable environmental profile, (6) high solubility in water; (7) no gelling, (8) ease of formulation, and (9) compatibilization or stabilization of other ingredients in a formula, (10) retains good hydrophobicity compared to linear hydrophobes, (11) tolerance of extreme pH, (12) antimicrobial activity, (13) biodegradability, such as according to OECD 301B and/or (14) an improved safety profile. This invention also provides effective reactants and processes to make branched surfactants and corresponding surfactant intermediates with fewer reaction byproducts, fewer reaction steps, and/or reduced reaction solvent.

In one embodiment, the compositions of this invention can provide one or more of the following properties: (1) low foaming, (2) effective oily soil and/or stain removal, especially in cold water, (3) high solubility in water; (4) no gelling, (5) ease of formulation, and (6) compatibilization or stabilization of other ingredients in a formula, (7) tolerance of extreme pH, (8) biodegradability, and/or (9) an improved safety profile.

Low foaming characteristics in combination with improved cleaning performance such as more effective soil and/or stain removal is important for laundry and dishwashing formulations where low foaming results in greater efficiency and durability of dishwashers, washing machines, upholstery and rug cleaners or other appliances utilizing them. Also, higher solubility in water and/or no gelling enable the compositions of the invention to be placed in a more concentrated liquid form prior to transfer, transport for both reactions and formulations. Branched surfactants can also reduce the viscosity of the formulation(s) that they are in which can provide benefits like easier dispensing and reduction in the requirement for added water in the formulation.

The invention provides novel branched hydrophobes for the production of surfactants with altered properties over typical linear hydrophobes. In one embodiment, the invention provides trialkylamine hydrophobes. In another embodiment, the invention provides branched enals and aldehydes useful in making the trialkylamines, the N-alkyl-N glucamines, and/or the alkyl-N-sarcosines of the invention. The trialkylamines of the invention are useful in making the quaternary ammonium salts or “quats”, alkyl betaines or alkyl hydroxysultaines, and/or trialkylamine oxides of the invention.

In another embodiment, the invention provides a process for making the branched enals and aldehydes, surfactant intermediates or surfactants that reduces or eliminates the formation of byproducts, reduces process steps or reaction solvent.

In another embodiment, the invention provides branched enals and aldehydes that are oxidized to branched fatty acids or hydrogenated to branched fatty alcohols and further derivatized to surfactants, through ethoxylation or esterification and other or subsequent reactions. The invention also provides surfactants made from the branched trialkylamine intermediates, including amphoteric, cationic and nonionic surfactants.

In the present invention, enals and aldehydes with more than one branch point can be produced by a combination of hydroformylation and aldol condensation. In one embodiment, the enals and aldehydes have two branch points. For example, 2-ethylhexanal can be reacted with either propionaldehyde or n-butyraldehyde in a crossed aldol reaction to produce a C11 or C12 enal. Alternately, the self-condensation product of propionaldehyde can be reacted with n-butyraldehyde to produce a C10 enal with two branch points. Examples of the reactions and products are depicted below.

Any process known in the art can be used to make the C10-C12 enals of the invention. In one embodiment, there is provided a process for the synthesis of C10-C12 enals useful in the invention wherein the ratio of phase transfer catalyst, (for example, any phase transfer catalyst described in this invention, and for example, tetrabutyl ammonium bromide), can be from 0.05 to 0.10 Mmol, the ratio of base (for example, sodium hydroxide) to aldehyde (for example, n-butyraldehyde) can be from 1.2 to 1.6 Mmol, and the ratio of enal (for example, 2-ethylhexanal) to (aldehyde) n-butyraldehyde can be from 1.8 to 2.2 Mmol.

In one embodiment, there is provided a process for the synthesis of C10-C12 enals useful in the invention wherein the ratio of phase transfer catalyst (for example, any phase transfer catalyst described in this invention, and for example, tetrabutyl ammonium bromide), to aldehyde (for example, n-butyraldehyde), can be 0.05 to 0.10 Mmol, the ratio of base (for example, sodium hydroxide) to aldehyde (for example, n-butyraldehyde) can be 1.2 to 1.6 Mmol, and the ratio of enal (for example, 2-ethylhexanal) to (aldehyde) n-butyraldehyde can be 1.8 to 2.2 Mmol and wherein the yield of the C10-C12 enals can be 50% or greater, or 55% or greater.

In one embodiment, there is provided a process for the synthesis of C10-C12 enals useful in the invention wherein the amount of aldehyde (for example, n-butryaldehyde) can be from 450 to 600, or 475 to 565, or 500 to 540, or 510 to 530 Mmol, the base (for example, NaOH), can be present in the amount of 570 to 670 Mmol, and the ratio of base to aldehyde can be from 1.0 to 1.5, or greater than 1.0 to 1.5, or from 1.05 to 1.5, or from 1.05 to 1.35, or from 1.05 to 1.30 Mmol. In this embodiment, the yield of C10-C12 enals can be 38% or greater, or 39% or greater, or 40% or greater.

In one embodiment, there is provided a continuous process for the synthesis of enals useful in the invention wherein ratio of base (for example, NaOH) to aldehyde (for example, n-butyraldehyde) can be from 1.30 to 1.80, or from 1.35 to 1.75, or from 1.35 to 1.65, or from 1.35 to 1.60, or from 1.35 to 1.55, or from 1.38 to 1.54 Mmol, the ratio of phase transfer catalyst to aldehyde (for example, n-butyraldehyde) can be from 0.03 to 0.1 or from 0.03 to 0.09, or from 0.03 to 0.08, or from 0.03 to 0.07, or from 0.03 to 0.06, or from 0.04 to 0.1 or from 0.04 to 0.09, or from 0.04 to 0.08, or from 0.04 to 0.07, or from 0.04 to 0.06, or from 0.045 to 0.055 Mmol, wherein the residence time can be from 50 to 120 minutes and wherein the temperature can be from 45 to 80 minutes or from 50 to 75 minutes, wherein the conversion of butyraldehyde can be from 90 to 100% or from 90 to 99%.

The C10 to C12 enals can be further hydrogenated to the corresponding aldehyde or alcohol.

In one embodiment, there is provided a process for the hydrogenation of C10-C12 enals useful in the invention, wherein the pressure (kPa) during hydrogenation can be 6500 or greater, or 6600 or greater, or 6700 or greater, or 6800 or greater or 6850 or greater or 6880 or greater.

In one embodiment, there is provided a process for the hydrogenation of C10-C12 enals wherein at least one enal useful in the invention (for example, 2,4-diethyl-2-octenal), and at least one solvent (for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol), can be brought to a pressure of 300 to 400, or from 325 to 375, or from 340 to 350 kPa with hydrogen and heated to 120° C. to 180° C., or 130° C. to 170° C., or 140° C. to 160° C., or 145° C. to 155° C. and wherein the pressure can then be raised to 6500 or greater, or 6600 or greater, or 6700 or greater, or 6800 or greater or 6850 or greater or 6880 or greater kPa.

In one embodiment, there is provided a process of hydrogenation of enals wherein the weight ratio of enal useful in the invention and at least one solvent (for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol) is from 0.80 to 1.2, or 1:1, wherein Pd loading is from 0.01 to 1.5, or from 0.05 to 1.2, or from 0.07 to 1.0, and using carbon support (for example, finely divided carbon). In this embodiment, the yield of C10-C12 enal can be greater than 50%, greater than 60%, greater than 70%, greater than 75%, greater than 78%.

In one embodiment, there is provided a process of hydrogenation of enal wherein the weight ratio of enal(s), for example, 2,4-diethyl-2-octenal, and at least one solvent (for example, any hydrocarbon from C4 to C10, or alcohol, for example, isopropanol or ethanol), can be from 0.80 to 1.2, or 1:1, wherein Pd loading is from 0.01 to 1.5, or 0.05 to 1.2, or from 0.07 to 1.0, using carbon support (for example, finely divided carbon), wherein the catalyst (for example Noblyst catalyst obtained from Evonik Corporation, is present at about 4.8% by weight of the total weight of the catalyst, enal(s) and solvent equals 100 weight %, and wherein the yield of C10-C12 enal is greater than 50%, greater than 60%, greater than 70%, greater than 75%, greater than 78%. In this embodiment, the enal conversion can be 70% or greater, 75% or greater, 80% or greater, 85% or greater or 90% or greater or 95% or greater and wherein the enal yield can be 60% or greater, or 65% or greater, or 70% or greater or 75% or greater.

In the hydrogenation process of the C10-C12 enals of the invention, the solvent can be any non-reactive solvent known to one of ordinary skill in the art.

Aldol condensation reactions, or aldolization reactions, are known in the art. Two types of aldol condensation reactions frequently encountered are the self-aldol condensation (Aldol I) and cross-aldol condensation (Aldol II) reactions. In an Aldol I reaction, two molecules of the same aldehyde starting material react to form a reaction product. Alternatively, in an Aldol II reaction, two different aldehyde starting materials react to form a reaction product.

The reaction between two of the same aldehyde molecules is a classic case with an equilibrium far to the right. In practice, the condensation of two molecules of the same aldehyde (Aldol I) to form an aldol can be followed immediately by dehydration to form an unsaturated aldehyde with twice the original number of carbon atoms.

In an Aldol II reaction, however, the condensation of two molecules of different aldehydes forms an aldol and, upon dehydration, further forms an unsaturated aldehyde having the sum of the carbon atoms of the two different aldehydes. Both Aldol I and Aldol II reactions are well known in the art, as are the conditions required to affect their condensation.

The C10 to C12 aldehydes are formed by reacting at least one aldehyde starting material in the presence of a basic catalyst to form aldol condensation products.

In one embodiment, the aldehyde starting materials can include but are not limited to C2 to C8 aldehydes selected from the group consisting of acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, valeraldehyde, 2-ethylbutyraldehyde, 2-methylpentanal, 2-ethylhexanal or mixtures thereof. although other aldehydes can also be suitable.

The aldol condensation can be enacted in a single step, as in the crossed aldol reaction of n-butyraldehyde and 2-ethylhexanal, or in more than one step, as in the aldol condensation or propionaldehyde to form 2-methyl-2-pentenal followed by hydrogenation to 2-methylpentanal, then a crossed aldol reaction between 2-methylpentanal and n-butyraldehyde to form 2,4-dimethyl-2-heptenal. U.S. Pat. No. 6,090,986 to Godwin et al. discloses an example of Aldol II in the formation of 2,4-dimethyl-2-heptenal from condensing 2-methyl-pentanal and propanal.

The cross aldol or homoaldol reactions run in utilization of this invention can be catalyzed by the addition of a base. A base can be defined in many ways such as any substance that releases hydroxide ions (OH) upon dissolution in water or a substance that accepts a proton (Bronsted-Lowry theory). A base can also be any substance that donates an electron pair (Lewis Theory) [Whitten and Gailey, 1981].

In the invention, the aldol reactions can be catalyzed by any substance or substances meeting any of the definitions described herein or in the art of a base. In the invention, the aldol reactions can be catalyzed by any substance or substances meeting any of the definitions described herein or in the art of a base. In one embodiment, the base can be any hydroxide, bicarbonate, or carbonate salt of the Group I or Group II metals; NaOH; KOH; NaHCO3; Na2CO3; LiO; CsOH; sodium methoxide; sodium ethoxide; sodium propoxide; potassium methoxide; potassium butoxide; cesium methoxide, or the like, or mixtures thereof. In one embodiment, the catalysts can include NaOH, NaHCO3, KOH, or K2CO3.

In one embodiment, the base can be any hydroxide, bicarbonate, or carbonate salt of the Group I or Group II metals. In another embodiment, the base can be one or more selected from NaOH, KOH, NaHCO3, Na2CO3, LiOH, CsOH, and the like. In another embodiment, the basic catalyst can also be chosen from sodium methoxide, sodium ethoxide, sodium propoxide, potassium methoxide, potassium butoxide, cesium methoxide, or the like. In another embodiment, the base is NaOH. When the base is NaOH, using a ratio of 1.15 to 1.25 of NaOH:nHbu can provide an enal yield of at least 40%.

The catalyst can also be other organic or inorganic bases and can, for example be carbonates, bicarbonates, phosphates, pyrophosphates, and hydrogenphosphates of alkali metals, and/or it may include quaternary ammonium compounds, tertiary amines, ion exchange resins, guanidine derivatives, amidine compounds, and combinations thereof. In one embodiment, tertiary amines can be the catalyst. In another embodiment, the catalyst can be NaOH. The concentration of the basic catalyst can be varied, but molar or similar concentrations of alkali metal hydroxides can be used, and concentrations selected will generally be in the range of about 1 to 50% or 1 to 30% or 1 to 25% 5 to 50% or 5 to 30% or 5 to 25% by weight. The amount of aqueous alkali to aldehyde reactant can also vary, for example, from about 15% by volume aqueous alkali up to about 75% by volume aqueous alkali. In one embodiment, the amount of aqueous alkali to aldehyde reactant can also vary, for example from about 20% by volume aqueous alkali up to about 45% by volume aqueous alkali. In yet another embodiment, the amount of aqueous alkali to aldehyde reactant can also vary, for example, from about 25% by volume aqueous alkali up to about 35% by volume aqueous alkali.

The base catalyst, especially the most commonly used bases, NaOH, KOH, NaHCO3, and the like, are introduced as aqueous solutions to the reaction mixture. As the chain length of the raw material aldehyde or ketone increases, the solubility of the base in the organic reaction medium can decrease. For instance, two molecules of 4 carbon n-butyraldehyde readily react in aqueous caustic, but one molecule of n-butyraldehyde and one molecule of 8 carbon 2-ethylhexanal may not react in the same basic solution. In order to increase the solubility of the longer chain molecule, a phase transfer catalyst (PTC) is used.

Phase transfer catalysts shuttle ions across organic and aqueous phase boundaries. A phase transfer catalyst (PTC) is effective in improving conversion in this procedure. In many cases, the phase transfer catalyst is a quaternary ammonium salt. The PTC can be any quaternary ammonium salt capable of transmitting organic and aqueous components across a phase boundary. The quaternary ammonium salt could be a pure component or a mixture of salts. Typical quaternary ammonium salts are comprised of tetra alkyl or tetra aromatic ammonium cations and a counter anion. Counter anions include halogens or polyatomic ions such as BF4, PF6, SO2, SO4, or the like. Common PTCs include tetrabutyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium iodide, tetramethyl ammonium chloride, and benzalkyl ammonium chloride. The use of co-solvents, such as methanol or diols, may also be used. The concentration of PTC can vary.

To avoid the formation of byproducts, such as Hoffman Elimination byproducts, from PTC such as tetrabutyl ammonium salts or mixtures of alkyl benzyl ammonium salts, this invention provides a phase transfer catalyst utilizing an amine derived from the aldehydes useful in the invention, for example, a C10, C11 or C12 aldehyde. For example, 2,4-diethyl-octenal, produced by the cross aldol reaction of n-butyraldehyde and 2-ethylhexanal, can be combined with N,N-diethylamine over a copper catalyst to produce 2,4-diethyl-N,N-dimethyloctan-1-amine. The product amine can then be reacted with benzyl chloride to form the PTC in excellent yield. Similarly, the product amine can be reacted with an alkyl chloride (ethyl chloride, propyl chloride, butyl chloride) to generate a PTC. In one embodiment, one quarternary ammonium salt of the invention is N-benzyl-2,4-diethyl-N,N-dimethyl-octyl ammonium chloride.

The resultant phase transfer catalyst is similar in structure to any of the components of the mixture alkyldimethylbenzylammonium chloride, but comprised of a single molecule. Its resultant use in cross aldol reactions can deliver similar or superior yields to BAC and to other PTCs described in the art, with the added benefit of producing a single high boiler component as identified by gas chromatography. The aldol products are easily separated from this single high boiler by distillation.

The PTCs of the invention or useful in the invention can be used in the cross aldol reaction of n-butyraldehyde and 2-ethylhexanal to produce 2,4-diethyloctenal in reasonable yield. The PTCs can also be used in any aldol condensation involving any two aldehydes compound containing a carbon chain from 1-20 carbons. Such aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, 2-methyl-propionaldehyde, valeraldehyde (1-pentanal), isovaleraldehyde (2-methyl-butyraldehyde), hexanal, 2-ethylhexanal, 1-octanal, 1-nonanal, and the like. The reaction utilizing this invention can contain two or more different aldehydes (cross aldol) of two or more molecules of the same aldehyde (homoaldol).

The aldol condensation reaction can be performed in an aqueous solution, in an organic solvent, or in a mixture of water and an organic solvent. Such organic solvents include methanol, ethanol, propanol, butanol, acetone, acetonitrile, pentane, hexane, heptane, cyclohexane. The solvent can also be any of the starting aldehydes or product aldehydes useful in the invention.

The reactions for forming aldol condensation products can be generally carried out at a pressure of from about 1 atm (atmospheric pressure) to about 1000 atm (elevated pressure) or from about 1 atm to about 500 atm or from about 1 to about 300 atm or from about 1 to about 100 atm or from about 1 to about 50 atm or from about 1 to about 20 atm. The reaction can be carried out over a wide range of temperatures and is not particularly limited. The reaction temperature can be within the range of from about −20° C. to 300° C., for example, within the range of from 20° C. to 100° C.

The reaction can be run at ambient temperature and pressure. Increased conversion can be accomplished by running at higher temperature or pressure. In one embodiment, the reaction can be run between 20° C. and 70° C. In another embodiment, the reaction can be run between 50° C. and 70° C.

The reaction temperature can be increased by running the reaction at higher pressures. In one embodiment, the reaction can be run anywhere from 100 kPa to 2000 kPa. In another embodiment, the reaction can be run from 100 to 1000 kPa. In yet another embodiment, the reaction can be run at ambient (atmospheric) pressure.

The aldol reaction can be run for a sufficient time to obtain the desired degree of conversion. The aldol condensation reactions can run for about 1 to 10 hours or 1 to 3 hours. They can be run as batch or continuous reactions. When run as continuous reactions, the residence time can be substantially shorter than 3 hours, for example, less than 2 hours, less than 1 hour, less than 30 minutes, less than 10 minutes, or less than 5 minutes. In one embodiment, batch reactions can be run in the range of about 30 minutes to about 3 hours or about 1 to about 3 hours.

The reaction can be stopped by permitting the reaction mixture to cool and separating the organic reaction phase from the aqueous alkali phase. The saturated or unsaturated aldehyde can be purified prior to further conversion, or may be used directly. Purification of the saturated or unsaturated aldehyde can be effected by decanting, extraction, distillation, filtration or chromatographic separation.

Following the aldol condensation step, the unsaturated product can be hydrogenated to produce the saturated aldehyde, which can be further hydrogenated to form the alcohol or, alternatively, can be oxidized to form the carboxylic acid. The unsaturated aldehyde or enal can be used directly as a substrate for reductive amination.

The branched C10 through C12 enals and aldehydes produced in the present process or otherwise useful in this invention can be especially suitable for conversion to other useful compositions. The present invention provides unsaturated and saturated aldehydes which can be converted to the corresponding saturated or unsaturated alcohols or acids, and further derivatized to form surfactants, such as alcohol ethoxylates or fatty acid esters, or sulfated or sulfonated forms of these molecules. The reactions can be effected at the enal stage, or with the saturated aldehydes.

Examples of C10 to C12 enals useful in this invention include but are not limited to: 4-ethyl-2-methyloct-2-enal (C11 enal), 2,4-diethyl-2-octenal (C12 enal), 2-propyl-heptenal (C10 enal), or 2-ethyl-4-methyl heptenal (C10 enal); Examples of C10 to C12 aldehydes include but are not limited to: aldehyde-4-ethyl-2-methyloctanal (C11 aldehyde), 2,4-diethyl-2-octanal (C12 aldehyde); 2-propyl-heptanal (C10 aldehyde), and 2-ethyl-4-methyl heptanal (C10 aldehyde).

Examples of products that can be made with the C10 to C12 enals and/or aldehydes useful in the invention are as follows: (A.) N-alkyl-N-methylglucamines: the C10 through C12 enals and aldehydes useful in this invention can be reacted with N-methylglycamines to generate sugar-based surfactants. For example, the C10 through C12 enals and aldehydes can be reacted with N-methylglucamine to generate N-alkyl-N-methylglucamines. Similarly, the C10 through C12 enals and aldehydes can be reacted with N-methyl amino acids to afford an amino acid based surfactant; (B.) Sarcosines: For example, the C10 through C12 enals and aldehydes described herein can be reacted with N-methylglycine to generate alkyl-N-sarcosines; (C.) Trialkylamines: The C10 to C12 enal or aldehydes described herein may be reacted with dialkyl amines such as dimethylamine to obtain N,N-dimethylalkylamines as surfactant intermediates. Similarly, the C10 to C12 enal or aldehydes can be reacted with diethanolamine, dipropylamine, diisopropylamine to obtain the corresponding trialkylamine. The trialkylamines described herein can be used to make other products, for example, (D.) Amphoterics: Betaines, including Carboxybetaines; and Hydroxysultaines; (E.) Quaternary Compounds; and (F.) Trialkylamine Oxides; as well as other compounds, as follows:

A. N-Alkyl-N-Methylglucamines

The C10 through C12 enals and aldehydes useful in this invention can be reacted with glucamines or N-methylglucamines to generate sugar-based surfactants. For example, the C10 through C12 enals and aldehydes can be reacted with N-methylglucamine to generate N-alkyl-N-methylglucamines. In one embodiment, the N-alkyl-N-methylglucamines can be N-(2-ethylhexyl)-N-methylglucamine or N-decyl-N-methylglucamine.

N-alkyl-N-methylglucamines have promising surfactant characteristics. The compounds can be useful in applications such as coatings, inks, adhesives, agricultural formulations, fountain solutions, photoresist strippers and developers, shampoos, and detergents and other cleaning compositions as well as other end-uses that would be apparent to one of ordinary skill in the art. In one embodiment, the N-alkyl-N glucamine surfactants can serve as exceptionally mild surfactants for applications that involve human contact, such as personal care and cleansing formulations.

In one embodiment, N-alkyl-N-methylglucamines prepared with branched aliphatic aldehydes are provided. The above described objectives can be achieved in a one-pot synthesis, if desirable. In one embodiment, the catalysts for the reductive amination reaction can be selected from Raney nickel, palladium, rhodium, ruthenium, platinum, or mixtures thereof. Typically, the catalyst is carried upon a heterogeneous support for ease of removal from the reaction medium. Representative supports can include carbon, alumina, silica, or mixtures thereof, and the like. The reaction can be carried out in an aqueous medium or in an organic solvent. In one embodiment, aldehydes useful in making the N-alkyl-N glucamines of the present invention contain aliphatic hydrocarbon chains, branched, saturated or unsaturated, comprising 2 to 30 carbon atoms. In another embodiment, aldehydes useful in making the N-alkyl-N glucamines of the invention are branched C8-C20 aldehydes, for example, 2-ethylhexanal, 2-propyl-pentanal, 2-propyl-hexanal, 2-propyl-heptanal, 2-propyl-octanal, 2,4-diethyloctanal, 2-ethyl-4-methyl-nonanal, 2-ethyl-4-methyloctanal, or 2-butyl-4-ethyloctanal or combinations thereof.

A representative N-alkyl-N-methylglucamine is shown by the formula below:

wherein R5, R6 and R7 can each be independently selected from methyl (CH3), ethyl (C2H5), propyl (C3H7), or hydrogen (H) or combinations thereof, and Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction. In one embodiment, each of R5, R6 and R7 can be all C3H7 or all C2H5, or all CH3, or all H. In another embodiment, each of R5, R6 and R7 can be mixtures of two or more of the following: C3H7, and C2H5, and CH3 and H. In yet another embodiment, R5 and R6 are at least two of the branch points. Examples of suitable reducing sugars include but are not limited to mono-, di-, or oligosaccharides such as glucose, mannose, fructose, sorbose, arabinose, maltose, isomaltose, maltulose, isomaltulose, trehalulose, lactose, glyceraldehyde, galactose, xylose, ribose, cellobiose, and xylobiose.

In one embodiment, R5 and R6 for the N-alkyl-N-methylglucamine can be C3H7, C2H5, CH3, or combinations thereof; and wherein R7 can be one of C3H7, C2H5, CH3, H or combinations thereof. In one embodiment, for the N-alkyl-N glucamine, R6 can be C2H5 or CH3, or R5 and R6 independently can be C2H5. In one embodiment, for the N-alkyl-N glucamine, R5 can be C2H5 or CH3. In one embodiment, for the N-alkyl-N glucamine, R6 can be C2H5 and R5 can be CH3. In one embodiment, for the N-alkyl-N glucamine, R5 can be C2H5 and R6 can be CH3.

In one embodiment, the N-alkyl-N glucamines can have one to three, or one to two, or only two branch points. In one embodiment, for the N-alkyl-N glucamine can have one branch point at either the R5 or R6 position. In one embodiment, the N-alkyl-N glucamine can have two branch points which are at the R5 and R6 positions.

In one embodiment, for the N-alkyl-N glucamines, the number of carbon atoms for the alkyl substituent at the R5 position can be from 1 to 3 or from 1 to 2.

In one embodiment, for the N-alkyl-N glucamines, the number of carbon atoms for the alkyl substituent at the R6 position can be from 1 to 3 or from 1 to 2.

In one embodiment, this invention provides an N-alkyl-N-methylglucamine having the formula:

In one embodiment, this invention provides an N-alkyl-N-methylglucamine having the formula:

In one embodiment, this invention provides an N-alkyl-N-methylglucamine having the formula:

In one embodiment, this invention provides an N-alkyl-N-methylglucamine having the formula:

wherein Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction; wherein said reducing sugar is glucose, mannose, fructose, sorbose, arabinose, maltose, isomaltose, maltulose, isomaltulose, trehalulose, lactose, sucrose, galactose, xylose, ribose, cellobiose, xylobiose or a combination thereof.

Advantageously, the reductive amination of glucose can be achieved at a temperature of 100° C. or less, or 70° C. or less, or 60° C. or less. The reaction between N-monoalkylglucamine and aldehydes according to the invention is suitably carried out at a temperature from 50 to 170° C., or from 75 to 145° C., or from 100 and 120° C. The molar ratio of aldehyde to N-monoalkylglucamine should be at least stoichiometric, or from 1 to 1.5, or from 1 to 1.2

In one embodiment, this invention provides a process for making any of the N-alkyl-N glucamines of the invention comprising any of the steps described herein, singly or in combination.

B. Sarcosines

Similarly, the C10 through C12 enals and aldehydes can be reacted with amino acids or N-methyl amino acids to afford an amino acid based surfactant. For example, the C10 through C12 enals and aldehydes useful in the invention can be reacted with N-methyl glycine (sarcosine) to generate N-alkylsarcosines; this invention also includes any products made by these processes.

C. Trialkylamines

The C10 to C12 enal or aldehydes can also be reacted with dialkyl amines such as dimethylamine to obtain N,N-dimethylalkylamines which can be useful, for example, as surfactant intermediates. Similarly, the C10 to C12 enal or aldehydes can be reacted with diethylamine, dipropylamine, or diisopropylamine to obtain the corresponding trialkylamines.

Among the more versatile surfactant intermediates are the trialkylamines, also called tertiary amines. In the present invention, C10 to C12 enals or aldehydes are reacted with a secondary amine under reductive conditions to produce trialkylamines.

Reductive amination processes are well known in the art for the synthesis of primary, secondary and tertiary amine. The term “amination” relates to the reaction part in which an amine functionality is incorporated into the substrate. The term “reductive” relates to the observation, when comparing the feed substrate and the product of a reductive amination reaction, that a reduction has necessarily also taken place. In chemistry, a reduction reaction refers in general to the gain of electrons of an atom or a molecule. In organic chemistry, reductions are usually related with the disappearance of unsaturated functionality, such as double bonds, from the substrate molecules. The net result of a reductive amination of a ketone or aldehyde is the conversion of a C═O double bond into a C—N single bond.

The reductive amination of ketones or aldehydes towards trialkylamines can be done in either one or two process steps in which the first step comprises the reaction of the ketone or aldehyde with an amination reagent such as dimethylamine to form an intermediary imine or enamine followed by the second process step in which the intermediary imine or enamine is hydrogenated towards the desired amine. The reductive amination reaction of ketones or aldehydes can be done in a gas- or liquid-phase process in the presence of a reducing agent, an amine and if deemed necessary, a suitable catalyst. The reductive amination reaction can be performed in a reaction medium comprising a solvent. In the context of the present invention a solvent is a compound which does not take part in the chemical reaction and which is capable of reducing the concentration in the reaction medium of any of the other compounds, such as reagents, catalysts and reaction products.

As for other hydrogenation reactions, stoichiometric reagents are sometimes used as reducing agents, for example, formic acid or hydrides such as borohydrides or aluminium hydrides. In one embodiment, hydrogen can be used as the reducing agents. Suitable catalysts can be either heterogeneous or homogeneous hydrogenation catalysts. In one embodiment, hydrogenation catalysts can comprise at least one active metal, either in elementary form or in the form of a compound, for example, oxides.

Examples of catalysts containing metals in their elementary form are Raney-nickel and Raney-cobalt. In one embodiment, the catalyst comprises a mixture of active metals. The metals can be present in ionic form or as covalently bound. When oxides of the active metals are used, the process can comprise a reduction of the oxide to the elementary metal, typically at higher temperatures, for example, 300° C. to 700° C. (the temperature used in typically determined by the metal and is referred to as “calcining”), and, for example, in the presence of hydrogen. Useful hydrogenation catalysts can be selected from one or more of the metals of groups IVb, Vb, Vlb, VIIb, VIIIb, Ib or IIb. In one embodiment, catalysts containing nickel, palladium, platinum, cobalt, rhodium, iridium, copper, manganese, tin or ruthenium can be used.

This reaction can be performed either batch wise or continuous. If a continuous installation is used, this can be either a continuous stirred tank reactor (CSTR) or plug flow reactor. The temperature can range from 80 to 300° C. and the pressure from 1 bara to 100 bara. As used herein, “bara” means (Absolute Pressure) Pressure reading relative to absolute vacuum.

The reaction can be performed in an excess of the ketone or aldehyde, in an excess of the amination agent such as dimethylamine or in stoichiometric amounts of the two reagents. The amination reagent may be added in a 10:1 to 1:1 molar ratio, or based on the enal or aldehyde reactant, preferably 5:1 to 1:1, or 4:1 to 1:1, or 4:1 to 2:1, or 3:1 or 4:1.

In one embodiment, the C10 to C12 enal or aldehydes useful in the invention may be reacted with dimethylamine under reductive conditions to obtain alkyl dimethyl amines, or N,N-dimethylalkylamines. In one embodiment, the trialkylamines can be selected from one 4-ethyl-N,N,2-trimethyloctan-1-amine, 4-ethyl, 2-methyl, N,N-dimethylhexan-1-amine, or 2,4-diethyl, N,N-dimethyloctan-1-amine.

In one embodiment, the invention includes a trialkylamine having the formula:

wherein R1 and R2 are each independently selected from straight or branched chain or cyclic hydrocarbon radicals having 1 to 8 carbon atoms;
wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or combinations thereof; and
wherein R5 and R6 are not H at the same time.

In one embodiment, for the trialkylamine, (a) R1 and R2 can be each independently substituted with groups selected from: —OR3; carboxyl; NHCOR4; —CONHR4; cyano; —CO2R3; OCOR3; hydroxy; aryl; heteroaryl; chlorine; or a combination thereof, (b) R3 can be selected from C1-C6 alkyl, substituted C1-C6 alkyl or combinations thereof and (c) R4 can be selected from C1-C4 alkyl or substituted C1-C15 alkyl.

In one embodiment, for the trialkylamine, R1 and R2 can be CH3.

In one embodiment, for the trialkylamine, R1 can be CH3 or C2H5 and R2 can be a carbohydrate or amino acid.

In one embodiment, for the trialkylamine, R5 and R6 can be C3H7, C2H5, CH3, or combinations thereof; and wherein R7 can be one of C3H7, C2H5, CH3, H or combinations thereof. In one embodiment, for the trialkylamine, R5 can be CH3 or C2H5; in one embodiment, R6 can be CH3 or C2H5; in one embodiment, R5 and R6 independently can be CH3; in one embodiment, R5 and R6 independently can be C2H5. In one embodiment, for the trialkylamine, R5 can be CH3 when R6 is C2H5, or R5 can be CH2H5 when R6 is CH3.

In one embodiment, the trialkylamine can have 1 to 3, or 1 to 2, or only two branch points. In one embodiment, the trialkylamine can have one branch point at either the R5 and/or R6 positions. In one embodiment, the trialkylamine can have two branch points which are at the R5 and R6 positions.

In one embodiment, for the trialkylamine, the number of carbon atoms for the alkyl substituent at the R5 position can be from 1 to 3 or 1 to 2.

In one embodiment, for the trialkylamine, the number of carbon atoms for the alkyl substituent at the R6 position can be from 1 to 3 or 1 to 2.

In one embodiment, the invention provides a composition comprising at least one trialkylamine of the invention but which does not contain any isomeric compound or mixtures, wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compound(s) can be selected from those of structures:

having from 10 to 18 carbon atoms in the R(R′)CHCH2-moiety in which R has 5 to 9 carbon atoms, and R′ has from 3 to 7 carbon atoms, with most of the compounds having additional methyl or ethyl branches, and in which R′ and R′″ are alkyl or hydroxyalkyl groups or hydrogen and X— is an anion.

In one embodiment, the invention provides a composition comprising at least one trialkylamine of the invention which does not contain any isomeric compound or mixture of isomers as described in the previous paragraph, wherein said mixtures contain a number of isomeric compounds, wherein said isomeric compound(s) can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 10 to 18 carbon atoms and an alkyl branch at the 2-position containing 3 to 7 carbon atoms, and additional branching in most of the isomers, with most of the additional branches being methyl groups.

In one embodiment, the invention provides a composition comprising at least one trialkylamine of the invention which does not contain any isomers or mixtures of isomers as described in the previous paragraph, wherein said mixtures contain a number of isomeric compounds, and wherein said isomeric compounds can be selected from tertiary amines with a higher branched-chain alkyl substituent characterized as having 12 carbon atoms and an alkyl branch at the 2-position containing 5 carbon atoms or greater, whether or not with additional branching in most of the isomers, whether or not with most of the additional branches are methyl groups and/or ethyl groups.

In one embodiment, the invention provides a composition comprising at least one trialkylamine of the invention which does not contain any trialkylamine or mixtures of trialkylamines other than those described herein as being within the scope of this invention.

Trialkylamine intermediates can be further reacted to form a variety of surfactants useful for personal care, home care and industrial applications. Potential surfactants based on a branched trialkylamine hydrophobe include nonionics such as ethoxylated amines; amphoterics such as imidazolines, alkyl betaines and hydroxysultaines and trialkylamine oxides, ethoxylated amine oxides and alkyl diethanolamine oxides; and cationics such as quaternary ammonium salts, bisquaternary ammonium compounds, and ethoxylated quats. Branched trialkylamine-based surfactants can include but are not limited to alkyl betaines, hydroxysultaines, quaternary ammonium salts, and trialkylamine oxides.

D. Amphoterics (Betaines and Hydroxysultaines)

Trialkylamines as included within the scope of this invention can be reacted to form the amphoteric surfactants alkyl betaines or alkyl hydroxysultaines (sulfobetaines) of the invention. For example, branched C10-12 N,N-dimethylalkylamines can be further converted to alkyl betaines or alkyl hydroxysultaines by reaction with chloroacetic acid or sodium 1-chloro-2-hydroxypropane sulfonate, respectively (the electrophiles). Examples of processes for making alkyl betaines and hydroxysultaines can be found in U.S. Pat. No. 5,371,250 and JP 02160757, which generally use water as the bulk solvent for the processes. However, with these branched amine substrates, this reaction in water may not afford the necessary high conversion of the desired product, even with excess reagent.

Changing the solvent system to where the majority solvent is a lower alcohol can result in improved conversion to the desired product, even though the reaction is heterogeneous due to limited electrophile insoluble in the reaction mixture. The lower alcohol can be chosen from C1-C4 alcohols, for example, ethanol or isopropanol. The electrophile can be used at about 1 to 3 molar equivalents, or 1.1 to 2 molar equivalents or 1.1-1.6 molar equivalents, based on the amine.

A base chosen from alkali metal hydroxides or alkali metal carbonates is also used in the process. In one embodiment, the bases can be selected from sodium hydroxide, sodium carbonate, potassium hydroxide, and potassium carbonate or mixtures thereof. In another embodiment, the base is sodium carbonate. The base can be used at about 0.1-0.5 molar equivalents or 0.1 and 0.3 molar equivalents, based on the amine. The reaction temperatures are generally between about 60° C. and 95° C., in one embodiment, between 70° C. and 85° C.

The carboxybetaines or hydroxysultaines of the invention can be made using any trialkylamine useful in this invention.

In one embodiment, the invention provides a process for making the alkyl betaines of the invention comprising reacting branched C10-12 N,N-dimethylalkylamines with monohalocarboxylic acid or a salt thereof, at least one alkali metal hydroxide or carbonate, and a C1-C4 alcohol and water wherein the amount of the C1-C4 alcohol is greater than that of water, wherein said reaction can occur at a temperature range of from 60° C. to 95° C. or from 70° C. to 85° C.

In one embodiment, this invention provides a process for making the alkyl hydroxysultaines of the invention comprising reacting branched C10-12 N,N-dimethylalkylamines with sodium 1-chloro-2-hydroxypropane sulfonate, at least one alkali metal hydroxide or carbonate, a C1-C4 alcohol and water wherein the amount of the C1-C4 alcohol is greater than that of water, wherein said reaction can occur at a temperature range of 60° C. to 95° C. or 70° C. to 85° C.

In one embodiment, the invention provides a carboxybetaine comprising the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 cannot both be H.

In one embodiment, the invention provides a carboxybetaine comprising the formula:

In one embodiment, the invention provides a carboxybetaine which is 2-(2,4-diethyloctyl)dimethylammonio)acetate.

In one embodiment, the invention provides a a hydroxysultaine comprising the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 cannot both be H.

In one embodiment, the invention provides at least one hydroxysultaine comprising the formula:

In one embodiment, the invention provides at least one hydroxysultaine which is 3-(4-ethyl-2-methyloctyl)dimethylammonio)-2-hydroxypropane-1-sulfonate.

In one embodiment, the invention provides at least one surfactant comprising at least one carboxybetaine of the invention and/or at least one hydroxysultaine of the invention, or combinations thereof.

In one embodiment, the invention provides a composition which does not contain carboxybetaines made from the mixtures of trialkylamines other than trialkylamines of the invention or provides a composition which does not contain hydroxysultaines made from the mixtures of trialkylamines other than trialkylamines of the invention. In another embodiment, the carboxybetaines or hydroxysultaines of the invention are not made using trialkylamines other than the trialkylamines of the invention.

In one embodiment, the invention provides a composition which does not contain carboxybetaines other than the carboxybetaines of this invention and/or provides a composition which does not contain hydroxysultaines other than the hydroxysultaines of this invention.

In one embodiment, the invention provides product(s) including but not limited to dish detergents, car wash detergents, shampoos, face washes, body washes; fabric stain removers or fabric cleaners comprising the at least one carboxybetaine of the invention or the compositions of the invention or surfactants of the invention, respectively. The end-uses will also be apparent to one of ordinary skill in the art.

In one embodiment, the invention provides a product comprising dish detergents, car wash detergents, shampoos, face washes, body washes; fabric stain removers or fabric cleaners comprising: (1) at least one carboxybetaine of the invention, or (2) at least one hydroxysultaine of the invention, or (3) the compositions or surfactants of the invention, or (4) any combinations of (1)-(3) of this embodiment.

In one embodiment, this invention provides a stain remover comprising at least one of any of alkyl betaines or carboxybetaines or hydroxysultaines of the invention which demonstrates at least two times the weight loss percentage of a fabric compared to pre-treatable stain removers which contain linear carboxyl betaines after beef fat stains on deposited on said fabric are pre-treated with 3 weight % of said stain remover and then washed through a complete washing machine cycle.

E. Quaternary Ammonium Compounds (Quats)

In one embodiment, this invention provides at least one quaternary ammonium compound made from any one of the trialkylamines or trialkylamine combinations or compositions of at least trialkyl amine of the invention. In another embodiment, this invention provides a process for making any of the quaternary ammonium compound and/or compositions containing at least one quaternary ammonium compound of the invention.

The quats of the invention can be stable toward electrophiles, oxidants, and acids. They can be used as disinfectants, surfactants, fabric softeners, and as antistatic agents for hair and textiles, e.g. in shampoos and fabric softeners.

In one embodiment, this invention provides at least one quaternary ammonium compound comprising the following formula:

wherein R8 is methyl, ethyl, butyl, or benzyl, and X is a halide or alkosulfate,
wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H; and
wherein R5 and R6 are not H at the same time.

In one embodiment, this invention provides at least one quaternary ammonium compound of the invention comprising the formula:

wherein R5 and R6 are C3H7, C2H5, CH3, or mixtures thereof; and
wherein R7 is one of C3H7, C2H5, CH3, H or mixtures thereof.

In one embodiment, for the quaternary ammonium compounds, R5 can be CH3 or C2H5; in one embodiment, R6 can be CH3 or C2H5; in one embodiment, R5 and R6 independently can be CH3; in one embodiment, R5 and R6 independently can be C2H5. In one embodiment, for the quaternary ammonium compound, R5 can be CH3 when R6 is C2H5, or R5 can be CH2H5 when R6 is CH3; R8 can be benzyl or butyl; X— can be halide, for example, chloride, bromide or iodide; in one embodiment, the quaternary ammonium compound can be selected from N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride or N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium bromide.

In one embodiment, this invention includes a composition comprising at least one quaternary ammonium compound of the invention wherein quaternary ammonium compounds other than those of the invention can be excluded.

In one embodiment, the composition containing the quaternary compound of the invention can comprise at least one nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or combinations thereof.

In one embodiment, a composition of the invention can comprise 0.01% to 30% by weight of said quaternary ammonium compound based on the total weight of the composition equaling 100 weight %.

In one embodiment, the invention provides a composition comprising at least one quaternary ammonium compound of the invention and does not contain any quaternary ammonium compound or mixtures of quaternary ammonium compounds other than those of the invention.

In one embodiment, the invention provides at least one quaternary ammonium compound of the invention or composition(s) comprising said quaternary ammonium compound which is a disinfecting agent.

In one embodiment, the invention provides at least one quaternary ammonium compound (for example, N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride) having a minimum lethal concentration against at least one microbe selected from gram-positive bacteria, gram-negative bacteria, and/or yeast, when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm, or less than 65 ppm.

In one embodiment, the invention provides at least one quaternary ammonium compound of the invention (for example, N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride) having a minimum lethal concentration against E. coli, S. aureus and/or C-albicans when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm, or less than 65 ppm.

In one embodiment, the invention provides at least one quaternary ammonium compound of the invention (for example, N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride) having a minimum lethal concentration against E. coli, S. aureus and/or C-albicans when used at concentrations of less than 200 ppm, or less than 150 ppm, less than 100 ppm, or less than 75 ppm where the quaternary ammonium compound is N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride.

As described herein, when the alkylating agent used to make the quaternary ammonium compound is benzyl chloride, the resulting product is a benzalkonium chloride which, along with the quaternary ammonium compounds of the invention, can have antimicrobial properties.

Benzalkonium chloride (BAC) is a cationic quaternary ammonium salt (quat) with demonstrated antimicrobial activity. BACs with C8 to C18 alkyl chain lengths are used as biocides in wood treatment, aqueous processes and as preservatives in water-based formulations. BACs are made from the corresponding alkyl dimethylamines by reaction with benzyl chloride. The alkyl component of the USP-grade BAC biocide and preservative is composed of a blend of alkyl chains with a well-defined C12 to C18 chain distribution based on fractionated coconut or palm kernel fatty acids. Other grades of BAC are also available with a more loosely defined alkyl chain distribution, or with a single alkyl chain length. With pressure to replace triclosan, BAC has become a leading active ingredient in antimicrobial hand wash. Benzalkonium chlorides or blends are also the active ingredient in many antimicrobial surface cleaners, including wipes

The quaternary ammonium compounds useful in the invention can also function as a phase transfer catalyst (PTC).

In one embodiment, the invention provides at least one process for using and/or making at least one quaternary ammonium compound of the invention.

In one embodiment, the invention provides at least one process for using at least one quaternary ammonium compound of the invention as a phase transfer catalyst. In one embodiment, the invention provides at least one process wherein the quaternary ammonium compound is used as phase transfer catalyst in a process for making a enal or aldehyde, whether branched or not, for example, any enal or aldehyde useful in making any product of this invention, for example, products including but not limited to trialkylamines (including branched or non-branched trialkylamines), amino acids, sarcosine products, N-alkyl-Nglucamines, trialkylamine oxides, quaternary ammonium compounds, carboxybetaines, and/or hydroxysultaines of the invention.

The invention also includes processes of making quaternary ammonium compounds of the invention. Any trialkylamines of the invention or combinations thereof can be reacted with alkylating agents such as halides (e.g. methyl chloride) or alkyl sulfates (e.g. dimethyl sulfate) to form the cationic quaternary ammonium salts (“quats”) of the invention. The branched C10-12 N,N-dimethylalkylamines useful in the invention can be reacted to form branched C10-C12 quaternary ammonium compounds of the invention. For example, branched BAC-b12 (N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride) and N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium bromide (branched C12-butyl quat.) are examples of branched C10-C12 quaternary ammonium compounds of the invention.

In one embodiment, this invention provides at least one quaternary ammonium compound of the invention wherein the alkylating agent selected to make the quaternary ammonium compound can be selected from at least one of C1-C4 alkyl chloride, C1-C4 alkyl bromide or C1-C4 alkyl iodide, benzyl chloride, benzyl bromide or benzyl iodide, or mixtures thereof.

In one embodiment, this invention provides at least one quaternary ammonium compound of the invention wherein the alkylating agent can be selected from at least one of methyl chloride, ethyl chloride, propyl chloride, butyl chloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, benzyl chloride, benzyl bromide or mixtures thereof. In one embodiment, the alkylating agent can be C1-C4 alkyl bromide.

In one embodiment, the alkylating agent can be the quaternary ammonium compound of the invention wherein the alkyl bromide is butyl bromide or any isomers thereof.

F. Trialkylamine Oxides

In one embodiment, this invention provides at least one trialkylamine oxide made from any one of the trialkylamines or trialkylamine combinations or compositions comprising at last one trialkylamine of the invention. In another embodiment, this invention provides a process for making any of the trialkylamine oxides or trialkylamine oxide compositions of the invention.

The trialkylamines can be oxidized at the nitrogen to form tertiary amine-N-oxides. Aliphatic amine oxides (AO) of the invention can be produced by the reaction of the trialkylamines of the invention and hydrogen peroxide. Branched C10-12 N,N-dimethylalkylamines of the invention can be oxidized to branched trialkylamine oxides of the invention using hydrogen peroxide. In one embodiment, the amount of hydrogen peroxide and tertiary amine can be present in the range of about 10:1 to about 1:1, or about 5:1 to about 1:1, or about 4:1 to about 1:1, or about 3:1 to about 1:1, moles of hydrogen peroxide per mole of tertiary amine or where the molar ratio of hydrogen peroxide and tertiary amine can be from 10:1, or 9:1, or 8:1, or 7:1, or 6:1, or 5:1, or 4:1, or 1-3:1, or 3:1, or 2:1, or 1:1, or 1-3:1 moles of hydrogen peroxide per mole of tertiary amine.

An example of a process for the production of amine oxides from N,N-dimethylalkylamines can be found in U.S. Pat. No. 6,037,497. Examples of branched trialkylamine oxides within the scope of the invention are: 4-ethyl-N,N-2-trimethyloctan-1-amine oxide (Branched C11-amine oxide); and 2,4-diethyl-N,N-dimethyloctan-1-amine oxide (Branched C12-amine oxide). Amine oxide synthesis from linear alkyl dimethylamines like dimethyl laurylamine (DIMLA) can be performed in water. The low water-solubility and branching pattern of the branched C10-12 N,N-dimethylalkylamines can reduce the effectiveness of a purely aqueous oxidation reaction. Using water as a sole reaction solvent can result in only trace amounts of product. To increase the reaction efficiency, a polar protic solvent, with or without water, may be used for the oxidation reaction. In one embodiment, an alcohol solvent or mixed solvent system of alcohol and water can be used. In one embodiment, the solvent can be an alcohol/water mixture, and the alcohol is ethanol. The ratio of water to alcohol (for example, ethanol or isopropanol), can be 1:1 to 10:1, or from 2:1 to 5:1, or 3:1, or 4:1. After the reaction, alcohol can be removed from the reaction mixture at low temperature. The removal of the alcohol, for example, ethanol, can be achieved under vacuum.

The trialkylamine oxides of the invention can be commercially important because of their surfactant properties, and can be used in liquid dish detergents, in liquid laundry detergents and in agrochemical formulations. They can be nonionic surfactants or cationic surfactants depending on pH. They can be used as surfactants in home care, coatings, fuels, and bleaches. The trialkylamine oxides of the invention can be used in both dish and laundry liquids and in some hard surface cleaners as surfactants and foam boosters. Trialkylamine oxides of the invention can be compatible with formulas across a broad pH range, including highly alkaline formulas, and formulas containing bleach and oxidizing agents like hydrogen peroxide. They can be excellent grease cutters, able to remove a variety of oily soils from surfaces and fabrics. Oily soils that are solid at room temperature or in cold water cleaning, like body soil (sebum), palm or coconut oil, animal fat and wax are especially difficult to remove.

Energy-saving high efficiency (HE) washing machines use cold water and low water volumes for washing laundry. The conventional hot water wash is not energy efficient and, in general, can be detrimental to some sensitive fabrics; therefore milder conditions can be desired in order to remove stains. Effective stain removal from fabric is temperature dependent and therefore there is an increasing demand for laundry detergents that can effectively remove stains at lower temperatures. Long chain amine oxides can be derived from naturally occurring linear C8-C14 alcohols which in turn are primarily obtained from palm and coconut trees. Due to the decline in cultivation and harvesting of these natural resources, the price of these alcohols is often unpredictable. Therefore, there is an increasing demand to use alternate chemical intermediates from feedstock materials for the synthesis of amine oxides that are feasible for cold water wash in high efficiency washing machines. In addition to excellent oily soil removal, the branched trialkylamine oxides of the invention also tend to generate less foam in a formula than their linear counterparts. In high-efficiency (HE) washing machines, excess foam can prolong the rinse cycle, increasing the water used for a load of laundry, defeating the resource efficiency of the appliance.

In one embodiment, this invention provides at least one trialkylamine oxide having the formula:

wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or mixtures thereof; and wherein R5 and R6 are not H at the same time.

In one embodiment, this invention provides at least one trialkylamine oxide having the formula:

wherein R5 and R6 can be C3H7, C2H5, CH3, or combinations thereof; and
wherein R7 can be one of C3H7, C2H5, CH3, H or combinations thereof.

In one embodiment, for the trialkylamine oxide, R5 can be CH3 or C2H5; in one embodiment, R6 can be CH3 or C2H5; in one embodiment, R5 and R6 independently can be CH3; for the trialkylamine oxide, R5 and R6 independently can be C2H5. In one embodiment, for the trialkylamine oxide, R5 can be CH3 when R6 is C2H5, or R5 can be CH2H5 when R6 is CH3.

In one embodiment, the trialkylamine oxide can have one to three, or one to two, or two branch points. In one embodiment, the trialkylamine can have one branch point at either the R5 and/or R6 positions. In one embodiment, the trialkylamine oxide can have two branch points which are at the R5 and R6 positions.

In one embodiment, for the trialkylamine oxide, the number of carbon atoms for the alkyl substituent at the R5 position can be from one to three or one to two.

In one embodiment, for the trialkylamine oxide, the number of carbon atoms for the alkyl substituent at the R6 position can be from one to three or one to two.

In one embodiment, this invention provides at least one trialkylamine oxide which is 2,4-diethyl-N,N-dimethyloctan-1-amine oxide or 4-ethyl-N,N-2-trimethyloctan-1-amine oxide.

In one embodiment, this invention provides any one of the trialkylamine oxides of the invention wherein foaming does not persist for more than 5 minutes when tested according to modified ASTM Method E2407, wherein the method modification is to substitute at least one of said trialkylamine oxides for sodium lauryl ether sulfate and to use no defoamer.

In one embodiment, this invention provides any one of the trialkylamine oxides of the invention (for example, 2,4-diethyl-N,N-dimethyloctan-1-amine oxide) having a Zein score of less than 1.0 when normalized to linear alcohol ethoxylate (LAE 10) using the Zein Solubilization Test. In one embodiment, the invention provides any one of the trialkylamine oxides of the invention (for example, 2,4-diethyl-N,N-dimethyloctan-1-amine oxide) having a Zein score of less than 0.50, or less than 0.40, or less than 0.30, or less than 0.20, or less than 0.10, or less than 0.05, or less than 0.02 when normalized to linear alcohol ethoxylate (LAE 10) using the Zein Solubilization Test.

In one embodiment, the invention provides any one of the trialkylamine oxide compositions of the invention comprising 0.05 weight % of trialkylamine oxide in (1500 ml) deionized water which has a Draves wet-out time (WOT) in seconds of greater than 300 seconds, or greater than 200 seconds, or greater than 100 seconds, or greater than 33 seconds, according to Draves Wetting Test or ASTM Method D2281-68.

In one embodiment, this invention provides a composition comprising one or more of any of the trialkylamine oxides of the invention.

In one embodiment, this invention provides a composition comprising at least one trialkylamine oxide of the invention wherein trialkylamines oxides other than those of the invention are excluded from the composition.

In one embodiment, this invention provides the composition comprising at least one trialkylamine oxide of the invention comprising at least one nonionic surfactant, anionic surfactant, cationic surfactant, amphoteric surfactant, or combinations thereof.

In one embodiment, this invention provides a composition comprising 0.01% to 30% by weight of at least one trialkylamine oxide of the invention based on the total weight of the composition equaling 100 weight %.

In one embodiment, the invention provides a composition wherein the trialkylamine(s) or trialkylamine mixtures of the invention are used to make the trialkylamine oxide(s) of the invention. In one embodiment, the invention provides a composition comprising at least one trialkylamine oxide of the invention which does not contain any amine oxides or mixtures of amine oxides other than those described herein as being within the scope of this invention.

In one embodiment, this invention provides a composition comprising at least one trialkylamine oxide of the invention further comprising at least one bleach compound, hydrogen peroxide compound, or combinations thereof.

In one embodiment, this invention provides a composition comprising 1.4 weight % of at least one trialkylamine oxide of the invention, 2.5 weight % NaCl, 4.3 weight % sodium lauryl sulfate, 4.3 weight % sodium lauryl ether sulfate in deionized water wherein said composition has a Brookfield viscosity of less than 4000 centipoise at a shear rate of 3/s.

In one embodiment, this invention provides a composition comprising 1.4 weight % of at least one trialkylamine oxide of the invention (for example, 4-ethyl-N,N-2-trimethyloctan-1-amine oxide), 3.0 weight % NaCl, 4.3 weight % sodium lauryl sulfate, 4.3 weight % sodium lauryl ether sulfate in deionized water wherein said composition has a Brookfield viscosity of less than 3500 centipoise at a shear rate of 3/s.

In one embodiment, this invention provides a composition comprising 1.4 weight % of at least one trialkylamine oxide of the invention (for example, 4-ethyl-N,N-2-trimethyloctan-1-amine oxide), 3.5 weight % NaCl, 4.3 weight % sodium lauryl sulfate, 4.3 weight % sodium lauryl ether sulfate in deionized water wherein said composition has a Brookfield viscosity of less than 2100 centipoise at a shear rate of 3/s.

In one embodiment, this invention provides a composition comprising 1.4 weight % of at least one trialkylamine oxide of the invention (for example, 4-ethyl-N,N-2-trimethyloctan-1-amine oxide), 4.0 weight % NaCl, 4.3 weight % sodium lauryl sulfate, 4.3 weight % sodium lauryl ether sulfate in deionized water wherein said composition has a Brookfield viscosity of less than 1500 or less than 1000 or less than 700 centipoise at a shear rate of 3/s.

In one embodiment, this invention provides home care products, industrial cleaners, agrochemical formulations, coatings, fuel treatments, oil cleaners, oil recovery, oil dispersants, disinfectants, water treatments, bleaches, detergents, stain removers, soap, oily soil cleaner, grease cutter, soft surface cleaners or hard surface cleaners comprising a composition further comprising any one of the trialkylamine oxides or trialkylamine oxide mixtures of the invention. The trialkylamine oxides or mixtures of trialkylamine oxides of the invention or compositions of the invention can be grease cutters or can be present in grease cutters which can be effective at oily soils such as sebum, palm or coconut oil, or animal fat.

In one embodiment, this invention provides dish detergents, kitchen surface cleaners, bathroom surface cleaners, upholstery cleaners, laundry stain removers, carpet cleaners, carpet spot removers, or laundry detergents further comprising any one of the trialkylamine oxides or trialkylamine oxide mixtures of the invention.

In one embodiment, this invention provides a laundry detergent comprising any trialkylamine oxide of the invention having at least a 1% or 2% or 3% or 4% or 5% or 6% or 7% or 8% or 9% or 10% or 11% or 12% or 13% or 15% increase in total stain removal index according to ASTM Method D4265, for example, 2% to 11% increase or 3 to 11% increase in total stain removal index according to ASTM Method. The laundry of this embodiment can comprise a commercial laundry liquid comprising ethoxylated lauryl alcohol, sodium laureth sulfate, sodium carbonate, tetrasodium iminosuccinate, acrylic polymer and stilbene disulfonic acid triazine brightener, and can contain no enzymes, dyes or fragrance, for example, the detergent can be ALL FREE CLEAR made by Henkel Corporation, USA.

This invention can be further illustrated by the following examples of preferred embodiments thereof, although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.

EXAMPLES

For the Examples herein, some of the abbreviations used herein are defined in the following Table and others are throughout the Description and the Examples:

Abbreviation Name APG Alkylpolyglucoside BAC Benzalkonium chloride CSTR Continuous stirred tank reactor (CSTR) ELSD Evaporative light scattering detector EtOH Ethanol GC-FID Gas chromatography-Flame ionization detector GC-MS Gas chromatography-Mass spectrometry HEH 2-Ethylhexanal LABS Linear alkylbenzene sulfonate LAE10 Linear alcohol ethoxylate, 10 moles EO average LAO N,N-dimethyl laurylamine oxide meq/g Milliequivalents/gram MilliQ Ultrapure water, 18.2 mega ohm resistivity nHBu n-Butyraldehyde NMG N-Methylglucamine Ru/C Ruthenium on carbon SLES Sodium lauryl ether sulfate SLS Sodium lauryl sulfate SDS Sodium dodecyl sulfate (TBABr) Tetrabutyl ammonium bromide Wt Weight

Example 1. Synthesis of C11 Enal (4-ethyl-2-methyloct-2-enal)

To a solution of NaOH (250 g, 3.12 mol) in water (303 mL) was added tributylmethylammonium chloride (49 g, 0.156 mol). To this solution, a premix solution of 2-ethyl hexaldehyde (500 g, 3.90 mol) and propionaldehyde (190 g, 3.28 mol) was added dropwise over the period of 5 h. The addition was maintained such that the temperature of the reaction did not exceed 55° C. The contents of the reaction were stirred at 50° C. for 12 h. The reaction was cooled to room temperature and the contents were transferred to a separatory funnel. The aqueous layer was separated and the organic layer was washed sequentially with water (500 mL), saturated aq. NH4Cl (500 mL) and water (500 mL). The organic layer was separated, dried over MgSO4 and filtered. The pure enal of this Example was distilled at 85° C. (vapour temperature) under 4 mm reduced pressure.

Example 2. Reduction of C11 enal 4-ethyl-2-methyloctanal (C11-aldehyde)

The C11-enal obtained in Example 1 was hydrogenated using palladium (Pd)—C (1 mol %) under hydrogen pressure (400 psi) at 120° C. The resultant aldehyde in this Example 2, 4-ethyl-2-methyloctanal, was distilled at 80° C.-85° C. (vapor temperature) under 3 mm reduced pressure.

Example 3. Synthesis of 2,4-diethyl-2-octenal

Charge a 3 neck, 1 L (liter) flask with Water (133 ml), sodium hydroxide (56.7 g, 1418 mmol), and tetrabutylammonium chloride (25.0 g, 90 mmol). Using a magnetic stir bar, stir to dissolve. Attach a 500 mL liquid dropping funnel charged with butyraldehyde (75.1 g, 1042 mmol) and 2-ethylhexanal (257.2 g, 2006 mmol). Add the aldehyde mixture to the aqueous mixture in the pot dropwise over 2-3 h. After aldehyde addition is complete, pour the mixture into a 1 L separatory funnel. Separate the aqueous layer and wash the organic layer with brine (1×100 mL) and water (2×100 mL). Separate the organic layer, dry over MgSO4, and filter. The crude reaction mixture (190 g) contains 46% 2-ethylhexanal and 33% 2,4-diethyloct-2-enal. This corresponds to 100% conversion of n-butyraldehyde and 56.9% yield, based on moles of butyraldehyde, of 2,4-diethyloctenal.

Example 4. Synthesis of 2,4-diethyl-2-octenal

Charge a 3 neck, 12 L flack with Water (1596 ml), sodium hydroxide (680.4 g), and tetrabutylammonium bromide (348.12 g). Using a magnetic stir bar, stir to dissolve. Attach 1 L liquid dropping funnel charged with butyraldehyde (901.2 g) and 2-ethylhexanal (3086.4 g). Add the aldehyde mixture to the aqueous mixture dropwise over 2 to 3 h. After aldehyde addition is complete, pour the mixture into a separatory funnel. Separate the aqueous layer and wash the organic layer with brine (300 ml) and water (600 ml). Separate the aqueous layer and wash the organic layer with 5% HCl (200 ml) and water (100 ml). Separate the organic layer, dry over MgSO4, filter, and analyze by gas chromatography. Crude reaction mixture (2278 g) contains 44% 2-ethylhexanal, 1% 2-ethyl-hex-2-enal, 1% 2-ethylhexanol, 2% 2-ethylhexanoic acid, 44% 2,4-diethyl-octenal, and the balance unidentified heavies. This corresponds to 60% yield of 2,4-diethyloctenal.

Example 5. Synthesis of 2,4-diethyl-2-octenal with Benzalkonium Chloride as the Phase Transfer Catalyst (PTC)

Charge a 3 neck, 1 L flask with Water (75 ml), sodium hydroxide (28.3 g, 708 mmol), and benzalkonium chloride (8.84 g, 26 mmol). Using a magnetic stir bar, stir to dissolve. Attach 1 L liquid dropping funnel charged with butyraldehyde (37.5 g, 520 mmol) and 2-ethylhexanal (133.4 g, 1040 mmol). Add the aldehyde mixture to the aqueous mixture dropwise over 2 to 3 h. After aldehyde addition is complete, drain mixture by parts into a 3 L separatory funnel. Separate the aqueous layer and wash the organic layer with brine (50 ml) and water (100 ml). Separate the aqueous layer and wash the organic layer with 5% HCl (50 ml) and water (100 ml). Separate the organic layer, dry over MgSO4, filter, and analzye by gas chromatography. Crude reaction mixture (167.03 g) contains 60% 2-ethylhexanal, 5.5% 2-ethyl-hex-2-enal, 0.5% 2-ethylhexanol, 1.5% 2-ethylhexanoic acid, 17% 2,4-diethyl-octenal, and the balance unidentified heavies. This corresponds to 30% yield of 2,4-diethyl-2-octenal.

Example 6. Synthesis of 2,4-diethyl-2-octenal without PTC

Charge a 3 neck, 1 L flask with water (133 ml), sodium hydroxide (56.7 g, 1418 mmol). Using a magnetic stir bar, stir to dissolve. Attach a 500 mL liquid dropping funnel charged with butyraldehyde (75.1 g, 1042 mmol) and 2-ethylhexanal (257.2 g, 2006 mmol). Add the aldehyde mixture to the aqueous mixture in the pot dropwise over 2-3 h if possible. After aldehyde addition is complete, pour the mixture into a 1 L separatory funnel. Separate the aqueous layer and wash the organic layer with brine (1×100 mL) and water (2×100 mL). Separate the organic layer, dry over MgSO4, filter, and analyze by gas chromatography. Crude reaction mixture contains 75% 2-ethylhexanal, 6.2% 2-ethyl-hex-2-enal, 2.7% 2,4-diethyloct-2-enal, and the balance being unidentified materials with a boiling point higher than that of 2,4-diethyloct-2-enal (heavies). Yield is 3.2%.

Examples 7-12. Synthesis of 2,4-diethyl-2-octenal with Varying PTC

These examples were carried out as described in Example 3 except the concentration of tetrabutyl ammonium bromide (TBABr) was varied relative to n-butyraldehyde (nHBu) as indicated in Table 1. 2HEH=2-ethylhexanal; C12=2,4-diethyloctenal

TABLE 1 Example C12 Number TBABr:nHBu NaOH:nHBu 2HEH:nHBu Yield 7 0.09 1.4 2.0 60% 8 0.07 1.4 2.0 60% 9 0.05 1.4 2.0 60% 10 0.04 1.4 2.0 40% 11 0.03 1.4 2.0 20% 12 0.02 1.4 2.0 38%

Examples 13-16. Synthesis of 2,4-diethyl-2-octenal with Varying NaOH Equivalents

These examples were carried out according to the procedure outlined in Examples 13-16 except the equivalents of NaOH relative to n-butyraldehyde (nHBu) were varied as shown in Table 2. The data in Table 2 demonstrates that using a ratio of 1.15 to 1.25 of NaOH:nHbu provides a enal yield of at least 40%.

TABLE 2 Example C12 Number Mmol nHBu Mmol NaOH NaOH:nHBu Yield 13 520 650 1.25 41% 14 520 598 1.15 42% 15 520 520 1.00 33% 16 520 260 0.5 28%

Examples 17-24. Continuous Synthesis of 2,4-diethyl-2-octenal

A jacketed 3 L glass round bottom with four necks and a bottom drain containing a stop cock, was used as a continuous stirred tank reactor. The center neck was fitted with an overhead stirrer controlled by an electric motor. The left neck was fitted with a Claisen tube to which are connected two vertically mounted 2 L glass feed tanks. Each feed tank was attached to a 0-20 mL Eldex brand liquid feed pump. The drain was connected to the intake of a high speed circulating pump. The discharge of the pump passes through an inline static mixer and returns to the CSTR through the right neck. A slip stream of product was removed on the downstream side of the static mixer through a 0-40 mL Eldex pump and into another vertically mounted 2 L glass tank that serves as a decanter. The fourth neck of the CSTR contains a J-type thermocouple connected to a JKEM type temperature indicator. Heating was provided by a circulating bath containing a 50/50 mixture of water and ethylene glycol. The heating medium was circulated through the glass jacket on the reactor to keep the reactor mixture at the desired temperature.

In a typical aldol experiment, one glass feed tank was filled with a 20% solution of NaOH and the other feed tank was filled with a mixture of 60% HEH, 35% nHBu, and 5% BAC. The reactor was charged with 1500 mL of a 2:1 mixture of crude material and NaOH solution. The contents were stirred at 250 rpm and heated to 55° C. The circulating pump was started and material was moved through the static mixer and returned to the CSTR. When the target temperature was reached, the organic feed pump was begun at 15.0 mL/min and the caustic feed pump was begun at 6.0 mL/min. The product takeoff pump was begun at 21.0 mL/min. Under these conditions, the residence time in the reactor was approximately 60 minutes. One hour after startup the product decanter was emptied and this material discarded. After this time, samples were collected every hour. The bottom aqueous material was decanted from the product tank and weighed. The upper organic layer was decanted, weighed, and analyzed by gas chromatography. The crude organic was retained for distillation. After 7 hours, the experiment was discontinued. In this way, approximately 3 L of crude organic was obtained daily.

Distillation of the decanted, crude organic material was conducted on a 2″ glass Oldershaw column. The column stands 10 feet tall and was approximately 24 trays. The column is attached to a 3 L three neck glass round bottom at the bottom and an overhead chilled glycol condenser. The top tray of the column was topped by a “swinging gate” style takeoff controller with a reflux control magnet attached to an electric timer. The distillate from the swinging gate passes through a second glycol chilled condenser before collecting in a glass fraction cutter. The entire column was maintained under 100 torr vacuum by a Welch type vacuum pump. A similar 1″ Oldershaw column was used employing 30 glass trays. Material was fed constantly into the column from a 4 L glass feed tank. The feed rate was controlled by a bellows type pump and passed through a pre-heater set to 120° C. The basepot overflow was removed through a glass sample thief attached to a glycol chilled condenser. A stainless steel solenoid valve and stainless steel needle valve were used to control the rate of overflow. The solenoid was controlled by an electric timer and the overflow product tank was held at 15 torr.

Organic samples were studied by gas chromatography on an Agilent 6890N. The aqueous samples were run on a Restek RTX-1 fused silica catalog #10126 column (length 60 m, diameter 250 um, film 0.25 um) analyzed by a flame ionization detector (GC-FID). The configuration settings were as follows. Heat the oven to 50° C. initially and hold for 3 minutes, ramp the temperature to 125° C. at 12° C./minute, and hold there for 3 minutes. Next, increase the temperature up 7° C./min to a temperature of 165° C. Then, increase the temperature up 15° C./min to a final temperature of 240° C. The detector setting was held at 300° C. Table 3 shows the yield of C12 enal obtained from a continuous process, changing the ratio of reactants, PTC loading, residence time and temperature.

TABLE 3 3L CSTR results at 2:1 HEH:nHBu ethyl-hex-2-enal C12 Yield (Based on Residence mols of Example Time Temperature Butyraldehyde butyraldehyde Number OH:C4 PTC:C4 (min) (° C.) Conversion fed) 17 1.41 0.05 60 53.1 97.4% 50.1% 18 1.46 0.05 110 54.2 93.1% 60.8% 19 1.49 0.05 110 62.6 93.2% 57.6% 20 1.23 0.05 60 57.1 84.5% 43.6% 21 1.10 0.05 60 56.9 88.6% 50.1% 22 1.04 0.05 60 56.9 89.3% 55.8% 23 1.17 0.03 60 55.0 87.9% 41.2% 24 1.51 0.05 60 70.5 98.6% 51.9%

Example 25. Hydrogenation of 2,4-diethyl-2-octenal

A 2 L Hastelloy Autoclave Engineers autoclave is charged with 400 g of purified 2,4-diethyl-2-octenal and 400 g of dry isopropanol. 10.0 g of 0.75% Pd on Al2O3 support is added to a steel mesh catalyst basket. The basket is attached to the stirring shaft of the autoclave above the impeller. The autoclave is sealed and purged with hydrogen gas. The autoclave is brought to 345 kPa with H2 and heated to 150° C. The autoclave is then brought 6895 kPa with H2. Using a gas reservoir system, the autoclave pressure is maintained for 6 h. After 6 h, the autoclave is cooled and vented. The reaction consumed 5.4 Gmol of hydrogen. The crude reaction mixture (782 g) contains 50% isopropanol, 45% 2,4-diethyloctanal, 2.37% 2,4-diethyloctenal, 7.7% 2,4-diethyloctanol, and 3.5% 2,4-diethyl-oct-2-en-1-ol. This corresponds to 98% conversion and 77% yield of 2,4-diethyloctenal.

Examples 26-28. Hydrogenation of 2,4-diethyl-2-octenal

Synthesis of 2,4-diethyl-2-octanal was carried out in the same manner as Example 25 above except the hydrogen pressure was varied as indicated in Table 4.

TABLE 4 Example Number Pressure (kPa) Enal Conversion 2,4-diethyloctanal Yield 26 6895 98% 77% 27 5171 66% 54% 28 3447 60% 55%

Examples 29-32. Catalyst Comparison

A series of catalysts of differing Pd loading and supports, obtained from Evonik Corporation, were tested in the following manner: A 300 mL stainless steel Autoclave Engineers autoclave is charged with 50 g of purified 2,4-diethyl-2-octenal and 50 g of dry isopropanol. 5.0 g of catalyst obtained from Evonik is added to a steel mesh catalyst basket. The basket is attached to the stirring shaft of the autoclave above the impeller. The autoclave is sealed and purged with hydrogen gas. The autoclave is brought to 345 kPa with H2 and heated to 150° C. The autoclave is then brought 6895 kPa with H2. Using a gas reservoir system, the autoclave pressure is maintained for 4 h. After 4 h, the autoclave is cooled and vented. The results are presented in Table 5.

TABLE 5 Example Number Catalyst Pd Loading Support Conversion Yield 29 Noblyst 1512 0.7% Carbon 92% 80% 30 Noblyst 1006 1.0% Carbon 91% 80% 31 Noblyst 1005 2.0% Silica 44% 33% 32 E 105 O/W 5.0% Carbon 62% 42%

Example 33. Hydrogenation of 2,4-diethyl-2-octenal with Ru

A 300 mL stainless steel Autoclave Engineers autoclave is charged with 50 g of purified 2,4-diethyl-2-octenal and 50 g of dry isopropanol. 5.0 g of 3% Run on 2 mm carbon extract support obtained from Johnson-Matthey is added to a steel mesh catalyst basket. The basket is attached to the stirring shaft of the autoclave above the impeller. The autoclave is sealed and purged with hydrogen gas. The autoclave is brought to 345 kPa with H2 and heated to 150° C. The autoclave is then brought 6895 kPa with H2. Using a gas reservoir system, the autoclave pressure is maintained for 4 h. After 4 h, the autoclave is cooled and vented. The reaction consumed 0.8 Gmol of hydrogen. The crude reaction mixture (85 g) contains 30% isopropanol, 12% 2-ethylhexanol, 3.4% 2,4-diethyloctanal, 14% 2,4-diethyloctenal, 18% 2,4-diethyloctanol, and 21% 2,4-diethyl-oct-2-en-1-ol. This corresponds to 76% conversion and 7% yield of 2,4-diethyloctenal.

Example 34. Biodegradability—OECD 301B

The biodegradability of the branched aldehyde intermediates of Example 2 (4-ethyl-2-methyloctanal) and Example 25 (2,4-diethyl-2-octenal) were determined by the Ready Biodegradability—CO2 Evolution Test—Degradation of test compound according to OECD Guidelines for Testing of Chemicals CO2 Evolution Test 301B.

TABLE 6 Biodegradation (%) sodium C11 C12 acetate aldehyde aldehyde Days control Example 2 Example 25 0 0 0 0 2 32 0 0 6 52 15 0 7 54 21 9 9 60 31 27 14 66 47 48 19 69 54 53 23 71 56 53 28 72 57 55 29 74 57 55 29 78 61 57

Examples 35, 36 and 37 demonstrate that the reaction between N-monoalkylglucamine and aldehydes can be catalyzed by Raney nickel or ruthenium supported on carbon, starting from either linear or branched aliphatic aldehydes.

Example 35. Synthesis of N-(2-ethylhexyl)-N-methylglucamine

10.0 g N-methylglucamine (NMG; 51.2 mmol), 6.6 g 2-ethylhexanal (51.5 mmol), 0.850 g 5 wt % Ru/C catalyst, and 15.0 g methanol were placed in a 100-mL stainless steel high-pressure reactor equipped with a mechanical stirrer, a thermocouple, an electric heating jacket, and inlets and outlets for feeds, products, and sampling. Prior to reaction, the reactor was flushed three times with nitrogen and three times with hydrogen at room temperature. After a reaction of 230 minutes at 60 bar H2, the reaction mixture was cooled, vented, and filtered. After drying under vacuum using a rotary evaporator, ca. 11 g product was obtained. Analysis of the product was done by GC-FID and GC-MS. Conversion of the starting 2-ethylhexanal was 99.5% with a selectivity to the desired N-(2-ethylhexyl)-N-methylglucamine of 88.0% and 2-ethylhexanol being the main by-product. Finally, N-(2-ethylhexyl)-N-methylglucamine was isolated by using a simple acid-base extraction workup.

Example 36. Synthesis of N-decyl-N-methylglucamine

The procedure of Example 35 was followed, with the difference that the reaction mixture contained 10.1 g N-methylglucamine (51.6 mmol), 8.1 g decanal (51.6 mmol), 0.850 g 5 wt % Ru/C catalyst, and 15.0 g methanol. Analysis of the product was done by GC-FID and GC-MS. Conversion of the starting decanal was 99.8% with a selectivity to the desired N-decyl-N-methylglucamine of 93.7%.

Example 37. Synthesis of N-decyl-N-methylglucamine

The procedure of Example 36 was followed except that 0.859 g Raney Ni was employed as the catalyst. Analysis of the product was done by GC-FID and GC-MS. Decanal was fully converted with a selectivity to the desired N-decyl-N-methylglucamine of 93.8%.

Examples 38-41. Reductive Amination of Branched Aldehydes Over a Ru/C Catalyst

Example 35 was repeated with different branched aldehydes instead of 2-ethylhexanal (i.e., 4-ethyl-2-methyloctanal, 2-ethyl-4-methylheptanal, 2-ethyl-4-methylhept-2-enal, and (E)-4-ethyl-2-methyloct-2-enal). Table 7 shows an overview of the reaction conditions and the GC-FID results obtained after 6 h reaction at 110° C.

TABLE 7 GC-FID results of the reaction product Reactants N-alkyl-N- NMG Aldehyde Ru/C Methanol H2 NMG methylglucamine Ex. Aldehyde (g) (g) (g) (g) (bar) (wt %) (area %) 38 4-Ethyl-2- 20.0 22.5 1.250 25.0 60 1.3 80.0 methyloctanal 39 2-Ethyl-4- 10.0 8.1 0.890 8.1 85 7.3 77.5 methylheptanal 40 2-Ethyl-4- 10.7 8.2 0.730 15.0 60 5.7 74.0 methylhept-2- enal 41 (E)-4-ethyl-2- 10.8 9.0 1.250 15.0 60 4.2 67.8 methyloct-2- enal

Example 42. Synthesis of Branched C10 and C12 N-alkyl-N-methylglucamines by Reductive Amination of Branched Aldehydes Over a Ru/C Catalyst

Example 35 was repeated with different branched aldehydes instead of 2-ethylhexanal. N-alkyl-N-methylglucamines were prepared starting from 2,4-diethyl-octenal and 2-ethyl-4-methyl heptanal, respectively. The reaction conditions are shown in Table 8.

After 21 h reaction under the specified conditions, the reaction mixtures were cooled to 80° C., flushed with nitrogen, and passed through a 2-μm filter. Next, the mixtures were titrated with 0.1 M HCl to quantify the amine concentration. Acid-base extraction was performed by dissolving the mixture in a solution of 1200 g distilled water, 1200 g ethyl acetate, and 0.6 mol HCl. The N-alkyl-N-methylglucamines were isolated by extracting the organic solution with 0.6 mol NaOH, by washing, and by drying the remaining organic solution using a rotavap at 150° C. and 30 mbara. The reductive amination reactions of 2,4-diethyl-octenal and 2-ethyl-4-methylheptanal yielded 142.0 and 95.3 g, respectively, of a yellowish, paste-like product. Table 9 shows the results obtained by GC-FID and by titration with 0.1 N HCl.

TABLE 8 Reaction conditions used for the reductive amination of 2- ethyl-4-methylheptanal and 2,4-diethyl-octenal, respectively. Red. amination of Red. amination of 2- Entry Parameter 2,4-diethyl-octenal ethyl-4-methylheptanal 1 NMG 79.0 g (0.405 mol) 92.9 g (0.476 mol) 2 Aldehyde 84.1 g (0.445 mol) 81.1 g (0.519 mol) 3 Molar ratio 1.10 1.09 (aldehyde/NMG) 4 5 wt % Ru/C 1.7 g 1.7 g 5 Methanol 75.0 g 75.0 g 6 Reaction 110° C. 110° C. temperature 7 Reactor pressure 80 barg 80 barg 8 Stirring rate 800 rpm 800 rpm 9 Reaction time 21 h 21 h

TABLE 9 GC-FID and titration results for the reductive amination of 2-ethyl-4-methylheptanal and 2,4-diethyl-octenal Red. amination Red. amination of of 2,4-diethyl- 2-ethyl-4- Method Result octenal methylheptanal GC-FID N-alkyl-N- 93.5 96.7 methylglucamines (area %) GC-FID Saturated/unsaturated 22:78 100:0 ratio GC-FID NMG (area %) N.D. N.D. Titration Total amines (meq/g) 2.71 N.A. Titration N-alkyl-N- 97.9 N.A. methylglucamines (%) (N.D., not determined; N.A., not applicable).

Examples 43-45. Solubility of Branched C8-C12 N-alkyl-N-methylglucamines

The solubility of three N-alkyl-N-methylglucamines (i.e., N-(2-ethyl-hexyl)-N-methylglucamine, N-decyl-N-methylglucamine, and N-(4-ethyl-2-methyloctyl)-N-methylglucamine) was investigated in pure MilliQ water and in a 10 wt % sodium lauryl sulfate (SLS) solution. The mixtures were heated to 80° C., ultrasonicated, and cooled to room temperature.

Table 10 shows that only N-(2-ethyl-hexyl)-N-methylglucamine was soluble at concentrations greater than 1000 ppm in pure MilliQ. The SLS formulations containing 1000 ppm N-alkyl-N-methylglucamine were diluted with MilliQ to obtain clear 0.05 wt % surfactant solutions, indicating that the glucamines are soluble up to 1000 ppm in a 10 wt % SLS solution even after dilution to a 0.05 wt % surfactant concentration.

TABLE 10 Solubility of N-(2-ethyl-hexyl)-N-methylglucamine, N-decyl- N-methylglucamine, and N-(4-ethyl-2-methyloctyl)-N-methylglucamine in pure MilliQ and in a 10 wt % SLS solution. Solubility Solubility Solubility Example in pure in 10 wt in 10 wt Numbers Product MilliQ % SLS % SDS 43 N-(2-ethyl- >1000 ppm >1000 ppm ≥1% hexyl)-N- (pH 9-9.5) (pH 10.8) (pH 12.1) methylglucamine 44 N-decyl-N- <1000 ppm >1000 ppm ≥1% methylglucamine (pH 9-9.5) (pH 11.1) (pH 11.8) 45 N-(4-ethyl-2- <1000 ppm >1000 ppm ≥1% methyloctyl)-N- (pH 9-9.5) (pH 11.0) (pH 12.0) methylglucamine (The corresponding pH values are shown between brackets).

Examples 46-49. Foaming Behavior of Branched C10 N-alkyl-N-methylglucamines

The high-shear foaming behavior of linear and branched N-alkyl-N glucamines was investigated, as this can have an impact on their performance in home care applications. Table 11 shows the foam volumes at time zero and after 5 minutes of solutions containing sodium lauryl sulfate, N-(2-ethyl-hexyl)-N-methylglucamine, N-decyl-N-methylglucamine, and lauryldimethylamine oxide (LDAO). The solutions were prepared by dissolving 1 wt % of the test substances in a 10 wt % sodium dodecyl sulfate solution, using MilliQ water as a solvent. The solutions were heated to 80° C., ultrasonicated for 1 h, and cooled to room temperature. Finally, the as-obtained solutions were diluted with MilliQ water to obtain a 0.05 wt % surfactant solution. In agreement with the literature on branched hydrophobes, the high-shear foaming tests performed in the commercial blender indicate that the linear N-decyl-N-methylglucamine (IC10 NMG) solution foams relatively more than its branched counterpart solution. For all solutions, the initial foam volume is between 40 and 53 mL. Lauramine oxide (LAO) appears to be foamier than the N-alkyl-N-methylglucamines.

TABLE 11 Foaming behavior of branched C10 N-alkyl-N-methylglucamines Foam volume after Example 5 seconds stirring Foam volume after 5 Number Sample at speed 1 (mL) minutes settling (mL) 46 Blank 48 42 47 bC10 NMG 40 38 48 IC10 NMG 50 49 49 LAO 53 50

Example 50. Conversion of C11 Aldehyde to 4-ethyl-N,N,2-trimethyloctan-1-amine (3) (C11-Amine)

To a 500 mL thick-walled parr-shaker flask, Raney-Ni (2 g) was added. A solution of dimethylamine (11% solution in EtOH, 193 g, 470 mmol) was added to this flask. To this solution was then added C11-aldehyde (2) (20 g, 117 mmol) obtained in the last step and the contents were hydrogenated using H2 gas (30 psi) for 12 h. After the reaction was complete, the catalyst was filtered and the volatiles were evaporated under reduced pressure. The residue was diluted with EtOAc (200 mL) and 10% aq. HCl (200 mL). The organic layer was separated and the product aq. Layer was washed with additional EtOAc (200 mL). The aq. Layer was separated and basified using saturated aq. NaHCO3 solution. This solution was then transferred to a separatory funnel and the pure product extracted using EtOAc (3×300 mL). The organic layer was separated, dried over MgSO4 and concentrated under reduced pressure to afford the pure C11 amine (3).

Example 51. Synthesis of 4-ethyl, 2-methyl, N,N-dimethylhexan-1-amine Via 4-ethyl, 2-methyloctanal

A vertical fixed bed reactor was charged with 50 ml (50 g) of a tableted CuO/ZnO/Al2O3 catalyst. After activation with hydrogen (180° C., ambient pressure, 24 h) a continuous gaseous flow was fed to the reactor which consist of hydrogen, dimethylamine and 4-ethyl, 2-methyloctanal (16) in the reactor at a pressure of 10 barg and a temperature of 250° C. The ratio of dimethylamine to the aldehyde to hydrogen was set at 3/1/50 and the aldehyde feed was set at 0.15 g/g catalyst/h. Bypass high pressure samples were taken from the reaction mixture downstream of the reactor and analyzed by gas chromatography. The experiments were run for 100 h and at steady state, the conversion was 99.9% and the yield towards the wanted 4-ethyl, 2-methyl, N,N-dimethylhexan-1-amine (17) was 85.04%. Yields of the different side-products (4-ethyl, 2-methylhexanol (20); 4-ethyl, 4-ethyl, 2-methyl, N-methylhexan-1-amine (18); N-(4-ethyl, 2-methyl hexyl)-N-methylhexan-1-amine (19) and bis (4-ethyl, 2-ethyl hexyl)amine) were respectively 0.36%, 8.15%, 1.63% and 0.18%.

Example 52. Synthesis of 2,4-diethyl, N,N-dimethyloctan-1-amine Via 2,4-diethyl-2-octenal

A vertical fixed bed reactor was charged with 50 ml (50 g) of a tableted CuO/ZnO/Al catalyst. After activation with hydrogen (180° C., ambient pressure, 24 h) a continuous gaseous flow was fed to the reactor which consist of hydrogen, dimethylamine and 2,4-diethyl-2-octenal (9) in the reactor at a pressure of 10 barg and a temperature of 250° C. The ratio of dimethylamine to the aldehyde to hydrogen was set at 3/1/50 and the aldehyde feed was set at 0.15 g aldehyde/g catalyst/hour. Bypass high pressure samples were taken from the reaction mixture downstream of the reactor and analyzed by gas chromatography. The experiments were run for 100 h and at steady state, the conversion was 99.9% and the yield towards the desired 2,4-diethyl, N,N-dimethyloctan-1-amine was 71.5%. Yields of the different side products 2,4-diethyloctanol; 2,4-diethyl, N-methyloctan-1-amine; 2,4-diethyl, N,N-dimethyloct-2-en-1-amine; N-(2,4-diethyloctyl)-N-methyloctan-1-amine and bis (2,4-diethyloctyl)amine) were respectively 2.13%, 5.20%, 11.14%, 3.20% and 1.25%.

Example 53. Synthesis of Branched C11 Hydroxysultaine

Preparation of 3-(4-ethyl-2-methyloctyl)dimethylammonio)-2-hydroxypropane-1-sulfonate (branched C11 hydroxysultaine)

4-Ethyl-N,N,2-trimethyloctan-1-amine (5.00 g; 25.08 mmol), sodium 3-chloro-2-hydroxypropanesulfonate (95.5%; 6.45 g; 31.35 mmol; 1.25 equiv), and sodium carbonate (0.425 g; 4.01 mmol; 0.16 equiv) were combined with 20 mL of isopropanol and 5 mL of water. The mixture was heated in an 85° C. oil bath for 18 h to afford 92.5% conversion of amine to product by HPLC. Additional sodium 3-chloro-2-hydroxypropanesulfonate (95.5%; 0.77 g; 3.76 mmol; 0.15 equiv), and sodium carbonate (0.266 g; 2.51 mmol; 0.1 equiv) were added and the mixture was heated for an additional 8 h in an 85° C. oil bath to afford 97.0% conversion to the desired branched C11 hydroxysultaine. The volatiles were removed at reduced pressure and water was added and the mixture was warmed to afford a homogeneous solution with a total weight of 27.4 g, indicating a 30 wt % solution of 3-((4-ethyl-2-methyloctyl)dimethylammonio)-2-hydroxypropane-1-sulfonate in water.

1H NMR (DMSO-d6): δ4.4 (m, 1H); 3.34 (m, 2H); 3.26 (m, 1H); 3.11 (s, 3H), 3.09 (s, 3H); 2.7 (m, 2H); 2.06 (m, 1H); 1.45-0.7 (m, 20H).

HPLC (150×4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1% trifluoroacetic acid) for 10 min, gradient to 100% methanol over 1 min, held at 100% methanol for 9 min, ELSD detection): tR 3.2 min. (starting amine); 3.5 min (branched C11 hydroxysultaine).

Example 54. Synthesis of Branched C12 Carboxybetaine

Preparation of 2-(2,4-diethyloctyl)dimethylammonio)acetate (Branched C12 Betaine)

2,4-diethyl-N,N-dimethyloctan-1-amine (3.00 g; 14.06 mmol), sodium chloroacetate (1.80 g; 15.46 mmol; 1.10 equiv), and sodium carbonate (0.149 g; 1.41 mmol; 0.1 equiv) were combined with 9 mL of isopropanol and 1.5 mL of water. The mixture was heated in an 85° C. oil bath for 24 h to afford 88% conversion of amine to product by HPLC. Additional sodium chloroacetate (0.25 g; 2.11 mmol; 0.15 equiv), and sodium carbonate (0.149 g; 1.41 mmol; 0.1 equiv) were added and the mixture was heated for an additional 8 h in an 85° C. oil bath to afford 89% conversion to the desired C12 betaine. Two additional charges of sodium chloroacetate (each 0.25 g; 2.11 mmol; 0.15 equiv) were added with a subsequent reaction time of 8 h in an 85° C. oil bath after each addition to afford a final conversion of amine to branched C12 betaine of 95% by HPLC. The volatiles were removed at reduced pressure and water was added to a total weight of 12.0 g as a 30% homogeneous solution of 2-((2,4-diethyloctyl)dimethylammonio)acetate in water.

HPLC (150×4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1% trifluoroacetic acid) for 10 min, gradient to 100% methanol over 1 min, held at 100% methanol for 9 min, ELSD detection): tR 3.6 min. (starting amine); 3.9 min (branched C12 betaine).

Example 55. Stain Removal of Branched C12 Carboxybetaine Added to Commercial Pre-Treaters

Standardized stain swatches (beef fat on poly/cotton, CFT-PC-61; Lot 004, TestFabrics, West Pittston, Pa.) were cut into 1-inch squares, accurately weighed and treated in triplicate with 0.1 ml of a commercial pre-treater formula, or with the commercial pre-treater supplemented with 3 wt % lauryl betaine (LB, linear) or 3 wt % Branched C12 carboxybetaine of Example 54, 2-(2,4-diethyloctyl)dimethylammonio)acetate. After 5 minutes, the swatches were washed in 200 ml diluted Tide for 30 minutes, rinsed in 200 ml de-ionized water for 30 minutes, then air-dried overnight. The % weight lost after pre-treatment, washing and drying (a measure of oily soil removal) is reported in Table 12 below. LB=Lauryl betaine (linear)

TABLE 12 Pre-treater with No additive Pre-treater 3% Branched C12 Treatment in Pre-treater with 3% LB carboxybetaine No Pre-treater 0.49 Zout 1.4 1.2 2.5 Spray 'n Wash 4.6 5.3 7.4 OxiClean Max Force 2.2 2.1 7.8

Example 56. Synthesis of Branched BAC-b12 (N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium Chloride)

2,4-Diethyl N,N-dimethyloctylamine (3.00 g; 14.06 mmol) and benzyl chloride (1.78 g; 14.06 mmol; 1.0 equiv) were combined in a 40 mL vial with a magnetic stir bar, which was heated with stirring in a 77° C. heat block for 6 h, at which point the mixture had solidified. Water (1.59 g) was added, and the mixture was stirred with heating at 77° C. for an additional 6 h to afford 99.3% conversion of the amine to branched BAC-b12 according to HPLC analysis. The resulting mixture is ca. 75% branched BAC-12 in water as a homogeneous liquid.

1H NMR (DMSO-d6): δ7.7-7.4 (m, 5H); 4.65 (m, 2H); 3.44 (m), 1H); 3.15 (t, J=11.7 Hz); 3.0-2.9 (m, 6H); 1.55-1.05 (m, 14H); 0.95-0.7 (m, 9H).

HPLC (150×4.6 mm Zorbax SB-C8 column, 75:25 (v:v) methanol:water (containing 0.1% trifluoroacetic acid) for 10 min, gradient to 100% methanol over 1 min, held at 100% methanol for 9 min, ELSD detection detection): tR 3.6 min. (starting amine); 4.1 min (branched BAC-b12).

Example 57. Antimicrobial Screening of BAC-b12

The minimum inhibitory concentration (MIC) and the minimum lethal concentration (MLC) of the chemicals were determined using a microplate dilution assay. Quats were provided as aqueous solutions, while Triclosan and Chloroxylenol were provide as powders which were first dissolved at 5 weight percent in absolute ethanol. A two-fold serial dilution series of each test chemical was prepared in Trypticase Soy Broth at 20% of the standard concentration (TSB20) and in Sabouraud Dextrose Broth at 20% of the standard concentration (SDB20) in 96-well micro-titer plates. A total of 10 dilutions were prepared and four replicate tests were performed for each dilution. The high concentration preparations of Triclosan and Chloroxylenol showed undissolved suspended material, but the suspensions were stable enough to prepare the dilutions series. Control solutions containing only media were included for each plate. Suspensions of Staphylococcus aureus, Escherichia coli, and Candida albicans were prepared from one-day old agar plate cultures in Butterfields Phosphate Diluent to a concentration of approximately 107 to 108 cells per milliliter. Each test well was inoculated with the diluted culture suspensions at a concentration of 103 to 104 cells per well and then incubated at 32° C. with shaking at 150 rpm for approximately 24 hours, after which the optical density of each well was determined spectrophotometrically at 600 nm. Wells containing uninoculated media without test chemical were included in each plate as negative controls and, following inoculation, as positive controls. MIC values were determined as the lowest concentration of test chemical for which all four replicates showed less than 10% (MIC<10%) or 50% (MIC<50%) of the positive control optical density.

Selected wells at or below the MIC were tested for MLC by spotting three microliters from each replicate well onto Trypticase Soy agar for S. aureus and E. coli, or Sabouraud Dextrose agar for C. albicans. The MLC was determined as the lowest concentration of test chemical for which at least three of the four replicates showed absence of growth on the agar.

The results are shown in Table 13.

TABLE 13 Antimicrobial effectiveness of BACs with different alkyl chain length and distribution. Weight percent Type Organism Compound MIC < 10% MIC < 50% MLC Gram Escherichia coli BAC (Sigma) 0.00020 0.00020 0.00078 neg BAC50 (Thor) 0.00039 0.00039 0.00078 bacteria BAC-12 linear 0.00078 0.00078 0.00078 BAC-b12 0.0063 0.0063 0.0063 branched Chloroxylenol >0.0083 >0.0083 >0.0083 Triclosan 0.00010 0.00010 0.00010 Gram Staphylococcus BAC (Sigma) 0.00020 0.00020 0.00020 pos aureus BAC50 (Thor) 0.00020 0.00020 0.00020 bacteria BAC-12 linear 0.00020 0.00020 0.00020 BAC-b12 0.00039 0.00039 0.00078 branched Chloroxylenol 0.0042 0.0042 >0.0083 Triclosan 0.00002 0.00002 0.00003 Yeast Candida BAC (Sigma) 0.00078 0.00078 0.00078 albicans BAC50 (Thor) 0.00078 0.00078 0.00078 BAC-12 linear 0.0016 0.00078 0.0016 BAC-b12 0.0063 0.0063 0.0063 branched Chloroxylenol 0.0083 0.0083 >0.0083 Triclosan 0.0016 0.0016 >0.0016 BAC = benzalkonium chloride, C8-18; BAC50 = benzalkonium chloride, C12-18; BAC-12 linear = benzalkonium chloride, C12; BAC-b12 = N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride (MIC = minimum inhibitory concentration; MIC <10% and MIC <50% are the lowest concentrations of test compound showing consistent reduction in growth to less than 10% and less than 50% of control level, respectively. MLC = minimum lethal concentration as judged by absence of any surviving cells following treatment.) (MIC = minimum inhibitory concentration; MIC <10% and MIC <50% are the lowest concentrations of test compound showing consistent reduction in growth to less than 10% and less than 50% of control level, respectively. MLC = minimum lethal concentration as judged by absence of any surviving cells following treatment.)

Example 58. Synthesis of Branched C12 Enal with (Branched BAC as PTC), NaOH, PTC, C4+C8

A 100 mL three neck round bottom flask is charged with 7.77 g (194 mmol) of NaOH pellets. 30 mL of water is added and the mixture stirred by means of a magnetic stir bar until the NaOH is dissolved. 3.14 g of a 75 weight % aqueous solution of N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride is added and stirring continues. A 50 mL dropping funnel, glycol chilled condenser, and thermometer are attached to the round bottom. The entire apparatus is brought to 50° C. The dropping funnel is charged with a mixture of n-butyraldehyde (10 g, 139 mmol) and 2-ethylhexanal (35.6 g, 277 mmol) and the aldehyde mixture is added slowly dropwise to the caustic mixture. After three hours, the mixture is cooled and poured into a 125 mL separatory funnel. The bottom aqueous layer is separated. The upper organic phase is washed with water and brine. The organic layer is dried over MgSO4, filtered, and the filtrate analyzed by GC. GC analysis shows 51% yield of 2,4-diethyl-oct-2-enal.

Example 59: Synthesis of Branched C12 Enal with (Branched BAC as PTC), NaOH, PTC, C8, then C4

A 100 mL three neck round bottom flask is charged with 7.77 g (194 mmol) of NaOH pellets. 30 mL of water is added and the mixture stirred by means of a magnetic stir bar until the NaOH is dissolved. 3.14 g of a 75 weight % aqueous solution of N-benzyl-2,4-diethyl-N,N-dimethyloctan-1-aminium chloride is added and stirring continues. 2-ethylhexanal (35.6 g, 277 mmol) is added. A 50 mL dropping funnel, glycol chilled condenser, and thermometer are attached to the round bottom. The entire apparatus is brought to 50° C. The dropping funnel is charged with of n-butyraldehyde (10 g, 139 mmol) and the aldehyde mixture is added slowly dropwise to the caustic mixture. After three hours, the mixture is cooled and poured into a 125 mL separatory funnel. The bottom aqueous layer is separated. The upper organic phase is washed with water and brine. The organic layer is dried over MgSO4, filtered, and the filtrate analyzed by GC. GC analysis shows 52% yield of 2,4-diethyl-oct-2-enal.

Example 60. Comparative Example

A 3 L three neck round bottom flask is charged with 20.8 g (708 mmol) of NaOH pellets. 75 mL of water is added and the mixture stirred by means of a magnetic stir bar until the NaOH is dissolved. 8.38 g (26 mmol) of tetrabutylammonium bromide is added. A 500 mL dropping funnel, glycol chilled condenser, and thermometer are attached to the round bottom. The entire apparatus is brought to 50° C. The dropping funnel is charged with a mixture of n-butyraldehyde (37.5 g, 520 mmol) and 2-ethylhexanal (133 g, 1040 mmol) and the aldehyde mixture is added slowly dropwise to the caustic mixture. After three hours, the mixture is cooled and poured into a 1 L separatory funnel. The bottom aqueous layer is separated. The upper organic phase is washed with water and brine. The organic layer is dried over MgSO4, filtered, and the filtrate analyzed by GC. GC analysis shows 65% yield of 2,4-diethyl-oct-2-enal. GC analysis also shows the mixture contains 3.5% tributyl amine by weight.

Example 61. Comparative Example

Alkyldimethylbenzylammonium chloride is purchased from Sigma Aldrich as a semi-solid mixture of components where the alkyl chain can vary from C8 to C18. This material is heated to 65° C. in an oven to obtain a flowable composition. A 3 L three neck round bottom flask is charged with 20.8 g (708 mmol) of NaOH pellets. 75 mL of water is added and the mixture stirred by means of a magnetic stir bar until the NaOH is dissolved. 8.84 g of alkyldimethylbenzylammonium chloride (20-30 mmol) is added. A 500 mL dropping funnel, glycol chilled condenser, and thermometer are attached to the round bottom. The entire apparatus is brought to 50° C. The dropping funnel is charged with a mixture of n-butyraldehyde (37.5 g, 520 mmol) and 2-ethylhexanal (133 g, 1040 mmol) and the aldehyde mixture is added slowly dropwise to the caustic mixture. After three hours, the mixture is cooled and poured into a 1 L separatory funnel. The bottom aqueous layer is separated. The upper organic phase is washed with water and brine. The organic layer is dried over MgSO4, filtered, and the filtrate analyzed by GC. GC analysis shows 52% yield of 2,4-diethyl-oct-2-enal.

Example 62. Synthesis of Branched C12 Butyl Quat

To a 25 mL sealed flask was added 2,4-diethyl-N,N-dimethyloctan-1-amine (3.0 g, 14.06 mmol) and 1-bromobutane 1.51 mL, 14.06 mmol). The tube was sealed tightly using a Teflon screw cap and placed in a preheated oil bath at 120° C. A blast shield was placed in front of the reaction. The contents of the tube was stirred at 120° C. for 12 h. The reaction tube was removed from the oil bath and allowed to cool to room temperature. 1H-NMR of the crude reaction mixture shows complete conversion of C12-dimethyl amine to N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium bromide (branched C12-butyl quat). The reaction mixture was diluted with water to make the final concentration to 75%.

1H NMR (500 MHz, CDCl3)) δ3.75-3.47 (m, 6H), 3.47-3.32 (m, 12H), 3.17 (ddd, J=13.4, 9.2, 3.9 Hz, 2H), 1.91-1.62 (m, 6H), 1.52 (tq, J=7.1, 3.1 Hz, 4H), 1.48-1.07 (m, 28H), 1.05-0.73 (m, 29H) ppm. 13C NMR (126 MHz, CDCl3) δ68.84, 68.77, 64.45, 51.42, 51.07, 37.89, 37.86, 36.06, 35.94, 35.90, 32.85, 32.38, 31.69, 31.63, 28.78, 28.61, 25.99, 25.96, 25.77, 25.25, 24.86, 23.11, 23.07, 19.64, 14.15, 14.11, 13.76, 10.73, 10.67, 10.46, 10.01, 9.94 ppm.

Example 63. Synthesis of C12-enal Using N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium Bromide (Branched C12-butyl quat.) as a PTC

To a 100 mL 3-neck flask equipped with a stir bar, reflux condenser, addition funnel and a temperature probe, NaOH (10.0 g, 125 mmol, 50% solution in water), water (12.16 mL) and N-butyl-2,4-diethyl-N,N-dimethyloctan-1-aminium bromide (2.92 g, 6.25 mmol, 75% solution in water) prepared in the last step was added. The flask was placed in an oil bath and the contents were stirred at 50° C. A mixture of 2-ethyl hexaldehyde (24.37 mL, 156 mmol) and n-butyraldehyde (11.83 mL, 131 mmol) was charged in a separatory funnel and added to the stirred mixture dropwise. The addition was maintained at such a rate that the internal temperature of the reaction did not rise above 55° C. After the addition was complete, the heating was continued for overnight and the crude reaction mixture was analyzed by GC which showed 38.9% (area %) of C12-enal.

Example 64. Comparative Example

To a 100 mL 3-neck flask equipped with a stir bar, reflux condenser, addition funnel and a temperature probe, NaOH (10.0 g, 125 mmol, 50% solution in water), water (12.16 mL) and methyl-tributyl ammonium chloride (1.96 g, 6.25 mmol, 75% solution in water) was added. The flask was placed in an oil bath and the contents were stirred at 50° C. A mixture of 2-ethyl hexaldehyde (24.37 mL, 156 mmol) and n-butyraldehyde (11.83 mL, 131 mmol) was charged in a separatory funnel and added to the stirred mixture dropwise. The addition was maintained at such a rate that the internal temperature of the reaction did not rise above 55° C. After the addition was complete, the heating was continued for overnight and the crude reaction mixture was analyzed by GC which showed 44.7% (area %) of C12-enal.

Example 65. Synthesis of 4-ethyl-N,N-2-trimethyloctan-1-amine Oxide (4) (Branched C11-Amine Oxide)

To a solution of C11-amine, 4-ethyl-N,N,2-trimethyloctan-1-amine (25 g, 125 mmol) in EtOH (125 mL) was added hydrogen peroxide (30% solution in water, 42.6 g, 376 mmol). The contents of the flask were stirred at 70° C. for 5 h. After the reaction was complete, the excess peroxide was quenched with activated charcoal (negative peroxide strip test). The contents of the flask were filtered through a 1 mm filter cloth. The filter cloth was washed with additional EtOH (200 mL). The combined filtrates were concentrated to dryness under reduced pressure. Residual EtOH and water was removed using nitrogen purge. The removal of any residual solvent using heat was avoided as the material caused decomposition through Cope-elimination at higher temperature.

Example 66. Synthesis of 2,4-diethyl-N,N-dimethyloctan-1-amine Oxide (Branched C12-Amine Oxide)

To a solution of C12-amine, 2,4-diethyl, N,N-dimethyloctan-1-amine (50 g, 234 mmol) in EtOH (234 mL) was added hydrogen peroxide (30% solution in water, 80 g, 703 mmol). The contents of the flask were stirred at 70° C. for 8 h. After the reaction was complete, the excess peroxide was quenched with activated charcoal (negative peroxide strip test). The contents of the flask were filtered through a 1 mm filter cloth. The filter cloth was washed with additional EtOH (300 mL). The combined filtrates were concentrated under reduced pressure. The residual EtOH and water was removed using nitrogen purge. The removal of any residual solvent using heat was avoided as the material caused decomposition through Cope-elimination at higher temperature).

Example 67. Modified Procedure for Synthesis of 2,4-diethyl-N,N-dimethyloctan-1-amine Oxide (Branched C12-Amine Oxide)

To a 500 mL 3-neck round bottom flask equipped with a stir bar, reflux condenser and a thermocouple, was added C12-amine, 2,4-diethyl, N,N-dimethyloctan-1-amine (50 g, 234 mmol), EtOH (58 mL) and water (150 mL). The mixture was stirred at 60° C. and hydrogen peroxide (34.5 g, 305 mmol, 30% solution in water) was added to it dropwise. The addition was maintained such that the internal temperature did not exceed 60-63° C. (˜30 minutes). The contents of the flask were stirred at 60° C. for 12 h. After the reaction was complete (as evidenced by HNMR), the excess hydrogen peroxide was quenched with activated charcoal (negative peroxide strip test). The contents of the flask were filtered through a 1 mm filter cloth. The filter bed was washed thoroughly with water in several small portions to ensure complete filtration of the C12-amine oxide. The combined filtrates were concentrated under reduced pressure. The EtOH removal was monitored by HNMR. If necessary, additional water was added to the flask to aid the removal of EtOH. After EtOH was removed completely from the reaction mixture, the final weight of the amine oxide was adjusted to 30% by additional water.

Example 68. Surface Wetting—Draves Wet Out Time

The surface wetting ability of the amine oxides with linear and branched hydrophobes from Examples 65 to 67 were compared using the Draves Wetting Test (ASTM D2281-68). A 0.05 wt % (actives basis) solution of amine oxide in deionized (DI) water was used to determine the Draves wet-out time (WOT) in seconds. 0.75 g of surfactant was dispersed in 1,500 ml of DI water. The wet-out time (WOT) in seconds is recorded in Table 14 (average of 3 measurements). LAO is Lauramine oxide (linear hydrophobe), Sigma catalog number 40236. The results are shown in Table 14.

TABLE 14 Wet out time Linear LAO    33 sec Oxo C11 AO >300 sec 4-ethyl-N,N-2- trimethyloctan-1- amine oxide Example 65 Oxo C12 AO >300 sec 2,4-diethyl-N,N- dimethyloctan-1- amine oxide Example 66

Example 69. Foam Height: High Shear

The surface foam volume and persistence of the amine oxides with linear and branched hydrophobes from Examples 65 and 66 were compared. A 0.05 wt % (actives basis) solution of the test surfactant was made in deionized water. 250 ml of the test solution was added the beaker of a Waring blender, capped, and then blended on High for 30 seconds and immediately transferred to a 1 L graduated cylinder. The total volume of foam plus liquid, as well as the liquid layer alone was recorded. The foam and liquid volumes were recorded again after 5 minutes. The foam volume only (excluding the liquid volume) is reported in Table 15.

TABLE 15 Foam volume Foam volume (ml) (ml) Initial 5 min % decrease Linear LAO 523 500 4% Oxo C11 AO 267 0 100% (4-ethyl-N,N-2- trimethyloctan- 1-amine oxide Example 65) Oxo C12 AO 370 0 100% (2,4-diethyl- N,N- dimethyloctan- 1-amine oxide Example 66)

Example 70. Salt Thickening

Amine oxides with linear and branched hydrophobes from Examples 65 to 66 were compared for salt-thickening in a formulation. Linear amine oxides tend to increase the viscosity of a formulation containing NaCl in a dose-dependent manner. The viscosity (cP; shear rate 3/s) of a simple formulation was measured as the salt concentration varied from 0 to 5 wt %.

TABLE 16 Ingredient Content SLS 4.3% SLES 4.3% Amine oxide 1.4% NaCl As noted DI water q.s.

TABLE 17 Viscosity with C11 AO (4-ethyl-N,N-2- trimethyloctan- NaCl content Viscosity with 1-amine oxide wt % LAO Example 65) 0 2 2 0.5 2 7 1.0 11 36 1.5 115 257 2.0 1,494 2,050 2.5 7,562 3,635 3.0 17,343 3,459 3.5 25,302 2,021 4.0 27,585 670 4.5 24,918 288 5.0 19,368 148

Example 71. Mildness Predicted by Zein Solubilization Test

Amine oxides with linear and branched hydrophobes from Examples 65 and 66 were compared in a screen to predict mildness of surfactants. There is a correlation between the ability of a surfactant to denature a protein and the skin irritation potential of that surfactant. The relationship is believed to result from surfactant binding to proteins like keratin, followed by the denaturation of these proteins, leading to skin irritation. A common screening test involves measuring the amount of zein (a corn protein which is insoluble in water) solubilized by a surfactant solution, the Zein Solubilization Test (Moore et al., 2003 and references therein)

For the test, 0.0750 g of zein protein is transferred into a 1.5 mL centrifuge tube. To this 1.5 mL of 1% surfactant solution is added, mixed, and placed in a 30 C incubator with mild stirring for 30 minutes. After 30 minutes has elapsed, the tube is centrifuged for 30 min at 3600 rpm. The solution is filtered through a pre-weighed 8 micron filter paper, and then dried overnight in a 50° C. oven. The insoluble zein residue is then weighed and the wt % Zein dissolved is calculated using the equation below. Each solution is analyzed in triplicate. The Zein score is normalized to a standard included in each set of tests, in this case LAE10.


% zein dissolved=(total zein added−total zein after drying Total zein added)×100

TABLE 18 Zein score - Sample normalized to LAE10 oxoC12 amine oxide, (2,4-diethyl-N,N- 0.018 dimethyloctan-1-amine oxide, Example 66) APG, alkylpolyglucoside 0.586 LAE10, Linear alcohol ethoxylate, EO10 1.000 SDS, sodium dodecyl sulfate 2.470 SLES, sodium lauryl ether sulfate 3.488 LAO, N,N-dimethyl laurylamine oxide 4.212 LABS, linear alkylbenzene sulfonate 4.670

Example 72. Stain Removal in Cold Water

Amine oxides with linear and branched hydrophobes were compared in a screen for stain removal in cold water. Simple laundry liquid formulations were made that included only surfactants and builder. The results are shown in Table 19.

TABLE 19 Component Wt % NaCitrate 1.55 Anionic Steol CS-230 6 SLES Anionic Biosoft S-101 6 LABS Nonionic Biosoft EC-690 12 LAE7 De-ionized water q.s.

Standard stain swatches were purchased from Testfabrics, Inc. (West Pittston, Pa.). STC/CFT PC-S-216 is diluted red lipstick on poly/cotton (65/35), and STC/CFT PC-S-132 is high discriminative sebum (synthetic) with pigment on poly/cotton, both made by Center for Testmaterials BV (CFT; The Netherlands). The swatches were pre-cut into 2 inch squares. The test formulation was diluted with DI water to 0.06% total surfactant to make the wash solution. Additives were added at a final concentration of 0.05% active in the wash solution. Stained fabric swatches were added to the wash solution, washed and rinsed at 20° C., and air-dried. The average swatch brightness (L*) for each treatment, and standard deviation, are reported for 3 replicates. A different lower-case letter in the last column indicates treatments that are significantly different from each other (p<0.02). All treatments are brighter than the untreated stain swatches. The nonionics NPE and LAE7 removed the lipstick and sebum stains to the same brightness. Three additives included at 0.05% in a base formulation containing 12% LAE7 significantly improved the removal of the lipstick stain, but not the synthetic sebum stain. Standard lauramine oxide (Sigma LAO) at 0.05% active resulted in a significantly brighter swatch after washing. An amine oxide made from a branched C11 aldehyde (branched C11 AO) was better than LAO at removing the lipstick stain, and created very little foam in the wash solution compared to LAO.

TABLE 20 Stain removal estimated by brightness (L*) Red lipstick CFT Sebum PC-S-216 CFT PC-S-132 Std Std avg L* dev avg L* dev No Treatment 70.3 0.58 a 71.2 1.4 a 12% LAE7 73.9 0.57 b 72.5 1.1 b 12% LAE7 + Sigma LAO 74.8 0.46 c 72.8 1.1 b 12% LAE7 + Branched 76.3 0.48 d 72.7 1.2 b C11 AO, (4-ethyl-N,N-2- trimethyloctan-1-amine oxide, Example 65)

Example 73. ASTM D4265 for Stain Removal in Cold Water (Branched C12 AO)

Amine oxides with linear and branched hydrophobes were compared in a washing machine test for stain removal in cold water. ASTM 4265 is a Standard Guide for Evaluating Stain Removal Performance in Home Laundering. A commercial laundry liquid was used as the base formulation. The commercial laundry liquid (all free clear) contains ethoxylated lauryl alcohol, sodium laureth sulfate, sodium carbonate, tetrasodium iminosuccinate, acrylic polymer and stilbene disulfonic acid triazine brightener, but no enzymes, dyes or fragrance. The base formulation was tested alone or augmented with 2% (volume, actives basis) amine oxide.

The test laundry formulations are evaluated in three separate loads in a household front-loading high-efficiency (HE) washing machine connected to a city water source. The cold water wash option was selected on the machine. The water temperature was monitored using an in-wash recording device, and stayed between 15 and 20° C. for the duration of the test period. Each load contained a pre-stained fabric swatch and clean ballast fabric. The manufacturer-recommended laundry liquid dose was 44 ml/load.

The stain/fabric combination used for this test is the standard SwissaTest EMPA 102; a pre-soiled Cotton-Jersey (23×19 cm) with 15 different stains (3 cm): Make-up, curry, red wine, tomato sauce, blood, chocolate dessert, peat, tea, beta-carotene, grass, animal fat/red dye, baby food, clay, butter and used engine oil. These swatches are available from TestFabrics, Inc., West Pittston Pa.

The test swatches are treated with the products being compared, and the relative degree of stain removal is assessed instrumentally. The stain removal index (SRI) is calculated for each stain type, and the total SRI across all 15 stains is reported. A higher SRI indicates better stain removal. The duration of the cycle is also noted. When LAO was added at 2%, the oversuds error was activated in the machine, and the rinse cycle continued indefinitely, or else the cycle aborted.

TABLE 21 Duration of full Laundry Liquid Total SRI cycle (min) Base formulation 508 48 Base + 1% oxoC12 AO 524 46 (2,4-diethyl-N,N-dimethyloctan-1- amine oxide, Example 66) Base + 2% oxoC12 AO 564 47 of Example 66 Base + 2% LAO No data Suds Error

Example 74. Stain Removal of Branched C12 Amine Oxide Added to a High Anionic Laundry Liquid

A high-anionic surfactant laundry liquid formula was made and diluted for use to a final surfactant concentration of 0.06% in the wash solution.

Ingredient “Lab Liquid A” AES, alkyl ether sulfate, 7.5% Steol CS-203 LABS, linear alkyl benzene sulfonate 7.5 Biosoft S101 Propylene Glycol 3.75 Sodium citrate 3.75 Sodium Lauryl Sulfate 3.75 LAE10 1.25 Lauric acid, sodium salt 0.625 Water Qs Total surfactant  20% Final pH 10 Dose per load (to 0.06% surfactant) 0.6 g/200 ml wash solution

Two-inch stain swatches (Tenside stain Swissatest EMPA 125 (Lot 03-04), Testfabrics) were washed in water, diluted “Lab Liquid A” detergent or diluted detergent with added Branched C12 amine oxide (2,4-diethyl-N,N-dimethyloctan-1-amine oxide, Example 66). After washing and drying, the fabric brightness was measured with a Konica Minolta colorimeter. Treatments were performed on triplicate swatches in three independent treatments, and the brightness (L*) average and standard deviation were calculated for each treatment. The three treatments were statistically different from each other (p<0.02).

TABLE 22 Fabric brightness (L*) Treatment avg stdev group No 55.17 0.40 A detergent No additive 60.31 1.1 B +3% 62.45 0.7 C Branched C12 amine oxide

Example 75. Foaming of C12 Amine Oxide Added to a Commercial Laundry Liquid

The surface foam volume and foam persistence of solutions of the amine oxides with linear and branched hydrophobes from Examples 25 and 26 were compared. A commercial laundry liquid was diluted in deionized water according to the dosing instructions; 4.2 ml/L Persil Original. The diluted detergent was supplemented with 0%, 2%, 5% (based on wt laundry liquid) of LAO or Branched C12 AO, (2,4-diethyl-N,N-dimethyloctan-1-amine oxide, Example 66), and the solutions mixed briefly and used immediately. 250 ml of each test solution was added the beaker of a Waring blender, capped, and then blended on High for 30 seconds and immediately transferred to a 1 L graduated cylinder. The total volume of foam plus liquid, as well as the liquid layer alone was recorded. The foam and liquid volumes were recorded again after 5 minutes. All tests were performed in triplicate. The average foam volume only (excluding the liquid volume) is reported in the Table 23 below.

TABLE 23 Foam Initial foam volume After Sample volume (ml) 5 min (ml) Difference Persil Original 553 327 226 Persil 2% LAO 527 473 54 Persil 5% LAO 513 507 6 Persil 2% oxoC12 560 303 257 Persil 5% oxoC12 560 280 280 Persil 5% oxoC12 810 530 280

Example 76. Branched C12 Amine Oxide Pre-Treater on Lipstick Stain

Different surfactants (6%) were incorporated into a simple Pre-Treater formula:

Standard Pre-Treater (PT) Formula

6% surfactant
6% propylene glycol
2% trisodium citrate
2% poly(acrylic acid), sodium salt, MW 5,000

Standardized stain swatches (Lipstick on polyester/cotton fabric, CFT PCS-216, Lot 110) were cut into 2-inch squares, and 0.2 ml of the Standard PT formula was applied to the center of each swatch. After 5 minutes, the swatches were washed in cold water (20 C) in a benchtop vessel in diluted Tide, rinsed and air dried. Treatments were performed in triplicate. The fabric brightness after washing is reported as (L*) and the change in the color of the swatches after treatment, washing and drying as delta E, with higher values representing better stain removal.

TABLE 24 Lipstick L* deltaE No pre-treatment 74.2 10.9 Surfactant in PT Formula (6%) LAE10 77.9 18.2 APG 78.0 18.9 LABS 78.4 19.4 Branched C12 amine oxide (2,4-diethyl-N,N- 80.2 23.3 dimethyloctan-1-amine oxide, Example 66)

Example 77. Stain Removal of Branched C12 Amine Oxide in a Stain Remover with Hydrogen Peroxide

A stain remover was formulated with surfactants and hydrogen peroxide.

Hydrogen Peroxide Pre-Treater (PT) Formula

3% hydrogen peroxide
3% amine oxide
1% linear alkylbenzene sulfonate
Adjust to pH 9 with NaOH

Standardized stain swatches (beef fat on poly/cotton, CFT-PC-61; Lot 004) were cut into 1-inch squares, accurately weighed and treated in triplicate with 0.1 ml of the Hydrogen Peroxide Pre-treater formula containing either a linear or branched amine oxide. After 5 minutes, the swatches were washed in 200 ml diluted Tide for 30 minutes, rinsed in 200 ml de-ionized water for 30 minutes, then air-dried overnight. The % weight lost after pre-treatment, washing and drying (a measure of oily soil removal) is reported in the Table 25 below.

TABLE 25 Amine oxide in Hydrogen Peroxide Pre-treater formula (3%) % wt loss Lauramine oxide (LAO) 9.7 Branched C12 amine oxide (2,4-diethyl-N,N- 13.4 dimethyloctan-1-amine oxide, Example 66)

Example 78. Stain Removal of Linear and Branched Amine Oxides Added to a Commercial Pre-Treater

A commercial stain remover pre-treater spray was used as the base formulation. The commercial pre-treater spray (Zout) contains Water; C14-15 pareth-7; C12-15 pareth-3; Boric acid; Calcium chloride; Sodium hydroxide; Propylene glycol; Sodium chloride; Protease, lipase, amylase; Dimethicone; Methylisothiazolone and Fragrance.

Standardized stain swatches (beef fat on poly/cotton, CFT-PC-61; Lot 004) were cut into 1-inch squares, accurately weighed and treated in triplicate with 0.1 ml of a commercial pre-treater formula, or with the commercial pre-treater Zout or with Zout supplemented with 3 wt % lauramine oxide or 3 wt % Branched C12 amine oxide, 2,4-diethyl-N,N-dimethyloctan-1-amine oxide. After 5 minutes, the swatches were washed in 200 ml diluted Tide for 30 minutes, rinsed in 200 ml de-ionized water for 30 minutes, then air-dried overnight. The % weight lost after pre-treatment, washing and drying (a measure of oily soil removal) is reported in the Table 26 below.

TABLE 26 % wt loss Additive in Zout (3%) Trial 1 Trial 2 Avg No additive in Pre-treater 0.31 0.41 0.36 Lauramine oxide 7.5 6.3 6.9 Branched C12 amine oxide (2,4-diethyl-N,N- 11.0 8.8 9.9 dimethyloctan-1-amine oxide, Example 66)

Example 79. ASTM 4265 Stain Removal in Cold Water (Branched C12 AO Added to Commercial Pre-Treater)

The stain-removal activities of a commercial stain pre-treater with and without the addition of 3 wt % branched C12 amine oxide were compared in a washing machine test for stain removal in cold water. ASTM 4265 is a Standard Guide for Evaluating Stain Removal Performance in Home Laundering.

A commercial stain remover pre-treater spray was used as the base formulation. The commercial pre-treater spray (Zout) contains Water; C14-15 pareth-7; C12-15 pareth-3; Boric acid; Calcium chloride; Sodium hydroxide; Propylene glycol; Sodium chloride; Protease, lipase, amylase; Dimethicone; Methylisothiazolone and Fragrance.

The base formulation was tested alone or augmented with 3 wt % branched C12 amine oxide. The pre-treater (0.3 ml) was applied to the center of each stain on a stain panel and allowed to sit for 5 minutes before washing in liquid laundry detergent. The stain panel was the standard SwissaTest EMPA 102; a pre-soiled Cotton-Jersey (23×19 cm) with 15 different stains (3 cm), available from TestFabrics, Inc., West Pittston Pa. The test laundry formulations were evaluated in separate loads in a household front-loading high-efficiency (HE) washing machine connected to a city water source. The cold water wash option was selected on the machine. The water temperature was monitored using an in-wash recording device, and stayed between 15 and 20 C for the duration of the test period. Each load contained a pre-stained fabric swatch and clean ballast fabric. The manufacturer-recommended laundry liquid dose was used for each detergent.

The relative degree of stain removal is assessed instrumentally. The stain removal index (SRI) is calculated for each stain type, and the average and total SRI across all 15 stains is reported. A higher SRI indicates better stain removal.

TABLE 27 Commercial Pre-treater + 3% Branched C12 amine oxide (2,4-diethyl- N,N-dimethyloctan-1- Detergent for No Pre- Commercial amine oxide, Example post-wash treater pre-treater 66) Average SRI Tide 34 40 47 Persil 31 40 45 All Free Clear 30 42 46 Total SRI Tide 511 594 701 Persil 467 600 678 All Free Clear 447 634 691

In the specification, there have been disclosed certain embodiments of the invention and, although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention being set forth in the following claims.

Claims

1. A trialkylamine having the formula:

wherein R1 and R2 are each independently selected from straight or branched chain or cyclic hydrocarbon radicals having 1 to 8 carbon atoms
wherein R5, R6 and R7 are independently at least one of C3H7, C2H5, CH3, or H, or mixtures thereof; and
wherein R5 and R6 are not H at the same time.

2. The trialkylamine of claim 1 wherein (a) R1 and R2 are each independently substituted with groups selected from: —OR3; carboxyl; —NHCOR4; —CONHR4; cyano; —CO2R3; —OCOR3; hydroxy; aryl; heteroaryl; chlorine; or mixtures thereof, (b) R3 is selected from C1-C6 alkyl, substituted C1-C6 alkyl or mixtures thereof and (c) R4 is selected from C1-C4 alkyl or substituted C1-C15 alkyl.

3. The trialkylamine of claim 1 wherein R1 and R2 are CH3.

4. The trialkylamine of claim 1 wherein R1 is CH3 or C2H5 and R2 is a carbohydrate or amino acid.

5. The trialkylamine of claim 1 wherein R5 and R6 are C3H7, C2H5, CH3, or mixtures thereof; and wherein R7 is one of C3H7, C2H5, CH3, H or mixtures thereof.

6. The trialkylamine of claim 1 wherein R5 is CH3 or C2H5.

7. The trialkylamine of claim 1 or 6 wherein R6 is CH3 or C2H5.

8. The trialkylamine of claim 1 selected from 4-ethyl-N,N,2-trimethyloctan-1-amine, 4-ethyl, 2-methyl, N,N-dimethylhexan-1-amine, or 2,4-diethyl, N,N-dimethyloctan-1-amine.

9. A carboxybetaine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 cannot both be H.

10. The carboxybetaine of claim 9 wherein R5 is CH3 or C2H5.

11. The carboxybetaine of claim 9 or 10 wherein R6 is CH3 or C2H5.

12. A composition comprising the carboxybetaine of claim 9.

13. A product comprising dish detergent, car wash detergent, shampoo, face wash, body wash; fabric stain remover or fabric cleaner comprising the carboxybetaine of claim 9.

14. A hydroxysultaine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3 or H wherein R6 and R7 cannot both be H.

15. The hydroxysultaine of claim 14 wherein R5 is CH3 or C2H5.

16. The hydroxysultaine of claim 14 or 15 wherein R6 is CH3 or C2H5.

17. A composition comprising the hydroxysultaine of claim 14.

18. A product comprising dish detergent, car wash detergent, shampoo, face wash, body wash; fabric stain remover or fabric cleaner comprising the hydroxysultaine of claim 14.

19. An N-alkyl-N glucamine having the formula:

wherein R5, R6 and R7 are C3H7, C2H5, CH3, or H, and Z is a polyhydroxyhydrocarbyl moiety derived from a reducing sugar in a reductive amination reaction;
wherein said reducing sugar is glucose, mannose, fructose, sorbose, arabinose, maltose, isomaltose, maltulose, isomaltulose, trehalulose, lactose, glyceraldehyde, galactose, xylose, ribose, cellobiose, xylobiose or a combination thereof.

20. A product comprising the N-alkyl-N glucamines of claim 19 selected from coatings, inks, adhesives, agricultural formulations, fountain solutions, photoresist strippers and developers, shampoos, and detergents, personal care products, skin cleansers, and cleaning compositions.

Patent History

Publication number: 20190218170
Type: Application
Filed: Jan 9, 2019
Publication Date: Jul 18, 2019
Applicant: Eastman Chemical Company (Kingsport, TN)
Inventors: Stephanie Kay Clendennen (Kingsport, TN), Vasudev R. Bhonde (Johnson City, TN), Damon Ray Billodeaux (Longview, TX), Matthew Allen Boone (Kingsport, TN), Kim Dumoleijn (Eede), Stijn Simonne Paul Van de Vyver (Gent), Kristof Moonen (Hamme), Neil Warren Boaz (Kingsport, TN)
Application Number: 16/243,229

Classifications

International Classification: C07C 211/04 (20060101); C07C 229/12 (20060101); A61Q 5/02 (20060101); A61Q 19/10 (20060101); A61K 8/41 (20060101); A61K 8/46 (20060101); C07C 309/14 (20060101); C07H 5/06 (20060101); C11D 1/90 (20060101); C11D 11/00 (20060101); A61K 8/44 (20060101);