Inventors: Mika L. Shiramizu, Alan A. Galuska, Alex E. Carpenter, Shiwen Li

CLAIM TO PRIORITY

[0001] This application claims priority to U.S. Provisional Application No. 62/864,299, filed June 20, 2019, and European Patent Application No. 19194190.5, filed August 28, 2019, the disclosures of which are incorporated herein by reference.

BACKGROUND

[0002] Surfactants are compounds that tend to lower the surface tension at an interface between two components. As such, surfactants may be used in a wide range of applications, which may include, for example, promoting solubility of an otherwise sparingly soluble solid, lowering viscosity of a fluid phase, and promoting foaming of a fluid. Surfactants may be found in a wide range of consumer and industrial products including, for example, soaps, detergents, cosmetics, pharmaceuticals, and dispersants

[0003] Surfactants feature both hydrophobic and hydrophilic portions within their molecular structure. As such, surfactants are amphiphilic. Hydrophobic portions are generally non-ionic and may include saturated or unsaturated hydrocarbyl groups, such as alkyl, alkenyl, or aryl groups. Hydrophilic portions, in contrast, feature polar head groups that may be ionic, non-ionic, or zwitterionic and encompass a range of polar functional groups or moieties. Ionic functional groups that may be present in the hydrophilic portion of surfactants include, for example, sulfonates, sulfates, carboxylates, phosphates, quaternary ammonium groups, and the like. Non-ionic hydrophilic portions may include functional groups or moieties bearing one or more heteroatoms that are capable of receiving hydrogen bonds, such as polyethers (e.g. , ethoxylates). Zwitterionic hydrophilic portions may include moieties such as betaines, sultaines, and related phospholipid compounds.

[0004] Surfactants finding extensive commercial use generally feature a relatively limited range of structure types. Common classes of commercial surfactants include, for example, alkylbenzene sulfonates, lignin sulfonates, long chain fatty alcohol sulfates, long chain fatty acid carboxylates, long chain fatty alcohol ethoxylates, long chain quaternary ammonium compounds, and alkylphenol ethoxylates. The various classes of surfactants may exhibit a range of surfactant properties, and there may be further property variation within the members or homologues within each class. Accordingly, a surfactant for a given application may be chosen based upon various application-specific requirements. There remains a need, however, for development of additional types of surfactants having additional structural diversity to accommodate presently unmet or unknown application-specific requirements within various industries.

[0005] Publications of interest include US 6,060,443; WO 2003/082782A1; WO

1998/23566A1; and US 2004/133037A1.

SUMMARY

[0006] Compositions comprising amphiphilic compounds described herein may comprise a reaction product of one or more lightly branched olefins, the lightly branched olefins made by combining C3-C6 with a heterogeneous zeolite catalyst; the reaction product comprising a hydrophobic portion and a hydrophilic portion comprising a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in each of the one or more lightly branched olefins undergoes a reaction to become saturated and to produce at least part of the hydrophobic portion; and wherein the one or more lightly branched olefins have a Branch Index within a range from 0.5 to 2.1, and wherein the lightly branched olefin comprises at least 70 wt%, by weight of the lightly branched olefin, of mono-methyl branched isomers and dimethyl branched isomers.

[0007] Detergent formulations described herein comprises an aqueous fluid; and the composition described herein comprising one or more amphiphilic compounds; wherein the amphiphilic compounds are present in the aqueous fluid at a concentration ranging from 10 wt% to 80 wt%.

BRIEF DESCRIPTION OF THE DRAWINGS

[0008] The following figures are included to illustrate certain aspects of the present disclosure, and should not be viewed as exclusive embodiments. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to one of ordinary skill in the art and having the benefit of this disclosure.

[0009] FIG. 1 shows a gas chromatography flame ionization desorption spectrum of the product of Example 1 (BI = 1.36).

[0010] FIG. 2 shows a ¹ H NMR spectrum of the product of Example 1 in deuterated chloroform (BI = 1.36).

[0011] FIG. 3 shows a ¹³ C NMR spectrum of the product of Example 1 in deuterated chloroform (BI = 1.36). [0012] FIG. 4 shows a gas chromatography flame ionization desorption spectrum of another product of Example 1 (BI = 1.00).

[0013] FIG. 5 shows a ¹ H NMR spectrum of another product of Example 1 in deuterated chloroform (BI = 1.00).

[0014] FIG. 6 shows a ¹³ C NMR spectrum of another product of Example 1 in deuterated chloroform (BI = 1.00).

[0015] FIG. 7 shows a ¹ H NMR spectrum of the product of Example 3 in deuterated chloroform.

[0016] FIG. 8 shows a ¹ H NMR spectrum of the product of Example 3 in deuterated chloroform.

DETAILED DESCRIPTION

[0017] The present disclosure generally relates to amphiphilic compounds and, more specifically, to surfactants formed from lightly branched olefins and methods for production thereof.

[0018] As discussed above, most surfactants in common commercial use are based upon a relatively limited number of chemical structural classes. The various structural classes, as well as specific members or homologues within each structural class, may exhibit a range of surfactant properties, which may be chosen for suitability or compatibility with a given application. Some existing and emerging applications may have application- specific needs that are not adequately met by presently available surfactants. For example, certain conventional surfactants may not provide sufficient surface modification effects and/or adequate performance at decreased temperatures.

[0019] The present disclosure describes various classes of amphiphilic compounds that are reaction products of lightly branched olefins and that may exhibit surfactant properties. Typically, the reaction products are formed from a mixture of different lightly branched olefins, such that the reaction products comprise a plurality of amphiphilic compounds having hydrocarbyl chain branches. Amphiphilic compounds of the present disclosure feature a hydrophobic portion formed, at least in part, from one or more lightly branched olefins (an olefin or mixture of olefins having a Branch Index (BI), discussed further below, less than or equal to 2.1 and greater than or equal to 0.5), and a hydrophilic portion comprising a polar head group appended (bonded) directly or indirectly to the hydrophobic portion. The branching of the lightly branched olefin, as measured by the Branch Index, may affect certain characteristics of the surfactant. For instance, the packing factor, which is the ratio of the volume of the hydrophobic portion to an interfacial area occupied by the hydrophilic portion and the length of the hydrophobic portion, is affected by branching of the lightly branched olefin. As another example, the surface activity of an amphiphilic compound may be impacted by the branching of the parent lightly branched olefin(s). Consequently, amphiphilic compounds formed from one or more lightly branched olefins may have distinctive characteristics in comparison to linear olefins or highly branched olefins.

[0020] Lightly branched olefins often are obtained synthetically as a mixture of olefins, and an example of how they are obtained is disclosed in PCT/US2019/053092, filed September 26, 2018. Typical, lightly branched olefins may feature either an internal or a terminal double bond within a given olefin molecule, including positional isomers of internal double bonds, and isomeric mixtures with respect to the location of the branch or branches. Further, the branch position relative to the double bond may vary, and the lightly branched olefins may be mono-, di-, tri-, or tetra- substituted olefins. Diolefins may be co-present with the lightly branched olefins in minimal amounts. The chain lengths of the lightly branched olefins also may vary within a given olefin mixture, or the lightly branched olefins may be all of the same length. When obtained as a mixture of olefins, the mixture of olefins may feature a Branch Index that characterizes the one or more olefins as being lightly branched. That is, some members within a mixture of olefins may have Branch Index values greater than 2.1 or less than 0.5, but on the whole, the mixture of olefins has a weighted average Branch Index from 0.5, or 0.8, or 1 to 1.6, or 1.8, or 2.1.

[0021] Advantageously, lightly branched olefins may undergo a wide variety of reactions to form reaction products that may have surfactant properties. The double bond is consumed (becomes saturated) when forming the reaction products, thereby affording a hydrophobic portion derived, at least in part, from the lightly branched olefin and a hydrophilic portion featuring a polar head group bound directly or indirectly to the hydrophobic portion, in which the branching originally present in the lightly branched olefins remains substantially constant and the branch positions are maintained in the hydrophobic portion of the resulting amphiphilic compound. Depending on particular application needs, various hydrophilic moieties may be introduced according to the disclosure herein. Illustrative amphiphilic compounds that may be produced from lightly branched olefins according to the disclosure herein include surfactants comprising alkylbenzene sulfonates, primary alcohols, secondary alcohols, diols, primary or secondary alcohol sulfates or diol sulfates, primary or secondary alcohol alkoxylates or diol alkoxylates, primary or secondary alcohol alkoxylate sulfonates, carboxylates, carboxylic acid esters, methyl ester sulfonates, sulfonates, and amine oxides. In non-limiting examples, reactions such as, for example, hydroformylation, hydroboration, oxidation, epoxidation, sulfonation, and hydroxysulfonation of the lightly branched olefins may be employed to produce such amphiphilic compounds. Further description of the reactions that lightly branched olefins may undergo to produce the amphiphilic compounds of the present disclosure is provided below.

[0022] The reaction products disclosed herein may have low Krafft points, high hard water tolerance, and improved solubility over previously characterized surfactants. Without being limited by theory, the foregoing properties may arise from low crystallinity of the amphiphilic compounds.

[0023] Unless otherwise indicated, room temperature is 25 °C.

[0024] For the purposes of the present disclosure, the new numbering scheme for groups of the Periodic Table is used. In said numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides).

[0025] The term“hydrocarbon” refers to a class of compounds containing hydrogen bound to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term“C _n ” refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer. Such hydrocarbons or hydrocarbyl groups may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, or aromatic.

[0026] The terms “saturated” or“saturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which all carbon atoms are bonded to four other atoms or bonded to three other atoms with one unfilled valence position thereon.

[0027] The terms“unsaturated” or“unsaturated hydrocarbon” refer to a hydrocarbon or hydrocarbyl group in which one or more carbon atoms are bonded to less than four other atoms, optionally with one unfilled valence position on the one or more carbon atoms.

[0028] The terms“hydrocarbyl” and“hydrocarbyl group” are used interchangeably herein.

The term“hydrocarbyl group” refers to any Ci-Cioo hydrocarbon group bearing at least one unfilled valence position when removed from a parent compound.“Hydrocarbyl groups” may be optionally substituted, in which the term“optionally substituted” refers to replacement of at least one hydrogen atom or at least one carbon atom with a heteroatom or heteroatom functional group. Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te. Heteroatom functional groups that may be present in substituted hydrocarbyl groups include, but are not limited to, functional groups such as O, S, S=0, S(=0) ₂ , NO2, F, Cl, Br, I, NR ₂ , OR, SeR, TeR, PR ₂ , AsR ₂ , SbR ₂ , SR, BR ₂ , SiR ₃ , GeR ₃ , SnR ₃ , PbR ₃ , where R is a hydrocarbyl group or H. Suitable hydrocarbyl groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycyl, and the like, any of which may be optionally substituted.

[0029] The term“alkyl” refers to a hydrocarbyl group having no unsaturated carbon-carbon bonds, and which may be optionally substituted. The term“alkylene” refers to an alkyl group having at least two open valence positions.

[0030] The term“alkenyl” refers to a hydrocarbyl group having a carbon-carbon double bond, and which may be optionally substituted. The terms“alkene” and“olefin” may be used synonymously herein. Similarly, the terms “alkenic” and “olefinic” may be used synonymously herein. Unless otherwise noted, all possible geometric and positional isomers are encompassed by these terms.

[0031] The terms“aromatic” and“aromatic hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a cyclic arrangement of conjugated pi-electrons that satisfy the Hiickel rule. The term“aryl” is equivalent to the term“aromatic” as defined herein. The term “aryl” refers to both aromatic compounds and heteroaromatic compounds, either of which may be optionally substituted. Both mononuclear and polynuclear aromatic compounds are encompassed by these terms.

[0032] Examples of saturated hydrocarbyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues. Examples of unsaturated hydrocarbyl groups include, but are not limited to, ethenyl, propenyl, allyl, butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl and the like, including their substituted analogues.

[0033] Examples of aromatic hydrocarbyl groups include, but are not limited to, phenyl, tolyl, xylyl, naphthyl, and the like, including all possible isomeric forms thereof. Polynuclear aromatic hydrocarbyl groups may include, but are not limited to, naphthalene, anthracene, indane, and indene. [0034] The terms“oligomer(s)” and“oligomeric product” refer to a molecule having a predetermined number of repeating monomer units, where the number of repeating monomer units is relatively small and specifiable. Illustrative oligomers include dimers, trimers, tetramers, higher oligomers, and mixtures thereof. The number of monomer units forming the lightly branched olefins of the present disclosure may be fewer than 30, and may be fewer than 10, particularly if formed from propylene and/or higher carbon count alkenes. The term “oligomerization process” refers to any process of catalytically joining monomer units together to form an oligomer or oligomers. The term“oligomerization conditions” refers to any and all variations of equipment, reaction conditions (e.g., temperatures, pressures, and/or flow rates), materials, and reactor configurations that are suitable to conduct an oligomerization process. Olefin oligomers may have some of the monomer units arranged such that light branching, as defined herein, is present upon the oligomer.

[0035] The terms“linear” and“linear hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a continuous carbon chain without side chain branching, in which the continuous carbon chain may be optionally substituted with heteroatoms or heteroatom groups.

[0036] The terms “branch,” “branched” and “branched hydrocarbon” refer to a hydrocarbon or hydrocarbyl group having a linear main carbon chain in which a hydrocarbyl side chain extends from the linear main carbon chain. Optional heteroatom substitution may be present in the linear main carbon chain or in the hydrocarbyl side chain.

[0037] The term“amphiphilic compound” refers to a compound having both a hydrophobic portion and a hydrophilic portion featuring a polar head group. The terms“polar head group” and“hydrophilic moiety” may be synonymously herein.

[0038] The term“ring atoms” refers to a plurality of atoms joined together in a loop to form a closed ring structure. Additional functional groups, rings, and/or chains may extend from one or more of the ring atoms, with atoms in the additional functional groups, rings, and/or chains not being included in the count of ring atoms.

[0039] The term“ethoxylate” refers to the moiety -(CthCthOj _a -, wherein a is an integer ranging from 1 to 60, or 2 to 10.

[0040] The term“alkoxylate” refers to the moiety -[(CtkjbOJa-, wherein a is an integer ranging from 1 to 60, or 2 to 10, and b is an integer ranging from 2 to 10. The term alkoxylate refers to moieties such as ethoxylate (b=2), propoxylate (b=3), and ethoxylate/propoxylate mixtures. [0041] The acronym“CMC” refers to critical micelle concentration given in wt%, where surface tension becomes independent of the surfactant concentration.

[0042] The acronym“ST” refers to surface tension, typically given in milli-newtons (mN) per meter.

[0043] The term“wetting” refers to the ability of a liquid to maintain contact with a surface, typically measured in seconds.

[0044] The term“Krafft point” refers to the minimum temperature where micelles are formed, typically given in °C.

Lightly Branched Olefins

[0045] As used herein, the term“lightly branched olefin” refers to an olefin or olefin mixture having an average number of branches, also denoted as branching or Branch Index (BI), of 0.5 to 2.1. It is to be understood that some olefins in an olefin mixture characterized as“lightly branched” may be unbranched and some olefins may have two or more branches, including two branches, three branches, four branches, five branches, and so on. The latter class of olefins may be referred to as“heavily branched” herein. Certain olefin mixtures classified as lightly branched may feature olefins that comprise at most three hydrocarbyl branches per olefin molecule. When unbranched or heavily branched olefins are present in an olefin mixture, other olefins are also present such that the weighted average of branches within the olefin mixture is sufficient to place the Branch Index within the foregoing range.

[0046] Branch Index within a particular lightly branched olefin or mixture of lightly branched olefins equals (0 x % linear + 1 x % monobranched + 2 x % di-branched + 3 x % tri- branched)/100; where % linear + % monobranched + % di-branched + % tri-branched = 100%. More highly branched individual olefins (e.g., tetra-branched and higher) may be weighted similarly to determine the Branch Index. In more specific examples of the present disclosure, an olefin oligomer or mixture of olefin oligomers as a whole may have a Branch Index of 1.8 or less, more typically 1.5 or less (e.g., 1.0 to 1.5). For example, a mixture of Cx olefin oligomers composed of 10% linear Cs, 30% monobranched Cx, 50% di-branched Cx, and 10% tri-branched Cs has a Branch Index of 1.6.

[0047] Also, values of methyl branching per carbon are disclosed, a measure of the average number of methyl branches of the lightly branched olefins. The Branch Index will equal the carbon number multiplied by the average methyl branching. For instance, in any embodiment the lightly branched olefins have an average methyl branching per carbon is within a range from 0.03, or 0.05 to 0.1, or 0.14, or 0.18. [0048] Lightly branched olefin oligomers are usually a mixture of isomers, both the skeletal arrangement of atoms and/or the double bond location within a carbon ring or chain. Olefins are further distinguished according to the degree of substitution of the double bond, from mono- to tetrasubstituted olefins. The degree of branching and double bond substitution may affect certain properties and performance of amphiphilic compounds formed from the lightly branched olefins, such as low temperature performance.

[0049] Lightly branched olefins of the present disclosure may be represented genetically by Structures 1 and 2 below. Structure 1 depicts an olefin oligomer having vinyl termination, in which x is an integer ranging from 0 to 34, R is a hydrogen or hydrocarbyl group, y is an integer ranging from 1 to 3, z is an integer ranging from 0 to 34, and w is an integer ranging from 1 to 10, with the proviso that in a given mixture characterized as being“lightly branched,” the variables are selected such that the Branch Index ranges from 0.5 to 2.1. As indicated above, any combination of unbranched, mono-branched, di-branched, tri-branched and more heavily branched olefins may be present in an olefin mixture if the olefin mixture exhibits a Branch Index in the foregoing range. Structure 2 depicts an internal olefin, in which x is an integer ranging from 0 to 34, R is a hydrogen or hydrocarbyl group, y is an integer ranging from 1 to 3, z is an integer ranging from 0 to 34, and w is an integer ranging from 1 to 10, with the proviso that the variables are selected such that the Branch Index ranges from 0.5 to 2.1 in a given olefin mixture.

Any combination of vinyl-terminated olefins and/or internal olefins may be present in a mixture of lightly branched olefins suitable for use in the disclosure herein.

[0050] Any of the lightly branched olefins described above or mixtures thereof may be used to form amphiphilic compounds having compositions defined by reaction products formed according to the reactions described further below. In each reaction, the olefin moiety undergoes a reaction to introduce a hydrophilic moiety as a polar head group onto a hydrophobic portion defined, at least in part, by a saturated reaction product of the lightly branched olefin. The olefin moiety is consumed in the course of introducing the polar head group and forming the hydrophobic portion. Alternately, the lightly branched olefin may become bonded to a substituent capable of undergoing a further reaction to introduce a hydrophilic moiety as a polar head group. Although particular reactions below may show a single type of olefin, typically a vinyl-terminated olefin, it is to be appreciated that either type of olefin described above (vinyl-terminated, internal or mixtures thereof) may be present in the one or more lightly branched olefins and differ from the particular lightly branched olefin depicted.

Oligomerization to Produce Lightly Branched Olefins

[0051] Amphiphilic compounds of the present disclosure comprise reaction products of one or more lightly branched olefins. The lightly branched olefins may be produced via oligomerization of shorter olefins having a chain length of thirty carbons or fewer, particularly Ci to C ₈ olefins. Suitable feedstocks for producing lightly branched olefins may include, for example, one or more of ethylene, propene, butenes, pentenes, hexenes, their isomers, and mixtures thereof. Example oligomerization processes include contacting a suitable feedstock comprising one or more olefins, typically multiple olefins of different numbers of carbon atoms, under oligomerization conditions in the presence of an oligomerization catalyst and recovering an oligomeric product comprising a plurality of oligomers in which the Branch Index of the oligomers is less than or equal to 2.1 and greater than or equal to 0.5. The individual olefin oligomers may comprise monomer units of the same olefin or different olefins, such as ethylene/propylene in particular process configurations.

[0052] Suitable oligomerization catalysts for oligomerizing olefin monomers into lightly branched olefin oligomers may be heterogeneous or homogeneous in nature. In particular embodiments, zeolite catalysts such as ZSM-22, ZSM-23, ZSM-57, and SAPO-11 may be suitable catalysts. Such catalysts can optionally be used in intimate combination with a hydrogenating component such as yttrium, tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, lanthanum, lanthanides, or a noble metal such as platinum or palladium, as well as any combination of the foregoing metals. Such hydrogenating components may be impregnated within zeolite catalysts, such as those named above. One such catalyst system, by way of nonlimiting example, comprises a nickel allyl/halide/phosphine/Lewis acid system, as described in U.S. Patent No. 4,533,651. A rare earth element impregnated Si/Al ZSM-23 catalyst or a Si/Al/T ZSM-23 catalyst may also be used. U.S. Patents 7,238,844, 6,884,914, and 7,183,450, which are incorporated herein by reference in their entirety, describe the olefin oligomerization process in further detail.

[0053] Oligomerization may be carried out in a fixed bed reactor, a packed bed reactor, a tubular reaction, a fluidized bed reactor, a slurry reactor, a continuous catalyst regeneration reactor, and any combination thereof. Suitable oligomerization conditions may include operating temperatures from 150°C to 350°C. More typically, the reaction temperature may be from 200°C to 300°C, alternatively from 220°C to 260°C, alternatively from 160°C to 240°C, or alternatively from 170°C to 210°C.

[0054] Once lightly branched olefins, discussed further below, are obtained from the oligomerization process, they may be reacted to form various amphiphilic compounds. Exemplary amphiphilic compounds derived as a reaction product from lightly branched olefins include, but are not limited to, alkylbenzene sulfonates, alcohol sulfates, alcohol ethoxylates and alkoxylates, alcohol ether sulfates, carboxylates, carboxylic acid esters, methyl ester sulfonates, amine oxides and olefin sulfonates. Amphiphilic compounds incorporating a hydrophobic portion derived, at least in part, from an olefin within a mixture of lightly branched olefins may have distinctive characteristics as compared to linear olefins or more highly branched olefins (BI greater than 2.1). For instance, the surface activity and Krafft point, defined as the minimum temperature where micelles are formed, may be affected. Some surfactants derived from lightly branched olefins may have low Krafft points, so as to provide surfactants suitable for cold water applications. Illustrative description of the reaction products and methods of synthesizing the amphiphilic molecules are provided hereinafter.

[0055] Given that the way in which the lightly branched olefins are made, and thus their final fingerprint (identity of isomers and relative percentages, etc.), this will also influence the formation of the inventive amphiphilic compound. Thus disclosed in any embodiment is a composition comprising a reaction product of one or more lightly branched olefins made from combining C3-C6 with a heterogeneous zeolite catalyst; the reaction product comprising a hydrophobic portion and a hydrophilic portion comprising a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in each of the one or more lightly branched olefins undergoes a reaction to become saturated and to produce at least part of the hydrophobic portion; and wherein the one or more lightly branched olefins have a Branch Index within a range from 0.5, or 0.8, or 1 to 1.6, or 1.8, or 2.1, and wherein the lightly branched olefin comprises at least 70 wt%, by weight of the lightly branched olefin, of mono-methyl branched isomers and dimethyl branched isomers. In any embodiment, the lightly branched olefin comprises methyl branching, and wherein 30, or 40 to 60, or 70 wt% of the branching is mono methyl branched isomers, and 20, or 25 to 40, or 50, or 60 wt% is dimethyl branched isomers; preferably there are less than 10, or 5 wt%, by weight of the lightly branched olefins, of trimethyl branched isomers. Finally, in any embodiment the one or more lightly branched olefins comprise one or more of a terminal olefin, an internal olefin, or a mixture thereof. Lightly Branched Olefin Alkylbenzene Sulfonate Reaction Products

[0056] Lightly branched olefins may be used to form lightly branched alkylbenzene sulfonates and/or isomeric mixtures thereof, represented by Structures 3, 3’ and 3” below, among others, in which the variables are defined as above. Structures 3 and 3’ may be formed from lightly branched olefins having a terminal double bond (vinyl termination), and Structure 3” may be formed from lightly branched olefins having an internal double bond. In various embodiments, the amphiphilic compounds may comprise a reaction product of benzene or a substituted benzene and a lightly branched olefin. As an initial step, one or more lightly branched olefins may be reacted with benzene or a substituted variant thereof in the presence of an acid catalyst to produce a lightly branched alkylbenzene, in which one carbon of the olefin moiety has reacted electrophilically with the aromatic ring. Depending on the catalyst used and the type of lightly branched olefin, alkylation may occur at a terminal or non-terminal carbon atom. The resulting lightly branched alkylbenzene composition may then be contacted with a sulfur trioxide composition to form a lightly branched alkylbenzene sulfonic acid, which may be subsequently neutralized with a base to produce a lightly branched alkylbenzene sulfonate. The attachment site of the sulfonate substituent on the aromatic ring may vary among product isomers.

[0057] To form products having Structure 3, benzene or a substituted variant thereof may be reacted with one or more lightly branched olefins in the presence of an acid catalyst to produce a reaction product comprising an alkylbenzene bearing light branching on the alkyl chain, thereby defining a hydrophobic group, as shown in Reaction 1 below. It is to be understood that alternate isomers may be produced similarly, including those formed from lightly branched internal olefins. Illustrative acid catalysts may include, but are not limited to, HF, AlCb, solid acid catalysts such as ones based on MCM-49, MCM-22, MCM-41, UZM-8, USY, Mordenite, ZSM-12, SC -doped silica, and clay. Catalyst choice may influence the predominant isomer formed. Reaction conditions are known in the art and may vary based upon the catalyst used (e.g. , temperatures from 10°C to over 500°C, as specified in U.S. Patents 4,954,325 and 5,334,795, which are incorporated herein by reference).

[0058] Unreacted benzene and lightly branched olefins, if present, may be removed by distillation before moving to subsequent steps in the production of amphiphilic compounds. Amphiphilic compounds may be produced via sulfonation of the lightly branched alkylbenzene by reacting a sulfur trioxide composition with the aromatic ring to form lightly branched alkylbenzene sulfonic acids. For example, sulfonation may be accomplished by reacting the alkylbenzene with SO3 under falling film reactor conditions or by reacting the alkylbenzene with oleum. The next step in the production of sulfonated amphiphilic compounds is neutralization of the resulting sulfonic acid with a base, such as, by way of non-limiting example, NaOH or KOH, to produce the sodium or potassium salt of the alkylbenzene sulfonate, which may exhibit surfactant properties.

Lightly Branched Olefin Primary Alcohol Reaction Products

[0059] In some embodiments, lightly branched olefins may be reacted to form amphiphilic compounds that are long-chain alcohols having a primary alcohol as the hydrophilic moiety, as shown in Structures 4 and 4’ below, where the variables are defined as above and are chosen to provide a Branch Index within a range from 0.5 to 2.1 in the alcohol product corresponding to the starting lightly branched olefins.

[0060] The primary alcohols in any embodiment have a from 10 to 30% higher degree of branching than the lightly branched olefins from which they derive; in any embodiment the primary alcohols have within a range from 0.04, or 0.06 to 0.1, or 0.15, or 0.2 methyl branches per carbon atom, compared to the average methyl branching per carbon is within a range from 0.03, or 0.05 to 0.1, or 0.14, or 0.18 for the starting lightly branched olefin.

[0061] The primary alcohol reaction products of Structures 4 and 4’ are one carbon longer than the lightly branched olefins from which they are produced. The primary alcohol reaction product shown in Structure 4’ results from double bond migration during hydroformylation. It is also to be understood that structurally related primary alcohol reaction products may be formed from internal olefins via a hydroformylation route as well.

[0062] With reference to Reaction 2, below, lightly branched olefins may be hydroformylated in the presence of a catalyst to form an aldehyde using synthesis gas. Hydroformylation adds an additional carbon atom (as an aldehyde group) to the backbone of the lightly branched olefin and consumes the olefin moiety. Reaction 2 shows the reaction taking place at the terminal carbon atom of a vinyl-terminated olefin, but it is to be appreciated that a similar reaction may take place at an internal carbon atom as well, either resulting from double bond rearrangement and/or by reacting an internal olefin. Synthesis gas or“syngas,” a mixture of carbon monoxide and hydrogen, may be obtained through the use of partial oxidation technology, steam reforming, or a combination thereof that is often referred to as autothermal reforming. Suitable catalysts for the hydroformylation reaction of a lightly branched olefin may be a metal catalyst, typically a homogeneous metal carbonyl complex such as of a carbon monoxide complex of a transition metal of Group VIII of the Periodic Table. Of the Group VIII metals, cobalt and rhodium are best known for their hydroformylation activity, but others may include palladium, iridium, ruthenium and platinum. By way of nonlimiting example, suitable catalysts may include HRh(CO)(PR3)3, HRh(CO) ₂ (PR3), HRh(CO)[P(OR) ]3, Rh(CH3COCH ₂ COCH3)(CO)2, Rh ₆ (CO)i ₆ , [Rh(norbomadiene)(PPh ₃ )2 ⁺ [PFe] , [Rh(C)3(PPh ₃ )2] ⁺ [BPh ₄ ] , RhCl(CO)(PEt ₃ ) ₂ , [RhCl(cyclooctadiene)] ₂ , [Rh(CO)3(PR ₃ )2] ⁺ BPh ₄ , [Rh(CO)3(PR ₃ )2] ⁺ PFe , HCo(CO) ₄ ,

Ru ₃ (CO)i2, [RuH(CO)(acetonitrile)2(PPli3)3 ⁺ [BF ₄ ] ^_ , PtCh (cyclooctadiene), [Ir(CO)3 (PPI13)] + [PFe]-, or [HPt(PEt3)3] ⁺ [PF ₆ ] . Other suitable catalysts may include, for example, HCo(CO)4, Co2(CO)8, HCO(CO)3(POR)3 (R = alkyl or aryl), HCo(CO)3(PR3) (R = alkyl or aryl), and Co(II)X ₂ (X = anionic ligand, such as carboxylate, sulfate, halide, alkoxide, amide, etc.). Inorganic salts and catalyst precursors, such as RH2O3, Pd(N0 ₃ ) ₂ and Rh(N0 ₃ ) ₃ , may be used, and halides such as, for example, RhChGILO (R = alkyl or aryl). In exemplary embodiments, a nickel catalyst in the presence of dimethylamine may be used. Hydroformylation may be carried out at temperatures from -20°C to 200°C, or from 25°C to 200°C, or from 30°C to 150°C, or from 0°C to 150°C, or from 0°C to 120°C, or from 0°C to 90°C, or from 0°C to 50°C, or less than 85 °C. Syngas pressures may range from 400 psig to 5000 psig, and the ratio of H2:CO in the syngas may range from 0.3 to 0.7.

Reaction 2

[0063] After hydroformylation, the resulting aldehyde may be hydrogenated or similarly reduced (e.g., with a metal hydride reagent) to form a primary alcohol. In this overall process, the lightly branched olefin is converted to a primary alcohol having one additional carbon atom. Branching of the carbon skeleton, the portion derived from the lightly branched olefin, may be preserved in the primary alcohol through careful choice of hydroformylation catalyst and conditions. U.S. Pat. Nos. 5,674,950 and 6,482,972, which are incorporated herein by reference in their entirety, describe the hydroformylation process conditions in further detail. Lightly Branched Olefin Diol Reaction Products

[0064] In some embodiments, lightly branched olefins may be reacted to form amphiphilic compounds having a glycol as the hydrophilic moiety, as shown in Structures 5 and 5’ below, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. The glycol reaction products having Structures 5 and 5’ are of the same carbon count as the lightly branched olefins from which they are produced. Glycol reaction products may also be prepared similarly from internal olefins (Structure 5’), in which case the glycol moiety instead comprises two secondary alcohols. Structure 5

Structure 5’

[0065] Lightly branched olefins may be oxidized to form glycol reaction products having either Structures 5 or 5’, depending upon whether the starting lightly branched olefins are terminal or internal. Glycol formation may occur catalytically or stoichiometrically through reaction of the lightly branched olefins with a reagent such as, for example, KMnCL, sodium periodate, or osmium tetroxide. Alternately, glycol reaction products may be formed via an epoxide intermediate, as shown in Reaction 3 below. Suitable oxidants for epoxidizing lightly branched olefins may include, for example, peracetic acid, m-chloroperoxybenzoic acid (MCPBA), dimethyldioxirane, and similar oxidants. The epoxide ring may then undergo opening with an aqueous acid to form a glycol, as shown in Reaction 3. Other nucleophiles may open the epoxide to produce related amphiphilic compounds. Like reactions in which a glycol is produced directly by oxidation, internal olefins may similarly undergo epoxidation to form glycols having two secondary alcohol groups.

Reaction 3

Lightly Branched Olefin Secondary Alcohol Reaction Products

[0066] In some embodiments, lightly branched olefins may be reacted to form secondary alcohol reaction products, as shown in Structures 6 and 6’ below, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. Secondary alcohol reaction products having Structure 6 may be produced concurrently with primary alcohol reaction products having Structure 6” in some embodiments, particularly when a vinyl- terminated lightly branched olefin is being reacted to form the reaction product (e.g., by hydroboration). The secondary alcohol reaction products defined by Structure 6 are of the same carbon count as the lightly branched olefin from which they are produced. Likewise, the corresponding primary alcohol reaction products shown in Structure 6’ are of the same carbon count as the lightly branched olefin from which they are produced. Internal olefins may form secondary alcohol reaction products (Structure 6”) without forming the corresponding primary alcohol reaction product. Secondary alcohol reaction products defined by Structure 6” likewise are of the same carbon count as the lightly branched olefin from which they are produced.

Structure 6’

[0067] To produce secondary alcohol reaction products, lightly branched olefins may be hydroborated to form a hydroborated intermediate having a carbon-boron bond at the secondary carbon atom, as shown in Reaction 4, wherein A may be a hydrocarbyl group. Oftentimes, a mixture of hydroborated intermediates may be produced, with a carbon-boron bond at a primary carbon atom being the major product and a carbon-boron bond at the secondary carbon atom being the minor product when hydroborating a vinyl-terminated lightly branched olefin. Hydroboration of lightly branched olefins having an internal olefin moiety (/. _<? ., corresponding to Structure 2) may form a secondary alcohol reaction product as the predominant product. Hydroboration may be accomplished by contacting the lightly branched olefin with a boron hydride (e.g. , B2¾) or a borane complex in the presence of a hydroboration catalyst, metal complex, or oxidizing agent to convert the carbon-boron bond into a secondary alcohol. Hydroboration reaction temperatures may range from -50°C to 200°C. The hydroborated intermediate may subsequently be reacted with a base and hydrogen peroxide to form a lightly branched olefin secondary alcohol reaction product, either as a minor product or a major product, optionally in combination with a lightly branched olefin primary alcohol reaction product (Structure 6”) in the case of a vinyl-terminated lightly branched olefin undergoing hydroboration.

Lightly Branched Olefin Alcohol Sulfate Reaction Products

[0068] In some embodiments, lightly branched olefin alcohols may be derivatized to introduce a sodium salt of a sulfate group as the hydrophilic moiety, as shown in Structures 7, 7’ and 7”, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. Structure 7 shows the primary alcohol sulfate formed from a hydroformylated intermediate, wherein hydroformylation has taken place upon the terminal carbon atom. Structure 7’ shows the corresponding secondary alcohol sulfate formed from a terminal olefin. It is to be appreciated that Structures 7 and 7’ are illustrative of the alcohol sulfate reaction products that may be produced according to the disclosure herein. For example, Structure 7 may be produced through sulfonation of a primary alcohol reaction product accessed via hydroformylation, but it is to be appreciated that a similar primary alcohol sulfate reaction product may be accessed by sulfating the primary alcohol reaction product accessed by hydroboration, such as those discussed above. It is also to be understood that primary alcohol sulfates obtained following double bond migration during hydroformylation are also possible in the present disclosure. Likewise, alcohol sulfate reaction products formed from internal olefins likewise reside within the scope of the present disclosure, such as those shown in Structure 7”. Mono- or bis-sulfate reaction products of glycols also reside within the scope of the disclosure herein.

Structure 7”

[0069] To form lightly branched olefin alcohol sulfates, a lightly branched olefin primary alcohol may be reacted with a sulfur trioxide composition or chlorosulfuric acid to form lightly branched olefin alcohol sulfate following neutralization, as shown in Reaction 5. Reaction 5 shows the formation of an alcohol sulfate having Structure 7, but it is to be appreciated that alcohol sulfates having Structures 7’, 7” or a related structure may be formed similarly. After sulfonation, the sulfated reaction product may be neutralized with a base (e.g., NaOH) to produce the corresponding sodium salt.

Lightly Branched Olefin Alcohol Alkoxylate Reaction Products

[0070] In some embodiments, lightly branched olefin alcohols may be derivatized to introduce an alkoxylate group (e.g., ethoxylate) as the hydrophilic moiety, as shown in Structures 8, 8’ and 8”, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1, and n is a positive integer and may be an average or a distribution of values when a plurality of alkoxylate chain lengths are present. The alkoxylates may be ethoxylate and/or propoxylate groups in particular embodiments of the present disclosure. Structure 8’ shows the structure of a secondary alcohol alkoxylate that may be produced according to the disclosure herein. It is to be appreciated that Structures 8 and 8’ are illustrative of the alcohol alkoxylate reaction products that may be produced according to the disclosure herein. For example, Structure 8 may be produced through alkoxylation of the primary alcohol reaction product accessed via hydroformylation, but it is to be appreciated that a similar primary alcohol alkoxylate reaction product may be accessed by alkoxylating the primary alcohol reaction product accessed by hydroboration, such as those discussed above. It is also to be understood that alcohol alkoxylates obtained following double bond migration during hydroformylation are also possible in the present disclosure. Likewise, alcohol alkoxylate reaction products formed from internal olefins (Structure 8”) also reside within the scope of the present disclosure. Mono- or bis-alkoxylate reaction products of glycols also reside within the scope of the disclosure herein.

Structure 8”

[0071] As shown in Reaction 6, below, a lightly branched olefin alcohol may subsequently undergo alkoxylation using ethylene oxide, propylene oxide, or any combination thereof to form the corresponding ethoxylate, propoxylate, or combination thereof. A typical value for n when ethoxylating with ethylene oxide is 8 to 10. The alcohol ethoxylate/propoxylate produced may be a homopolymer or a random or block copolymer of ethylene oxide and/or propylene oxide units attached to the alcohol functionality. Reaction 6 shows the formation of an alcohol alkoxylate having Structure 8, but it is to be appreciated that alcohol alkoxylates having Structures 8’ and 8” may be formed similarly.

Lightly Branched Olefin Alcohol Alkoxylate Sulfate Reaction Products

[0072] In some embodiments, lightly branched olefin alcohols may be derivatized to introduce an alkoxylate group (e.g., ethoxylate) and a sulfate group as the hydrophilic moiety, as shown in Structures 9, 9’ and 9”, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. A mixture of alkoxylated reaction products is possible, so that variable n, on average, may be a non-integer value. A typical value for variable n when ethoxylating with ethylene oxide is approximately 8 to 10. The alkoxylates may be ethoxylate and/or propoxylate groups in particular embodiments of the present disclosure. Structure 9’ shows the structure of a secondary alcohol alkoxylate sulfate. It is to be appreciated that Structures 9 and 9’ are illustrative of the alcohol alkoxylate sulfate reaction products that may be produced according to the disclosure herein. For example, Structure 9 may be produced through alkoxylation of the primary alcohol reaction product accessed via hydroformylation, followed by sulfonation thereof, but it is to be appreciated that a similar primary alcohol alkoxylate sulfate reaction product may be accessed by alkoxylating the primary alcohol reaction product accessed by hydroboration, such as those discussed above, and then sulfating. Similarly, alcohol alkoxylate sulfate reaction products formed from internal olefins (Structure 9”) likewise reside within the scope of the present disclosure.

Structure 9”

[0073] After alkoxylation of a lightly branched olefin alcohol, as previously described above in reference to Reaction 6, the terminal alcohol of the alkoxylate may be further converted into a sulfate salt by reacting the terminal alcohol with SO3 or chlorosulfuric acid and then neutralizing the resulting sulfuric acid with a base, as shown in Reaction 7 below. Reaction 7 shows the formation of an alcohol alkoxylate sulfate having Structure 9, but it is to be appreciated that alcohol alkoxylate sulfates having Structures 9’ and 9” may be formed similarly.

Lightly Branched Olefin Carboxylate Reaction Products

[0074] In some embodiments, lightly branched olefins may be derivatized to amphiphilic compounds having a carboxylate as the hydrophilic moiety, as shown in Structures 10, 10’ and 10” below, in which f is 0 or 1 and the other variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. The carboxylate reaction products having Structure 10 are formed via hydroformylation of a terminal olefin and are one carbon longer than the lightly branched olefins from which they are produced. The carboxylate reaction product having Structure 10’ is also formed from a terminal olefin via a hydroformylated intermediate, in which introduction of an aldehyde and subsequent carboxylic acid moiety takes place with double bond migration. Structure 10” shows the carboxylate reaction product formed from an internal olefin by a hydroformylated intermediate.

[0075] As described above, an intermediate aldehyde is produced during hydroformylation of lightly branched olefins. Instead of reducing the aldehyde, as above, the aldehyde may alternately be oxidized to form a carboxylic acid variant of the lightly branched olefins. Oxidation may be carried out, for example, by contacting the intermediate aldehyde with oxygen in the presence of a multimetallic catalyst under oxidation conditions that are known in the art. Other standard oxidation conditions for converting an aldehyde into a carboxylic acid may also be used. In the net reaction, the lightly branched olefin is converted to a carboxylic acid having an additional carbon atom, as shown in Reaction 8. Reaction 8 shows the formation of a lightly branched carboxylate having Structure 8 formed from a hydroformylated intermediate, but it is to be appreciated that carboxylates having Structures 8’ and 8” may be formed similarly. Reaction 8’ shows the corresponding formation of a lightly branched carboxylate formed via hydroboration of a terminal olefin. Following oxidation, the lightly branched carboxylic acid may be neutralized with a base such as, for example, NaOH, to form the sodium salt of the carboxylic acid. Other bases may also be suitable. Carboxylates of the present disclosure may be of any length defined by the length of the lightly branched olefin and remain lightly branched following introduction of the carboxylate group.

Lightly Branched Olefin Carboxylic Acid Ester Reaction Products

[0076] Lightly branched olefin carboxylic acids (Structures 10, 10’ and 10”) may be converted to an ester by esterification methods known in the art to form, for example, glyceryl, polyglyceryl, propylene glycol, and/or sorbitol esters, as shown in Reaction 9 below, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. In Reaction 9, R’ represents a hydrocarbyl group, including those comprising a glyceryl, polyglyceryl, propylene glycolate, or sorbitol ester moiety. Although Reaction 9 has shown esterification to take place using a carboxylic acid produced via a hydroformylated intermediate, wherein hydroformylation has taken place at the terminal carbon atom, it is to be appreciated that carboxylic acid ester reaction products having related structures may be formed similarly.

Lightly Branched Olefin Methyl Ester Sulfonate Reaction Products

[0077] Additionally, lightly branched olefin carboxylic acid reaction products may be converted into the corresponding methyl ester, which may be subsequently sulfonated and neutralized, as shown in Reaction 10, where the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1. Although Reaction 10 has shown esterification and sulfonation to take place using a carboxylic acid produced via a hydroformylated intermediate, it is to be appreciated that methyl ester sulfonate reaction products having related structures may be formed similarly.

Lightly Branched Olefin Sulfonate Reaction Products

[0078] In some embodiments, lightly branched olefins may be derivatized through direct sulfonation of the olefin moiety with sulfur trioxide to form a range of amphiphilic compounds having a sulfonate as the polar head group. Illustrative products that may form via direct olefin sulfonation are shown in Reactions 11 and 12 below. A range of sulfonated reaction products may be formed when sulfonating an olefin moiety directly, and the product distribution may vary depending upon whether the lightly branched olefin has vinyl termination or an internal olefin moiety. It is not necessarily implied that all of the lightly branched olefin sulfonate reaction products depicted in Reactions 11 and 12 form in any given reaction. Moreover, no particular mass percentage distribution of the various lightly branched olefin sulfonate reaction products is implied by Reactions 11 and 12. In Reactions 11 and 12, R” is a hydrocarbyl group and B represents unspecified hydrocarbyl branching upon the hydrocarbon chain, provided that the amount of B affords a Branch Index ranging from 0.5 and 2.1.

Reaction 11

Reaction 12

[0079] Structures 11 and 11’ below show two of the lightly branched olefin sulfonate reaction products that may form when sulfonating a lightly branched olefin having vinyl termination. In Structures 11 and 11’, the variables are defined as above and are chosen to provide a collective Branch Index of 0.5 to 2.1, wherein p is an integer ranging from 1 to 3.

Structure 11 Structure 11’

Other particular olefin sulfonate reaction products formed from lightly branched olefins corresponding to Formulas 1 or 2 may also be contemplated in view of Reactions 11 and 12. [0080] Referring again to Reactions 11 and 12, lightly branched olefin sulfonate reaction products may be formed by contacting the lightly branched olefins with a sulfur trioxide composition, and hydrolyzing to form lightly branched hydroxyalkane sulfonates and/or lightly branched alkene sulfonates. In some embodiments, lightly branched alkene b, g, and/or d sultone intermediates may be formed, which may undergo hydrolysis (e.g., upon addition of aqueous NaOH) at varying rates to form the corresponding hydroxyalkane sulfonates. The branching present in the lightly branched olefin is preserved in the sulfonated reaction products. Lightly Branched Olefin Amine Oxide Reaction Products

[0081] In some embodiments, lightly branched olefins may be reacted to form amphiphilic compounds having an amine oxide as the polar head group, as shown in Structures 12 and 13 below, wherein the variables are defined above and are selected to provide a collective Branch Index of 0.5 to 2.1. Structure 12 corresponds to a lightly branched olefin amine oxide reaction product resulting from a hydroformylation reaction product that has been further reacted to form an amine oxide group. Synthesis of the amine oxide reaction product corresponding to Structure 12 may take place according to Reaction 13 below, wherein the amine oxide reaction product has one additional carbon atom compared to the lightly branched olefin from which it was produced. Structure 13 corresponds to a lightly branched olefin amine oxide reaction product resulting from a direct reaction of dimethylamine or a similar secondary amine with the olefin moiety to form an amine oxide group. Synthesis of the amine oxide reaction product corresponding to Structure 13 may take place according to Reaction 14 below, wherein the amine oxide reaction product has the same number of carbon atoms as the lightly branched olefin from which it was produced. Although Structures 12 and 13 show amine oxide reaction products that are formed from lightly branched olefins having vinyl termination, it is to be appreciated that related amine oxide reaction products may be prepared by utilizing a lightly branched olefin having an internal olefin moiety.

Structure 13

Structure 14

[0082] Referring to Reaction 13 below, an aldehyde introduced to a lightly branched olefin via hydroformylation may be reacted with dimethylamine to generate a dimethyliminium ion. The dimethyliminium ion may then be hydrogenated in situ with ¾ to produce the corresponding dimethylamine compound, which may then undergo subsequent oxidation with hydrogen peroxide or a similar oxidant to afford the corresponding amine oxide as the polar head group.

Reaction 13

[0083] Referring to Reaction 14, lightly branched olefin amine oxide reaction products having the same number of carbon atoms as the lightly branched olefin may be formed by reacting the lightly branched olefin directly with dimethylamine under hydrogen bromide promotion to produce a dimethylamine compound as a reaction product. As in Reaction 13, the dimethylamine compound may be subsequently oxidized with hydrogen peroxide or a comparable oxidant to afford the corresponding lightly branched olefin amine oxide reaction product.

Reaction 14 Surfactant Compositions

[0084] The above-disclosed lightly branched olefin reaction products may be formulated in solid form or dispersed or dissolved in a fluid phase to form suitable surfactant compositions for use in particular applications. The fluid phase may comprise an aqueous fluid in some embodiments. The surfactant compositions may be a detergent formulation in particular instances.

[0085] Surfactant compositions of the present disclosure may comprise an aqueous fluid, and a lightly branched olefin reaction product that is present in the aqueous fluid at a concentration ranging from 10 wt % to 80 wt %.

[0086] Surfactant compositions of the present disclosure may comprise an aqueous fluid in which one or more lightly branched olefin reaction products described herein are dissolved or dispersed. Suitable aqueous fluids are not particularly limited and may be selected from deionized water, tap water, fresh water, surface water, ground water, brackish water, salt water, sea water, brine, or any combination thereof. Other aqueous fluid sources may also be suitable The aqueous fluid may further comprise a water-miscible organic solvent such as one or more alcohols, for example, in some embodiments.

[0087] When dissolved in a suitable aqueous fluid, the reaction products disclosed herein may exhibit a range of surfactant properties. According to some embodiments, the reaction products may be present in the aqueous fluid above a critical micelle concentration.

[0088] Exemplary suitable applications of the surfactant compositions disclosed herein include, by way of non- limiting example, household laundry liquids, household laundry detergent capsules, household machine dishwash capsules, household hand dishwash liquids, and industrial/institutional laundry detergents.

[0089] For household laundry liquids, the total surfactant content may be 10 wt% to 50 wt% of the total laundry liquid. Other components may include, for example, enzymes, polymers, builders, complexing agents, and solvents in addition to water. The surfactants may comprise one or more reaction products disclosed herein, such as alkylbenzene sulfonates, alcohol ethoxylate sulfates, alcohol ethoxylates, amine oxides, and carboxylates. In addition to the reaction products disclosed herein, other conventional surfactants may also be present.

[0090] For household laundry detergent capsules, the total surfactant content may be from

40 wt% to 70 wt% of the household laundry detergent capsules. Other components may include, for example, enzymes, polymers, builders, complexing agents, and solvents in addition to water. The surfactants may comprise one or more reaction products disclosed herein, such as alkylbenzene sulfonates, alcohol ethoxylate sulfates, alcohol ethoxylates, amine oxides, and carboxylates. In addition to the reaction products disclosed herein, other conventional surfactants may also be present.

[0091] Household machine dishwash capsules may contain a total surfactant content from 10 wt% to 30 wt% of the capsules. The remaining components may comprise one or more of enzymes, polymers, builders, complexing agents, solvents, and fillers in addition to water. The surfactants may comprise one or more reaction products disclosed herein, such as alcohol ethoxylates and/or propoxylates. In addition to the reaction products disclosed herein, other conventional surfactants may also be present.

[0092] Household hand dishwash liquids may contain a total surfactant content from 10 wt% to 30 wt% of the liquid. The remaining components may comprise one or more of builders, polymers, complexing agents, fillers and solvents in addition to water. The surfactants may comprise one or more reaction products disclosed herein, such as alcohol ethoxylates and/or propoxylates, or amine oxides. In addition to the reaction products disclosed herein, other conventional surfactants may also be present.

[0093] For industrial applications such as industrial or institutional laundry detergent, total surfactant content may be from 10 wt% to 40 wt% by weight of the detergent. Other components may include alkalis, such as sodium hydroxide; inorganic salt, such as sodium metasilicate, pentasodium triphosphate, and polymeric material such as the sodium salt of polyacrylic acid; solvents; and enzymes. The surfactant system may be composed of one or more of alcohol ethoxylates, alcohol propoxylates, alcohol ethoxylate/propoxylates, alkylamine ethoxylate, alkyl ether phosphate, alcohol polyglycol ethers, or alkylbenzene sulfonates, such as the reaction products disclosed herein. In addition to the reaction products disclosed herein, other conventional surfactants may also be present.

[0094] Embodiments disclosed herein include:

[0095] A. Compositions comprising one or more amphiphilic compounds. The compositions comprise a reaction product of one or more lightly branched olefins, the reaction product comprising a hydrophobic portion and a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in the one or more lightly branched olefins reacts to produce the hydrophobic portion; and wherein the one or more lightly branched olefins have a Branch Index ranging from 0.5 and 2.1 and branching is retained in the hydrophobic portion of the reaction product. [0096] B. Detergent formulations. The detergent formulations comprise: an aqueous fluid; and a reaction product of one or more lightly branched olefins, the reaction product comprising a hydrophobic portion and a polar head group bonded to the hydrophobic portion; wherein an olefin moiety in the one or more lightly branched olefins reacts to produce the hydrophobic portion; and wherein the one or more lightly branched olefins have a Branch Index ranging from 0.5 and 2.1 and branching is retained in the hydrophobic portion of the reaction product; wherein the surfactant is present in the aqueous fluid at a concentration ranging from 10 wt% to 80 wt%.

[0097] Each of embodiments A and B may have one or more of the following additional elements in any combination:

[0098] Element 1 : wherein the one or more lightly branched olefins comprise one or more of a terminal olefin, an internal olefin, or a mixture thereof.

[0099] Element 2: wherein the reaction product is an alkylation product of an aromatic ring, and the polar head group is a sulfonate group bound to the aromatic ring

[0100] Element 3: wherein the reaction product is a hydroformylation reaction product in which an aldehyde group formed during hydroformylation is reduced to a primary alcohol or a derivative of a primary alcohol, the primary alcohol or the derivative of the primary alcohol comprising the polar head group.

[0101] Element 4: wherein the derivative of the primary alcohol is selected from the group consisting of an alcohol sulfate, an alcohol alkoxylate, an alcohol alkoxylate sulfate, and any combination thereof.

[0102] Element 5: wherein the reaction product is a hydroboration reaction product comprising a primary alcohol, a secondary alcohol, a derivative of a primary alcohol, or a derivative of a secondary alcohol, the primary alcohol, the derivative of the primary alcohol, the secondary alcohol, or the derivative of the secondary alcohol comprising the polar head group.

[0103] Element 6: wherein the derivative of the primary alcohol or the derivative of the secondary alcohol is selected from the group consisting of an alcohol sulfate, an alcohol alkoxylate, an alcohol alkoxylate sulfate, and any combination thereof.

[0104] Element 7: wherein the reaction product is an oxidation product comprising a glycol or a derivative of the glycol, the glycol or the derivative of the glycol comprising the polar head group. [0105] Element 8: wherein the derivative of the glycol is selected from the group consisting of a glycol mono-sulfate, a glycol bis-sulfate, a glycol mono-alkoxylate, a glycol bis-alkoxylate, and any combination thereof.

[0106] Element 9: wherein the reaction product is a hydroformylation reaction product in which an aldehyde group formed during hydroformylation is oxidized to a carboxylic acid or a derivative of a carboxylic acid, the carboxylic acid or the derivative of the carboxylic acid comprising the polar head group.

[0107] Element 10: wherein the derivative of the carboxylic acid is selected from the group consisting of a carboxylate salt, a carboxylic acid ester, a methyl ester sulfate, and any combination thereof.

[0108] Element 11: wherein the reaction product comprises one or more of a sulfonation reaction product of the lightly branched olefin, a hydroxysulfonation reaction product of the lightly branched olefin, or any combination thereof, a sulfonate group comprising the polar head group.

[0109] Element 12: wherein the reaction product is an amine oxide formed from the lightly branched olefin.

[0110] Element 13: wherein the reaction product is formed from a mixture of lightly branched olefins having a Branch Index from 0.5 to 2.1.

[0111] Element 14: wherein the one or more lightly branched olefins comprise at most three hydrocarbyl branches per olefin molecule.

[0112] By way of non-limiting example, exemplary combinations applicable to A and B include, but are not limited to, Element 1 in combination with one or more of Elements 2-14, Elements 2, 4, 6, 8, and 10- 14 in combination with one or more of Elements 13 and 14; Element 3 in combination with one or more of Elements 4, 13, and 14; Element 5 in combination with one or more of Elements 6, 13 and 14; Element 7 in combination with one or more of Elements 8, 13 and 14; and Element 9 in combination with one or more of Elements 10, 13 and 14.

[0113] To facilitate a better understanding of the embodiments described herein, the following examples of various representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the present disclosure

EXAMPLES

[0114] Example 1. Sulfonated Reaction Products: To produce an alkylbenzene sulfonate reaction product, 4.0 g of pre-dried MCM-49-based catalyst was placed in a catalyst basket of a Parr autoclave (the reactor). The catalyst was dried in the reactor for 1 hour at 160°C under N2 flow. Benzene (120 g) was subsequently introduced to the reactor at 150°C and agitated from 400 - 500 rpm. The temperature was allowed to equilibrate for 30 min before 85.3 g of C12 lightly branched olefins (C12H24, BI of 1.36) was introduced. The reactor pressure was maintained at 300 psig under N2 flow and a consistent temperature of 150°C. The reaction was monitored by taking approximately 1 mL aliquots of offline sample via dip tube sample line and analyzing by gas chromatography (GC), both flame ionization detector (FID) GC and mass spectrometry (MS) GC. After 144 hours, the conversion of olefin was 93%. The product was predominantly monoalkylated, with an insignificant amount of dialkylate/polyalkylate (<1%).

[0115] The gas chromatography (GC) analysis of an exemplary C12 lightly branched olefin

(C12H24, BI of 1.36) is given in Table 1. From the GC analysis, the mono-branched C12 isomer includes the following isomers: 2-methyldodecene, 3-methyldodecene, 4-methyldodecene, 5- methyldodecene, 6-methyldodecene; the di -branched C12 isomer could be, not limited to : 2,4-dimethylundecene, 2,5-dimethylundecene, 2,6-dimethylundecene, 2,7-dimethylundecene, 2,8-dimethylundecene, 2,9-dimethylundecene, 3,3-dimethylundecene, and 3,8- dimethylundecene.

Table 1 Distribution of C12 lightly branched olefins with BI 1.36

[0116] After cooling, the reactor content was collected. Unreacted benzene and lightly branched olefins were removed under reduced pressure using a rotary evaporator. After rotary evaporation, 63 g of clear, colorless liquid was collected. In the final product analysis, the bulk of the product was monoalkylate at 95.8%, with remaining lightly branched olefin forming 1.9% of the product, and dialkylate 2.3%.

[0117] The product was analyzed via GC-FID (FIG. 1), and showed a strong signal between 25 and 30 minutes, indicating that monoalkylates predominated. Analysis of the product in deuterated chloroform via ¹ H NMR (FIG. 2) and ¹³ C NMR (FIG. 3) confirmed that the reaction product was predominately monoalkylated.

[0118] The resulting C12 alkylbenzene (50.5 g) was subsequently sulfonated by reaction with oleum (67.3 g). The C12 alkylbenzene was placed into a glass flask and stirred, with temperature adjusted to 25-30°C. Oleum was slowly dripped into the flask at a temperature between 35-40°C. After addition of all of the oleum, the contents of the flask were maintained at 25-35°C with stirring. Sulfuric and sulfonic acid levels were monitored periodically and the flask was continually stirred until the sulfuric and sulfonic acid levels were unchanged. Subsequently, 10% water was added to the reaction mixture and mixed well. No visible separation was observed. The sample was placed into a 90°C oven overnight. No visible separation was observed. The sample was centrifuged for 1 hour at 2600 rpm. The sample showed separation, with the sulfonic acid concentrating into the top layer. Samples (2 g) were carefully removed from the top layer and analyzed for sulfuric and sulfonic acids. The remainder was centrifuged, and additional samples were taken. This procedure was repeated and sulfonic acid samples were accumulated until the sulfuric acid increased in concentration. In total, 39 g of sulfonic acid was collected from the top layer, and 72 g of sulfuric acid was collected from the bottom layer. Performance tests were ran by making a 1.00 wt% active sodium sulfonate, and then diluting to the desired concentration

[0119] The above procedure was repeated for Cn lightly branched olefins with a Branch Index of 1.00. After 48.5 hours at 150°C, conversion of Cn lightly branched olefins was 92%. After unreacted benzene and Cn lightly branched olefins were removed under reduced pressure using a rotary evaporator, 78.5 g of a clear, colorless liquid was obtained. Analysis via GC- FID showed that the product was 97% monoalkylate, with 1.4% of the sample consisting of unreacted C12H24, and 1.6% of the sample constituting dialkylate. The product was analyzed via GC-FID (FIG. 4), and showed a strong signal between 25 and 30 minutes, indicating that monoalkylates predominated. Analysis of the product in deuterated chloroform via ¹ H NMR (FIG. 5) and ¹³ C NMR (FIG. 6) confirmed that the reaction product was predominately monoalkylated. The resulting C12 alkylbenzene (50.5 g) was subsequently sulfonated by reaction with oleum (67.5 g), as described above. In total, 44 g of sulfonic acid was collected from the top layer, and 65 g of sulfuric acid was collected from the bottom layer.

[0120] In one example procedure, 0.5 g of the sulfonated C12 alkylbenzene was purified by column chromatography to remove unreacted alkylbenzenes or H2SO4 (hexanes -EtO Ac or hexanes-CFbCk). Once purified, 400 mg of the alkylbenzene sulfonic acid was dissolved in 3 mL of methanol. To adjust the pH, 25% NaOMe/MeOH solution was added dropwise until the solution was neutral. A white solid precipitate was observed. The precipitate was recovered by filtration, washed once with a small amount of cold methanol, and dried in a 50°C vacuum oven overnight. Approximately 200 mg of solid was recovered. ¹ H NMR in DMSO-d ₆ showed the expected sodium salt product.

[0121] In another example procedure, 14.67 g of the sulfonated Cn alkylbenzene was dissolved in 140 mL of methanol. Once dissolved, concentrated aqueous NaOH (50% in water) was added slowly while the sample was stirred. A white solid precipitate was observed. The precipitate was recovered by filtration, washed twice with a small amount of cold methanol, and dried in a 40°C vacuum oven overnight. Approximately 9.48 g of solid was recovered. ¹ H NMR in DMSO-d ₆ showed the expected sodium salt product.

[0122] Data in Table 2 below was taken as the sodium salt prepared directly from sulfonated samples. The sodium salt was not isolated in any instance, but was in situ neutralized to make a 1% active solution. Samples A-C were synthesized in the same manner except for differences in the olefin source used. Sample A used linear 1-dodecene as the feed. Sample B used Cn lightly branched olefins with a Branch Index of 1.00 as the feed, and Sample C used Cn lightly branched olefins with a Branch Index of 1.36 as the feed. Lightly branched alkyl benzene sulfonate reaction products showed improvement in the Krafft point. In particular, the Krafft point showed a decrease from 23.5°C to 8.5 °C in the lightly branched olefin reaction products, while other parameters stayed relatively constant.

Table 2. Analysis of sulfonated Cn alkylbenzene

[0123] Surfactant activities were measured using conditions specified in ASTM D3049.

Critical micelle concentrations in water and 1% NaCl solution, surface tension values at the critical micelle concentration, and C20 values were measured using conditions specified in ISO 4311. Foaming properties were measured using conditions specified in ASTM D1173-07. Wetting was measured using conditions specified in ASTM D2281. C20 values represent the surfactant concentration needed to decrease the surface tension of the solvent by 20 rnN/m.

[0124] Calcium tolerance was tested using the following procedure. A 0.1 wt% solution of the surfactant was prepared by dissolving 0.050 g of the surfactant in 50 mL of distilled water in a 200 mL Erlenmeyer flask. This solution was used as a blank to set a turbidity value of 0 on a LaMotte 2020 Turbidity Meter. A 1.00 wt% solution of calcium chloride was titrated into the surfactant solution in 0.20 mL increments using a 5 mL micro-buret. The solution was then mixed and the turbidity was read again after each calcium chloride aliquot addition. The haze reading was then plotted against the titer (volume of added calcium chloride solution). The amount of added calcium chloride solution needed to produce a haze reading of 50 was then determined. This reading represents the lowest perceptible haze. The titer volume and concentration and the sample concentration may then be used to determine the number of milligrams of calcium that may be tolerated per gram of sample before haziness occurs.

[0125] Example 2. Hydroformylated Reaction Product. A high-pressure, C-276 alloy autoclave reactor (250 mL) fitted with an interior glass liner and equipped with supervisory control and data acquisition capabilities was utilized to conduct the hydroformylation reaction. In a typical experiment, a feed comprising lightly branched olefins (130 mL) was introduced to the reactor through an air-free injection port connected to a feed storage vessel. Agitation was initiated, and the reactor was brought to the process temperature (150°C) and a syngas pressure 100 psig (1:1 PpiCO) less than the specified process pressure. The reaction mixture was then allowed to stir for 10 min. to equilibrate. A solution of 20 mL of the specified catalyst (and ligand, if applicable) in lightly branched olefin diluent was then delivered through an injection port on the autoclave reactor. Syngas was utilized to promote the catalyst injection while simultaneously bringing the unit to the specified process pressure. The process pressure was then maintained throughout the reaction and metered through a mass flow controller. At the end of the run (5 hour run time), the syngas supply was halted, and the autoclave reactor was depressurized and purged with nitrogen. Once cool, the autoclave reactor was opened and the liquid product was transferred to a sample container for off-line analyses. Process conditions are specified in Table 3. Table 3. Hydroformylated Reaction Process Features

[0126] Example 3. Hydroformylated Reaction Product with Finishing. 80 g of lightly branched olefin feed was introduced into the glass-lined, stirred autoclave reactor of Example 2 and heated to 150°C at a syngas pressure of 1200 psig (1:1 H2/CO). A solution of OoiCOb

(0.435 g) dissolved in 20 g lightly branched olefin diluent was then injected, while simultaneously raising the syngas pressure to 1500 psig. The reactor was operated in constant pressure mode for a ran time of 4.5 hours, followed by an additional 20 hours of ran time in batch mode. At the end of the run time, the reactor was cooled to room temperature, and the crude product was recovered. The crude product was then filtered through a column packed with activated basic alumina to remove residual cobalt catalyst. The crude product was obtained as yellow/brown liquid.

[0127] A sample of the crude hydroformylation product (50 g) was hydrogenated for 3 hours using PtCb (100 mg, 0.1 wt%) at 135°C in the absence of solvent at a ¾ pressure of 1800 psig. Following hydrogenation, a sample of the colorless liquid product

(17 g) was dissolved in 50 mL of tetraethylene glycol dimethyl ether and reacted with NaBH ₄ (1 equiv.) at 70°C for 2 h. The reaction mixture was then combined with a saturated ammonium chloride solution (500 mL) and 50 mL pentane. The mixture was neutralized to a pH of ~7 using 1 M HC1. The aqueous and organic phases were separated, and the organic phase was washed (2x30 mL) with additional brine. Thereafter, the organic phase was dried with Na ₂ S0 ₄ and filtered. Pentane solvent was removed under gentle nitrogen flow to afford the product. GC-MS analysis indicates that the product composition was ~78 % C13 alcohol and the balance alkanes. The product yield was 14 g.

[0128] A portion of the alcohol product was distilled using a short path distillation apparatus at a distillation pressure of 800 mtorr. The distillate was then analyzed by GC-MS and NMR to confirm the formation of lightly branched alcohol reaction products. FIGS. 7 and 8 show ¹ H and ¹³ C NMR spectra of the finished reaction product in CDCb. The NMR spectra were consistent with the formation of alcohol functional groups.

[0129] Compared to the staring lightly branched olefins, the alcohol product will have 1 carbon number higher, with branching increased 20% from the starting lightly branched olefins. For example, the Cn lightly branched olefin with Branch Index of 1, converted to an alcohol, would be a C ₁₃ alcohol with branching of 1.2.

[0130] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby.

[0131] One or more illustrative embodiments are presented herein. Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to one having ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present disclosure.