ALKOXY CARBOXYLATE SURFACTANTS

BACKGROUND OF THE INVENTION

Enhanced Oil Recovery (abbreviated EOR) refers to techniques for increasing the amount of unrefined petroleum, or crude oil, that may be extracted from an oil reservoir (e.g. an oil field). Using EOR, 40-60% of the reservoir's original oil can typically be extracted compared with only 20-40% using primary and secondary recovery (e.g. by water injection or natural gas injection). Enhanced oil recovery may also be referred to as improved oil recovery or tertiary recovery (as opposed to primary and secondary recovery).

Enhanced oil recovery may be achieved by a variety of methods including miscible gas injection (which includes carbon dioxide flooding), chemical injection (which includes polymer flooding, alkaline flooding and surfactant flooding), microbial injection, or thermal recovery (which includes cyclic steam, steam flooding, and fire flooding). The injection of various chemicals, usually as dilute aqueous solutions, has been used to improve oil recovery. Injection of alkaline or caustic solutions into reservoirs with oil that has organic acids naturally occurring in the oil (also referred to herein as “unrefined petroleum acids”) will result in the production of soap that may lower the interfacial tension enough to increase production. Injection of a dilute solution of a water soluble polymer to increase the viscosity of the injected water can increase the amount of oil recovered from geological formations. Aqueous solutions of surfactants such as petroleum sulfonates may be injected to lower the interfacial tension or capillary pressure that impedes oil droplets from moving through a reservoir. Special formulations of oil, water and surfactant microemulsions, have also proven useful. Application of these methods is usually limited by the cost of the chemicals and their adsorption and loss onto the rock of the oil containing formation.

Some unrefined petroleum contains carboxylic acids having, for example, C₁₁to C₂₀alkyl chains, including napthenic acid mixtures (also referred to herein as “unrefined petroleum acids”). The recovery of such “reactive” oils may be performed using alkali (e.g. NaOH or Na₂CO₃) in a surfactant composition. The alkali reacts with the acid (unrefined petroleum acid) in the reactive oil to form soap. These soaps serve as an additional source of surfactants enabling the use of much lower level of surfactants initially added to effect enhanced oil recovery (EOR). However, when the available water supply is hard, the added alkali causes precipitation of cations, such as Ca⁺²or Mg⁺². In order to prevent such precipitation an expensive chelant such as EDTA may be required in the surfactant composition. Alternatively, expensive water softening processes may be used.

Therefore, there is a need in the art for cost effective methods for enhanced oil recovery using chemical injection. Provided herein are methods and compositions addressing these and other needs in the art.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1. (A) Schematic representations of the interaction of the alkoxy (ether) carboxylate and (B) the alkoxy (ether) sulfate surfactants with the carboxylic acid in a reactive oil.

FIG. 2. (A) Solubilization ratios for light crude oil using the surfactant formulation 0.5% C32-7PO-32EO Carboxylate, 0.5% C19-23 IOS as a function of the total dissolved solids in the hard brine. (B) Phase behavior data recording sheet corresponding to the plot shown in (A) for the system comprising 0.5% C32-7PO-32 EO Carboxylate, 0.5% C19-23 IOS (hard injection sea brine salinity scan).

FIG. 3 Oil recovery from a surfactant flood of a laboratory core using the blend of carboxylate and IOS surfactants of FIG. 2.

FIG. 4. Solubilization ratios using surfactant formulation 0.7% C₂₈-25PO-55EO Carboxylate, 0.3% C11 alkyl benzene sulfonate as a function of brine salinity.

FIG. 5. Data recording for microemulsion phase behavior data shown in FIG. 4 with no alkali and no co-solvents.

FIG. 6. Solubilization ratios using surfactant formulation 0.25% C32-7PO-32EO-carboxylate and 0.25% C19-23 IOS at 100 C as a function of total dissolved solids in the brine.

FIG. 7. Regression of data showing the optimum size of the hydrocarbon chain length of surfactants increases as the temperature increases.

FIG. 8. Regression equation relating the condition variables with the optimum surfactant structure under those conditions.

FIG. 9. Regression data set for optimum surfactant formulations.

FIG. 10. Comparison of experimental and calculated optimum value of the mole average number of carbons in surfactant hydrophobe.

FIG. 11. Regression data showing the optimum size of the hydrocarbon chain length increases with both oil EACN and temperature.

FIG. 12. Schematic representation of surfactant phase behavior and IFT correlation.

FIG. 13. Photographs of phase behavior salinity scan for Oil #1 using formulation 0.5% C32-7PO-32EO-carboxylate, 0.5% C19-23 IOS showing stable microemulsions after 290 days at 100° C. Properties of Oil #1: API gravity: 32.6; viscosity: 2.1 cP at 100° C.; total acid number: ˜0.05 mg KOH/g oil.

FIG. 14. Solubilization ratios for Oil #1 using formulation 0.5% C32-7PO-32EO-Carboxylate, 0.5% C19-23 IOS after 290 days.

FIG. 15. Solubilization Ratios for Oil #2 using formulation 0.5% C28-25PO-25EO-carboxylate, 0.5% C15-18 IOS showing stable aqueous solution (photograph on left) and stable microemulsion (photograph on right) after 170 days at 100 C. Properties of Oil#2: API gravity: 22; viscosity: 2.1 cP at 100° C.

FIG. 16. Summary of carboxylate formulations with active and non-active oils.

FIG. 17. Schematic representation of the interaction between carboxylic acids in active oil and carboxylate, sulfate and sulfonate surfactants.

FIG. 18. Solubilization ratios for active Oil #3 using formulation 0.25% C24-25PO-18EO-Carboxylate, 0.25% C12-ABS, 0.25% C13-13PO-sulfate, 0.25% TEGBE. Properties of Oil #3: viscosity: 20 cP at 21° C.; total acid number: 0.7-0.8 mg KOH/g oil.

FIG. 19. Activity map for active Oil #3 using formulation 0.25% C24-25PO-18EO-carboxylate, 0.25% C12-ABS, 0.25% C13-13PO-sulfate, 0.25% TEGBE indicating carboxylate surfactant is interacting with acids from oil.

FIG. 20. Microemulsion phase behavior for active Oil #4 using formulation 0.25% C28-25PO-15EO-carboxylate, 0.15% C15-18 IOS, 0.1% C20-24 IOS at salinities close to optimum salinity for 10% oil. Properties of Oil #4: API gravity: 19; viscosity: 83 cP at 30° C.; total acid number: 2.36 mg KOH/g oil.

FIG. 21. Activity map for active Oil #4 using formulation 0.25% C28-25PO-15EO-carboxylate, 0.15% C15-18 IOS, 0.1% C20-24 IOS.

FIG. 22. Surfactant-polymer (SP) flood conditions in an Ottawa F95 sand pack with Oil #4 at 30° C.

FIG. 23. Photographs of surfactant-polymer solution displacing Oil #4 from sand (early times on left and later times on right).

FIG. 24. Summary of oil recovery and surfactant retention results from two sand pack experiments.

FIG. 25. Solubilization ratios for non-active Oil #1 using formulation 0.5% C32-7PO-32EO-carboxylate, 0.5% C19-23 IOS.

FIG. 26. Surfactant-polymer (SP) core flood conditions in Silurian dolomite rock with Oil #1 at 100° C.

FIG. 27. Salinity gradient tracer test in heterogeneours Silurian dolomite rock at 100° C.

FIG. 28. Recovery of Oil #1 from Silurian dolomite rock during injection of surfactant-polymer solution containing large-hydrophobe carboxylate.

FIG. 29. Pressure drop during recovery of Oil #1 shows favorable behavior of carboxylate formulation.

FIG. 30. Solubilization ratios for non-active Oil #1 using formulation 0.50% C28-25PO-45EO-carboxylate, 0.50% C15-18 IOS after 154 days at 100 C.

FIG. 31. Dilute surfactant-polymer core flood conditions in Estillades carbonate with Oil#1 at 100° C.

FIG. 32. Recovery of non-active Oil #1 using dilute surfactant solution at 100° C.

BRIEF SUMMARY OF THE INVENTION

In a first aspect, the present invention provides a compound having the formula:

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In formula (Ia) or (Ib), R¹is R¹⁰-substituted or unsubstituted C₈-C₁₅₀alkyl, R⁴-substituted or unsubstituted aryl or R⁴-substituted or unsubstituted cycloalkyl. R²is independently hydrogen or unsubstituted C₁-C₆alkyl. R³is independently hydrogen or unsubstituted C₁-C₆alkyl. R⁴is independently an R⁵-substituted or unsubstituted C₁-C₅₀alkyl, R⁵-substituted or unsubstituted aryl or R⁵-substituted or unsubstituted cycloalkyl. R⁵is independently R⁶-substituted or unsubstituted C₁-C₅₀alkyl, R⁶-substituted or unsubstituted aryl or R⁶-substituted or unsubstituted cycloalkyl. R⁶is independently R⁷-substituted or unsubstituted C₁-C₅₀alkyl, R⁷-substituted or unsubstituted aryl or R⁷-substituted or unsubstituted cycloalkyl. R⁷is independently R⁸-substituted or unsubstituted C₁-C₅₀alkyl, R⁸-substituted or unsubstituted aryl or R⁸-substituted or unsubstituted cycloalkyl. R⁸is independently R⁹-substituted or unsubstituted C₁-C₅₀alkyl, R⁹-substituted or unsubstituted aryl or R⁹-substituted or unsubstituted cycloalkyl. R⁹is independently unsubstituted C₁-C₅₀alkyl, unsubstituted aryl or unsubstituted cycloalkyl. R¹⁰is independently unsubstituted aryl or unsubstituted cycloalkyl. The symbol n is an integer from 2 to 210, z is an integer from 1 to 6, and M⁺is a monovalent, divalent or trivalent cation.

In another aspect, an aqueous composition is provided including a co-surfactant and a compound described herein (e.g. a compound of formula (Ia), (Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa), ((IVb)) or (V)).

In another aspect, an emulsion composition including an unrefined petroleum phase and an aqueous phase is provided. The aqueous phase includes a compound described herein (e.g. a compound of formula (Ia), (Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa), ((IVb)) or (V)).

In another aspect, a method of displacing a hydrocarbon material in contact with a solid material is provided. The method includes contacting a hydrocarbon material with a compound described herein (e.g. a compound of formula (Ia), (Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa), ((IVb)) or (V)), wherein the hydrocarbon material is in contact with the solid material. The hydrocarbon material is allowed to separate from the solid material thereby displacing the hydrocarbon material in contact with the solid material.

In another aspect, a method of converting an unrefined petroleum acid into a surfactant is provided. The method includes contacting a petroleum material with an aqueous composition thereby forming an emulsion in contact with the petroleum material, wherein the aqueous composition includes a compound described herein (e.g. a compound of formula (Ia), (Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa), ((IVb)) or (V)) and a co-surfactant. An unrefined petroleum acid within the unrefined petroleum material is allowed to enter the emulsion, thereby converting the unrefined petroleum acid into a surfactant.

DEFINITIONS

The abbreviations used herein have their conventional meaning within the chemical and biological arts.

Where substituent groups are specified by their conventional chemical formulae, written from left to right, they equally encompass the chemically identical substituents that would result from writing the structure from right to left, e.g., —CH₂O— is equivalent to —OCH₂—.

The term “alkyl,” by itself or as part of another substituent, means, unless otherwise stated, a straight (i.e. unbranched) or branched chain which may be fully saturated, mono- or polyunsaturated and can include di- and multivalent radicals, having the number of carbon atoms designated (i.e. C₁-C₁₀means one to ten carbons). Examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, homologs and isomers of, for example, n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. An unsaturated alkyl group is one having one or more double bonds or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and the higher homologs and isomers. Alkyl groups which are limited to hydrocarbon groups are termed “homoalkyl”. An alkoxy is an alkyl attached to the remainder of the molecule via an oxygen linker (—O—).

The term “alkylene” by itself or as part of another substituent means a divalent radical derived from an alkyl, as exemplified, but not limited, by —CH₂CH₂CH₂CH₂—, and further includes those groups described below as “heteroalkylene.” Typically, an alkyl (or alkylene) group will have from 1 to 24 carbon atoms, with those groups having 10 or fewer carbon atoms being preferred in the present invention. A “lower alkyl” or “lower alkylene” is a shorter chain alkyl or alkylene group, generally having eight or fewer carbon atoms.

The term “heteroalkyl,” by itself or in combination with another term, means, unless otherwise stated, a stable straight or branched chain or combinations thereof, consisting of at least one carbon atom and at least one heteroatom selected from the group consisting of O, N, P, Si and S, and wherein the nitrogen and sulfur atoms may optionally be oxidized. and the nitrogen heteroatom may optionally be quaternized. The heteroatom(s) O, N, P and S and Si may be placed at any interior position of the heteroalkyl group or at the position at which the alkyl group is attached to the remainder of the molecule. Examples include, but are not limited to, —CH₂—CH₂—O—CH₃, —CH₂—CH₂—NH—CH₃, —CH₂—CH₂—N(CH₃)—CH₃, —CH₂—S—CH₂—CH₃, —CH₂—CH₂, —S(O)—CH₃, —CH₂—CH₂—S(O)₂—CH₃, —CH═CH—O—CH₃, —Si(CH₃)₃, —CH₂—CH═N—OCH₃, —CH═CH—N(CH₃)—CH₃, O—CH₃, —O—CH₂—CH₃, and —CN. Up to two heteroatoms may be consecutive, such as, for example, —CH₂—NH—OCH₃. Similarly, the term “heteroalkylene” by itself or as part of another substituent means a divalent radical derived from heteroalkyl, as exemplified, but not limited by, —CH₂—CH₂—S—CH₂—CH₂— and —CH₂—S—CH₂—CH₂—NH—CH₂—. For heteroalkylene groups, heteroatoms can also occupy either or both of the chain termini (e.g., alkyleneoxy, alkylenedioxy, alkyleneamino, alkylenediamino, and the like). Still further, for alkylene and heteroalkylene linking groups, no orientation of the linking group is implied by the direction in which the formula of the linking group is written. For example, the formula —C(O)₂R′— represents both —C(O)₂R′— and —R′C(O)₂—.

The terms “cycloalkyl” and “heterocycloalkyl,” by themselves or in combination with other terms, represent, unless otherwise stated, cyclic versions of “alkyl” and “heteroalkyl”, respectively. Additionally, for heterocycloalkyl, a heteroatom can occupy the position at which the heterocycle is attached to the remainder of the molecule. Examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-cyclohexenyl, 3-cyclohexenyl, cycloheptyl, and the like. Examples of heterocycloalkyl include, but are not limited to, 1-(1,2,5,6-tetrahydropyridyl), 1-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-morpholinyl, 3-morpholinyl, tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, 1-piperazinyl, 2-piperazinyl, and the like. A “cycloalkylene” and a “heterocycloalkylene,” alone or as part of another substituent means a divalent radical derived from a cycloalkyl and heterocycloalkyl, respectively.

The term “aryl” means, unless otherwise stated, a polyunsaturated, aromatic, hydrocarbon substituent which can be a single ring or multiple rings (preferably from 1 to 3 rings) which are fused together (i.e. a fused ring aryl) or linked covalently. A fused ring aryl refers to multiple rings fused together wherein at least one of the fused rings is an aryl ring. The term “heteroaryl” refers to aryl groups (or rings) that contain from one to four heteroatoms selected from N, O, and S, wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. Thus, the term “heteroaryl” includes fused ring heteroaryl groups (i.e. multiple rings fused together wherein at least one of the fused rings is a heteroaromatic ring). A 5,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 5 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. Likewise, a 6,6-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 6 members, and wherein at least one ring is a heteroaryl ring. And a 6,5-fused ring heteroarylene refers to two rings fused together, wherein one ring has 6 members and the other ring has 5 members, and wherein at least one ring is a heteroaryl ring. A heteroaryl group can be attached to the remainder of the molecule through a carbon or heteroatom. Non-limiting examples of aryl and heteroaryl groups include phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 2-imidazolyl, 4-imidazolyl, pyrazinyl, 2-oxazolyl, 4-oxazolyl, 2-phenyl-4-oxazolyl, 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 5-benzothiazolyl, purinyl, 2-benzimidazolyl, 5-indolyl, 1-isoquinolyl, 5-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 3-quinolyl, and 6-quinolyl. Substituents for each of the above noted aryl and heteroaryl ring systems are selected from the group of acceptable substituents described below. An “arylene” and a “heteroarylene,” alone or as part of another substituent means a divalent radical derived from an aryl and heteroaryl, respectively.

The term “oxo” as used herein means an oxygen that is double bonded to a carbon atom.

Where a substituent of a compound provided herein is “R-substituted” (e.g. R⁷-substituted), it is meant that the substituent is substituted with one or more of the named R groups (e.g. R⁷) as appropriate. In some embodiments, the substituent is substituted with only one of the named R groups.

The symbol “ custom-character ” denotes the point of attachment of a chemical moiety to the remainder of a molecule or chemical formula.

Each R-group as provided in the formulae provided herein can appear more than once. Where a R-group appears more than once ach R group can be optionally different.

The term “contacting” as used herein, refers to materials or compounds being sufficiently close in proximity to react or interact. For example, in methods of contacting a hydrocarbon material bearing formation and/or a well bore, the term “contacting” includes placing an aqueous composition (e.g. chemical, surfactant or polymer) within a hydrocarbon material bearing formation using any suitable manner known in the art (e.g., pumping, injecting, pouring, releasing, displacing, spotting or circulating the chemical into a well, well bore or hydrocarbon bearing formation).

The terms “unrefined petroleum” and “crude oil” are used interchangeably and in keeping with the plain ordinary usage of those terms. “Unrefined petroleum” and “crude oil” may be found in a variety of petroleum reservoirs (also referred to herein as a “reservoir,” “oil field deposit” “deposit” and the like) and in a variety of forms including oleaginous materials, oil shales (i.e. organic-rich fine-grained sedimentary rock), tar sands, light oil deposits, heavy oil deposits, and the like. “Crude oils” or “unrefined petroleums” generally refer to a mixture of naturally occurring hydrocarbons that may be refined into diesel, gasoline, heating oil, jet fuel, kerosene, and other products called fuels or petrochemicals. Crude oils or unrefined petroleums are named according to their contents and origins, and are classified according to their per unit weight (specific gravity). Heavier crudes generally yield more heat upon burning, but have lower gravity as defined by the American Petroleum Institute (API) and market price in comparison to light (or sweet) crude oils. Crude oil may also be characterized by its Equivalent Alkane Carbon Number (EACN).

Crude oils vary widely in appearance and viscosity from field to field. They range in color, odor, and in the properties they contain. While all crude oils are mostly hydrocarbons, the differences in properties, especially the variation in molecular structure, determine whether a crude oil is more or less easy to produce, pipeline, and refine. The variations may even influence its suitability for certain products and the quality of those products. Crude oils are roughly classified intro three groups, according to the nature of the hydrocarbons they contain. (i) Paraffin based crude oils contain higher molecular weight paraffins, which are solid at room temperature, but little or no asphaltic (bituminous) matter. They can produce high-grade lubricating oils. (ii) Asphaltene based crude oils contain large proportions of asphaltic matter, and little or no paraffin. Some are predominantly naphthenes and so yield lubricating oils that are sensitive to temperature changes than the paraffin-based crudes. (iii) Mixed based crude oils contain both paraffin and naphthenes, as well as aromatic hydrocarbons. Most crude oils fit this latter category.

“Reactive” crude oil as referred to herein is crude oil containing natural organic acidic components. More terms used interchangeably for oil throughout this disclosure are hydrocarbon material or petroleum material. An “oil bank” or “oil cut” as referred to herein, is the crude oil that does not contain the injected chemicals and is pushed by the injected fluid during an enhanced oil recovery process.

The term “polymer” refers to a molecule having a structure that essentially includes the multiple repetitions of units derived, actually or conceptually, from molecules of low relative molecular mass. In some embodiments, the polymer is an oligomer.

The term “bonded” refers to having at least one of covalent bonding, hydrogen bonding, ionic bonding, Van Der Waals interactions, pi interactions, London forces or electrostatic interactions.

The term “productivity” as applied to a petroleum or oil well refers to the capacity of a well to produce hydrocarbons (e.g. unrefined petroleum); that is, the ratio of the hydrocarbon flow rate to the pressure drop, where the pressure drop is the difference between the average reservoir pressure and the flowing bottom hole well pressure (i.e., flow per unit of driving force).

The term “oil solubilization ratio” is defined as the volume of oil solubilized divided by the volume of surfactant in microemulsion. All the surfactant is presumed to be in the microemulsion phase. The oil solubilization ratio is applied for Winsor type I and type III behavior. The volume of oil solubilized is found by reading the change between initial aqueous level and excess oil (top) interface level. The oil solubilization ratio is calculated as follows:

$σ_{o} = \frac{V_{o}}{V_{s}},$

wherein

ρ_o=oil solubilization ratio;

V_o=volume of oil solubilized;

V_s=volume of surfactant.

The term “water solubilization ratio” is defined as the volume of water solubilized divided by the volume of surfactant in microemulsion. All the surfactant is presumed to be in the microemulsion phase. The water solubilization ratio is applied for Winsor type III and type II behavior. The volume of water solubilized is found by reading the change between initial aqueous level and excess water (bottom) interface level. The water solubilization parameter is calculated as follows:

$σ_{w} = \frac{V_{w}}{V_{s}},$

wherein

σ_w=water solubilization ratio;

V_w=volume of water solubilized.

The optimum solubilization ratio occurs where the oil and water solubilization ratios are equal. The coarse nature of phase behavior screening often does not include a data point at optimum, so the solubilization ratio curves are drawn for the oil and water solubilization ratio data and the intersection of these two curves is defined as the optimum. The following is true for the optimum solubilization ratio:

σO=σW=σ*;

σ*=optimum solubilization ratio.

The term “solubility” or “solubilization” in general refers to the property of a solute, which can be a solid, liquid or gas, to dissolve in a solid, liquid or gaseous solvent thereby forming a homogenous solution of the solute in the solvent. Solubility occurs under dynamic equilibrium, which means that solubility results from the simultaneous and opposing processes of dissolution and phase joining (e.g. precipitation of solids). The solubility equilibrium occurs when the two processes proceed at a constant rate. The solubility of a given solute in a given solvent typically depends on temperature. For many solids dissolved in liquid water, the solubility increases with temperature. In liquid water at high temperatures, the solubility of ionic solutes tends to decrease due to the change of properties and structure of liquid water. In more particular, solubility and solubilization as referred to herein is the property of oil to dissolve in water and vice versa.

“Viscosity” refers to a fluid's internal resistance to flow or being deformed by shear or tensile stress. In other words, viscosity may be defined as thickness or internal friction of a liquid. Thus, water is “thin”, having a lower viscosity, while oil is “thick”, having a higher viscosity. More generally, the less viscous a fluid is, the greater its ease of fluidity.

The term “salinity” as used herein, refers to concentration of salt dissolved in a aqueous phases. Examples for such salts are without limitation, sodium chloride, magnesium and calcium sulfates, and bicarbonates. In more particular, the term salinity as it pertains to the present invention refers to the concentration of salts in brine and surfactant solutions.

The term “aqueous solution or aqueous formulation” refers to a solution in which the solvent is water. The term “emulsion, emulsion solution or emulsion formulation” refers to a mixture of two or more liquids which are normally immiscible. A non-limiting example for an emulsion is a mixtures of oil and water

DETAILED DESCRIPTION

While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not limit the scope of the invention.

Provided herein, inter alia, are large hydrophobe alkoxy carboxylate compounds and methods of using the same for a variety of applications including enhanced oil recovery. The compounds provided herein may be used with broad oil concentrations, at a wide range of salinities and are surprisingly effective even in the absence of alkali. They may be functional at high reservoir temperatures and over a broad pH range. Further, by using the compounds of the present invention enhanced oil recovery may be performed in the absence of water softening. Furthermore, compared to sulfate or sulfonate surfactants, the carboxylate surfactants provided herein may form a surprisingly stronger interaction with the carboxylic acids in reactive crude oils thereby increasing the efficiency of oil recovery without the use of alkali. The alkoxy carboxylate compounds may also significantly improve the effectiveness of co-surfactant sulfonate compounds such as ABS or IOS to a surprising degree. Where these sulfonate compounds are combined with the compounds provided herein, the combination may be more stable and effective when compared to the stability and effectiveness of the sulfonate compounds in the absence of the compounds provided herein (e.g. a compound of formula (Ia), (Ib), (IIa), (IIb), (IIIa), (IIIb), (IVa), ((IVb)) or (V)).

In a first aspect, the present invention provides a compound having the formula:

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In formula (Ia) and (Ib), R¹is R¹⁰-substituted or unsubstituted C₈-C₁₅₀alkyl, R⁴-substituted or unsubstituted aryl or R⁴-substituted or unsubstituted cycloalkyl. R²is independently hydrogen or unsubstituted C₁-C₆alkyl. R³is independently hydrogen or unsubstituted C₁-C₆alkyl. R⁴is an R⁵-substituted or unsubstituted C₁-C₅₀alkyl, R⁵-substituted or unsubstituted aryl or R⁵-substituted or unsubstituted cycloalkyl. R⁵is R⁶-substituted or unsubstituted C₁-C₅₀alkyl, R⁶-substituted or unsubstituted aryl or R⁶-substituted or unsubstituted cycloalkyl. R⁶is R⁷-substituted or unsubstituted C₁-C₅₀alkyl, R⁷-substituted or unsubstituted aryl or R⁷-substituted or unsubstituted cycloalkyl. R⁷is R⁸-substituted or unsubstituted C₁-C₅₀alkyl, R⁸-substituted or unsubstituted aryl or R⁸-substituted or unsubstituted cycloalkyl. R⁸is R⁹-substituted or unsubstituted C₁-C₅₀alkyl, R⁹-substituted or unsubstituted aryl or R⁹-substituted or unsubstituted cycloalkyl. R⁹is unsubstituted C₁-C₅₀alkyl, unsubstituted aryl or unsubstituted cycloalkyl. R¹⁰is unsubstituted aryl or unsubstituted cycloalkyl. Where R⁴-R¹⁰are each alkyls, the total number of carbons does not exceed 150. The symbol n is an integer from 2 to 210, z is an integer from 1 to 6, and M⁺is a monovalent, divalent or trivalent cation. In some embodiments, z is 1 to 3. In other embodiments, z is 1 or 2. In formula (Ia) and (Ib) each of R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹and R¹⁰can appear more than once and can be optionally different. For example, in some embodiments where n is 2, R²appears twice and can be optionally different. In other embodiments, where z is 5, R³appears five times and can be optionally different.

In other embodiments, the symbol n is an integer from 25 to 210. In other embodiments, the symbol n is an integer from 30 to 210. In other embodiments, the symbol n is an integer from 35 to 210. In other embodiments, the symbol n is an integer from 40 to 210. In other embodiments, the symbol n is an integer from 45 to 210. In other embodiments, the symbol n is an integer from 50 to 210. In other embodiments, the symbol n is an integer from 55 to 210. In other embodiments, the symbol n is an integer from 60 to 210. In other embodiments, the symbol n is an integer from 25 to 100. In other embodiments, the symbol n is an integer from 30 to 100. In other embodiments, the symbol n is an integer from 35 to 100. In other embodiments, the symbol n is an integer from 40 to 100. In other embodiments, the symbol n is an integer from 45 to 100. In other embodiments, the symbol n is an integer from 50 to 100. In other embodiments, the symbol n is an integer from 55 to 100. In other embodiments, the symbol n is an integer from 60 to 100. In some embodiments, n is 5 to 180. In other embodiments, n is 10 to 100. In some embodiments, n is 15 to 60. In other embodiments, n is 20 to 50. In some embodiments, n is 25. In other embodiments, n is 35. In some related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₁₅₀alkyl. In other related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₁₅₀alkyl. In other related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₁₅₀alkyl. In other related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₅₀alkyl. In other related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₅₀alkyl. In other related embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₅₀alkyl.

In some embodiments, R¹is branched unsubstituted C₈-C₁₅₀alkyl or R⁴-substituted phenyl. In other embodiments, R¹is branched or linear unsubstituted C₈-C₁₅₀alkyl or R⁴-substituted phenyl. In some embodiments, R¹is branched or linear unsubstituted C₁₂-C₁₀₀alkyl, (C₆H₅—CH₂CH₂)₃C₆H₂-(TSP), (C₆H₅—CH₂CH₂)₂C₆H₃-(DSP), (C₆H₅—CH₂CH₂)₁C₆H₄-(MSP), or R⁴-substituted or unsubstituted naphthyl. In some embodiments, the naphthyl is a mono-, di-, or tri-alkyl naphthyl or any combination thereof. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

R¹may be linear or branched unsubstituted alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₁₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₁₀₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₅₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₅₀alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₄₀alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₄₀alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₃₆alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₃₆alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₀-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₂-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₄-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₆-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₁₈-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₀-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₂-C₂₈alkyl. In some embodiments, R¹is R¹⁰-substituted or unsubstituted C₂₄-C₂₈alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is branched unsubstituted C₁₂-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₁₀₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₁₀₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₈-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₈-C₁₀₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₀-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₀-C₁₀₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₂-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₂-C₁₀₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₁₀₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₁₀₀alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is branched unsubstituted C₁₂-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₅₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₅₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₈-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₈-C₅₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₀-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₀-C₅₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₂-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₂-C₅₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₅₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₅₀alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is branched unsubstituted C₁₂-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₄₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₄₀alkyl. In some embodiments, R¹is branched unsubstituted C₁₈-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₁₈-C₄₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₀-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₀-C₄₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₂-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₂-C₄₀alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₄₀alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₄₀alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is branched unsubstituted C₁₂-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₃₆alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₃₆alkyl. In some embodiments, R¹is branched unsubstituted C₁₈-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₁₈-C₃₆alkyl. In some embodiments, R¹is branched unsubstituted C₂₀-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₂₀-C₃₆alkyl. In some embodiments, R¹is branched unsubstituted C₂₂-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₂₂-C₃₆alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₃₆alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₃₆alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, R¹is branched unsubstituted C₁₂-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₂₈alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₂₈alkyl. In some embodiments, R¹is branched unsubstituted C₁₈-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₁₈-C₂₈alkyl. In some embodiments, R¹is branched unsubstituted C₂₀-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₂₀-C₂₈alkyl. In some embodiments, R¹is branched unsubstituted C₂₂-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₂₂-C₂₈alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₂₈alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₂₈alkyl. In some related embodiments, the alkyl is a saturated alkyl. In other related embodiments, n is as defined in an embodiment above (e.g. n is at least 25; or at least 35, e.g. 35 to 100).

In some embodiments, where R¹is a linear or branched unsubstituted alkyl (e.g. branched unsubstituted C₁₂-C₁₀₀alkyl), the alkyl is a saturated alkyl (e.g. a linear or branched unsubstituted saturated alkyl or branched unsubstituted C₁₂-C₁₀₀saturated alkyl). A “saturated alkyl,” as used herein, refers to an alkyl consisting only of hydrogen and carbon atoms and are boded exclusively by single bonds. Thus, in some embodiments, R¹may be linear or branched unsubstituted saturated alkyl. In some embodiments, R¹is branched unsubstituted C₁₂-C₁₀₀saturated alkyl. In other embodiments, R¹is linear unsubstituted C₁₂-C₁₀₀saturated alkyl. In some embodiments, R¹is branched unsubstituted C₁₆-C₁₀₀saturated alkyl. In other embodiments, R¹is linear unsubstituted C₁₆-C₁₀₀saturated alkyl. In some embodiments, R¹is branched unsubstituted C₂₄-C₃₆saturated alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₃₆saturated alkyl. In other embodiments, R¹is linear unsubstituted C₂₄-C₂₈saturated alkyl. In other embodiments, R¹is branched unsubstituted C₂₄-C₂₈saturated alkyl.

In some embodiments, R¹is formed using the Guerbet reaction.

In some embodiments, R²is independently hydrogen or unsubstituted C₁-C₅alkyl. In some embodiments, R²is a branched unsubstituted C₁-C₅saturated alkyl. In some embodiments, R²is hydrogen or a branched unsubstituted C₁or C₂saturated alkyl. In some embodiments, R²is hydrogen or a branched unsubstituted C₁saturated alkyl. In other embodiments, R²is C₂-C₆alkyl. In some embodiments, R²is a branched unsubstituted C₂-C₆saturated alkyl. In some embodiments, R²is not C₂alkyl. In other embodiments, R²is C₁alkyl or C₃-C₆alkyl. In some embodiments, R²is a branched unsubstituted C₃-C₆saturated alkyl. In other embodiments, R³is hydrogen.

In some embodiments, z is 1. M⁺ may be a monovalent, divalent or trivalent cation. In some embodiments, M⁺ is a monovalent, divalent or trivalent metal cation. In some embodiments, M⁺ is a monovalent or divalent cation (e.g. metal cation). In some embodiments, M⁺ is a monovalent cation (e.g. metal cation). In some embodiments, M⁺ is a divalent cation (e.g. metal cation). In some embodiments, M⁺ is Na⁺, NH₄⁺, Ca⁺², Mg⁺²or Ba⁺².

In some embodiments the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein (e.g. formula, the compound has a molecular weight of at least about 1500 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least 1 about 600 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 1700 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 1800 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 1900 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2000 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2100 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2200 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2300 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2400 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2500 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2600 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2700 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2800 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 2900 g/mol. In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, the compound has a molecular weight of at least about 3000 g/mol.

In some embodiments, where multiple R²substituents are present and at least two R²substituents are different, R²substituents with the fewest number of carbons are present to the carboxyl or carboxylate side of the compound of formula (Ia) or (Ib), respectively. In this embodiment, the compound of formula (Ia) or (Ib) will be increasingly hydrophilic in progressing from the R¹substituent to the carboxyl or carboxylate side of the compound of formula (Ia) or (Ib), respectively. The term “carboxyl or carboxylate side of the compound of formula (Ia) or (Ib), respectively” refers to the side of the compound indicated by asterisks in the below structures:

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In some embodiments of the compound of formula (Ia) or (Ib), or embodiments thereof disclosed herein, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 21 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 25 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 30 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 35 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 40 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 45 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 50 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 55 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 60 to 210. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 25 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 30 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 35 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 40 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 45 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 50 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 55 to 100. In other embodiments, where R¹is unsubstituted C₈-C₁₈alkyl, the symbol n is an integer from 60 to 100.

In some embodiments, the compound has the formula

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In formula (IIa) or (IIb) M⁺, R¹, R², R³and z are as defined above. The symbol y is an integer from 1 to 100, w is an integer from 1 to 70, v is an integer from 0 to 40. In some embodiments, R²is unsubstituted C₂-C₆alkyl (e.g. ethyl). In some embodiments, R²is unsubstituted C₃-C₆alkyl. In some embodiments, R²is ethyl. In some embodiments, y is an integer from 10 to 50, w is an integer from 5 to 50 and v is an integer from 0 to 30. In other embodiments, y is an integer from 10 to 40. In certain embodiments, y is 10 to 60. In certain embodiments, y is 10 to 56. The symbol w may be an integer from 5 to 40. In certain embodiments, w is 25 to 35. The symbol v may be an integer from 0 to 20. The symbol v may be an integer from 0 to 10. The symbol v may also be 0.

In some embodiments, y is 10 to 100. In some related embodiments, y is 10 to 90. In some related embodiments, y is 10 to 80. In some related embodiments, y is 10 to 70. In some related embodiments, y is 10 to 60. In some related embodiments, y is 10 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 15 to 100. In some related embodiments, y is 15 to 90. In some related embodiments, y is 15 to 80. In some related embodiments, y is 15 to 70. In some related embodiments, y is 15 to 60. In some related embodiments, y is 15 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 20 to 100. In some related embodiments, y is 20 to 90. In some related embodiments, y is 20 to 80. In some related embodiments, y is 20 to 70. In some related embodiments, y is 20 to 60. In some related embodiments, y is 20 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 25 to 100. In some related embodiments, y is 25 to 90. In some related embodiments, y is 25 to 80. In some related embodiments, y is 25 to 70. In some related embodiments, y is 25 to 60. In some related embodiments, y is 25 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 30 to 100. In some related embodiments, y is 30 to 90. In some related embodiments, y is 30 to 80. In some related embodiments, y is 30 to 70. In some related embodiments, y is 30 to 60. In some related embodiments, y is 30 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 35 to 100. In some related embodiments, y is 35 to 90. In some related embodiments, y is 35 to 80. In some related embodiments, y is 35 to 70. In some related embodiments, y is 35 to 60. In some related embodiments, y is 35 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 40 to 100. In some related embodiments, y is 40 to 90. In some related embodiments, y is 40 to 80. In some related embodiments, y is 40 to 70. In some related embodiments, y is 40 to 60. In some related embodiments, y is 40 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 45 to 100. In some related embodiments, y is 45 to 90. In some related embodiments, y is 45 to 80. In some related embodiments, y is 45 to 70. In some related embodiments, y is 45 to 60. In some related embodiments, y is 45 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In some embodiments, y is 50 to 100. In some related embodiments, y is 50 to 90. In some related embodiments, y is 50 to 80. In some related embodiments, y is 50 to 70. In some related embodiments, y is 50 to 60. In some related embodiments, y is 50 to 56. In some further related embodiments, w is 5 to 60. In other further related embodiments, w is 10 to 50. In other further related embodiments, w is 15 to 40. In other further related embodiments, w is 20 to 40. In other further related embodiments, w is 25 to 35. In other further related embodiments, w is more than 10, 15, or 20. Moreover, in still further related embodiments, v is 0. In other still further related embodiments, v is 0 to 20. In other still further related embodiments, v is 0 to 10. In other still further related embodiments, v is 0 to 5. In other still further related embodiments, v is 0 to 3. In other still further related embodiments, v is 0 to 2. In other still further related embodiments, v is 1. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl).

In other embodiments, the compound has the formula

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In formula (IIIc) or (IIIb), M⁺, R¹, R², R³and z are as defined above (e.g. in formula (Ia), (Ib), (IIa), and (IIb)). The symbols x and y are independently integers from 1 to 100, and R²is unsubstituted C₁-C₆alkyl. In some embodiments, R²is C₃-C₆. In some embodiments, R²is ethyl. In some embodiments, R²is methyl. In some embodiments, y is an integer from 10 to 50 and x is an integer from 5 to 50. In other embodiments, y is an integer from 10 to 40. In certain embodiments, y is 10 to 60. In certain embodiments, y is 10 to 56. The symbol x may be an integer from 5 to 40. In certain embodiments, x is 25 to 35. In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 10 to 100. In some related embodiments, y is 10 to 90. In some related embodiments, y is 10 to 80. In some related embodiments, y is 10 to 70. In some related embodiments, y is 10 to 60. In some related embodiments, y is 10 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 15 to 100. In some related embodiments, y is 15 to 90. In some related embodiments, y is 15 to 80. In some related embodiments, y is 15 to 70. In some related embodiments, y is 15 to 60. In some related embodiments, y is 15 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 20 to 100. In some related embodiments, y is 20 to 90. In some related embodiments, y is 20 to 80. In some related embodiments, y is 20 to 70. In some related embodiments, y is 20 to 60. In some related embodiments, y is 20 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 25 to 100. In some related embodiments, y is 25 to 90. In some related embodiments, y is 25 to 80. In some related embodiments, y is 25 to 70. In some related embodiments, y is 25 to 60. In some related embodiments, y is 25 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 30 to 100. In some related embodiments, y is 30 to 90. In some related embodiments, y is 30 to 80. In some related embodiments, y is 30 to 70. In some related embodiments, y is 30 to 60. In some related embodiments, y is 30 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 35 to 100. In some related embodiments, y is 35 to 90. In some related embodiments, y is 35 to 80. In some related embodiments, y is 35 to 70. In some related embodiments, y is 35 to 60. In some related embodiments, y is 35 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 40 to 100. In some related embodiments, y is 40 to 90. In some related embodiments, y is 40 to 80. In some related embodiments, y is 40 to 70. In some related embodiments, y is 40 to 60. In some related embodiments, y is 40 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 45 to 100. In some related embodiments, y is 45 to 90. In some related embodiments, y is 45 to 80. In some related embodiments, y is 45 to 70. In some related embodiments, y is 45 to 60. In some related embodiments, y is 45 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, y is 50 to 100. In some related embodiments, y is 50 to 90. In some related embodiments, y is 50 to 80. In some related embodiments, y is 50 to 70. In some related embodiments, y is 50 to 60. In some related embodiments, y is 50 to 56. In some further related embodiments, x is 5 to 60. In other further related embodiments, x is 10 to 50. In other further related embodiments, x is 15 to 40. In other further related embodiments, x is 20 to 40. In other further related embodiments, x is 25 to 35. In other further related embodiments, x is more than 10, 15, or 20. R¹may be any of the embodiments described above (e.g. an C₂₀-C₅₀alkyl such as a C₂₀-C₄₀alkyl, C₂₀-C₃₆alkyl or C₂₄-C₂₈alkyl). In some embodiments, z is 1. As stated above, R³may be hydrogen.

In some embodiments, the compound has the formula:

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In formula (IVa) or ((IVb)), M⁺, R¹, x, y and z are as defined above (e.g. in formula (Ia), (Ib), (IIa), and (IIb)). For example, in some embodiments, z is 1, R³is hydrogen, x and y are independently 5 to 100, and R¹is unsubstituted C₁₆-C₅₀alkyl or unsubstituted tristyrylphenyl. In some embodiments, y is an integer from 10 to 50 and x is an integer from 5 to 50. In other embodiments, y is an integer from 10 to 40. In certain embodiments, y is 10 to 60. In certain embodiments, y is 10 to 56. The symbol x may be an integer from 5 to 40. In certain embodiments, x is 25 to 35.