BACKGROUND OF THE DISCLOSURE

Field of the Disclosure

This invention relates to processes for making a quaternary ammonium compound from a tertiary amine.

Technical Background

Alkoxylated quaternary ammonium compounds derived from fatty amines can be prepared by reacting a tertiary amine with an alkylene oxide in the presence of acid. This reaction is conventionally performed in water or a mixture of a polar, water-soluble solvent such as ethanol or isopropanol, and water.

For several applications of such an alkoxylated quaternary ammonium compound, a substantially dry product (i.e., low water content) is required. Currently, preparing an alkoxylated quaternary ammonium compound for such an application requires several steps- after performing the quaternization reaction in, e.g., an ethanol-water mixture, an anhydrous solvent is added to the reaction mixture, after which the ethanol and water are removed from the reaction mixture (e.g., by vacuum distillation). Such a multi-step procedure is complicated and produces solvent waste that must be subsequently disposed of or recycled.

Accordingly, there remains a need for a process for making alkoxylated quaternary compounds that does not require multiple steps and/or solvent exchange.

SUMMARY OF THE DISCLOSURE

In one aspect, the disclosure provides methods for making a quaternary ammonium compound, comprising

1 ) combining

a) an amine of the formula R[CONH(CH2) _n ] _z N(R ¹ )(R ² ), wherein z is 0-1 , n is 2-5,

R is C10-C22 alkyl or C10-C22 alkylene, and

R ¹ and R ² independently represent hydroxy C Cs alkyl or C Cs alkyl, wherein at least one of R ¹ and R ² is hydroxy C Cs alkyl; b) a solvent with a solubility in water of less than 5 % by weight; and c) water;

d) an acid; and

e) a C Cs alkylene oxide,

whereby these compounds a)-e) can be combined in any sequence, and 2) allowing the reaction mixture to react.

In another aspect, the disclosure provides methods for making a composition comprising a mixture of quaternary ammonium compounds, the process comprising contacting

a mixture comprising

N,N-bis(hydroxyethyl)-N-tallow amine;

a solvent with a solubility in water of less than 5 % by weight; and water

with

an acid; and

a C Cs alkylene oxide.

DETAILED DESCRIPTION

The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and/or examples making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparati, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

The terms“a,”“an,”“the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. Ranges can be expressed herein as from“about” one particular value, and/or to“about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent“about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non- claimed element essential to the practice of the invention.

Unless the context clearly requires otherwise, throughout the description and the claims, the words‘comprise’,‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of“including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term“comprise” or“comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase“consisting of excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of limits the scope of the embodiment to the specified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term“about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. When further clarity is required, the term“about” has the meaning reasonably ascribed to it by a person skilled in the art when used in conjunction with a stated numerical value or range, i.e. denoting somewhat more or somewhat less than the stated value or range, to within a range of ±20% of the stated value; ±19% of the stated value; ±18% of the stated value; ±17% of the stated value; ±16% of the stated value; ±15% of the stated value; ±14% of the stated value; ±13% of the stated value; ±12% of the stated value; ±11 % of the stated value; ±10% of the stated value; ±9% of the stated value; ±8% of the stated value; ±7% of the stated value; ±6% of the stated value; ±5% of the stated value; ±4% of the stated value; ±3% of the stated value; ±2% of the stated value; or ±1 % of the stated value.

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

All percentages, ratios and proportions herein are by weight, unless otherwise specified. A weight percent (weight %, also as wt. %) of a component, unless specifically stated to the contrary, is based on the total weight of the composition in which the component is included (e.g., on the total amount of the reaction mixture).

The term “alkyl” as used herein, means a straight or branched chain hydrocarbon containing from 1 to 26 carbon atoms unless otherwise specified. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. The term“alkylene” refers to a divalent alkyl group, where alkyl is as defined herein.

Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and/or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

Several embodiments of this invention are described herein. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context. All patents and printed publications are individually incorporated herein by reference in their entirety.

It is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may be utilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.

In various aspects and embodiments, the disclosure relates to processes for making a quaternary ammonium compound. The disclosure demonstrates such processes to be comparable in reaction rate and conversion percentage to conventional processes, without requiring a solvent that is readily soluble, or in certain embodiments, highly soluble in water. The process of the disclosure provides several additional advantages over conventional processes. Inefficient and time-consuming solvent changes are unnecessary for the process of the disclosure. The process obviates the need for disposing or recycling of unwanted ethanol. The process also produces a compound that has a substantially small ethylene glycol content. This low ethylene glycol content is particular advantageous for compounds that are used, for example, in fuels. The process also produces compounds with low water content, which are also useful for use in fuels.

One aspect of the disclosure is a process for making a quaternary ammonium compound, comprising providing an amine composition comprising an amine of the formula R[CONH(CH ₂ ) _n ]zN(R ¹ )(R ² ), wherein z is 0-1 , n is 2-5, R is C10-C22 alkyl or C10-C22 alkylene, and R ¹ and R ² independently represent hydroxy C Cs alkyl or C Cs alkyl; at least about 15 % by weight of a solvent with a solubility in water of less than 5 % by weight; and about 2 % to about 20 % by weight water; and adding to the amine composition an acid; and an C Cs alkylene oxide to produce a reaction mixture.

The amine composition includes an amine of the formula (I):

wherein R is C ₁₀ -C ₂₆ alkyl or C ₁₀ -C ₂₆ alkylene, and R ¹ and R ² independently represent hydroxy C Cs alkyl or C Cs alkyl. In some embodiments, R is C ₁₀ - C ₂₆ alkyl, e.g., C ₁₂ -C ₂₆ alkyl, C _M -C ₂₆ alkyl, or C ₁₆ -C ₂₆ alkyl, or C ₁₈ -C ₂₆ alkyl, or C ₂₀ -C ₂₆ alkyl, or C ₂₂ -C ₂₆ alkyl, or C ₂₄ -C ₂₆ alkyl, or Cio-C ₂₄ alkyl, or C ₁₀ -C ₂₂ alkyl, or C ₁₀ -C ₂₀ alkyl, or C ₁₀ -C ₁₈ alkyl, or C ₁₀ -C ₁₆ alkyl, or Cio-Ci ₄ alkyl, or C ₁₀ -C ₁₂ alkyl, or Ci ₂ -C ₂₄ alkyl, or C ₁₂ -C ₂₂ alkyl, or C ₁₂ -C ₂₀ alkyl, or C ₁₂ -C ₁₈ alkyl, or C ₁₂ - C ₁₆ alkyl, or Ci ₂ -Ci ₄ alkyl, or CM-C2 ₄ alkyl, or C ₁₆ -C ₂₂ alkyl, or C ₁₀ alkyl, or alkyl, or C ₁₂ alkyl, or C ₁₃ alkyl, or CM alkyl, or C ₁₅ alkyl, or C ₁₆ alkyl, or C ₁₇ alkyl, or C ₁₈ alkyl, or C ₁₉ alkyl, or C ₂₀ alkyl, or C ₂₁ alkyl, or C ₂₂ alkyl.

In some embodiments, R is C ₁₀ -C ₂₂ alkylene, e.g., C ₁₂ -C ₂₂ alkylene, C _H -C ₂₂ alkylene, or C ₁₆ -C ₂₂ alkylene, or C ₁₈ -C ₂₂ alkylene, or C ₂₀ -C ₂₂ alkylene, or C ₁₀ - C ₂₀ alkylene, or C ₁₀ -C ₁₈ alkylene, or C ₁₀ -C ₁₆ alkylene, or Cio-Ci ₄ alkylene, or C ₁₀ -C ₁₂ alkylene, or C ₁₂ -C ₂₀ alkylene, or C ₁₂ -C ₁₈ alkylene, or C ₁₂ -C ₁₆ alkylene, or Ci ₂ -Ci alkylene, or C _M -C ₂₀ alkylene, or C ₁₆ -C ₁₈ alkylene, or C ₁₀ alkylene, or C ₁₁ alkylene, or C ₁₂ alkylene, or C ₁₃ alkylene, or CM alkylene, or C ₁₅ alkylene, or C ₁₆ alkylene, or C ₁₇ alkylene, or C ₁₈ alkylene, or C ₁₉ alkylene, or C ₂₀ alkylene, or C ₂₁ alkylene, or C ₂₂ alkylene. In some embodiments, R is C ₁₀ -C ₂₂ alkylene and contains one degree of unsaturation. In other embodiments, R is C ₁₀ -C ₂₂ alkylene and contains two or more degrees of unsaturation, e.g., two degrees of unsaturation, three degrees of unsaturation, etc.

In some embodiments, R is straight chain alkyl or alkylene, e.g. n-dodecyl, n- tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, 9-octadecylene, or the like. In other embodiments, R is branched alkyl or alkylene, e.g. isododecyl, isododecylene, isohexadecyl, isohexadecylene, or the like. In some embodiments, R represents a mixture of alkyl and/or alkylene groups, such as tallow alkyl. As used herein, the term“tallow alkyl” refers to the mixture of alkyl groups found in rendered beef or mutton fat. Thus, in certain embodiments, R is any Ci ₆ or Cis straight-chain alkyl, or Cis straight-chain alkylene with one degree of unsaturation. Tallow alkyl groups can also be hardened (hydrogenated), either partially or fully, to remove one or more C=C double bonds.

R ¹ and R ² independently represent C Cs alkyl, e.g., C2-C8 alkyl, or C3-C8 alkyl, or C ₄ -Cs alkyl, or Cs-Cs alkyl, or C ₆ -Cs alkyl, or C ₇ -Cs alkyl, or C ₁ -C ₇ alkyl, or C ₁ -C ₆ alkyl, or C ₁ -C ₅ alkyl, or CrC ₄ alkyl, or C ₁ -C ₃ alkyl, or C ₁ -C ₂ alkyl, or C ₂ -C ₇ alkyl, or C ₃ -C ₆ alkyl, or C ₄ -C ₅ alkyl, or C ₁ alkyl, or C ₂ alkyl, or C ₃ alkyl, or C ₄ alkyl, or C ₅ alkyl, or C& alkyl, or C ₇ alkyl, or Cs alkyl, or hydroxyl Cr Cs alkyl, e.g., hydroxy C ₂ -C ₈ alkyl, or hydroxy C ₃ -C ₈ alkyl, or hydroxy C ₄ -Cs alkyl, or hydroxy Cs-Cs alkyl, or hydroxy C ₆ -Cs alkyl, or hydroxy C ₇ -Cs alkyl, or hydroxy C ₁ -C ₇ alkyl, or hydroxy C ₁ -C ₆ alkyl, or hydroxy C ₁ -C ₅ alkyl, or hydroxy CrC ₄ alkyl, or hydroxy C ₁ -C ₃ alkyl, or hydroxy C ₁ -C ₂ alkyl, hydroxy C ₂ -C ₇ alkyl, or hydroxy C ₃ -C ₆ alkyl, or hydroxy C ₄ -C ₅ alkyl, or hydroxy C ₁ alkyl, or hydroxy C ₂ alkyl, or hydroxy C ₃ alkyl, or hydroxy C ₄ alkyl, or hydroxy C ₅ alkyl, or hydroxy C ₆ alkyl, or hydroxy C ₇ alkyl, or hydroxy Cs alkyl.

In some embodiments, R ¹ and/or R ² are straight-chain hydroxy C Cs alkyl or C Cs alkyl. In other embodiments, R ¹ and/or R ² are branched hydroxy C ₃ -C ₈ alkyl or C ₃ -C ₈ alkyl. In some embodiments, R ¹ and R ² are the same. In other embodiments, R ¹ and R ² are different. In one example, R ¹ and R ² are both 2- hydroxyethyl. In some embodiments, at least one of R ¹ and R ² is hydroxy Cr Cs alkyl.

The amine composition includes a solvent, present in the amine composition in an amount of at least 20 wt. %, e.g., at least 22 wt. %, or at least 24 wt. %, or at least 26 wt. %, or at least 28 wt. %, or at least 30 wt. %, or at least 32 wt. %, or at least 34 wt. %, or at least 36 wt. %, or at least 38 wt. %, or at least 40 wt. %, or at least 42 wt. %, or at least 44 wt. %, or at least 46 wt. %, or at least 48 wt. %, or at least 50 wt. %. The solvent has a solubility in water of less than 5 wt. %, e.g., less than 4.75 wt. %, or less than 4.5 wt. %, or less than 4.25 wt. %, or less than 4 wt. %, or less than 3.75 wt. %, or less than 3.5 wt. %, or less than 3.25 wt. %, or less than 3 wt. %, or less than 2.75 wt. %, or less than 2.5 wt. %, or less than 2.25 wt. %, or less than 2 wt. %, or less than 1.75 wt. %, or less than 1.5 wt. %, or less than 1.25 wt. %, or less than 1 wt. %, or less than 0.75 wt. %, or less than 0.5 wt. %, or less than 0.25 wt. %, or less than 0.2 wt. %, or less than 0.15 wt. %, or less than 0.1 wt. %.

Solvent solubility can be determined by adding an amount of solvent (e.g. 1 wt. % adding successively by 1 % increments) to water at 20° C, stirring with a stir bar at 200 RPM for 5 minutes and observing the solution with the naked eye. If the solution appears cloudy or has two phases, the amount of solvent is not soluble in water. If the solution clear, then the added solvent amount is soluble in water.

In some embodiments, the solvent is a low polarity solvent, i.e., a solvent with a dielectric constant of less than about 15. In some embodiments, the solvent is a straight-chain alcohol. In some embodiments, the solvent is a branched alcohol. In some embodiments, the solvent is a saturated alkane or alcohol. In some embodiments, the solvent is a mixture, e.g., or two or more solvents, each with a solubility in water of less than 5 wt. %. In some embodiments, the solvent is an C5-C10 alcohol, e.g., an C6-C10 alcohol, or an C7-C10 alcohol, or an Cs-Cio alcohol, or an C9-C10 alcohol, or an C5-C9 alcohol, or an Cs-Cs alcohol, or an C ₅ - C ₇ alcohol, or an C ₅ -C ₆ alcohol, or an C ₅ alcohol, or an C& alcohol, or an C ₇ alcohol, or an Cs alcohol, or an C9 alcohol, or an C10 alcohol. In one example, the solvent is 2-ethylhexanol.

The amine composition includes water in an amount within the range of 2 wt. % to about 20 wt. %, e.g., about 6 wt. % to about 20 wt. %, or about 10 wt. % to about 20 wt. %, or about 14 wt. % to about 20 wt. %, or about 18 wt. % to about 20 wt. %, or about 2 wt. % to about 16 wt. %, or about 2 wt. % to about 12 wt. %, or about 2 wt. % to about 8 wt. %, or about 2 wt. % to about 4 wt. %, or about 6 wt. % to about 16 wt. %, or about 10 wt. % to about 12 wt. %, or the amount is about 2 wt. %, or about 4 wt. %, or about 6 wt. %, or about 8 wt. %, or about 10 wt. %, or about 12 wt. %, or about 14 wt. %, or about 16 wt. %, or about 18 wt. %, or about 20 wt. %. The amount of water may be adjusted to minimize the amount of water present in the reaction mixture while still allowing the reaction of the amine to proceed at a desirable rate. In some embodiments, the water is added to the amine composition along with an initial addition of the acid and/or C Cs alkylene oxide.

The process includes adding to the amine composition an acid. The acid may be any acid that is capable of facilitating the reaction of an alkylene oxide and an amine to form a quaternary ammonium compound. In some embodiments, the acid is a carboxylic acid, e.g., formic acid, acetic acid, propionic acid, oxalic acid, or the like. In some embodiments, the acid is a mineral acid, e.g., HCI, H ₂ S0 ₄ , alkyl sulfonic acid, aryl sulfonic acid, or the like. In one example, the acid is acetic acid.

The process includes adding to the amine composition an C Cs alkylene oxide, e.g., an C ₂ -Cs alkylene oxide, or an C ₃ -C ₈ alkylene oxide, or an C ₄ -Cs alkylene oxide, or an Cs-Cs alkylene oxide, or an C ₆ -Cs alkylene oxide, or an C ₇ -Cs alkylene oxide, or an C ₁ -C ₇ alkylene oxide, or an C ₁ -C ₆ alkylene oxide, or an C ₁ -C ₅ alkylene oxide, or an CrC ₄ alkylene oxide, or an C ₁ -C ₃ alkylene oxide, or an CrC ₂ alkylene oxide, or an C Cs alkylene oxide, or an C ₂ -C ₇ alkylene oxide, or an C ₃ -C ₆ alkylene oxide, or an C ₄ -C ₅ alkylene oxide, or an C ₁ alkylene oxide, or an C ₂ alkylene oxide, or an C ₃ alkylene oxide, or an C ₄ alkylene oxide, or an C ₅ alkylene oxide, or an C& alkylene oxide, or an C ₇ alkylene oxide, or an Cs alkylene oxide. In some embodiments, the alkylene oxide is ethylene oxide. In some embodiments, the C Cs alkylene oxide can include an alcohol group in addition to the epoxide group.

The acid and the C Cs alkylene oxide may be added to the amine composition in different orders and combinations, and over different periods of time. In some embodiments, the acid is added to the amine composition before the alkylene oxide. In some embodiments, the process further comprises initiating mixing of the reaction mixture and adding additional acid and additional alkylene oxide over a period of time after initiating mixing. In some embodiments, additional acid is added before additional alkylene oxide. In some embodiments, the adding is repeated, typically with mixing between additions. In one example, the steps of adding additional acid followed by adding additional alkylene oxide are repeated twice, i.e., acid, followed by alkylene oxide, is added to the amine composition to produce a reaction mixture; mixing of the reaction mixture is initiated; additional acid, followed by additional alkylene oxide, is added; and additional acid, followed by additional alkylene oxide, is added again. This sequence can be repeated until a desired level of consumption of the amine is achieved.

In some embodiments, the amount of additional acid and/or alkylene oxide added is based on the amount of tertiary amine remaining in the reaction mixture, e.g., the amount added is about 1 molar equivalent, 1.25 molar equivalents, 1.5 molar equivalents, 1.75 molar equivalents, or 2 molar equivalents of the amount of tertiary amine remaining in the reaction mixture. The amount of tertiary amine remaining in the reaction mixture can be determined by a variety of means known in the art, e.g., titration, nuclear magnetic resonance (NMR), etc.

In some embodiments, the adding is repeated until at least about 85 mole %, e.g., at least about 87.5 mole %, or at least about 90 mole %, or at least about 92.5 mole %, or at least about 95 mole %, or at least about 97.5 mole %, or at least about 99 mole % of the amount of amine in the amine composition is consumed. As used herein, the term “the amine in the amine composition” described the amount of amine in the amine composition before addition of any acid or alkylene oxide, i.e., the initial amount of amine in the amine composition.

In some embodiments, the amount of time over which the alkylene oxide and/or acid is added to the amine composition and the amount of time over which the additional alkylene oxide and/or additional acid is added to the reaction mixture is different. In some embodiments, the acid is added to the amine composition or reaction mixture before the alkylene oxide, over a period of time of about 10 seconds to about 1 hour, e.g., about 30 seconds to about 1 hour, or about 1 minute to about 1 hour, or about 1 minute to about 50 minutes, or about 1 minute to about 40 minutes, or about 1 minute to about 30 minutes, or about 1 minute to about 20 minutes, or about 1 minute to about 10 minutes, or about 1 minute, or about 5 minutes, or about 10 minutes, or about 15 minutes, or about 20 minutes, or about 25 minutes, or about 30 minutes, or about 40 minutes, or about 50 minutes, or about 1 hour.

In some embodiments, the reaction is carried out at a temperature between about 50 °C and 100 °C, or between about 50 °C and 90 °C, or between about 50 °C and 80 °C, or between about 50 °C and 70 °C, or between about 60 °C and 100 °C, or between about 60 °C and 90 °C, or between about 60 °C and 80 °C, or between about 70 °C and 100 °C, or between about 70 °C and 90 °C, or between about 80 °C and 100 °C.

In some embodiments, the alkylene oxide is added to the amine composition or the reaction mixture after the acid, over a time period of about 5 minutes to about 5 hours, e.g., about 10 minutes to about 5 hours, or about 15 minutes to about 5 hours, or about 20 minutes to about 5 hours, or about 25 minutes to about 5 hours, or about 30 minutes to about 5 hours, or about 40 minutes to about 5 hours, or about 50 minutes to about 5 hours, or about 1 hour to about 5 hours, or about 1.25 hours to about 5 hours, or about 1.5 hours to about 5 hours, or about 2 hours to about 5 hours, or about 2.5 hours to about 4.5 hours, or about 2.5 hours to about 4 hours, or about 2.5 hours to about 3.5 hours, or about 5 minutes to about 4.5 hours, or about 5 minutes to about 4 hours, or about 5 minutes to about 3.5 hours, or about 5 minutes to about 3 hours, or about 5 minutes to about 2.5 hours, or about 5 minutes to about 2 hours, or about 5 minutes to about 1 .5 hours, or about 5 minutes to about 1.25 hours, or about 5 minutes to about 1 hour, or about 10 minutes to about 50 minutes, or about 10 minutes to about 40 minutes, or about 10 minutes to about 30 minutes, or about 10 minutes, or about 15 minutes, or about 20 minutes, or about 25 minutes, or about 30 minutes, or about 40 minutes, or about 50 minutes, or about 1 hour, or about 1.25 hours, or about 1.5 hours, or about 2 hours, or about 2.5 hours, or about 3 hours, or about 3.5 hours, or about 4 hours, or about 4.5 hours, or about 5 hours.

In some embodiments, the total amount of acid and additional acid added to the amine composition is an amount within the range of about 1 molar equivalent to about 3 molar equivalents, e.g., about 1.25 molar equivalents to about 3 molar equivalents, or about 1.5 molar equivalents to about 3 molar equivalents, or about 1.75 molar equivalents to about 3 molar equivalents, or about 2 molar equivalents to about 3 molar equivalents, or about 1 molar equivalents to about 2.75 molar equivalents, or about 1 molar equivalents to about 2.5 molar equivalents, or about 1 molar equivalent to about 2.25 molar equivalents, or about 1 molar equivalent to about 2 molar equivalents, or about 1.25 molar equivalents to about 2.75 molar equivalents, or about 1.5 molar equivalent to about 2.5 molar equivalents, or the about is amount 1.25 molar equivalents, or about 1.5 molar equivalents, or about 1.75 molar equivalents, or about 2 molar equivalents, or about 2.25 molar equivalents, or about 2.5 molar equivalents of the amine in the amine composition. As used herein, the term“the amine in the amine composition” described the amount of amine in the amine composition before addition of any acid or alkylene oxide, i.e., the initial amount of amine in the amine composition.

In some embodiments, the total amount of alkylene oxide and additional alkylene oxide added to the amine composition is an amount within the range of about 1 molar equivalent to about 4 molar equivalents, e.g., about 1.25 molar equivalent to about 4 molar equivalents, or about 1.5 molar equivalents to about 4 molar equivalents, or about 1.75 molar equivalents to about 4 molar equivalents, or about 2 molar equivalents to about 4 molar equivalents, or about 2.25 molar equivalents to about 4 molar equivalents, or about 2.5 molar equivalents to about 4 molar equivalents, or about 2.75 molar equivalents to about 4 molar equivalents, or about 3 molar equivalents to about 4 molar equivalents, or about 1 molar equivalents to about 3.75 molar equivalents, or about 1 molar equivalent to about 3.5 molar equivalents, or about 1 molar equivalent to about 3.25 molar equivalents, or about 1 molar equivalent to about 3 molar equivalents, or about 1 molar equivalent to about 2.75 molar equivalents, or about 1 molar equivalent to about 2.5 molar equivalents, or about 1 molar equivalent to about 2.25 molar equivalents, or about 1 molar equivalent to about 2 molar equivalents, or about 1.25 molar equivalents to about 3.75 molar equivalents, or about 1.5 molar equivalents to about 3.5 molar equivalents, or about 1.75 molar equivalents to about 3.25 molar equivalents, or about 2 molar equivalents to about 3 molar equivalents, or the amount is about 1.5 molar equivalents, or about 1.75 molar equivalents, or about 2 molar equivalents, or about 2.25 molar equivalents, or about 2.5 molar equivalents, or about 2.75 molar equivalents, or about 3 molar equivalents, or about 3.25 molar equivalents, or about 3.5 molar equivalents.

In some embodiments, the acid and alkylene oxide are added to the amine composition simultaneously. In some embodiments, the process further comprises initiating mixing of the reaction mixture before addition of the acid and alkylene oxide. In some embodiments, a portion of the acid is added to the amine composition before the alkylene oxide is added to the amine composition simultaneously with the remainder of the acid. In some embodiments, the process further comprises initiating mixing of the reaction mixture after addition of a portion of the acid, before addition of the alkylene oxide and the remainder of the acid. In some embodiments, the acid and alkylene oxide are added to the amine composition simultaneously over a period of time of about 1 hour to about 10 hours, e.g., about 1.5 hours to about 9.5 hours, or about 2 hours to about 9 hours, or about 2.5 hours to about 8.5 hours, or about 3 hours to about 8 hours, or about 3.5 hours to about 7.5 hours, or about 4 hours to about 7 hours, or about 4 hours to about 6 hours, or about 2.5 hours, or about 2.75 hours, or about 3 hours, or about 3.25 hours, or about 3.5 hours, or about 3.75 hours, or about 4 hours, or about 4.25 hours, or about 4.5 hours, or about 4.75 hours, or about 5 hours, or about 5.25 hours, or about 5.5 hours, or about 5.75 hours, or about 6 hours.

In some embodiments, the acid is added to the amine composition simultaneously with the alkylene oxide, the acid in an amount within the range of about 1 molar equivalent to about 2 molar equivalents, e.g., about 1 molar equivalent to about 1 .9 molar equivalents, or about 1 molar equivalent to about 1.8 molar equivalents, or about 1 molar equivalent to about 1.7 molar equivalents, or about 1 molar equivalent to about 1.5 molar equivalents, or about 1.1 molar equivalents to about 2 molar equivalents, or about 1.2 molar equivalents to about 2 molar equivalents, or about 1.3 molar equivalents to about 2 molar equivalents, or about 1.4 molar equivalents to about 2 molar equivalents, or about 1.5 molar equivalents to about 2 molar equivalents, or the amount is about 1 molar equivalent, or about 1.1 molar equivalents, or about 1.2 molar equivalents, or about 1.3 molar equivalents, or about 1.4 molar equivalents, or about 1.5 molar equivalents, or about 1.6 molar equivalents, or about 1.7 molar equivalents, or about 1.8 molar equivalents, or about 1.9 molar equivalents, or about 2 molar equivalents of the amine in the amine composition.

In some embodiments, the alkylene oxide is added to the amine composition simultaneously with the acid, the alkylene oxide in an amount within the range of about 1 molar equivalent to about 3 molar equivalents, e.g., about 1.25 molar equivalents to about 3 molar equivalents, or about 1.5 molar equivalents to about 3 molar equivalents, or about 1.75 molar equivalents to about 3 molar equivalents, or about 2 molar equivalents to about 3 molar equivalents, or about 2.25 molar equivalents to about 3 molar equivalents, or about 1 molar equivalent to about 2.75 molar equivalents, or about 1 molar equivalent to about 2.5 molar equivalents, or about 1 molar equivalent to about 2.25 molar equivalents, or about 1 molar equivalent to about 2 molar equivalents, or about 1 molar equivalent to about 1.75 molar equivalents, or the amount is about 1 molar equivalent, or about 1.25 molar equivalents, or about 1.5 molar equivalents, or about 1.75 molar equivalents, or about 2 molar equivalents, or about 2.25 molar equivalents, or about 2.5 molar equivalents, or about 2.75 molar equivalents, or about 3 molar equivalents. Such addition may increase the conversion rate.

In some embodiments, at least about 85 mole %, e.g., at least about 87.5 mole %, or at least about 90 mole %, or at least about 92.5 mole %, or at least about 95 mole %, or at least about 97.5 mole %, or at least about 99 mole % of the amount of amine in the amine composition is converted to a quaternary ammonium compound.

In some embodiments, the process further comprises removing water from the reaction mixture after a period of time to provide a dried composition. The person of ordinary skill in the art will appreciate that water may be removed or stripped from the reaction mixture by a variety of means, e.g., drying agents, distillation, vacuum distillation, sparging, evaporation, and the like. In some embodiments, the resulting dried composition comprises water in an amount of less than 1 wt. %, e.g., less than 0.9 wt. %, or less than 0.8 wt. %, or less than 0.7 wt. %, or less than 0.6 wt. %, or less than 0.5 wt. %, or less than 0.4 wt. %, or less than 0.3 wt. %, or less than 0.2 wt. %, or less than 0.1 wt. %, or less than 0.05 wt. %, or less than 0.01 wt. %.

In some embodiments, the quaternary ammonium compound comprises three straight-chain hydroxy C Cs alkyl groups. In some embodiments, the quaternary ammonium compound comprises two or more identical groups, e.g., two hydroxyethyl groups, or three hydroxyethyl groups. In some embodiments, the quaternary ammonium compound comprises three hydroxyethyl groups and a tallow alkyl group, i.e., N,N,N-tris(2-hydroxyethyl)-N-tallow alkyl ammonium.

In some embodiments, the quaternary ammonium counterion is the conjugate base of the acid added to the amine composition. In some embodiments, the counterion is a carboxylate, e.g., formate, acetate, propionate, oxalate, or the like. In some embodiments, the counterion is a mineral ion, e.g., chloride, bisulfate, alkyl sulfonate, aryl sulfonate, or the like. In one example, the counterion is acetate.

Another aspect of the disclosure is a process for making a composition comprising a mixture of quaternary ammonium compounds, the process comprising contacting a mixture comprising N,N-bis(2-hydroxyethyl)-N-tallow alkyl amine; at least about 20 % by weight of a solvent with a solubility in water of less than 5 % by weight; and about 2 % to about 20 % by weight water; with an acid; and an C Cs alkylene oxide.

Yet another aspect of the disclosure is a product produced by a process disclosed herein. In some embodiments, the product comprises ethylene glycol in an amount of less than 15 wt. %, e.g., less than 14 wt. %, or less than 13 wt. %, or less than 12 wt. %, or less than 11 wt. %, or less than 10 wt. %, or less than 9 wt. %, or less than 8 wt. %, or less than 7 wt. %, or less than 6 wt. %, or less than 5 wt. %, or less than 4 wt. %, or less than 3 wt. %, or less than 2 wt. %, or less than 1 wt. %. EXAMPLES

The Examples that follow are illustrative of specific embodiments of the invention, and various uses thereof. They are set forth for explanatory purposes only, and are not to be taken as limiting the invention.

Example 1. Simultaneous Addition Process

500.0 g of N,N-bis(2-hydroxyethyl)-N-tallow amine was diluted with 270 g of 2-ethylhexanol and 18.0 g of acetic acid in an autoclave. 100 g of water was added to the reaction vessel, after which it was purged with N ₂ , sealed, and heated to 70 °C. Over 5 hours, 71.9 g of acetic acid and 94.9 g ethylene oxide were added gradually and simultaneously. Upon completion of the addition, the reaction vessel was held at 70 °C for 1 hour. The reaction yielded N,N,N-tris(2- hydroxyethyl)-N-tallow ammonium acetate, with an amine conversion of 86.7%. The simultaneous addition of acetic acid and ethylene oxide was repeated twice, using 1 molar equivalent of acetic acid and 1.5 molar equivalents of ethylene oxide with respect to the amount of unreacted amine remaining in the reaction vessel, which was determined by titrating with potassium hydroxide, sodium tetraphenylborate, and hydrochloric acid. 10.7 g of acetic acid and 12.4 g of ethylene oxide were added in the first repetition, and 7.8 g of acetic acid and 8.5 g of ethylene oxide were added in the second repetition. The overall amine conversion after the final process was 95.1 %.

The compound produced from the Example 1 process contained 5.4% ethylene glycol and 7.8% water content. Example 2. Sequential Addition Process

130.0 kg of N,N-bis(2-hydroxyethyl)-N-tallow amine was diluted with 67.7 kg of 2-ethylhexanol, 26.0 kg of water and 25.7 kg of acetic acid in a reaction vessel. The vessel was purged with N ₂ , sealed, and heated to 80 °C. Over 3.5 hours, 29.5 kg of ethylene oxide was gradually added to the reaction vessel. The reaction vessel was held at 80 °C for 1.5 hours, after which 4.01 kg of acetic acid, and then 2.95 kg of ethylene oxide were added to the reaction vessel. The reaction vessel was held at 80 °C for 0.5 hour, after which 4.01 kg of acetic acid, and then 2.95 kg of ethylene oxide were added to the reaction vessel. This sequence was repeated once more, and the reaction vessel was held at 80 °C for 40 min, yielding N,N,N-tris(2-hydroxyethyl)-N-tallow ammonium acetate with an overall amine conversion of 81.3%.

Water was stripped from the reaction mixture under vacuum at 80 °C for a total of 10 hr. The dried composition contained 0.3 wt. % water, and 9% ethylene glycol.

Example 3. No Added Water

141.3 g of N,N-bis(2-hydroxyethyl)-N-tallow amine was heated in a reaction vessel at 1 10 °C for 1 hour with 300 mL/min of N ₂ sparge to dry the amine to a low level of residual water. The amine was cooled to 70 °C and 121.5 g of 2-ethylhexanol and 24.0 g of acetic acid were added to the reaction vessel, after which it was purged with N ₂ , sealed, and heated to 80 °C. Over 3 hours, 18 g of ethylene oxide was added. Upon completion of the addition, the reaction vessel was held at 80 °C for 2 hours. A sample of the reaction vessel contents showed 0.192 meq/g of unreacted acid. An addition 2.6 g of ethylene oxide was added and the reaction vessel temperature was held at 80 °C for 1.7 hours. The reaction yielded N,N,N-tris(2-hydroxyethyl)-N-tallow ammonium acetate, with an amine conversion of 42.9%. The Example 3 results demonstrate that while low water content {e.g., 2-20 wt. %) is desirable, at least some water is needed to efficiently convert the tertiary amine to the quaternary ammonium compound.

It is understood that the examples and embodiments described herein are for illustrative purposes only and that various modifications or changes in light thereof will be suggested to persons skilled in the art and are to be incorporated within the spirit and purview of this application and scope of the appended claims.