Dispersant additives and methods for making and using same

Abstract

Imidazoline additives and methods for making and using the additives are provided. [Solution] Imidazoline additives and methods for making and using the additives are described. The additives may be provided as concentrates for addition to process compositions containing acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid, or other free-radically polymerizable monomers to prevent contamination. The additives are made by reacting glycerol-limited vegetable oil fatty acids with amines, and the glycerol-limited vegetable oil fatty acids are at least partially purified to remove glycerol. The imidazoline additives can be further reacted to provide ammonium salts, which can be added to aqueous compositions, for example, as aqueous dispersants.

Description

[Technical Field]

[0001] The present invention relates to imidazoline additives, imidazoline ammonium salt additives, and methods for making and using the additives. The additives are derived from an amine compound and one or more glycerol-limited vegetable oil fatty acids, such as glycerol-limited soybean oil fatty acids. The additives can be used, for example, as dispersants in the synthesis or polymerization of unsaturated monomers, but can also be used as corrosion inhibitors, lubricants, antifoam agents, foaming agents, and release agents. [Background technology]

[0002] A common method for producing acrylic acid and methacrylic acid is by the vapor-phase catalytic oxidation of alkanes, alkenes, alkanols, or alkenals containing 3 to 4 carbon atoms. The reaction product from the oxidation process is separated, and the (meth)acrylic acid is purified in a recovery and purification section. The design of the recovery and purification section varies in process equipment and operating conditions, but essentially involves extraction and distillation separation. In a generalized (meth)acrylic acid recovery and purification process, the effluent from the oxidation process is cooled in an absorber to remove light components in the product effluent. The (meth)acrylic acid is then concentrated in an extraction column with a selected solvent to remove water, acetic acid, or both water and acetic acid. The crude (meth)acrylic acid stream is then purified from residual extractive solvent and reaction by-products in a subsequent distillation column. Design variations exist depending on the choice of solvent.

[0003] (Meth)acrylic acid and many other addition polymerization monomers containing unsaturated functional groups are reactive monomers, prone to polymerization with any minor change in the environment. This is the case during recovery and purification operations in the production of (meth)acrylic acid, where high temperatures promote polymerization of (meth)acrylic acid. Under these conditions, unwanted polymerization can become so severe that polymer buildup can contaminate process equipment. Eventually, shutdown and cleaning of the equipment is required to remove the polymer foulant. Traditionally, polymerization inhibitors are used in the monomer production process to inhibit this unwanted polymerization. Typical polymerization inhibitors are phenolic compounds, amine compounds, quinones, nitroxyl compounds, and certain inorganic complexes. Phenothiazine (PTZ), hydroquinone (HQ), and monomethylhydroquinone ether (MEHQ) are examples of widely used inhibitors. These inhibitors are designed to interrupt the polymerization reaction and prevent polymer formation. However, none of the available polymerization inhibitors are effective enough to completely eliminate unwanted polymer formation. Even in the presence of these inhibitors, polymer formation and subsequent contamination is still significant, so periodic washing is part of the normal (meth)acrylic acid process.

[0004] In industrial practice, dispersants can also be used in addition to polymerization inhibitors to improve fouling prevention. Dispersants often contain molecules that have affinity for the foulant particle surface and good solubility in liquid process streams. Unlike inhibitors, dispersants generally do not interfere with the polymerization reactions involved in foulant formation. Dispersant molecules prevent the formed polymer particles from agglomerating, thereby keeping them suspended in the process medium. Selecting an effective dispersant remains an experimental technique, since the usefulness of such a dispersant is highly dependent on the detailed properties of the foulant material and the liquid medium, both of which are specific to a given process.

[0005] A manufactured batch of additive formulation is typically stored for a period of time before use or further processing. During storage and / or transportation, it is desirable for the additive formulation to be stable against, for example, excessive phase separation into separate liquids, precipitation of solids and / or gels, sedimentation, or other undesirable phase separation. Additive formulations that exhibit such changes may require special processing to return the additive formulation to its original state. In fact, it may not even be possible to return the additive formulation to its original state; in its altered form, the additive formulation may be unusable. For example, in an additive formulation containing precipitate, the settled material may not be pumpable or pourable. In any event, excessive phase separation of the additive composition during storage or transportation is highly undesirable. In contrast, in some cases, phase separation during actual use in an industrial process may be tolerable or even desirable if the additive can still provide the desired function (e.g., dispersion in the case of a dispersant). In other instances, it may be desirable to protect against phase separation even during use in an industrial process.

[0006] For addition to industrial process streams or batches, additive formulations can be conveniently provided in various forms, such as in the form of a solution or dispersion in an organic solvent that is miscible in the process stream or batch. Because such solutions or dispersions of additives are typically transported and stored, it is economical if the solution or dispersion is relatively concentrated with respect to the additive, thereby avoiding the extra costs associated with transporting and storing commodities such as organic solvents. Such solutions or dispersions offer flexibility in that they can be easily further diluted, if desired, at a more appropriate time, such as at or near the point of use, while still being usable without further dilution if a higher concentration is desired.

[0007] Such solutions and / or dispersions or more dilute formulations of the additive, as well as the additive itself, are desirably sufficiently stable during storage, transport, and use. Solutions, dispersions, and / or more dilute formulations of the additive are typically stored and / or transported in unheated winter environments, which may reach temperatures of, for example, 0° C. or below, −10° C. or below, −20° C. or below, −30° C., or even −40° C. or below. Summary of the Invention [Problem to be solved by the invention]

[0008] It would therefore be advantageous to find dispersant and other additive formulations that do not phase separate and / or settle excessively during storage, handling, or use, and that, when provided in solution and / or dispersion in organic solvents, do not separate excessively even when stored, handled, shipped, or otherwise used at low temperatures. [Means for solving the problem]

[0009] The present inventors have discovered that additive compositions with limited glycerol content, when provided in compositions with organic solvents, are more stable against phase separation and precipitate formation, even at lower temperatures, such as -20°C or lower. One or more additives derived from vegetable oil fatty acids, such as soybean oil fatty acids, are more stable against phase separation when at least a portion of the vegetable oil fatty acid content has a reduced glycerol content. In a preferred embodiment, the additive composition with improved stability incorporates one or more additives derived from glycerol-limited soybean oil fatty acids. In other embodiments, the formulation or one or more components thereof can be treated to remove at least a portion of the glycerol content, thereby improving stability against phase separation.

[0010] The inventors have also found that compositions of additives in organic solvents, when made from glycerol-limited soybean oil fatty acids, are more stable to precipitation (i.e., exhibit little or no precipitation) when stored at temperatures such as 0°C and -10°C for 3 weeks than equivalent concentrates made from tall oil fatty acids.

[0011] In one aspect, an additive composition comprising a plurality of imidazoline compounds, a plurality of ammonium salts of imidazoline compounds, or combinations thereof, wherein at least a portion of the imidazoline compounds comprise a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid, the glycerol-limited soybean oil fatty acid comprising less than 0.1 wt. % glycerol based on the weight of the mixture of fatty acids and the glycerol-limited soybean oil fatty acid, and the amine has the formula NH—(CH)—NH—R 1 -OH, wherein R 1 is a divalent moiety comprising one or more C atoms and optionally one or more heteroatoms, and n is 2 or 3.

[0012] For example, if a glycerol-limited soybean oil fatty acid contains 0.06 parts by weight of glycerol and 100 parts by weight of soybean oil fatty acid, the total weight of the glycerol-limited soybean oil fatty acid is 100.06 parts by weight and the glycerol content is 0.06 / 100.06 x 100% = 0.06%. The imidazoline compounds and / or ammonium salts thereof, in some embodiments, function as dispersant additives in the additive composition to help protect against contamination, for example, in processes incorporating unsaturated monomers.

[0013] In a further aspect, a concentrate is provided that includes an additive composition, the additive composition comprising a plurality of imidazoline compounds, a plurality of ammonium salts of imidazoline compounds, or combinations thereof, wherein at least a portion of the imidazoline compounds comprise a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid, the glycerol-limited soybean oil fatty acid comprising less than 0.1 wt. % glycerol based on the weight of the mixture of fatty acids and the glycerol-limited soybean oil fatty acid, and the amine has the formula NH—(CH)—NH—R 1 -OH, wherein R 1 is a divalent moiety comprising one or more C atoms and optionally one or more heteroatoms, n is 2 or 3, and the composition comprises about 0.1 parts by weight to 75 parts by weight of at least one organic solvent per 99.9 parts by weight to 25 parts by weight of the imidazoline compounds, the ammonium salts of the imidazoline compounds, or a combination thereof. The imidazoline compounds, the ammonium salts of the imidazoline compounds, or a combination thereof may be dispersed or dissolved in the at least one organic solvent, and the at least one organic solvent may be miscible with the process stream or batch, such that the concentrate may be readily dispersed in the process stream or batch when added thereto, thereby imparting favorable properties to the process stream or batch, such as reduced tendency to foul.

[0014] In a further aspect, a treated composition is provided that includes an additive composition, the additive composition comprising a plurality of imidazoline compounds and / or a plurality of ammonium salts thereof, at least a portion of the imidazoline compounds comprising a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid, the glycerol-limited soybean oil fatty acid comprising less than 0.1 wt. % glycerol based on the weight of the mixture of fatty acids and the glycerol-limited soybean oil fatty acid, and the amine has the formula NH—(CH)—NH—R 1 -OH, where R 1is a divalent moiety comprising one or more C atoms and optionally one or more heteroatoms, n is 2 or 3, and the composition further comprises a free-radically polymerizable monomer. Such treated compositions have a lower tendency to undesirably contaminate equipment in contact with the composition, for example, when exposed to heat, than comparable compositions that do not comprise imidazoline compounds and / or ammonium salts thereof.

[0015] In a further aspect, a method for making an additive composition includes: (a) combining an amine and a glycerol-limited soybean oil fatty acid to provide a reaction mixture; and (b) heating the reaction mixture to form an additive composition, wherein the additive composition comprises a plurality of imidazoline compounds, at least a portion of the imidazoline compounds comprising a reaction product from a reactant comprising an amine and the glycerol-limited soybean oil fatty acid, wherein the glycerol-limited soybean oil fatty acid in step (a) comprises a mixture of fatty acids and comprises less than 0.1 wt. % glycerol based on the weight of the glycerol-limited soybean oil fatty acid in step (a), and wherein the amine in step (a) has the formula NH—(CH)—NH—R 1 -Y, wherein R 1 is a divalent moiety containing one or more C atoms and optionally one or more heteroatoms, n is 2 or 3, and Y is -NH or -OH. The additive composition can be used in a wide variety of applications, for example, as an antifouling agent and / or dispersant for polymers.

[0016] In a further aspect, there is provided the use of an additive composition as one or more of a corrosion inhibitor, a dispersant, a lubricant, an antifoaming agent, an antifouling agent, and a release agent, the additive composition comprising a plurality of imidazoline compounds, a plurality of ammonium salts of imidazoline compounds, or a combination thereof, at least a portion of the imidazoline compounds comprising a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid, the glycerol-limited soybean oil fatty acid comprising less than 0.1 wt. % glycerol based on the weight of the mixture of fatty acids and the glycerol-limited soybean oil fatty acid, and the amine has the formula NH2-(CH2)n-NH-R 1 -OH, wherein R1 is a divalent moiety containing one or more C atoms and optionally one or more heteroatoms, and n is 2 or 3. DETAILED DESCRIPTION OF THE INVENTION

[0017] While this disclosure provides reference to various embodiments, those skilled in the art will recognize that changes may be made in form and detail without departing from the spirit and scope of the present application. Various embodiments are described in detail with reference to the drawings. Reference to various embodiments does not limit the scope of the claims appended hereto. Furthermore, any examples set forth in this application are illustrative and not intended to be limiting, merely describing some of the many possible embodiments of the appended claims.

[0018] definition

[0019] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of this application, the methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety and for all purposes.

[0020] As used herein, the terms "comprise(s)," "include(s)," "having," "has," "can," "contain(s)," and variations thereof are intended to be open-ended transitional phrases, terms, or words that do not exclude the possibility of additional acts or structures. The singular forms "a," "and," and "the" include plural referents unless the context clearly dictates otherwise.

[0021] As used herein, the terms "optional" or "optionally" mean that the subsequently described material, condition, feature, event, or circumstance may occur, but need not occur, and that its use includes instances where the material, condition, feature, event, or circumstance occurs and instances where it does not occur.

[0022] As used herein, any recited range of values ​​should be construed as supporting claims that contemplate all values ​​within the range and that recite any subranges with endpoints that are real values ​​within the recited range. As an example, a disclosure herein of a range of 1 to 5 is intended to support claims of any of the following ranges: 1 to 5, 1 to 4, 1 to 3, 1 to 2, 2 to 5, 2 to 4, 2 to 3, 3 to 5, 3 to 4, and 4 to 5, and fractions thereof, e.g., 1.5 to 3.5, 1.7 to 4.8, etc.

[0023] As used herein, a combination of fatty acids that can be produced by hydrolysis of a single vegetable oil is referred to as a "vegetable oil fatty acid." Because a single vegetable oil contains esters of various fatty acids, hydrolysis of the vegetable oil produces a combination of fatty acids. For example, hydrolysis of soybean oil can produce "soybean oil fatty acid" in combination with the by-product glycerol. Although used alone, soybean oil fatty acid contains not only a single fatty acid compound but also a combination of different fatty acid compounds. Vegetable oils are natural products and can vary in composition, for example, with respect to the relative content of various fatty acid compounds in the form of esters. However, the type and range of each fatty acid compound in a vegetable oil fatty acid is generally characteristic of the type of vegetable oil from which the vegetable oil fatty acid is derived. While the singular "vegetable oil fatty acid" refers to a combination of fatty acid compounds that can be produced by hydrolysis of the named vegetable oil, "multiple vegetable oil fatty acids" as used herein refers to a combination of fatty acids that can be produced by hydrolysis of a combination of two or more vegetable oils.

[0024] As used herein, the term "glycerol-limited" with respect to a material generally means that the material contains 0.1 wt.% or less glycerol based on the weight of the material (including glycerol, if present). For example, "glycerol-limited fatty amide" refers to a material that includes fatty amide(s) that contains 0.1 wt.% or less glycerol based on the weight of the glycerol-limited fatty amide.

[0025] As used herein, the term "glycerol-limited vegetable oil fatty acid" specifically refers to a mixture containing 0.1% or less by weight of glycerol and 99% or more by weight of fatty acids, based on the weight of the mixture. Glycerol-limited vegetable oil fatty acids can be produced by various means. One commercially important means of producing glycerol-limited vegetable oil fatty acids is by hydrolysis of the named vegetable oil, followed by refining to remove glycerol (a by-product of hydrolysis). The types of fatty acids and their proportions in glycerol-limited vegetable oil fatty acids depend on the composition of the hydrolyzed vegetable oil, particularly the type of vegetable oil, i.e., the type of plant from which the vegetable oil is derived. For example, soybean oil, as a natural product, can vary in composition with respect to fatty acid esters, but within the ranges characteristic of soybean oil. However, in principle, glycerol-limited vegetable oil fatty acids can also be produced by combining the correct types of fatty acids in the correct proportions, provided that the cumulative glycerol content, if any, is sufficiently low so that the resulting mixture is glycerol-limited as defined in accordance with the present invention. In such embodiments, since the fatty acid material is initially appropriately glycerol-limited, no degree of refinement to reduce the glycerol content is required. For illustrative purposes only, a glycerol-limited soybean oil fatty acid may, in a particular example, contain 10% palmitic acid, 4% stearic acid, 23% oleic acid, 51% linoleic acid, and 9% α-linolenic acid by weight, based on the total weight of fatty acids. However, such glycerol-limited soybean oil fatty acids could, in principle, be produced by combining 10 parts palmitic acid, 4 parts stearic acid, 23 parts oleic acid, 51 parts linoleic acid, and 9 parts α-linolenic acid, and any other components of a glycerol-limited soybean oil fatty acid, where glycerol is limited as supplied or the mixture is refined to remove glycerol. Thus, glycerol-limited vegetable oil fatty acids refer to mixtures containing a combination of fatty acids characteristic of those produced by a particular named vegetable oil.

[0026] As used herein, "hydrolyzed vegetable oil" and similar terms, including specific vegetable oil names, refer to compositions produced by hydrolysis of vegetable oils. For example, a composition containing soybean oil fatty acids and glycerol that can be produced by hydrolysis of soybean oil is referred to herein as "hydrolyzed soybean oil."

[0027] As used herein, "(meth)acrylic acid" means methacrylic acid and / or acrylic acid.

[0028] As used herein, "prevention" includes inhibition.

[0029] As used herein, the term "concentrate" generally refers to a composition in which the concentration of additive(s) is greater than the concentration of those additives after the composition is diluted for its intended use. Concentrates may be solids, liquids, dispersions, gels, or gases. Concentrates may or may not contain solvent until further diluted. In exemplary embodiments, concentrates may contain 0 to 80 parts, or even 0 to 50 parts, or even 0 to 25 parts, or even 0 to 10 parts of solvent per 100 parts by weight of additive(s) prior to dilution with solvent. If desired, concentrates can be diluted by adding some amount of additional solvent, which may be the same and / or different from the solvent in the concentrate. By way of example, dilution can be performed by adding 1 to 1,000 parts by weight, or even 10 to 500 parts by weight, or even 10 to 100 parts by weight of additional solvent per 50 to 100 parts by weight of solvent in the concentrate. All reaction schemes herein are for illustrative purposes only and illustrate some reactants and some reaction products.

[0030] Consideration

[0031] In commercial practice, fatty acid-derived imidazoline compounds have been used as dispersants or other types of additives in the synthesis and processing of vinyl monomers, such as (meth)acrylic acid and / or vinyl acetate. Imidazoline compounds can be produced by reacting tall oil or tall oil fatty acids with amine compounds. Tall oil and tall oil fatty acids (TOFA) are convenient sources of fatty acids. Tall oil is a by-product of the Kraft process for wood pulp production. Crude tall oil typically contains rosin, which contains a mixture of resin acids (mainly abietic acid and its isomers), fatty acids (mainly palmitic acid, oleic acid, and linoleic acid), fatty alcohols, sterols, and other alkyl hydrocarbon derivatives. Tall oil fatty acids are a refined form of tall oil and contain a lower weight percentage of rosin (1-10% by weight) than tall oil. Tall oil fatty acids contain fatty acids, primarily oleic acid.

[0032] Tall oil fatty acid (TOFA) can be reacted with one or more amine compounds to produce TOFA imidazoline, a reaction product comprising a mixture of imidazoline compounds and other components derived from the resin acids in TOFA. The reaction can be summarized as follows: Scheme 1 TOFA + amine → mixture of imidazoline compounds + other components + water

[0033] The reaction proceeds via an intermediate amide, which can cyclize, for example, if the amine contains an NH2(CH2)nNH- group (where n is 2 or 3).

[0034] TOFA-derived imidazoline compounds can be used as dispersant additives, for example, in the processing of vinyl monomers. Conveniently, the additives may be provided as concentrates in organic solvents. Such concentrates can be provided neat or in diluted form with high imidazoline concentrations, for example, greater than 40 wt. %, 50 wt. %, 60 wt. %, 70 wt. %, 80 wt. %, or even 90 wt. % imidazoline compounds, based on the weight of the concentrate. Such concentrates can be stored, transported, and provided to processing plants for addition to process streams or batches therein. However, even such concentrated or diluted forms of TOFA-derived additives can be unstable when stored at low temperatures, for example, below 0°C, below -10°C, or below -20°C, for days or weeks, exhibiting precipitation, other phase separation, or other instability such that the affected composition cannot be easily redissolved or redispersed. For example, dispersant compositions incorporating reaction products containing imidazoline compounds derived from TOFA and 2-(2-aminoethyl)ethanolamine (AEEA) exhibited precipitation after only a few days at 0°C, -10°C, or -20°C, respectively. Long-term storage, e.g., 64 days at -10°C or -20°C, resulted in precipitates that could not be redissolved even after warming to room temperature (15-25°C or approximately 20°C). Thus, conventionally used concentrates of TOFA-derived corrosion inhibitors, even in diluted form, may be less stable than desired at lower temperatures. Such precipitates or other phase separation exhibited by concentrates are highly undesirable because, if the concentrates experience irreversible cold-induced precipitation or other phase separation, they can be difficult or impossible to pour or pump, either at low temperatures or above 20°C.

[0035] Without wishing to be bound by theory, it is believed that this instability may be a direct or indirect result of the rosin content in the TOFA.

[0036] Although the rosin acid content can be removed using separation techniques, further drawbacks are very difficult to overcome. It is becoming increasingly difficult to obtain tall oil or TOFA materials from commercial sources at economically viable prices. Therefore, it is becoming increasingly desirable to find fatty amide materials that can be more easily sourced as a substitute for tall oil or TOFA materials.

[0037] Imidazolines can also be made, for example, by the reaction of vegetable oils with one or more amines, as shown in Schemes 2 and 3. Scheme 2 Vegetable oil + amine → mixture of imidazoline compounds + glycerol

[0038] Alternatively, one or more vegetable oils may be hydrolyzed to produce hydrolyzed vegetable oils containing a mixture of fatty acids and the by-product glycerol. The hydrolyzed vegetable oils (fatty acids and glycerol) can then be reacted with amines to produce fatty amides in combination with the glycerol. The reaction can be summarized as follows: Scheme 3 (i) Vegetable oil + water → Hydrolyzed vegetable oil (a mixture of fatty acids and glycerol) (ii) Hydrolyzed vegetable oil + amine → mixture of imidazoline compound + glycerol + water

[0039] In Schemes 2 and 3, other components may be present. For example, the hydrolysis of vegetable oils, as represented by Scheme 3, reaction (i), may be catalyzed by acids or bases. It will be further understood that, depending on the pH, fatty acids may be present as their salts.

[0040] Imidazolines derived from vegetable oils show great potential as alternative dispersants to imidazolines derived from tall oil or TOFA. One advantage is that imidazolines derived from one or more vegetable oils can provide excellent dispersant and / or antifouling properties, and as natural materials, they contain rosin acid content (even insignificant amounts). Unfortunately, a technical challenge to the use of such materials relates to stability. Compositions incorporating imidazolines derived from vegetable oils tend to be less stable in that they undergo phase separation.

[0041] As can be seen from Schemes 2 and 3, the production of imidazoline additives from vegetable oils results in reaction products containing glycerol. Imidazoline products derived from the reaction of vegetable oils with amines can be prone to phase separation. Without being bound by theory, the inventors believe that the presence of the by-product glycerol in the imidazoline product provides an additive composition, more specifically one derived from soybean oil and 2-aminoethylethanolamine (NH2CH2CH2NHCH2CH2OH), that is more prone to phase separation.

[0042] However, the present inventors have found that imidazoline additives derived from reacting amine compounds with glycerol-limited soybean oil fatty acids are much more stable and resistant to phase separation. The preparation of stable fatty imidazoline products can be represented by Scheme 4(iii), where glycerol-limited vegetable oil fatty acids can be produced by steps (i) and (ii). In step (ii), glycerol is removed from hydrolyzed vegetable oil. According to the present invention, glycerol-reduced imidazoline additives can be produced, for example, according to the reaction shown in Scheme 4. Scheme 4 (i) Vegetable oil + water → Hydrolyzed vegetable oil (vegetable oil fatty acids + glycerol) (ii) Hydrolyzed vegetable oil-glycerol → glycerol-limited vegetable oil fatty acids (VOFAs) (iii) Glycerol-limited vegetable oil fatty acid + NH2-(CH2)n-NH-R 1-OH-HO → intermediate containing multiple amides (iv) Intermediate reaction product - HO → Final reaction product containing multiple imidazolines

[0043] Importantly, practice of the present invention provides a technical solution that makes vegetable oil-derived imidazoline compounds much more stable. As a result, the imidazoline materials of the present invention can be used as a total or partial replacement for previously used tall oil and TOFA materials.

[0044] Glycerol-limited soybean oil fatty acids (SOFA) are commercially available. Glycerol-limited vegetable oil fatty acids (including those derived from soybean oil) can be produced by the following procedure: An alkali, such as aqueous sodium hydroxide and / or aqueous potassium hydroxide, is added to one or more vegetable oils to form a mixture thereof. The mixture can be heated to a suitable temperature (such as in the range of 30°C to 100°C, e.g., 30°C to 100°C, or 40°C to 90°C, or 50°C to 100°C, or 60°C to 100°C, or 50°C to 90°C, or 50°C to 80°C, or 50°C to 70°C, or 55°C to 65°C, or about 60°C) for a suitable time (such as 1 hour to 24 hours, e.g., 1 hour to 10 hours, or 2 hours to 7 hours, or 3 hours to 6 hours, or 3 hours to 5 hours, or about 4 hours) effective to cause saponification of the one or more vegetable oils to the desired degree of completion. Saponification, or hydrolysis, of one or more vegetable oils produces fatty acid salts and the by-product glycerol. To generate free fatty acids from the fatty acid salts, the pH of the mixture is lowered by adding a mineral acid, such as sulfuric acid, hydrochloric acid, or a combination thereof. For example, the pH may be lowered to 1-4, or 1-3, or about 2. The aqueous phase, containing water, mineral acid salts, and glycerol, separates into a separate layer from the organic phase, which is then separated from the organic phase. The organic phase may be dried. The organic phase can be further purified by separating it into multiple fractions, each fraction having a different range of acid value. For the present invention, the glycerol-limited vegetable oil fatty acids may be derived from a fraction having an acid value of 170-230 mg KOH / g, or 180-220 mg KOH / g, or 190-210 mg KOH / g, or about 192-205 mg KOH / g. For example, the glycerol-limited vegetable oil fatty acid can comprise, consist of, or consist essentially of a glycerol-limited soybean oil fatty acid having an acid number of from about 192 to about 205 mg KOH / g.

[0045] The reaction between 2-aminoethylethanolamine and glycerol-limited vegetable oil fatty acids, such as glycerol-limited soybean oil fatty acids, can be represented as in Scheme 5, where R-COOH represents a mixture of fatty acids, each with a different R group. [ka] The composition of the mixture of fatty acids, represented by RCOOH, is characteristic of the type of vegetable oil fatty acid, e.g., glycerol-limited soybean oil fatty acids differ from glycerol-limited corn oil fatty acids with respect to the type and / or relative proportions of individual fatty acids.

[0046] The method for producing the additive composition disclosed herein can provide an imidazoline reaction product that contains little or no glycerol, no rosin acids and / or their derivatives, and little or no reaction products of glycerol and resin acids, e.g., 0.1 weight percent (wt%) or less of these, based on the total weight of imidazoline compounds in the reaction product. The method uses multiple glycerol-limited vegetable oil fatty acids, which are reacted with an amine compound according to Scheme 5 to produce a combination of imidazoline compounds whose glycerol content is limited. The use of multiple glycerol-limited vegetable oil fatty acids avoids the content of rosin acids, such as rosin acids or their derivatives. The use of tall oil fatty acids can limit the glycerol content, but still produce an additive composition that contains rosin and / or its derivatives.

[0047] The use of multiple glycerol-limited vegetable oil fatty acids, as opposed to tall oil or tall oil fatty acids, avoids rosin acid content, such as rosin acid or its derivatives. Rosin acid content is a natural component of tall oil and tall oil fatty acids. Because of their acidity, rosin acids can have a tendency to be corrosive in refinery equipment. Therefore, avoiding rosin acid is highly desirable. Advantageously, soybean oil and many other vegetable oils have little, if any, rosin acid content. As a result, fatty amides and fatty esters derived from soybean oil and other vegetable oils avoid the corrosion risks associated with rosin acid. Unfortunately, however, vegetable oil-derived additives are prone to phase separation, thereby reducing the attractiveness of using such additives. However, the present invention teaches how to improve the stability of these materials, making their use practical and desirable. An important result is that the present invention not only avoids rosin acid corrosives, but also allows more stable vegetable oil-derived materials to be used for corrosion protection.

[0048] First aspect of the invention

[0049] These embodiments illustrate glycerol-limited fatty acid imidazolines that can be derived from one or more vegetable oils and then used as additives in additive compositions for various purposes, such as dispersants in industrial systems, such as industrial chemical facilities, that handle or process unsaturated monomers. Thus, in a first aspect of the present invention, an additive composition is provided that comprises, consists of, or consists essentially of a plurality of imidazoline compounds. At least a portion of the plurality of imidazoline compounds comprises, consists of, or consists essentially of a reaction product derived from a reactant that comprises, consists of, or consists essentially of one or more glycerol-limited vegetable oil fatty acids and an amine.

[0050] The reaction product comprises, consists of, or consists essentially of an imidazoline compound. As shown in Scheme 5, the reaction of an amine with a glycerol-limited vegetable oil fatty acid can produce a reaction product (comprising, consisting of, or consisting essentially of an imidazoline compound) and by-product water. Preferably, the by-product water

[0051] At least a portion of the water is separated from the reaction product. Advantageously, at least a portion, or most or all, of the by-product water can be removed during the reaction. Removal of water during the reaction helps drive the imidazoline-forming reaction. Thus, the dried reaction product may comprise, consist of, or consist essentially of the imidazoline compound. In this context, "consisting essentially of" allows for the presence of small amounts of water in the imidazoline compound. Even when dry or partially dried, the imidazoline compound may contain small amounts of residual water from the reaction and / or some water taken from the environment. The reaction product may contain about 0% to 1% by weight water, or about 0% to 5% by weight water, or about 0% to 2% by weight water, or about 0% to 3% by weight water, or about 0% to 4% by weight water, or about 0.5% to 5% by weight water, or about 0.5% to 4% by weight water, or about 0.5% to 3% by weight water, or about 0.5% to 2% by weight water, or about 0.5% to 1% by weight water, or about 0% to 10% by weight water, or about 0% to about 20% by weight water, or about 0.5% to about 10% by weight water, or about 0.5% to about 20% by weight water, based on the weight of the total imidazoline content in the reaction product.

[0052] Preferably, the reaction product contains mostly or exclusively imidazoline compounds, no or minimal glycerol, no or minimal rosin acid, and no or minimal amide content. The reaction product may contain 0 to 1 wt. %, 0 to 2 wt. %, 0 to 3 wt. %, 0 to 4 wt. %, 0 to 0.1 wt. %, 0 to 0.01 wt. %, or 0 wt. % of the total of rosin acid, rosin acid salt, rosin acid amide, rosin acid ester, fatty acid ester, and C1 to C10 monohydric alcohol, based on the weight of the total imidazoline content in the reaction product.

[0053] Because the cyclization reaction to the imidazoline compound proceeds via an amide intermediate, the reaction product may contain some non-cyclized fatty amide. The additive composition and / or reaction product may contain a total weight of fatty amide of 0 wt.% to 15 wt.%, or 0.01 wt.% to 12 wt.%, or 0.1 wt.% to 10 wt.%, or 0 wt.% to 10 wt.%, or 0 wt.% to 5 wt.%, or 0 wt.% to 2 wt.%, or about 0 wt.%, or 0.01 wt.% to 0.1 wt.%, or 0.01 wt.% to 1 wt.%, based on the weight of the total imidazoline content in the additive composition.

[0054] At least a portion of the plurality of imidazoline compounds comprises, consists of, or consists essentially of the reaction product. The reaction product may be used without further purification to provide the additive composition, may be further purified, or additional imidazoline compounds may be combined with the reaction product to form the plurality of imidazoline compounds, provided that the additional imidazoline compounds are free or relatively free of glycerol, rosin acid, or derivatives thereof. The plurality of imidazoline compounds may comprise 80% to 100% by weight of the reaction product, or 85% to 99% by weight of the reaction product, or 90% to 99% by weight, or 94% to 98% by weight, or 95% to 97% by weight, or 95% to 98% by weight, or 94% to 96% by weight, or 96% to 97% by weight, or 95% to 96% by weight, or 94% to 95% by weight, or about 100% by weight of the reaction product, based on the weight of the plurality of imidazoline compounds.

[0055] The reactants may comprise, consist of, or consist essentially of one or more glycerol-limited vegetable oil fatty acids and one or more amine compounds having the formula NH(CH)NHR 1 OH, where n is 2 or 3. In a preferred embodiment, the one or more amine compounds may comprise, consist of, or consist essentially of 2-aminoethylethanolamine (AEEA) (NHCHCH—NH—CHCHOH).

[0056] The one or more glycerol-limited vegetable oil fatty acids may be selected from one or more of glycerol-limited avocado oil fatty acids, canola oil fatty acids, corn oil fatty acids, cottonseed oil fatty acids, grapeseed oil fatty acids, hazelnut oil fatty acids, hemp seed oil fatty acids, linseed oil fatty acids, olive oil fatty acids, palm kernel oil fatty acids, peanut seed oil fatty acids, rapeseed oil fatty acids, rice bran oil fatty acids, safflower oil fatty acids, sesame oil fatty acids, glycerol-limited soybean oil fatty acids, sunflower seed oil fatty acids, and walnut oil fatty acids. In some preferred embodiments and aspects disclosed herein, the one or more glycerol-limited vegetable oil fatty acids may comprise, consist of, or consist essentially of glycerol-limited soybean oil fatty acids.

[0057] The one or more glycerol-limited vegetable oil fatty acids may comprise from 0% to 0.01% by weight, or from 0% to 0.02% by weight, or from 0% to 0.03% by weight, or from 0% to 0.05% by weight, or from 0.05% to 0.1% by weight, or about 0% by weight of glycerol, based on the total weight of the one or more glycerol-limited vegetable oil fatty acids.

[0058] The one or more glycerol-limited vegetable oil fatty acids can include, consist of, or consist essentially of glycerol-limited soybean oil fatty acids. While the composition of soybean oil as a natural product can vary, the composition of soybean oil tends to fall within a specific range. Thus, hydrolysis of soybean oil produces multiple fatty acids, each of which tends to fall within a specific range of fatty acid content. The glycerol-limited soybean oil fatty acids may comprise, consist of, or consist essentially of, based on the weight of the glycerol-limited soybean oil fatty acid, about 2% to 15% by weight of α-linolenic acid, about 46% to 56% by weight of linoleic acid, about 17% to 28% by weight of oleic acid, about 1% to 10% by weight of stearic acid, and about 5% to 15% by weight of palmitic acid and / or their respective salts. For clarity, the weight of glycerol-limited soybean oil fatty acids includes the glycerol content, if present.

[0059] Second Aspect of the Invention

[0060] In a second aspect of the present invention, there is provided a concentrate comprising, consisting of, or consisting essentially of (1) one or more organic solvents and (2) any of the additive compositions, reaction products, imidazoline compounds, and / or imidazoline compounds described above in the first aspect of the present invention. The additive compositions, reaction products, imidazoline compounds, and / or imidazoline compounds are dissolved, dispersed, and / or otherwise mixed with the one or more organic solvents, thereby providing a convenient means for addition to a chemical mixture, for example, to facilitate dispersion of one or more components of the chemical mixture.

[0061] The one or more organic solvents may be selected from esters, alcohols, hydrocarbons, and combinations thereof. In a preferred embodiment, the one or more organic solvents are liquid at 20°C and 1 atmosphere. The hydrocarbon may be selected from one or more of aromatics, alkanes, heavy aromatic naphtha, toluene, xylene (o-xylene, m-xylene, p-xylene, or a combination thereof), and alkenes. Examples of suitable hydrocarbons include, but are not limited to, benzene, toluene, C5-C17 alkanes, alkenes, and naphtha. Examples of esters include, but are not limited to, phthalate esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, and combinations thereof.

[0062] The weight ratio of the additive composition, reaction product, concentrate, or imidazoline compounds to the one or more organic solvents may be from 3:7 to 2:3, or from 2:3 to 1:1, or from 1:1 to 3:2, or from 3:2 to 7:3, or from 7:3 to 4:1, or from 4:1 to 9:1, or from 5:1 to 3:1, respectively. The concentrate may comprise, consist of, or consist essentially of (1) one or more organic solvents and (2) the additive composition, reaction product, concentrate, or imidazoline compounds. Alternatively, the concentrate may comprise, consist of, or consist essentially of (1) one or more organic solvents, (2) additional components, and (3) the additive composition, reaction product, concentrate, or imidazoline compounds. The additive composition may be any additive composition disclosed herein or any combination of the additive compositions disclosed herein.

[0063] The concentrate may contain 30-40% by weight solids, or 40-50% by weight solids, or 50-60% by weight solids, or 60-70% by weight solids, or 70-80% by weight solids, or 80-90% by weight solids, or 80-95% by weight solids, or 85-95% by weight solids, or 30-95% by weight solids, or 20-50% by weight solids, or 50-95% by weight solids.

[0064] Third Aspect of the Invention

[0065] In a third aspect of the present invention, there is provided an additive composition comprising, consisting of, or consisting essentially of one or more ammonium salts of any of the imidazoline compounds described above in the first aspect. The resulting ammonium salts can be incorporated into additive compositions, such as dispersant compositions, optionally in combination with water, optionally one or more additional optional ingredients, and combinations thereof. The ammonium salts and their aqueous solutions and / or dispersions are particularly useful for addition to aqueous chemical compositions, for example, as dispersants or to impart other desirable properties to aqueous chemical compositions.

[0066] Ammonium salts can be made by reacting imidazoline compounds with one or more of an inorganic acid, an organic acid, an alkyl halide, and an aryl halide.

[0067] The inorganic acid may comprise, consist of, or consist essentially of hydrochloric acid. The organic acid may comprise, consist of, or consist essentially of acetic acid, acrylic acid, methacrylic acid, or a combination thereof. The alkyl halide may comprise, consist of, or consist essentially of an alkyl chloride. The aryl halide may comprise, consist of, or consist essentially of an aryl chloride.

[0068] In general, the reaction between an acid and multiple imidazoline compounds can be summarized as shown in Scheme 6. Scheme 6 Multiple imidazoline compounds + acid (aqueous solution) → multiple ammonium salts (aqueous solution)

[0069] Similarly, one or more of the amine groups of the imidazoline compounds can be converted to an alkyl or aryl ammonium group by reaction with an alkyl or aryl halide, preferably a C1-C3 alkyl or aryl halide.

[0070] In general, the reaction between a hydrocarbyl halide and multiple imidazoline compounds can be summarized as follows: Scheme 7 Multiple imidazoline compounds + hydrocarbyl halide → Multiple N-hydrocarbyl imidazoline ammonium salts

[0071] Additive compositions comprising, consisting of, or consisting essentially of imidazoline compounds are particularly useful, for example, as additives to organic media, while the ammonium salts disclosed herein are particularly useful as additives for aqueous process streams and other aqueous media, for example, as aqueous dispersants.

[0072] Any of the additives and concentrates of the first, second and third aspects may further comprise one or more of a polymerization inhibitor, an oxidation inhibitor and an amine compound.

[0073] Fourth aspect of the invention

[0074] In a fourth aspect of the present invention, there is provided a method for producing the first additive described above with respect to Schemes 4(iii)-(iv) and 5. The method comprises: (1) combining one or more glycerol-limited vegetable oil fatty acids with one or more amine compounds to form a reaction mixture, optionally, but preferably, at a rate such that the temperature of the reaction mixture does not exceed 100° C. The one or more glycerol-limited vegetable oil fatty acids may comprise, consist of, or consist essentially of fatty acids and may be one or more hydrolyzed vegetable oils that have been at least partially refined to remove glycerol.

[0075] The molar ratio of the one or more glycerol-limited vegetable oil fatty acids to the one or more amine compounds in the reaction mixture may be from 3:1 to 1:3, or from 2:1 to 1:2, or from 3:2 to 2:3, or from 6:5 to 5:6, or about 1:1, or 1:1. Although the one or more glycerol-limited vegetable oil fatty acids comprise a mixture of fatty acid compounds, the acid value of the one or more glycerol-limited vegetable oil fatty acids may be used to calculate the molecular weight of the one or more glycerol-limited vegetable oil fatty acids in order to calculate the aforementioned molar ratios.

[0076] The method optionally includes (2) a first heating step, which comprises, consists of, or consists essentially of heating the reaction mixture at a first temperature, optionally under an inert gas such as nitrogen, for a first period of time, wherein the first temperature is between 150°C and 200°C, or between 160°C and 190°C, or between 160°C and 175°C, or between 165°C and 170°C, or about 180°C, and the first period of time is between 30 minutes and 20 hours, or between 1 hour and 15 hours, or between 1 hour and 10 hours, or between 5 hours and 15 hours, or between 7 hours and 9 hours, or between 5 hours and 10 hours, or about 8 hours.

[0077] The method includes (3) a second heating step, the second heating step comprising, consisting of, or consisting essentially of heating the reaction mixture at a second temperature for a second time period, the second time period being from 30 minutes to 20 hours, or from 30 minutes to 10 hours, or from 2 hours to 7 hours, or from 3 hours to 7 hours, or about 5 hours, and the second temperature being from 200°C to 300°C, or from 210°C to 250°C, or from 220°C to 240°C, or from 220°C to 230°C, or about 225°C.

[0078] Preferably, the method further comprises (4) removing water from the reaction mixture during the first and / or second heating steps, for example, by trapping water in a Dean-Stark trap during heating.

[0079] Either the imidazoline additives of the first or second aspects of the present invention may be used in the synthesis or other processing of vinyl compounds such as (meth)acrylic acid.

[0080] In an exemplary embodiment, glycerol-limited soybean oil fatty acids (70.99 parts by weight) are added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. 2-Aminoethylethanolamine (29.00 parts by weight) is then charged to the well-stirred reaction mixture. The temperature of the reaction mixture increases from 21°C to approximately 57°C. The reaction is heated to approximately 180°C and held for approximately 8 hours. The reaction is then heated to 225°C and held at 225°C for 5 hours. Approximately 4 mL of water is collected in the Dean-Stark trap. The reaction is cooled to below 100°C, and the reaction product is transferred to a jar.

[0081] Fifth aspect of the invention

[0082] In a fifth aspect of the present invention, there is provided a method of preventing fouling in a batch or process stream comprising free radically polymerizable monomers, the method comprising, consisting of, or consisting essentially of adding to the batch or process stream an effective antifouling amount of any one or more of an additive composition, reaction product, concentrate, or imidazoline compound(s) comprising one or more imidazoline compounds, as described in the first through fourth aspects of the present invention disclosed herein.

[0083] The additive composition, reaction product, concentrate, or imidazoline compound(s) may be added to the batch or process stream in an amount of from 1 to 10,000 parts by weight of the additive composition, reaction product, concentrate, or imidazoline compound(s) per million parts by weight of the batch or process stream, or from 10 ppm to 5000 ppm, or from 10 ppm to 1000 ppm, or from 10 ppm to 500 ppm, or from 20 ppm to 500 ppm, or from 30 ppm to 300 ppm of the additive composition, reaction product, concentrate, or imidazoline compound(s) by weight of the batch or process stream.

[0084] The batch or process stream composition may include one or more of: (a) one or more free-radically polymerizable monomers, such as (meth)acrylic acid; (b) one or more polymerization inhibitors; and (c) one or more organic solvents, provided that the composition includes one or more free-radically polymerizable monomers. The one or more free-radically polymerizable monomers may include, consist of, or consist essentially of one or more of: acrylic acid, methacrylic acid, one or more salts of acrylic acid, one or more salts of methacrylic acid, acrolein, one or more esters of acrylic acid, one or more esters of methacrylic acid, vinyl acetate, acrylonitrile, and methacrylonitrile. The one or more free-radically polymerizable monomers may include, consist of, or consist essentially of one or more of: (a) acrylic acid, (b) methacrylic acid, (c) one or more salts of acrylic acid, (d) one or more salts of methacrylic acid, and (e) vinyl acetate.

[0085] However, the additive compositions, reaction products, concentrates, or imidazoline compounds of the first, second, and / or third aspects of the invention described herein may also be added to other industrial material batches and / or process streams, for example to prevent fouling and / or to act as dispersants.

[0086] Any of the imidazoline compounds described herein, including additive compositions, reaction products, concentrates, and one or more imidazoline compounds, may be used in compositions and methods for contamination in processes involving unsaturated monomers, for example, in the manner described in U.S. Patent No. 7,005,0087 (B2), which is incorporated herein by reference in its entirety for all purposes. Additionally, any of the imidazoline compounds described herein, including additive compositions, reaction products, concentrates, and one or more imidazoline compounds, may be used in compositions and methods for downstream oil processes, for example, in the manner described in U.S. Patent No. 3,766,053, which is incorporated herein by reference in its entirety for all purposes.

[0087] Sixth aspect of the invention

[0088] Any of the additive compositions, reaction products, concentrates, or imidazoline compounds described herein, including one or more imidazoline compounds, in the first through fifth aspects of the present invention, can be added to chemicals and chemical compositions to impart desired properties. For example, an additive composition, reaction product, concentrate, or imidazoline compound(s) can be added to a chemical composition containing one or more unsaturated monomers to act as a dispersant for any undesired polymers formed. Such treated compositions may exhibit reduced fouling and settling when the imidazoline(s) in the additive composition, reaction product, concentrate, or imidazoline compound(s) act as a dispersant for any polymers and / or oligomers formed in the chemical composition.

[0089] Thus, in a sixth aspect of the present invention, there is provided a treated composition comprising, consisting of, or consisting essentially of (a) any of the additive compositions, reaction products, concentrates, or imidazoline compounds comprising one or more imidazoline compounds and described herein in the first through fifth aspects of the present invention, and (b) one or more free-radically polymerizable monomers. The one or more free-radically polymerizable monomers may comprise, consist of, or consist essentially of one or more of acrylic acid, methacrylic acid, one or more salts of acrylic acid, one or more salts of methacrylic acid, acrolein, one or more esters of acrylic acid, one or more esters of methacrylic acid, vinyl acetate, acrylonitrile, and methacrylonitrile. The one or more free-radically polymerizable monomers may comprise, consist of, or consist essentially of one or more of: (a) acrylic acid, (b) methacrylic acid, (c) one or more salts of acrylic acid, (d) one or more salts of methacrylic acid, and (e) vinyl acetate.

[0090] The ratio of the weight of the total imidazoline content to the weight of the treated composition can be from 1 to 10,000 parts by weight of the total imidazoline content to 1 million parts by weight of the treated composition, or from 10 ppm to 5000 ppm by weight of the total imidazoline additive composition to the weight of the treated composition, or from 10 ppm to 1000 ppm, or from 10 ppm to 500 ppm, or from 20 ppm to 500 ppm, or from 30 ppm to 300 ppm. [Example]

[0091] The following examples are intended to illustrate different aspects and embodiments of the present invention and should not be considered as limiting the scope of the invention, it will be appreciated that various modifications and variations can be made without departing from the scope of the claims.

[0092] Example 1: Synthesis of SOFA-2-aminoethylethanolamine (AEEA) imidazoline compound from glycerol-limited soybean oil fatty acids obtained from Supplier A

[0093] Glycerol-limited soybean oil fatty acids (70.99 g) obtained from the first supplier, Supplier A, were added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. Next, 2-aminoethylethanolamine (29.00 g, 0.278 mol) was added to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to increase from 21 °C to approximately 57 °C. The reaction was heated to approximately 180 °C and held there for approximately 8 hours. The reaction was then heated to 225 °C and held at 225 °C for 5 hours. Approximately 4 mL of water was collected in the Dean-Stark trap. The reaction was cooled to below 100 °C and transferred to a jar. The product remained a clear liquid and showed no signs of phase separation over time.

[0094] Example 2: SOFA-2 from glycerol-limited soybean oil fatty acids obtained from Supplier B

[0095] Synthesis of α-aminoethylethanolamine (AEEA) imidazoline compounds Glycerol-limited soybean oil fatty acids (71.31 g) obtained from a second supplier, Supplier B, were added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. 2-Aminoethylethanolamine (28.96 g, 0.275 mol) was then added to the well-stirred reaction mixture. The temperature of the reaction mixture was observed to increase from 20 °C to approximately 48 °C. The reaction was heated to approximately 180 °C and held there for approximately 8 hours. The reaction was then heated to 225 °C and held at 225 °C for 5 hours. Approximately 4.5 mL of water was collected in the Dean-Stark trap. The reaction was cooled to below 100 °C and transferred to a jar. The product remained a clear liquid and showed no signs of phase separation over time.

[0096] Example 3: Imidazoline additive from soybean oil and diethylenetetramine

[0097] To a 1 L, four-necked, round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar, 343.5 g of soybean oil was added along with a few drops (0.01 g) of antifoam silicone. The flask and its contents were heated to 80 °C under a nitrogen purge, and diethylenetetramine (129.99 g, 1.26 mol) was added slowly to prevent the flask contents from exceeding 100 °C and to avoid foaming. After the addition was complete, the contents of the flask were heated to 165 °C for 1 hour to form the amide. A small sample was removed and analyzed by infrared spectroscopy to determine the amide at 1742 cm. -1 The disappearance of the peak associated with the ester carbonyl at 1645 cm -1 The reaction mixtures were monitored for the formation of amides by examining them for the appearance of a peak associated with the amide carbonyl at RT.

[0098] The contents of the reaction flask were then heated to 245°C for 3 hours to cyclize the amide to the imidazoline. A small sample was removed and infrared spectroscopy revealed a peak at 1645cm -1 Disappearance of the amide carbonyl peak at 1602 cm -1 The reaction was monitored for the formation of the imidazoline by examining the appearance of the imine peak at .

[0099] The contents of the reaction vessel were cooled and transferred to a jar. Immediately after transfer, the contents of the jar were a clear liquid, but after 3 days, the contents of the jar were cloudy and had separated into multiple layers.

[0100] Example 4: Imidazoline additive concentrate from glycerol-limited soybean oil fatty acids

[0101] Glycerol-limited soybean oil fatty acids (approximately 70.99 g) were added to a 250 mL four-neck round-bottom flask equipped with a temperature probe, nitrogen inlet, Dean-Stark apparatus, condenser, and magnetic stir bar. 2-Aminoethylethanolamine (29.00 g, 0.278 mol) was then added to the thoroughly stirred reaction mixture. The temperature of the flask contents increased from room temperature to approximately 50 to 60 °C. The viscous reaction mass was heated to approximately 180 °C for approximately 8 hours. The reaction mixture was then heated to 225 °C and held at this temperature for approximately 5 hours. Approximately 4 to 5 mL of water was collected in the Dean-Stark trap. The contents of the flask were cooled to below 100 °C and transferred to a jar.

[0102] A sample of the reaction product, SOFA-imidazoline, was stored at -10°C and showed no cloudiness or precipitate after 11 days.

[0103] A sample of the SOFA-imidazoline product (8 g) was blended with dimethyl phthalate (2 g) to form a concentrate, which was stored at -10°C and showed no cloudiness or precipitate after 1 week, 44 days, or even 95 days.

[0104] Example 5: Imidazoline additive concentrate from tall oil fatty acids

[0105] The procedure of Example 4 was repeated except that tall oil fatty acids were used instead of the glycerol-limited soybean oil fatty acids.

[0106] A sample of the reaction product, TOFA imidazoline, was stored at -10°C for 11 days, and a precipitate was observed.

[0107] A sample of the TOFA-imidazoline product (8 g) was blended with dimethyl phthalate (2 g) to form a concentrate. The concentrate was stored at -10°C and exhibited precipitation after only a few days. After 64 days of storage at -10°C, the precipitate could not be readily redissolved.

[0108] Comparison with Example 4 shows that the SOFA-imidazoline additive was more stable when stored at low temperatures than the corresponding TOFA-imidazoline additive, both in 100% form and when prepared as a concentrate in an organic solvent (dimethyl phthalate).

[0109] Example 6: Dispersant performance of imidazoline concentrates with 2-ethylhexyl acrylate foulant.

[0110] Three samples, Samples O, S, and T, were prepared by mixing the components in a sparger tube.

[0111] Two concentrates of imidazoline additive in dimethyl phthalate were prepared: Concentrate S and Concentrate T. Each concentrate was prepared by combining 8 parts by weight of the imidazoline additive with 2 parts by weight of dimethyl phthalate. Concentrate S contained imidazoline compounds made from SOFA and AEEA, while Concentrate T contained imidazoline compounds made from TOFA and AEEA. Concentrate S was prepared as described in Example 4, and Concentrate T was prepared as described in Example 5.

[0112] Sample O was prepared by mixing 2-ethylhexyl acrylate foulant (1 mL) with methyl methacrylate (10 mL) in a sparging tube (similar to a test tube but tapered at the bottom). Sample S was prepared by mixing 2-ethylhexyl acrylate foulant (1 mL), methyl methacrylate (10 mL), and 100 μL of concentrate S in a sparging tube. Sample T was made by mixing 2-ethylhexyl acrylate foulant (1 mL), methyl methacrylate (10 mL), and 100 μL of concentrate T in a sparging tube. All three samples were made using the same raw mixture of 2-ethylhexyl acrylate and methyl methacrylate.

[0113] All dispersion tubes were mounted vertically in racks. In Sample O (no dispersant), the foulants were seen to begin to settle after only 5 minutes, while in Samples S and T, the foulants remained dispersed and did not appear to settle. The tubes were observed after 40 minutes, 60 minutes, and 24 hours. After all of these times, the foulants appeared to remain dispersed throughout the sample in Samples S and T, while from Sample O the foulants gradually settled, leaving a clearer supernatant liquid on top.

Claims

1. 1. An additive composition comprising: comprising a plurality of imidazoline compounds and / or ammonium salts thereof, at least a portion of the plurality of imidazoline compounds comprises a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid; the glycerol-limited soybean oil fatty acid comprises a mixture of fatty acids and less than 0.1% by weight of glycerol based on the weight of the glycerol-limited soybean oil fatty acid; The amine has the formula NH ２ - (CH ２ ) n-NH-R １ -OH, wherein R １ is a divalent moiety comprising one or more C atoms and optionally one or more heteroatoms, and n is 2 or 3.

2. 10. The additive composition of claim 1, wherein the additive composition comprises 0% to 3% by weight of glycerol, based on the weight of the additive composition.

3. R １ is the formula (CH ２ CH ２ NH)xCH ２ CH ２ 3. The additive composition of claim 1 or 2, having the formula:

4. R １ is the formula CH ２ CH ２ 3. The additive composition of claim 1 or 2, comprising:

5. The additive composition according to any one of claims 1 to 4, wherein the additive composition comprises a plurality of imidazoline compounds.

6. 6. The additive composition of any one of claims 1 to 5, wherein the glycerol-limited soybean oil fatty acids comprise, by weight of the glycerol-limited soybean oil fatty acids, from about 2% to about 15% alpha-linolenic acid, from about 46% to about 56% linoleic acid, from about 17% to about 28% oleic acid, from about 1% to about 10% stearic acid, and from about 5% to about 15% palmitic acid.

7. The amine has the formula NH ２ CH ２ CH ２ -NH-CH ２ CH ２ The additive composition of any one of claims 1 to 6, comprising OH.

8. The additive composition comprises:

8. The additive composition of any one of claims 1 to 7, comprising, based on the weight of the plurality of imidazoline compounds, the plurality of ammonium salts of imidazoline compounds, or combinations thereof, 0 wt% to 10 wt% total amide content, 0 wt% to 5% rosin acid, 0 wt% to 5 wt% salts of rosin acid, 0 wt% to 5 wt% amides of rosin acid, 0 wt% to 5 wt% esters of rosin acid, 0 wt% to 5 wt% total C1 to C10 monohydric alcohols, and 0 wt% to 5 wt% total fatty acid esters.

9. 9. The additive composition of any one of claims 1 to 8, wherein the total amount of amides in the additive composition is from 0.01 wt% to 10 wt%, based on the weight of the additive composition.

10. 9. The additive composition of any one of claims 1 to 8, wherein the total amount of amides in the additive composition is 0 wt%, based on the weight of the additive composition.

11. A concentrate comprising: (a) the additive composition of any one of claims 1 to 10; (b) about 0.1 parts by weight to 75 parts by weight of at least one organic solvent per 99.9 parts by weight to 25 parts by weight of the plurality of imidazoline compounds, the plurality of ammonium salts of the imidazoline compounds, or a combination thereof; Concentrates, including:

12. 12. The concentrate of claim 11, wherein the concentrate comprises from about 10 parts by weight to about 30 parts by weight of the at least one organic solvent per 70 to 90 parts by weight of the plurality of imidazoline compounds, the plurality of ammonium salts of imidazoline compounds, or a combination thereof.

13. 13. The concentrate of claim 11 or 12, wherein the at least one organic solvent comprises one or more phthalates.

14. The concentrate of any one of claims 11 to 13, wherein the at least one organic solvent comprises dibutyl phthalate, dimethyl phthalate, or a combination thereof.

15. 15. The concentrate of any one of claims 11 to 14, wherein the at least one organic solvent consists of dibutyl phthalate, dimethyl phthalate, or a combination thereof, and the composition is free of other organic solvents.

16. 16. The concentrate of any one of claims 11 to 15, wherein the concentrate comprises, based on the weight of the concentrate, 0 to 2 wt. % glycerol, 0 to 2 wt. % rosin acid, 0 to 2 wt. % salts of rosin acid, 0 to 2 wt. % amides of rosin acid, 0 to 2 wt. % esters of rosin acid, 0 to 2 wt. % total C1 to C10 monohydric alcohols, and 0 to 2 wt. % total fatty acid esters.

17. 1. A treated composition comprising: (i) an additive composition comprising a plurality of imidazoline compounds and / or ammonium salts thereof; (ii) a free-radically polymerizable monomer; and Including, at least a portion of the plurality of imidazoline compounds comprises a reaction product derived from a reactant comprising an amine and a glycerol-limited soybean oil fatty acid; the glycerol-limited soybean oil fatty acid comprises a mixture of fatty acids and 0% to 0.1% by weight of glycerol based on the weight of the glycerol-limited soybean oil fatty acid; The amine has the formula NH ２ - (CH ２ ) n-NH-R １ -OH, wherein R １ is a divalent moiety comprising one or more C atoms and optionally one or more heteroatoms, and n is 2 or 3.

18. 18. The treated composition of claim 17, wherein the treated composition comprises 0% to 1% glycerol by weight of the treated composition.

19. The amine has the formula NH ２ CH ２ CH ２ -NH-CH ２ CH ２ 19. The treated composition of claim 17 or 18, comprising OH.

20. 20. The treated composition of any one of claims 17 to 19, wherein the free radically polymerizable monomer is selected from one or more of acrylic acid, methacrylic acid, salts of acrylic acid, salts of methacrylic acid, acrolein, esters of acrylic acid, esters of methacrylic acid, acrylonitrile, methacrylonitrile, and vinyl acetate.

21. 21. The treated composition of any one of claims 17-20, wherein the treated composition further comprises one or more of a polymerization inhibitor, an oxidation inhibitor, and a pour point depressant.

22. The treated composition of any one of claims 17 to 21, wherein the treated composition further comprises a phenol formaldehyde polymer.

23. 1. A method of making an additive composition, the method comprising: (a) combining an amine and a glycerol-limited soybean oil fatty acid to provide a reaction mixture; (b) heating the reaction mixture to form water and the additive composition; Including, the additive composition comprises a plurality of imidazoline compounds; at least a portion of the imidazoline compounds comprise a reaction product derived from a reactant comprising the amine and the glycerol-limited soybean oil fatty acid; the glycerol-limited soybean oil fatty acid in (a) comprises a mixture of fatty acids and comprises less than 0.1% by weight of glycerol based on the weight of the glycerol-limited soybean oil fatty acid in (a); The amine in (a) is of the formula NH ２ - (CH ２ ) n-NH-R １ -Y, wherein R １ is a divalent moiety containing one or more C atoms and optionally one or more heteroatoms, n is 2 or 3 and Y is -NH ２ or —OH.

24. 24. The method of claim 23, further comprising reacting the plurality of imidazoline compounds with at least one acid to form a plurality of ammonium salts of the imidazoline compounds.

25. 25. The method of claim 24, wherein the at least one acid comprises one or more of hydrochloric acid, sulfuric acid, acetic acid, carbonic acid, acrylic acid, and methacrylic acid.

26. 24. The method of claim 23, further comprising reacting the plurality of imidazoline compounds with at least one alkyl halide, at least one aryl halide, or a combination thereof to form a plurality of ammonium salts of the imidazoline compounds.

27. 27. The method of any one of claims 23 to 26, wherein the additive composition comprises 0% to 3% by weight of glycerol, based on the weight of the additive composition.

28. The amine has the formula NH ２ CH ２ CH ２ -NH-CH ２ CH ２ 28. The method of any one of claims 23 to 27, wherein the OH group is a hydroxyl group.

29. 29. The method of any one of claims 23-28, wherein the glycerol-limited soybean oil fatty acids comprise, by weight of the glycerol-limited soybean oil fatty acids, from about 2% to about 15% alpha-linolenic acid, from about 46% to about 56% linoleic acid, from about 17% to about 28% oleic acid, from about 1% to about 10% stearic acid, and from about 5% to about 15% palmitic acid.

30. 30. The method of any one of claims 23-29, wherein the reaction mixture comprises 98% to 100% by weight of the combination of 2-aminoethylethanolamine and glycerol-limited soybean fatty acids, based on the weight of the reaction mixture.

31. 31. The method of any one of claims 23 to 30, wherein the additive composition comprises, based on the weight of the plurality of imidazoline compounds, 0 wt% to 10 wt% total amide content, 0 wt% to 5 wt% rosin acid, 0 wt% to 5 wt% salts of rosin acid, 0 wt% to 5 wt% esters of rosin acid, 0 wt% to 5 wt% total C1 to C10 monohydric alcohol, and 0 wt% to 5 wt% total fatty acid esters.

32. 17. Use of the additive composition of any one of claims 1 to 10 or the concentrate of any one of claims 11 to 16 as one or more of a corrosion inhibitor, a dispersant, a lubricant, an antifoam agent, an antifouling agent, and a release agent.

Images