Emulsion composition containing a mixed surfactant containing a fatty acid or fatty ester reaction product of a saccharide polymer

Abstract

An aqueous composition containing the reaction product of a saccharide polymer with a fatty acid or fatty acid ester can be obtained in an aqueous fluid in the presence of a hydroxide base and a neutral surfactant or its reaction product form, where the saccharide polymer contains a dextran, a dextrin compound, or any combination thereof. When further combined with a sufficient concentration of a zwitterionic surfactant, an emulsified composition can be obtained. The emulsified composition can be contacted with an oily material to produce an emulsified fluid, which can define an oil-in-water emulsion.

Description

[Background technology]

[0001] The present invention relates to an emulsion composition containing a mixed surfactant, which contains a fatty acid or fatty ester reaction product of a saccharide polymer, a method for producing the emulsion composition, and a fluid emulsified with the emulsion composition.

[0002] Amphiphilic compounds that have both hydrophobic and hydrophilic moieties in their molecular structure are commonly referred to as "surfactants" or "surfactant compounds." Surfactants, due to their molecular structure, tend to reduce the surface tension at the interface between two components. Surfactants can be found in a wide range of consumer and industrial products, including, for example, soaps, detergents, cosmetics, pharmaceuticals, and dispersants. Surfactants are also commonly used in the oil and gas industry. Among other functions in these applications and others, surfactants may increase the solubility of poorly soluble substances, increase foaming, promote emulsification or demulsification, and / or reduce viscosity in certain cases.

[0003] Various conventional surfactants have drawbacks. Some common synthetic surfactants have poor biodegradability (including slow biodegradation in liquid environments) and / or poor biocompatibility, which can adversely affect consumer and industrial products and processes in which such surfactants are used. In addition, some common surfactants can be expensive, have poor water solubility, and / or be subject to environmental and governmental regulations regarding their use. Some surfactants can exhibit high surface tension values ​​at their critical micelle concentration, which can complicate fluid handling during formulation of consumer and industrial products containing such surfactants. A further drawback associated with conventional surfactants is that the hydrophilic-lipophilic balance (HLB) is fixed by the molecular structure of the particular amphiphilic compound used, and thus may not be suitable for a particular application, even if the surfactant is otherwise chemically compatible with the expected conditions of use.

[0004] As described in US Patent Publication No. 2021 / 0340429, a versatile class of surfactants can be obtained in the aqueous phase by combining the reaction products of fatty acids and saccharide polymers with fatty acid amide neutral surfactants (cosurfactants), such as fatty acid alkanolamides. The fatty acid and its amount relative to the saccharide polymer may be varied to tailor the hydrophilic-lipophilic balance of these types of surfactants. Low surface tension values ​​may result as a result of the synergistic interaction of the reaction products with the neutral surfactant. The surfactants may promote short-term emulsification of oil-based fluids and then spontaneously degrade over a period of hours. DISCLOSURE OF THEINVENTION

[0005] The present disclosure relates generally to surfactant technology, and more specifically to an emulsion composition that contains a surfactant formed from a biologically derived material and can promote emulsification of oily substances to form emulsions with longer term stability, particularly oil-in-water emulsions.

[0006] As mentioned above, conventional surfactants may exhibit various problems such as high cost, poor biocompatibility, and / or poor solubility, which may limit their application in various applications. Moreover, there is no easy way to change the hydrophobic-lipophilic balance (HLB) of conventional surfactants. Surface tension (interfacial tension) values ​​are also often high for some types of surfactants as well, which may complicate their handling in various applications and / or hinder their incorporation into various consumer and industrial products.

[0007] As described in U.S. Patent Application Publication No. 2021 / 0340429, which is incorporated herein by reference, aqueous surfactant compositions containing reaction products of fatty acids and saccharide polymers, such as dextran or dextrin compounds, in combination with neutral surfactants (co-surfactants), such as various fatty acid-based alkanolamides, are a versatile class of surfactant compounds. Varying the type and amount of fatty acid not only easily alters the hydrophilic-lipophilic balance, but also can achieve surprisingly low surface tension values ​​when the reaction products are present in combination with a neutral surfactant. Specifically, when present in combination with a suitable neutral surfactant, the reaction product of a fatty acid and a saccharide polymer may have a lower surface tension than the neutral surfactant itself at substantially the same concentration in an aqueous fluid. That is, the reaction product of a fatty acid and a saccharide polymer may synergistically interact with the neutral surfactant to reduce the surface tension value compared to the neutral surfactant alone at substantially the same concentration. Fatty acid esters may be reacted under similar conditions to form reaction products, with the accompanying production of alcohols, such as glycerol, derived from the fatty acid esters.

[0008] As used herein, the term "fatty acid" refers to a carboxylic acid having 4 or more carbon atoms, which is linear and optionally unsaturated. As used herein, the term "fatty acid ester" refers to a compound containing one or more ester moieties, which contains an alcohol component and a fatty acid component. The alcohol component may be a monohydric alcohol or a polyhydric alcohol, such as a diol or triol (e.g., glycerol). The fatty acid may be a linear, saturated or unsaturated fatty acid, examples of which are provided below. Thus, the reaction products, emulsion compositions, and emulsified fluids described herein may be free or substantially free of branched fatty acids or products formed therefrom, according to various embodiments. That is, the reaction products, emulsion compositions, and emulsified fluids described herein include reaction products derived from one or more fatty acids consisting of linear fatty acids.

[0009] Combining the above reaction products with zwitterionic (amphoteric) surfactants can provide additional surprising results and beneficial advantages. That is, the compositions briefly described above (i.e., aqueous surfactant compositions containing the reaction product of a saccharide polymer in combination with a neutral surfactant or its reaction product form, such as fatty acid alkanolamides) may be combined with a zwitterionic surfactant to promote emulsification of oily materials, particularly as oil-in-water emulsions. In other words, the above saccharide polymer reaction products, when present in a composition containing both a zwitterionic surfactant and a neutral surfactant, such as a fatty acid alkanolamide, or its reaction product, may promote emulsion formation, and preferably the emulsion exhibits stability over an extended period of time, such as a period of about one day or more. Surprisingly, such emulsification performance can be achieved even when the zwitterionic surfactant alone, or the combination of the saccharide polymer reaction product and neutral surfactant alone, is not effective in promoting emulsification over an extended period of time under similar conditions and concentrations. Thus, when a zwitterionic surfactant is further combined with the above reaction product in an amount sufficient to promote stable emulsion formation over an extended period of time, an unexpected synergistic enhancement of emulsification performance is observed. The terms "emulsion" and "emulsified fluid" are used equivalently and interchangeably herein.

[0010] Without being limited by theory, the reaction product produced from a saccharide polymer and a fatty acid or fatty acid ester may include at least one fatty acid ester saccharide polymer formed from the reaction between a saccharide polymer (e.g., a dextran or dextrin compound) and a fatty acid component of a fatty acid or fatty acid ester, which fatty acid ester saccharide polymer may then synergistically interact with a neutral surfactant to provide low surface tension values. As described herein, the reaction product may exhibit further synergy in combination with a zwitterionic surfactant when promoting the formation of oil-in-water emulsions with long-term stability lasting for several days or longer.

[0011] To form the fatty acid ester saccharide polymer, the fatty acid ester may be first hydrolyzed under alkaline conditions to produce a fatty acid moiety or its salt form, which is then reacted with the saccharide polymer to form at least one fatty acid ester reaction product. Alternatively, the fatty acid ester may be directly transesterified with the saccharide polymer to form at least one fatty acid ester reaction product. In contrast, the free fatty acid or its salt form may be directly reacted with the saccharide polymer to form the reaction product described herein. Any one or more of the primary alcohol functional groups or secondary alcohol functional groups on the glucose monomer unit of the saccharide polymer may react to form the fatty acid ester reaction product in the present disclosure.

[0012] During the process of forming a fatty acid ester saccharide polymer reaction product from a fatty acid ester such as an animal fat or vegetable oil, the alcohol component of the fatty acid ester may be released into the aqueous fluid during which the fatty acid ester saccharide polymer reaction product is being formed. The alcohol component may remain with the fatty acid ester saccharide polymer reaction product in the aqueous fluid or may be at least partially removed therefrom. Advantageously and surprisingly, the alcohol component released into the aqueous fluid does not significantly affect the low surface tension values ​​achievable when the fatty acid ester saccharide polymer reaction product and the neutral surfactant are both present. The alcohol component (e.g., glycerol) released into the aqueous fluid may aid in solubilizing other components of the composition and / or other components mixed with the composition to produce various consumer and industrial products. Optionally, additional glycerol or another alcohol may be mixed into the composition, including the composition made from free fatty acids or the composition made from other types of fatty acid esters, without significantly affecting the resulting surface tension values ​​and / or emulsification performance.

[0013] Thus, the reaction products described herein may be advantageous because they are substantially bio-derived, low cost, and can reduce surface tension values ​​when present in combination with a suitable neutral surfactant. For example, the reaction products of maltodextrin are a particularly useful class of dextrin-based reaction products because this saccharide polymer is low cost and has a convenient molecular weight range. A variety of fatty acids with a range of molecular weights may be used to produce reaction products with a range of HLB values. Furthermore, many fats, oils, and similar glycerol esters can serve as convenient and inexpensive sources for the fatty acid esters used in forming the reaction products described herein, or the fatty acids derived therefrom. Similarly, the fats, oils, similar glycerol esters, and other fatty acid esters, as well as the amounts thereof, may be selected to facilitate tailoring of surfactant properties, such as, for example, modifying HLB values ​​and / or altering emulsification performance.

[0014] Maltodextrin represents an advantageous saccharide polymer for use in the present disclosure due to its low cost, environmentally friendly nature, and the relative ease with which it can be chemically reacted with a variety of free fatty acids or fatty acids derived from fatty acid esters (e.g., glycerol esters). Depending on the fatty acid reacted with the maltodextrin, the hydrophilic-lipophilic balance (HLB) of the reaction product may range from about 5 to about 20 or more, where known molecular contributions may be used to calculate the HLB value. In addition to the variation in properties provided by the size and amount of fatty acid, maltodextrin is available in a variety of oligomer sizes (e.g., 3 to 20 glucose monomers, or up to about 25 glucose monomers), which may provide further property tuning. Thus, maltodextrin reaction products may be adapted for use under a wide range of conditions expected to be present in a given application. Dextran reaction products may offer similar advantages and characteristics to maltodextrin reaction products, such as the ability to provide low surface tension values.

[0015] Maltodextrins and other dextrin compounds suitable for use in the present disclosure may contain from 2 to about 20 glucose monomers, or up to about 25 glucose monomers, linked by α(1,4) glycosidic linkages. At least a portion of the glucose monomers are fatty acids or fatty acid esters (fatty acid salts derived therefrom, e.g., C4-C 30 Fatty Acids or C4-C 20 The fatty acid or fatty acid ester may form a reaction product when contacted with a fatty acid salt (including a salt of a fatty acid) under suitable conditions. The fatty acid or fatty acid ester may include one or more fatty acids or fatty acid components, which may be any combination of saturated or unsaturated fatty acids. Without being limited by theory, at least a portion of the glucose monomers in the dextrin compound may react to form a fatty acid ester dextrin compound, which may be present in the aqueous fluid in combination with unreacted fatty acid salts, if desired. When formed, the fatty acid ester dextrin reaction product may occur at any hydroxyl group of the dextrin compound, including any combination of primary and / or secondary hydroxyl groups. Hydroxyl groups of neutral surfactants may undergo similar esterification reactions under the same reaction conditions.

[0016] Dextran is a saccharide polymer characterized by having predominantly α(1,6) glycosidic linkages between adjacent glucose monomers, with a limited number of glucose side chains attached to the polymer backbone via α(1,3) glycosidic linkages. The α(1,3) glycosidic linkages may introduce crosslinks between adjacent saccharide polymer chains. Depending on the biological source, the degree of branching and molecular weight of dextran may vary widely, any of which may be used in the present disclosure. At least a portion of the glucose monomers in dextran are branched with a fatty acid or fatty acid ester (a fatty acid salt derived therefrom, e.g., C4-C 30 Fatty Acids or C4-C 20When the glucose monomers are contacted with the fatty acid salts (including salts of fatty acids) under appropriate conditions, a reaction product may form. Without being limited by theory, in some embodiments, at least a portion of the glucose monomers may react to form fatty acid ester dextran, which may be present in the aqueous fluid in combination with unreacted fatty acid salts, if desired. When formed, the fatty acid ester dextran reaction product may occur at any hydroxyl group of the dextran.

[0017] In some embodiments, the reaction products of the present disclosure may include dextrin compounds having 3 to about 20 glucose monomers, or up to about 25 glucose monomers, covalently linked by α(1,4) glycosidic bonds. The following formula (I) shows the general structure of dextrin compounds having only α(1,4) glycosidic bonds between adjacent glucose monomers, where the variable "a" is a positive integer ranging from 1 to about 18, thus providing 3 to about 20 glucose monomers in the dextrin backbone. For dextrin compounds containing up to 25 glucose monomers, the variable "a" may range from 1 to about 23. Although the terminal glucose units are shown in closed form, they may also be present in the corresponding reducing sugar (open chain or acyclic) form.

[0018] [ka]

[0019] Other dextrin compounds may contain only α(1,6) glycosidic linkages or a mixture of α(1,4) and α(1,6) glycosidic linkages, and such dextrin compounds may also be suitable for use in forming the reaction products of the present application. Particularly suitable dextrins may have a molecular weight (e.g., Mn) in the range of about 1200 to about 1400 or about 1100 to about 1500.

[0020] In some or other embodiments, the reaction product may include dextran obtained from any suitable source. The structure of dextran is shown below in Formula 2, but for clarity, the α(1,3) glycosidic linkages are not shown. The α(1,3) glycosidic linkages, when they occur, may be added as side chains of terminal glucose monomers to the α(1,6)-linked saccharide polymer backbone, may form crosslinks between adjacent α(1,6)-linked saccharide polymer backbones, may interrupt the α(1,6)-linked saccharide polymer backbones with α(1,3) glycosidic linkages, or any combination thereof. Depending on the source, up to about 5% of the glucose monomers may be linked by α(1,3) glycosidic linkages. Linkage by α(1,3) glycosidic linkages may occur on any glucose monomer. The numbering of the single glucose monomers is shown below in Formula 3.

[0021] [ka]

[0022] Suitable dextrans may have a molecular weight of about 1200, about 1400, about 5000 to about 50,000,000, or about 100,000 to about 20,000,000. Thus, the variable "b" may range from about 30 to about 300,000, depending on the particular dextran selected. Particularly suitable dextrans may have a molecular weight (e.g., Mn) in the range of about 1200 to about 1400, about 1100 to about 1500, about 1000 to about 100,000, about 100,000 to about 1,000,000, about 2,000,000 to about 5,000,000, or about 5,000,000 to about 50,000,000. Another suitable dextran may have a molecular weight of about 500,000 and an activity level of about 9%.

[0023] [ka]

[0024] The saccharide polymer may comprise maltodextrin according to some embodiments of the present disclosure. Maltodextrin may be characterized by its dextrose equivalent (DE) value. Dextrose equivalent is a measure of the amount of reducing sugar (e.g., glucose monomer) present in a saccharide polymer (especially dextrin) and is expressed as a percentage of dextrose. Dextrose itself has a dextrose equivalent of 100, whereas starch, which is functionally non-reducing, is defined as having a dextrose equivalent of 0. Dextrose equivalent may be calculated by dividing the molecular weight of glucose by Mn and multiplying the result by 100. A higher dextrose equivalent value is characteristic of a smaller number of covalently attached glucose monomers (a higher relative proportion of terminal reducing sugars due to a shorter polymer backbone length). Maltodextrins suitable for forming reaction products with one or more fatty acids or one or more fatty acid esters described in the present disclosure may exhibit a dextrose equivalent value ranging from 3 to about 25, or from 3 to about 20. In more specific embodiments, the dextrose equivalent value of the maltodextrin may range from about 4.5 to about 7.0, or from about 7.0 to about 10.0, or from about 9.0 to about 12.0.

[0025] According to some embodiments, maltodextrins suitable for forming the reaction product may be obtained from the hydrolysis or pyrolysis of starch, specifically the amylose component of starch. For example, maltodextrins having formula 1 may be formed by the hydrolysis or pyrolysis of amylose. Alternatively, suitable dextrins may be obtained from the hydrolysis or pyrolysis of the amylopectin component of starch, in which case the dextrins may contain α(1,6) glycosidic linkages if the dextrins are obtained by hydrolysis of amylopectin side chains. Starch that may yield dextrins may be obtained from any starch source.

[0026] Thus, the reaction product suitable for use in the present disclosure may include an aqueous fluid, a neutral surfactant or reaction product form thereof, and a reaction product of a saccharide polymer with a fatty acid or fatty acid ester, where the saccharide polymer includes a dextran, a dextrin compound, or any combination thereof, and the reaction product of the saccharide polymer with a fatty acid or fatty acid ester, and the reaction product form of the neutral surfactant, if present, is formed in the presence of a hydroxide base in an aqueous fluid (e.g., under aqueous alkaline conditions). The zwitterionic surfactant may be present in combination with the zwitterionic surfactant and the neutral surfactant in an amount sufficient to promote the formation of an emulsion when combined with an oily substance, thereby defining an emulsified composition. The emulsified composition may form an emulsified fluid when contacted with an oily substance under appropriate conditions. The emulsified fluid may define an oil-in-water emulsion, and / or the emulsified fluid may remain stable for at least about one day, as further discussed herein. Water-in-oil emulsions may also be possible by appropriate modification of the disclosure herein.

[0027] Aqueous fluids that may be used to form the emulsified compositions described herein include, but are not limited to, water, salt water, seawater, brine, salt water solutions, mixtures of water or salt water solutions with water-miscible organic solvents, or any combination thereof. Any of these aqueous fluids may be present in the emulsified fluid resulting from contacting the emulsified composition with an oily material.

[0028] The oily substances that may undergo emulsification in accordance with the present disclosure are not believed to be particularly limited. Exemplary oily substances that may be suitably emulsified include, for example, petroleum, refined petroleum, diesel, vegetable oil, vegetable oil, or any combination thereof.

[0029] Thus, an emulsified fluid of the present disclosure may include an oily material emulsified with an emulsification composition, the emulsification composition containing: an aqueous fluid; a neutral surfactant or a reaction product form thereof; a reaction product of a saccharide polymer and a fatty acid or fatty acid ester, the saccharide polymer comprising a dextran, a dextrin compound, or any combination thereof, the reaction product of the saccharide polymer and the fatty acid or fatty acid ester, and the reaction product form of the neutral surfactant, if present, formed in the presence of a hydroxide base in an aqueous fluid; and a zwitterionic surfactant. The emulsified fluid may, in certain embodiments, define an oil-in-water emulsion.

[0030] The emulsifying composition and the oleaginous material may be present in any ratio that forms an emulsion. In a non-limiting example, the ratio of the emulsifying composition to the oleaginous material may range from about 1:99 to about 99:1, or from about 1:1 to about 1:9, by volume. In some examples, the emulsifying composition and the oleaginous material may be present in a suitable ratio such that the combination of the emulsifying composition and the oleaginous material as a whole defines an oil-in-water emulsion.

[0031] In the emulsion compositions and emulsified fluids described herein, the saccharide polymer reaction product and the zwitterionic surfactant may be present in any ratio. In some examples, the zwitterionic surfactant may be present in an amount greater than the amount of the saccharide polymer reaction product, measured by weight. In non-limiting examples, the ratio of zwitterionic surfactant to the saccharide polymer reaction product may be about 1.5:1 or more, about 2:1 or more, about 3:1 or more, about 4:1 or more, about 5:1 or more, about 6:1 or more, about 7:1 or more, about 8:1 or more, or about 9:1 or more, such as about 2:1 to about 8:1, about 4:1 to about 8:1, about 5:1 to about 7:1, or about 4:1 to about 6:1. By providing more zwitterionic surfactant than the saccharide polymer reaction product, extended stability of the emulsified fluid may be achieved.

[0032] The emulsified fluid, once emulsified, may be stable for a predetermined period of time. The emulsified fluid may be classified as stable if the degree of disruption of the emulsion is about 10% or less over a predetermined period of time. Preferably, the degree of disruption may be about 50% or less over a predetermined period of time. More preferably, the degree of disruption may be about 5% or less over at least 1 hour. In non-limiting examples, the emulsified fluid may remain emulsified (stable) for at least about 1 hour, at least about 2 hours, at least about 4 hours, at least about 6 hours, at least about 8 hours, at least about 12 hours, at least about 24 hours (1 day), at least about 2 days, at least about 4 days, at least about 1 week (7 days), at least about 2 weeks (14 days), at least about 3 weeks (21 days), or at least about 1 month (30 days). Preferably, the emulsified fluid may remain stable (emulsified) for at least about 1 day, or at least about 2 days, or at least about 4 days, or at least about 7 days, or at least about 10 days, or at least about 15 days, or at least about 30 days, or at least about 60 days, e.g., from about 1 day to about 60 days, from about 1 day to about 30 days, from about 5 days to about 30 days, or from about 10 days to about 60 days.

[0033] Examples of fatty acids (or fatty acid components within fatty acid esters) that may be suitable for forming reaction products included in the emulsified fluids and emulsion compositions of the present disclosure include, for example, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelabonic acid, capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachidic acid, heneicosylic acid, behenic acid, triosylic acid, lignoceric acid, pentacosylic acid, cerotic acid, carboceric acid, montanic acid, nonacosylic acid, melissic acid, crotonic acid, cervonic acid, linoleic acid, linoleic acid, linolenic acid, arachidonic acid, docosatetraenoic acid, myristoleic acid, palmitoleic acid, sapienic acid, sappen ... acid), vaccenic acid, paulic acid, oleic acid, pinolenic acid, stearidonic acid, eleostearic acid, elaidic acid, gondoic acid, gadoleic acid, erucic acid, eicosenoic acid, eicosadiencoic acid, eicosatrienoic acid, eicosatetraenoic acid, docosadienoic acid, nervonic acid, mead acid, adrenic acid, and the like, and any combination thereof.

[0034] The fatty acid ester has at least one alcohol component and at least one fatty acid component (one or more of the fatty acids listed above) that may be liberated under the alkaline conditions used to form the saccharide polymer reaction product. Suitable fatty acid esters for forming the reaction product are not believed to be particularly limited, provided that the fatty acid ester undergoes effective hydrolysis to release the alcohol component and one or more fatty acid components of the fatty acid ester. Suitable fatty acids derived from the fatty acid esters for forming the reaction products of the present disclosure may be selected (by selection of an appropriate fatty acid ester containing one or more desired fatty acids) to result in a reaction product having an HLB value in a range, such as an HLB value of about 5 to about 20. Exemplary types of fatty acid esters are shown below. Fatty acids derived from fatty acid esters range from about C4 to about C 30 Or, about C4 to about C 20 Or, about C6 to about C18 Or about C8 to about C 24 The fatty acids suitable for forming the reaction product according to the disclosure herein may be saturated or unsaturated. When the reaction product is formed from fatty acid esters sourced from vegetable oil, at least one unsaturated fatty acid, such as oleic acid, linoleic acid, or linolenic acid, may be present in the reaction product.

[0035] In some embodiments, the fatty acid ester used to form the reaction product may contain glycerol esters, which may also be present in the emulsion composition and emulsified fluids formed therefrom. The glycerol esters may be subjected to alkaline hydrolysis to liberate glycerol as the alcohol component, and up to three carboxylic acid components per glycerol alcohol component may be liberated to undergo reaction with the saccharide polymer in accordance with the disclosure herein. According to some embodiments of the present disclosure, the carboxylic acid components released from the glycerol esters may be the same or different, and / or at least one unsaturated fatty acid may be present in the carboxylic acid components. Thus, the reaction products, emulsion compositions, and emulsified fluids described herein may further include glycerol, especially when the composition includes a reaction product formed from a glycerol fatty acid ester.

[0036] Glycerol esters suitable for forming a reaction product, emulsion composition, or emulsified fluid in accordance with the disclosure herein are not believed to be particularly limited and may include any vegetable oil, animal oil, vegetable fat, animal fat, or any combination thereof that contains one or more desired fatty acids. The glycerol esters may undergo hydrolysis or transesterification reactions in the course of forming the reaction product with the saccharide polymer. Suitable glycerol esters may be present in vegetable or animal sources such as soybean oil, grape seed oil, olive oil, palm oil, rice bran oil, safflower oil, corn oil, coconut oil, sunflower seed oil, canola oil, rapeseed oil, peanut oil, cottonseed oil, hazelnut oil, tea seed oil, linseed oil, sesame oil, acai oil, almond oil, beech nut oil, Brazil nut oil, cashew oil, macadamia nut oil, pecan oil, pine nut oil, pistachio oil, walnut oil, pumpkin seed oil, apricot oil, avocado oil, grapefruit oil, lemon oil, orange oil, mango oil, flax seed oil, fish oil, cocoa butter, hemp seed oil, castor oil, tall oil, beef tallow, buffalo tallow, sheep tallow, goat tallow, duck tallow, pork tallow, poultry tallow, and any combination thereof.

[0037] For example, soybean oil contains a mixture of saturated and unsaturated fatty acids, primarily palmitic, stearic, oleic, linoleic, and linolenic acids, with the majority of fatty acids obtainable from soybean oil being composed of monounsaturated and polyunsaturated fatty acids (oleic, linoleic, and linolenic). Palm oil contains approximately 50% saturated fatty acids (palmitic, stearic, and myristic acids) and approximately 50% unsaturated fatty acids (oleic, linoleic, and linolenic acids). Coconut oil contains primarily saturated fatty acids (caprylic, capric, lauric, myristic, palmitic, and stearic acids) with less than 10% unsaturated fatty acids (oleic and linoleic acids). Specific examples of fatty acid mixtures that may be present in the reaction products, emulsion compositions, and emulsified fluids described herein include mixtures of these fatty acids.

[0038] When glycerol esters are used as a direct (in situ) source of fatty acid for forming the reaction product of the present disclosure, glycerol may be present in the emulsion composition and emulsified fluids obtained therefrom. Optionally, glycerol may be at least partially removed from the aqueous fluid or emulsified fluid of the emulsion composition as needed. Otherwise, the amount of glycerol present in the emulsion composition and emulsified fluid may be determined by the amount of glycerol esters present in forming the reaction product. For example, C8-C 24 For glycerol esters containing fatty acids, particularly unbranched fatty acids in this size range, the weight percentage of glycerol in the glycerol ester may range from about 7% to about 17% by weight, based on the total weight of the glycerol ester. Thus, the corresponding weight percentage of glycerol in the emulsion composition and emulsified fluids containing the reaction products may range from about 7.5% to about 20% by weight, as measured relative to the fatty acids derived from glycerol upon alkaline hydrolysis. Alternatively, since each glycerol ester may release one glycerol molecule upon complete hydrolysis, the weight percentage of glycerol in the emulsion composition and emulsified fluids may be substantially equal, by mass, to the weight percentage of glycerol esters present in the reaction mixture, relative to the entire composition. However, it should be understood that additional glycerol may be added to the emulsion composition and emulsified fluid beyond that liberated upon conversion of the glycerol fatty acid esters to the reaction products formed from the saccharide polymers, or that glycerol may be further added to the emulsion composition containing the reaction products prepared directly from the fatty acids.

[0039] Suitable hydroxide bases for forming the reaction product may include, for example, alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, or any combination thereof. There may be a stoichiometric excess or stoichiometric deficiency of the hydroxide base relative to the amount of fatty acid ester or fatty acid.

[0040] In the reaction product of the saccharide polymer, the molar ratio of fatty acid or fatty acid derived from fatty acid ester to glucose monomer is 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on about 0.05 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on approximately 0.08 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on about 0.1 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on about 0.2 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on about 0.3 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on approximately 0.4 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on approximately 0.5 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on approximately 0.6 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on approximately 0.7 or more moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or greater than about 0.8 based on moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー The maximum ratio of fatty acid to dextrin compound or dextran in the saccharide polymer reaction product may be about 1.0 based on glucose monomers in most cases, although molar ratios greater than 1.0 are within the scope of the present disclosure. Thus, in some embodiments, the molar ratio of fatty acid to glucose monomers in the saccharide polymer reaction product is about 0.05 molar or more. 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 1.0 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.9 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.8 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.7 moles脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.6 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.5 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.05 mole 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.4 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.9 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.8 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.7 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.6 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.5 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.1 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.4 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.9 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.8 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.7 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.6 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸: Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.5 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.2 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.4 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.9 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.8 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.7 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.6 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.5 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.3 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.4 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.4 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.9 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.4 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.8 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.4 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.7 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.4 mol 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.6 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー or about 0.4 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー ~ approx. 0.5 moles 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマーThe ratio may range from 0.1 to 0.5. The above ratio may represent the molar ratio of fatty acid reacted with dextran or dextrin compound. One or more hydroxyl groups per glucose monomer may react in some cases, especially at a molar ratio of 1.0 or more. At least a portion of the glucose monomers may remain unfunctionalized, especially at low molar ratios. Unreacted fatty acid, if present, may remain in the reaction product as a fatty acid salt of a hydroxide base.

[0041] Thus, a reaction product suitable for use in the present disclosure may contain one or more fatty acid ester dextrins and / or one or more fatty acid ester dextran, optionally in further combination with a fatty acid salt (e.g., an alkali metal carboxylate) and / or a hydroxide base (e.g., an alkali metal hydroxide base). When a fatty acid ester is used to form the reaction product, the hydroxide base may be present in at least a molar amount sufficient to react with at least a portion of the fatty acid ester to promote its hydrolysis and convert the fatty acid component of the fatty acid ester to a fatty acid salt (e.g., an alkali metal carboxylate) for reaction with the saccharide polymer. Alternatively, the hydroxide base may be present in a molar amount sufficient to form a fatty acid salt (e.g., an alkali metal carboxylate) when forming the reaction product directly from free fatty acids. The alcohol component released from the fatty acid ester (e.g., glycerol) after hydrolysis may be present in combination with any reaction product as well. The hydroxide base may be neutralized with an acid or at least partially removed by washing, and the emulsion composition containing the reaction product may maintain a low surface tension even after neutralization or washing. Alcohol components, if present, may likewise be at least partially removed from the reaction product and emulsified composition, if desired, for example by distillation or solvent extraction.

[0042] Alternatively, other saccharide polymers may be used to form the reaction products in the emulsion compositions and emulsified fluids described herein.Other saccharide polymers that may be used in this regard include, but are not limited to, glycogen, guar, xanthan, welan, scleroglucan, chitosan, schizophyllan, levan, pectin, inulin, arabinoxylan, pullulan, gellan, carrageenan, chitin, cellulose, starch, or combinations thereof.Saccharide polymer fragments obtained from the above and containing about 3 to about 25 monomers per fragment may also be used to form the reaction products, emulsion compositions, and emulsified fluids disclosed herein.

[0043] In some embodiments, the reaction products of the present disclosure may preferably facilitate reducing the surface tension of a neutral surfactant, preferably a fatty acid alkanolamide neutral surfactant, in an aqueous fluid, i.e., the reaction products may be present in an emulsion composition or emulsified fluid at a concentration effective to reduce the surface tension of the neutral surfactant compared to the surface tension of the neutral surfactant alone at a substantially similar concentration in the aqueous fluid.

[0044] At the same time, the neutral surfactant or reaction product form thereof may be present at a concentration sufficient to solubilize the saccharide polymer in the aqueous fluid prior to forming the reaction product and the reaction product of the saccharide polymer with the fatty acid or fatty acid ester after the reaction has occurred. In the emulsion compositions and emulsified fluids of the present disclosure, the neutral surfactant may be present at a concentration of about 20% by weight or less, about 10% by weight or less, or about 5% by weight or less, for example, about 1% to about 10% by weight, or about 3% to about 8% by weight, based on the total weight of the emulsion composition.

[0045] Suitable neutral surfactants may contain one or more fatty acid alkanolamide surfactants. Fatty acid alkanolamide surfactants that can be combined with the reaction product of the present disclosure to reduce surface tension include cocamide-based surfactants, such as cocamide diethanolamine, cocamide monoethanolamine, cocamide monoisopropanolamine, cocamide diisopropanolamine, etc. Cocamide diethanolamine (CocoDEA) or cocamide diisopropanolamine (CocoDIPA) can be particularly suitable neutral surfactants for use in the present disclosure. Other fatty acid amide alkanolamines (alkanolamides), such as palmitic acid amide diethanolamine, palmitic acid monoethanolamine, or palmitic acid diisopropanolamine, can also be suitable for use in the present disclosure.

[0046] Zwitterionic surfactants (also known as amphoteric surfactants) suitable for use in the present disclosure are not considered to be particularly limited in structure and may be selected from betaines and sultaines.Specific examples of suitable zwitterionic surfactants may include, for example, cocamidopropyl betaine, alkanoyl hydroxysultaines (e.g., lauryl hydroxysultaine), cocamidopropyl hydroxysultaine, alkanamidopropyl hydroxysultaines (e.g., lauramidopropyl hydroxysultaine), sodium cocoamphohydroxypropyl sulfonate, and the like.

[0047] The zwitterionic surfactant may be present in a sufficient concentration in the aqueous fluid of the emulsion compositions described herein to promote the formation of an emulsified fluid, such as an oil-in-water emulsion, when combined with an oily substance. In the emulsified fluids and emulsion compositions of the present disclosure, one or more zwitterionic surfactants may be present at a concentration of about 15% by volume or less, about 10% by volume or less, about 5% by volume or less, about 2.5% by volume or less, about 1% by volume or less, about 0.5% by volume or less, about 0.4% by volume or less, about 0.3% by volume or less, about 0.2% by volume or less, about 0.1% by volume or less, about 0.09% by volume or less, about 0.08% by volume or less, about 0.07% by volume or less, about 0.06% by volume or less, about 0.05% by volume or less, about 0.04% by volume or less, about 0.03% by volume or less, about 0.02% by volume or less, or about 0.01% by volume or less, based on the total amount of the emulsified fluid or emulsion composition.

[0048] Emulsion compositions and emulsified fluids comprising the reaction products disclosed herein, once formed, may have a pH in the range of about 1 to about 14, e.g., about 1 to about 5, about 5 to about 7, about 7 to about 9, or about 9 to about 14. After forming the reaction products according to the disclosures herein, the pH may be increased or decreased as needed. A reduction in surface tension values ​​may result in a decrease in pH in some cases. A reduction in surface tension may also result in the presence of dissolved salts, such as potassium chloride.

[0049] The reaction products of the present disclosure (which may include those formed by the reaction of one or more fatty acids or one or more fatty acid esters with dextrin compounds and / or dextran) may be prepared by a process that includes heating a saccharide polymer containing dextran, a dextrin compound (e.g., a dextrin compound containing 3 to about 20 glucose monomers or up to about 25 glucose monomers linked together by α(1,4) glycosidic linkages, such as maltodextrin), or any combination thereof, a fatty acid or fatty acid ester, a neutral surfactant, (e.g., a fatty acid alkanolamide), and a hydroxide base in an aqueous fluid, and obtaining a reaction product of the saccharide polymer and the fatty acid or fatty acid ester in the aqueous fluid. The aqueous fluid may further include glycerol, which may be from the fatty acid ester used to form the reaction product, and / or additional glycerol may be added separately to the reaction product. The reaction product may be present in the aqueous fluid at a concentration effective to reduce the surface tension of the neutral surfactant, as measured relative to a comparable concentration of the neutral surfactant alone in the aqueous phase. For example, a 5% by weight aqueous solution of a neutral surfactant may have a higher surface tension than an emulsion composition containing 5% by weight of a neutral surfactant in combination with a surface tension reducing amount of a reaction product of the present disclosure. Any of the reaction products of dextran or dextrin compounds may constitute saccharide polymers having low surface tension suitable for forming emulsion compositions or emulsified fluids further containing at least one zwitterionic surfactant. Heating may be performed at a temperature of about 100°C or less, for example, from about 50°C to about 80°C, from about 60°C to about 70°C, or from about 50°C to about 60°C.

[0050] In the presence of a neutral surfactant, the surface tension value of the reaction product of the present disclosure may be about 40 dyn / cm or less, about 38 dyn / cm or less, about 36 dyn / cm or less, about 34 dyn / cm or less, about 32 dyn / cm or less, about 30 dyn / cm or less, or about 28 dyn / cm or less. Alternatively, the surface tension value may be reduced by up to about 40%, by up to about 30%, by up to about 20%, by up to about 15%, or by up to about 10% compared to the surface tension of the neutral surfactant alone in an aqueous fluid at a comparable concentration. In certain examples, the surface tension value may be reduced by an amount of about 10% to about 25%, by about 10% to about 20%, or by about 15% to about 25%, when measured compared to the surface tension of the neutral surfactant alone in an aqueous fluid at substantially the same concentration as the neutral surfactant in the composition including the reaction product.

[0051] In forming a reaction product suitable for use in the disclosure herein, the method may include combining a fatty acid or fatty acid ester, a hydroxide base, and a neutral surfactant in water to form a mixture, and heating the mixture until the fatty acid or fatty acid ester dissolves (e.g., by undergoing hydrolysis and / or by forming a fatty acid salt) to form a homogeneous mixture. A saccharide polymer may be combined with the fatty acid or fatty acid ester during this process, or the saccharide polymer may be combined with the homogeneous mixture after the homogeneous mixture is formed. Once the saccharide polymer is present in the homogeneous mixture, heating may be continued until a sufficient degree of reaction product is formed. The resulting aqueous phase may be directly utilized for further applications, after being concentrated, neutralized, or diluted as appropriate, or by further combining with additional components for specific formulations, such as zwitterionic surfactants to form the emulsion compositions disclosed herein. Formulations and products in which the emulsion compositions and emulsified fluids of the present disclosure may be used are discussed below. In some cases, the emulsion composition may at least partially replace another surfactant (e.g., a charged surfactant) in a specific formulation. In other instances, the emulsifying composition may at least partially replace an ethoxylated alcohol surfactant in the formulation. (Underground processing work)

[0052] Recovery of hydrocarbon resources (such as oil and gas) from subterranean formations is often performed in conjunction with the introduction of one or more subterranean treatment chemicals downhole. As used herein, the terms "treat," "treatment," "treating," and grammatical equivalents refer to any compound, fluid, or combination thereof, that is introduced into a subterranean formation to achieve a desired function and / or for a desired purpose. An appropriate treatment chemical or treatment fluid may be selected based on the particular conditions that are present or expected to be present downhole.

[0053] The reaction products of the present disclosure, including reaction products formed from maltodextrin, other dextrin compounds, or dextran, may be formulated as subterranean treatment fluids, or the emulsion compositions further containing zwitterionic surfactants or emulsified fluids formed therefrom may be formulated as subterranean treatment fluids. The treatment fluids may be used in various subterranean treatment operations to facilitate or promote desired outcomes within subterranean formations. As used herein, the term "treatment fluid" refers to any fluid used in a subterranean treatment operation that involves achieving a desired function and / or a desired objective. Unless otherwise specified, the use of the term "treatment fluid" does not imply any particular action by the treatment fluid or its components. Examples of treatment operations that may be facilitated by the use of the reaction products, emulsion compositions, and emulsified fluids of the present disclosure include, but are not limited to, drilling operations, stimulation operations, production operations, remediation operations, erosion control operations, and the like, which may include, for example, fracturing operations, gravel packing operations, acidizing operations, descaling operations, consolidation operations, workover operations, cleanup operations, diversion operations, and the like. Any of these treatment operations may feature emulsification, demulsification, modification of surface wetting characteristics downhole, or any combination thereof.

[0054] As used herein, the term "drilling operation" refers to the process of forming a well bore in a subterranean formation. As used herein, the term "drilling fluid" refers to a fluid used in drilling a well bore.

[0055] As used herein, the term "stimulation operations" refers to actions taken within a wellbore to increase production from the wellbore. As used herein, the term "stimulation fluids" refers to fluids used downhole during stimulation actions to increase production of hydrocarbon resources from a subterranean formation. In some cases, stimulation fluids may include fracturing fluids or acidizing fluids.

[0056] As used herein, the term "cleanup operation" or "damage control operation" refers to any operation to remove foreign material from a wellbore to increase production. As used herein, the term "cleanup fluid" or "damage control fluid" refers to a fluid used to remove unwanted material from a wellbore that blocks the flow of desired fluids. In one example, the cleanup fluid can be an acid treatment fluid to remove material resulting from one or more drilling treatments. In another example, the cleanup fluid can be used to remove filter cake on the wellbore wall. For example, the reaction products, emulsion compositions, or emulsified fluids of the present disclosure may facilitate the liberation of hydrocarbon resources from the subterranean formation by altering the surface wetting properties to facilitate wellbore cleanup. In another embodiment, a treatment fluid containing the reaction products of the present disclosure may be introduced in an emulsified form into a subterranean formation and subsequently broken down (demulsified) therein to facilitate desired actions within the formation.

[0057] As used herein, the term "fracturing operation" refers to a high pressure operation that creates or extends multiple flow paths within a subterranean formation. As used herein, the term "fracturing fluid" refers to a fluid of increased viscosity that is used in conjunction with a fracturing operation. A number of proppant particulates may be present in the fracturing fluid to maintain the flow paths created or extended by the fracturing operation in an open condition.

[0058] As used herein, the term "remediation operation" refers to any operation designed to maintain, increase, or restore a particular production rate from a well, which may include stimulation or cleanup operations. As used herein, the term "remediation fluid" refers to any fluid used in conjunction with a remediation operation.

[0059] As used herein, the term "acid treatment operation" refers to any operation designed to remove acid soluble material from a wellbore (e.g., acid soluble material that comprises at least a portion of a subterranean formation). As used herein, the term "acid treatment fluid" refers to a fluid used during an acid treatment operation. Mineral acids (e.g., hydrochloric acid or hydrobromic acid) or organic acids may be present in compositions used in the acid treatment of carbonate formations, whereas hydrofluoric acid may be present in compositions used in the acid treatment of siliceous formations.

[0060] As used herein, the term "spotting fluid" refers to a fluid designed for localized treatment of a subterranean formation. In one example, the spotting fluid may include a lost circulation agent for treatment of a specific portion of a wellbore, such as to plug fractures and prevent sinking in the wellbore. In another example, the spotting fluid may include a water control material or a material designed to clear plugs in drilling or extraction equipment.

[0061] As used herein, the term "completion fluid" refers to fluids (including cementing compositions and cementing fluids) used during the completion stage of a well.

[0062] As used herein, the term "cementing fluid" refers to a fluid used during cementing operations in the wellbore.

[0063] The reaction products, emulsion compositions, and emulsified fluids of the present disclosure may also be used in conjunction with Enhanced Oil Recovery (EOR) operations. When used in conjunction with EOR operations, the reaction products of the present disclosure may alter surface wetting within subterranean formations to enhance recovery of hydrocarbon resources from the formations.

[0064] In any of the aforementioned treatment operations, the treatment fluid may be foamed. Foamed fracturing fluids may be advantageous, for example, in transporting proppant particulates into the wellbore, as compared to treatment fluids with increased viscosity. When foamed, the treatment fluid may have a foam quality ranging from about 1% to about 99%. The foaming process may be further enhanced by incorporating a zwitterionic surfactant into the emulsion composition or the emulsified fluid.

[0065] The reaction products, emulsion compositions, or emulsified fluids of the present disclosure may be present in any of the process fluids described above. The process fluids of the present disclosure may be characterized by a concentration of the reaction products of about 0.1 gpt (per thousand gallons) to about 10 gpt, or about 0.1 gpt to about 1 gpt, or about 0.2 gpt to about 0.5 gpt. These concentrations correspond to volume percents ranging from about 0.01% to about 1%, or about 0.01% to about 0.1%, or about 0.02% to about 0.05%. The concentrations selected may vary depending on the specific requirements for a given process operation and / or the unique subsurface conditions encountered downhole. In some examples, the reaction products may be present in a concentration effective to reduce the surface tension of a neutral surfactant also present in the process fluid.

[0066] Treatment fluids including the reaction products of the present disclosure may further contain any number of additives that may be used in the oilfield service industry, as appropriate. Examples of additives that may be present in the treatment fluid in combination with the reaction products of the present disclosure include, for example, surfactants, viscosity enhancers, gelling agents, gel stabilizers, antioxidants, polymer degradation inhibitor additives, relative permeability modifiers, scale inhibitors, corrosion inhibitors, chelating agents, foaming agents, defoamers, antifoaming agents, emulsifiers, demulsifiers, iron control agents, proppants or other particulates, particulate diverters, salts, acids, fluid loss control additives, gases, catalysts, other clay control agents, dispersants, flocculants, scavengers (e.g., H2S scavengers, CO2 scavengers, or O2 scavengers), lubricants, breakers, friction reducers, crosslinkers, weighting agents, solubilizers, pH adjusters (e.g., buffers), hydrate inhibitors, caking agents, biocides, and the like, as well as any combination thereof. Suitable examples of these additives will be known to those skilled in the art. (Other products)

[0067] The composition of the present disclosure, which contains the reaction product of dextrin compounds, dextran, or any combination thereof, together with fatty acid or fatty acid ester, can be incorporated into a wide range of industrial or consumer products in which surfactants can be used. Considering the relatively harmless nature of the reaction products, emulsion compositions, and biomolecules present in the emulsified fluids disclosed herein, personal care products may represent a beneficial type of product in which the composition of the present disclosure can be present. Exemplary industrial and consumer products in which the above can be present are further presented below.

[0068] An adjuvant is a composition used in combination with an active agent to increase the effect or potency of the active agent. In non-limiting examples, the active agent may be a pharmaceutical compound, a personal care compound, or an agricultural compound.

[0069] The emulsion composition or emulsified fluid of the present disclosure may be present in an adjuvant composition, where various types of surfactants may be used. The foregoing may replace the surfactants used in the adjuvant composition, or may be used in combination with surfactants already present in the adjuvant composition. In the adjuvant composition, the emulsion composition or emulsified fluid may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total adjuvant composition.

[0070] The active compound may be present in the adjuvant composition, or the adjuvant composition may be applied separately from the active compound, in which case the adjuvant composition may be applied before or after the active compound.

[0071] Examples of suitable additional components that may be present in the adjuvant composition comprising the reaction product of the present disclosure include, but are not limited to, other surfactants, antifoam compounds, particulates, metal oxides (e.g., silica, alumina, titania, zirconia, etc.), electrolytes, salts, organic solvents, wetting agents, dispersants, emulsifiers, demulsifiers, penetrants, preservatives, colorants, acids, bases, buffers, chelating agents, viscosity enhancers, thixotropes, stabilizers, film formers, plasticizers, antioxidants, and the like, as well as any combination thereof. Other surfactants that may be present in the adjuvant composition are not particularly limited and may include any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0072] A foaming agent is a composition in which a large volume of gas is stably dispersed in the form of bubbles of various sizes in a relatively small volume of liquid, or a composition in which bubbles can be formed by the appropriate introduction of gas (foamable formulation).

[0073] The emulsion composition and emulsified fluid of the present disclosure may be present in the foaming agent, where various types of surfactants may be used. The aforementioned may replace the surfactants used in the foaming agent, or may be used in combination with surfactants already present in the foaming agent. In the foaming agent, the emulsion composition and emulsified fluid may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total foaming agent.

[0074] The foaming agent may comprise any combination of cationic surfactants, anionic surfactants, zwitterionic surfactants, or neutral surfactants. The emulsifying composition disclosed herein may be present in the foaming agent with any cationic surfactants, anionic surfactants, zwitterionic surfactants, neutral surfactants, or any combination of two or more of these surfactants. Alternatively, the emulsifying composition disclosed herein may replace all or part of any one or more of these surfactants in the foaming agent. The composition may, for example, replace or be used in combination with sulfosuccinate type surfactants in some foaming agent embodiments.

[0075] Examples of suitable additional ingredients that may be present in the foaming agent, including the reaction product of the present disclosure, include, but are not limited to, other surfactants, amines (any one or combination of primary amines, secondary amines, tertiary amines, diethanolamines, triethanolamines, ethoxylated amines, and amidoamines), foam boosters (e.g., amine oxides), solvents, water, salts, skin conditioners (e.g., ethylhexylglycerin, hydroxyethylurea, urea, panthenol, glycerin, isopropyl myristate, propylene glycol, tocopherol acetate, and polyquaternium-11), moisturizers, liquefied gases, supercritical gases, acids, bases, buffers, chelating agents, and the like, and any combination thereof. Suitable examples of these additional ingredients will be known to those skilled in the art. Other surfactants that may be present in the foaming agent are not particularly limited and may include any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0076] Hard surface cleaners are compositions that can be used to remove a variety of materials from surfaces such as glass, metal, plastic, stone, concrete, etc. Hard surfaces that can be cleaned with hard surface cleaners include, for example, windows, counters, appliances, floors, driveways, toilets, showers and bathtubs, sinks, etc. The materials that can be removed from these types of hard surfaces are wide-ranging and include, but are not limited to, dirt, grease, soap scum, limescale and similar hard water deposits.

[0077] The emulsion composition and emulsified fluid of the present disclosure may be present in hard surface cleaners where various types of surfactants may be used. The aforementioned may replace surfactants used in the hard surface cleaners or may be used in combination with surfactants already present in the hard surface cleaners. In the hard surface cleaners, the emulsion composition and emulsified fluid may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total hard surface cleaner.

[0078] Examples of suitable additional components that may be present in hard surface cleaners including the reaction products of the present disclosure include, but are not limited to, other surfactants, foaming compounds, antifoam compounds, salts (e.g., alkali metal carbonates), organic solvents (e.g., glycols or glycol ethers), wetting agents, dispersants, emulsifiers, demulsifiers, colorants, acids, bases, buffers, chelating agents, anti-streaking agents, alkanolamines, and the like, as well as any combination thereof. Other surfactants that may be present in the hard surface cleaners are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0079] Skin creams and lotions are compositions that may moisturize or improve the appearance of the skin. Skin creams and lotions include gels formulated for application to the skin, which may have a higher viscosity than creams or lotions.

[0080] The emulsion compositions and emulsified fluids of the present disclosure may be present in skin creams and lotions where surfactants may be used. The foregoing may replace surfactants used in the skin cream or lotion or may be used in combination with surfactants already present in the skin cream or lotion. In the skin cream or lotion, the emulsion compositions and emulsified fluids may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total skin cream or lotion.

[0081] Examples of suitable additional ingredients that may be present in the skin creams or lotions disclosed herein include, but are not limited to, other surfactants, emulsifiers, essential oils, waxes, fats, solvents, viscosity enhancers, monoalcohols, diols, polyols, diol ethers and polyol ethers, milk proteins, emollients, moisturizers, skin conditioners, preservatives, acids, bases, buffers, chelating agents, thickeners, vitamins, lubricants, wrinkle removers, moisturizers, radical inhibitors and other antioxidants, vitamin A, vitamin E, ceramides, fatty acids, fatty acid esters, fatty alcohols, hyaluronic acid, sodium pyroglutamic acid, glycerin, aloe vera, fragrances, colorants, sunscreens, and the like, and any combination thereof. Other surfactants that may be present in the skin creams and lotions are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants. The reaction product may replace at least a portion of one or more existing surfactants in the skin cream or lotion, or may supplement the amount of one or more existing surfactants in the skin cream or lotion.

[0082] Personal washes and shampoos are cleansing compositions formulated for application to the skin or hair. Liquid soaps for more generalized personal cleansing are similar in composition to some personal washes and shampoos and may be formulated using many of the same ingredients.

[0083] The emulsion composition and emulsified fluid of the present disclosure may be present in body washes, shampoos, and liquid soaps where surfactants may be used. The foregoing may replace surfactants used in body washes, shampoos, or liquid soaps, or may be used in combination with surfactants already present in the body washes, shampoos, or liquid soaps. In the body washes, shampoos, or liquid soaps, the emulsion composition and emulsified fluid may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total body wash, shampoo, or liquid soap.

[0084] Examples of suitable additional ingredients that may be present in the personal wash, shampoo, or liquid soap disclosed herein include, but are not limited to, other surfactants, conditioners, amidoamines, fragrances, colorants, essential oils, foaming agents, humectants, fatty acids, fatty acid esters, fatty alcohols, waxes, biocides, soaps, preservatives, acids, bases, buffers, chelating agents, thickeners, vitamins, pearling agents, viscosity enhancers, moisturizers, antioxidants, sunscreens, and the like, as well as any combination thereof. Illustrative personal washes, shampoos, and liquid soaps may contain water, an effective amount of the composition (optionally further combined with another surfactant), 0-4% pearling agent, 0-1% suspending aid, 0-2% fragrance, 0-0.25% chelating agent, 0-1% preservative, 0-2% colorant, and 0-25% conditioner. Other surfactants that may be present in personal washes, shampoos, and liquid soaps are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0085] Sunscreens are substances that can be applied to the skin to protect it from the sun. Sunscreens may be formulated as creams or in "stick" form with a suitable wax base for application to the skin.

[0086] The emulsion compositions and emulsified fluids of the present disclosure (e.g., dextrin (dextrin compound) or reaction product of dextran and fatty acid ester, as identified above, in combination with a neutral or zwitterionic surfactant) may be present in sunscreens where surfactants may be used. The foregoing may replace surfactants used in the sunscreen or may be used in combination with surfactants already present in the sunscreen. In the sunscreen, the emulsion compositions and emulsified fluids may be present in an amount of about 0.01% to about 20%, about 0.1% to about 10%, about 1% to about 15%, or about 5% to about 20% by weight of the total sunscreen.

[0087] Examples of suitable additional ingredients that may be present in the sunscreen include, but are not limited to, other surfactants, conditioners, titanium dioxide, zinc oxide, organic UV absorbers, film formers, solvents, aerosol propellants, waxes, fats, oils, moisturizers, fragrances, colorants, essential oils, fatty acids, fatty acid esters, fatty alcohols, preservatives, acids, bases, buffers, chelating agents, thickeners, insect repellents, skin conditioners, and the like, as well as any combination thereof. Other surfactants that may be present in the sunscreen are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0088] Organic UV absorbers that may be present in the sunscreen in combination with the composition include, but are not limited to, para-aminobenzoic acid, avobenzone, cinoxate, dioxybenzone, homosalate, menthyl anthranilate, octyl salicylate, oxybenzone, padimate O, phenylbenzimidazole sulfonic acid, sulisobenzone, trolamine salicylate, diethanolamine methoxycinnamate, digalloyl trioleate, diisobenzoxane ... trioleate), ethyl dihydroxypropyl PABA, glyceryl aminobenzoate, dihydroxyacetone containing lawsone, red petrolatum, ethylhexyl triazone, dioctyl butamide triazone, benzylidene malonate polysiloxane, terephthalidene dicamphor sulfonic acid, disodium phenyl dibenzimidazole tetrasulfonate, diethylamino hydroxybenzoyl hexyl benzoate, bis diethylamino hydroxybenzoyl benzoate, bis benzoxazolyl phenyl ethylhexyl imino triazine, drometrizole trisiloxane xanthane, methylene bisbenzotriazolyl tetramethylbutylphenol, and bisethylhexyloxyphenol methoxyphenyl triazine, 4-methylbenzylidene camphor, 4-methoxycinnamate isopentyl, phenylbenzimidazole sulfonate, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-(2-β-glucopyrano-siloxy)propoxy-2-hydroxybenzophenone, and bis-sodium phenylene-1,4-bis(2-benzimidazyl)-3,3'-5,5'-tetrasulfonate. phenylene-1,4-bis(2-benzimidazyl)-3,3′-5,5′-tetrasulfonate), 2-ethylhexyl p-methoxycinnamate, 4-tert-4′-methoxydibenzoylmethane, octocrylene, 2,4-bis-[{4-(2-ethylhexyloxy)-2-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine5-triazine), methylene bis-benzotriazolyl tetramethylbutylphenol, 2,4,6-tris-[4-(2-ethylhexyloxycarbonyl)anilino]-1,3,5-triazine, diethylamino hydroxybenzoyl hexyl benzoate, oxybenzone, and dihydroxydimethoxybenzophenone, and mixtures thereof.

[0089] Still other organic UV absorbers that may be suitable for inclusion in sunscreens include, but are not limited to, bis-resorcinyl triazines; benzimidazole derivatives; 4-methylbenzylidene camphor; benzoylpiperazine derivatives; benzoxazole derivatives; diarylbutadiene derivatives; phenylbenzotriazole derivatives; benzylidene malonate; TEA-salicylate; imidazoline derivatives; naphthalates; merocyanine derivatives; aminobenzophenone derivatives; dibenzoylmethane derivatives; β,β-diphenylacrylate derivatives; camphor derivatives; salicylate derivatives; anthranilate derivatives; and benzalmalonate derivatives.

[0090] In addition to formulations that are sunscreens alone, the emulsion compositions and emulsified fluids of the present disclosure may be present in sunscreens that are incorporated into other products (e.g., lotions, colognes, cosmetics, personal washes, shampoos, and the like).

[0091] Hair gels and hair sprays are preparations that can be used to hold hair in place or, if desired, to detangle hair. Hair sprays are in aerosolized form, while hair gels are thick fluids that can be applied by hand.

[0092] The emulsion compositions and emulsified fluids of the present disclosure may be present in hair sprays and hair gels where surfactants may be used. The foregoing may replace surfactants used in the hair spray or hair gel, or may be used in combination with surfactants already present in the hair spray or hair gel. In the hair spray or hair gel, the emulsion compositions and emulsified fluids may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total hair gel or hair spray.

[0093] Examples of suitable additional ingredients that may be present in hair sprays or hair gels include, but are not limited to, other surfactants, cellulosic biopolymers, water soluble polymers, polyalkylene glycols, polyalkylene glycol esters, conditioning agents, emollients, moisturizers, emulsifiers, opacifiers, thickening agents, foam stabilizers, viscosity enhancers, sequestering agents, antioxidants, antidandruff agents, suspending agents, proteins, fragrances, sunscreens, plant extracts, essential oils, fatty acids, fatty acid esters, fatty alcohols, preservatives, acids, bases, buffers, chelating agents, thickeners, vitamins, waxes, oils, aerosol propellants, polyvinylpyrrolidone, polyvinyl acetate, vinyl acetate-crotonic acid copolymers, acrylic acid copolymers, plasticizers, alcohols, and the like, and any combination thereof. Other surfactants that may be present in hair sprays and hair gels are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants.

[0094] One or more examples of hair sprays or hair gels may contain the emulsion composition or emulsified fluid of the present disclosure and one or more of cetearyl alcohol, behentrimonium chloride, cyclopentasiloxane, dimethicone, ethylhexyl isononanoate, behenyl alcohol, meadowfoam oil, cyclohexasiloxane, olive fruit oil, almond oil, stearamidopropyl dimethylamine, behentrimonium methosulfate, amodimethicone, panthenol, glycol stearate, ceteth-2, hydroxyethylcellulose, phenoxyethanol, methylparaben, propylparaben, citric acid, mica, titanium dioxide, iron oxide, fragrance, or any combination thereof.

[0095] One or more examples of hair sprays or hair gels may contain the emulsion composition or emulsified fluid of the present disclosure and one or more of cyclomethicone, jojoba esters, dimethicone copolyol, nonfat dry milk, soy protein, stearic acid, caprylic / capric / stearic triglyceride, jojoba oil, hybrid sunflower oil, cetearyl alcohol, glyceryl stearate, PEG-40 stearate, aloe vera gel, acrylates / C10-30 alkyl acrylates crosspolymer, propylene glycol, tocopherol acetate, methylparaben, propylparaben, fragrance, or any combination thereof.

[0096] Cosmetics are preparations that can be used to change or improve appearance. Examples of cosmetics include, but are not limited to, lipstick, blusher, mascara, foundation, eyeliner, etc. Forms of cosmetics can include, for example, emulsions, creams, gels, dispersions, sticks, etc. Suitable emulsions in cosmetics can include oil-in-water or water-in-oil emulsions.

[0097] The emulsion composition and emulsified fluid of the present disclosure may be present in various types of cosmetics where surfactants may be used. The foregoing may replace surfactants used in cosmetics or may be used in combination with surfactants already present in the cosmetics. In cosmetics, the emulsion composition and emulsified fluid may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total cosmetic.

[0098] Examples of suitable additional ingredients that may be present in the cosmetic include, but are not limited to, other surfactants, fragrances, preservatives, colorants, UV absorbers, moisture retaining agents, emulsifiers, gelling agents, oils, thickeners, foam stabilizers, viscosity enhancers, sequestering agents, antioxidants, suspending agents, proteins, fragrances, sunscreens, plant extracts, essential oils, fats (e.g., shea butter, mango seed butter, and cocoa butter), fatty acids, fatty acid esters, fatty alcohols, biocides, soaps, acids, bases, buffers, chelating agents, thickeners, vitamins, waxes (e.g., myristyl myristate, tea leaf extract, jojoba, sunflower seed, carnauba wax, candelilla wax, and beeswax), and the like, and any combination thereof. Some examples of ingredients that may be present in the cosmetic product may include, for example, fatty higher alcohols such as cetyl alcohol, stearyl alcohol, and behenyl alcohol; higher fatty acids, including caprylic / capric triglyceride, lauric acid, myristic acid, palmitic acid, and stearic acid; hydrocarbons, including ceresin; natural oils, including meadowfoam oil, sunflower seed oil, macadamia seed oil, green tea seed oil, ginger oil, ginseng oil, coconut oil, olive oil, and camellia oil; esters, including di(phytosteryl / octyldodecyl) lauroyl glutamate, isostearyl isostearate, methylheptyl isostearate, dicaprylyl carbonate, and isopropyl palmitate; ethers, including dicaprylyl ether; silicone oils, including dimethicone, cyclopentasiloxane, cyclohexasiloxane, phenyl trimethicone, trisiloxane, and methyl trimethicone; and hydrocarbons, including squalane. Other surfactants that may be present in the cosmetic product are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants. The cosmetic product of the present disclosure may be formulated in any suitable form, including sticks, creams, powders, gels, and the like.

[0099] Deodorants and antiperspirants are formulations that can be used to control body odor. The deodorants and antiperspirants of the present disclosure may be formulated in stick, gel, powder or aerosolizable forms.

[0100] The emulsion compositions and emulsified fluids of the present disclosure may be present in deodorants and antiperspirants where surfactants may be used. The foregoing may replace surfactants used in the deodorant or antiperspirant or may be used in combination with surfactants already present in the deodorant or antiperspirant. In the deodorant or antiperspirant, the emulsion compositions and emulsified fluids may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total deodorant or antiperspirant.

[0101] Examples of suitable additional ingredients that may be present in the deodorants or antiperspirants disclosed herein include, but are not limited to, other surfactants, aluminum salts (e.g., alum, aluminum chloride, aluminum chlorohydrate, aluminum-zirconium compounds, and aluminum-zirconium tetrachlorohydrex glycine), antimicrobials, parabens, alcohols, propylene glycol, hexamethylenetetramine, acids, bases, buffers, chelating agents, fragrances, preservatives, colorants, moisture absorbents (desiccant), emulsifiers, gelling agents, oils, thickeners, foam stabilizers, viscosity enhancers, sequestering agents, antioxidants, suspending agents, fragrances, essential oils, fats, fatty acids, fatty acid esters, fatty alcohols, waxes, and the like, and any combination thereof. Other surfactants that may be present in the deodorants and antiperspirants are not particularly limited and may be any one or combination of cationic, anionic, neutral, or zwitterionic surfactants. The deodorants and antiperspirants of the present disclosure may be formulated in any suitable form, including sticks, creams, powders, gels, and the like.

[0102] The emulsion compositions and emulsified fluids of the present disclosure may find exemplary uses and formulations outside the realm of personal care as well. In addition to the oil field applications described above, the emulsion compositions and emulsified fluids of the present disclosure may be incorporated into applications where metal sequestration from a fluid is required (e.g., during a froth flotation process). Froth flotation processes may be performed in a variety of cases, such as mining runoff treatment or water treatment. In such applications, the emulsion compositions of the present disclosure may replace surfactants used in froth flotation or may be used in combination with surfactants already present in the froth flotation process. In a given froth flotation process, the emulsion composition may be present in an amount of about 0.01% to about 20% by weight, about 0.1% to about 10% by weight, about 1% to about 15% by weight, or about 5% to about 20% by weight of the total froth flotation fluid.

[0103] In some examples, the emulsion compositions and emulsified fluids of the present disclosure may be utilized in rougher and cleaner circuits to aid in the dispersion of clays, water conditioning, additive enhancement, and / or emulsification of metal inhibitors (e.g., Mn and Fe). Any conventional foaming agent may be utilized in combination with the emulsion compositions and emulsified fluids disclosed herein. Details regarding suitable foaming agents and foaming agents will be well known to those skilled in the art.

[0104] Embodiments disclosed herein include:

[0105] A. Emulsified Fluid. The emulsified fluid: comprises an oily material emulsified with an emulsifying composition, which comprises: an aqueous fluid; a neutral surfactant or a reaction product form thereof; a reaction product of a saccharide polymer and a fatty acid or fatty acid ester, the saccharide polymer comprising a dextran, a dextrin compound or any combination thereof, the reaction product of the saccharide polymer and the fatty acid or fatty acid ester, and the reaction product form of the neutral surfactant, if present, formed in the presence of a hydroxide base in the aqueous fluid; and a zwitterionic surfactant.

[0106] A1. Underground treatment fluid containing emulsified fluid of A.

[0107] A2. A personal care product containing an emulsified fluid of A.

[0108] B. A method of forming an oil-in-water emulsion, the method comprising the steps of: providing a zwitterionic surfactant, providing an aqueous surfactant composition containing the reaction product of a saccharide polymer and a fatty acid or fatty acid ester in an aqueous fluid, the aqueous surfactant composition also containing a neutral surfactant or its reaction product form, combining the zwitterionic surfactant with the aqueous surfactant composition to form an emulsified composition, and contacting the emulsified composition with an oily material to form an oil-in-water emulsion.

[0109] Embodiments A, A1, A2, and B may include one or more of the following further embodiments in any combination.

[0110] Element 1: The emulsion composition further contains glycerol.

[0111] Element 2: The reaction product is formed from fatty acid esters, and at least a portion of the glycerol is derived from the fatty acid esters.

[0112] Element 3: The fatty acid ester comprises a glycerol ester containing up to three fatty acids having from about 4 to about 30 carbon atoms.

[0113] Element 4: The reaction product of a saccharide polymer and a fatty acid or fatty acid ester is present in the emulsifying composition in a concentration effective to reduce the surface tension of the neutral surfactant.

[0114] Element 5: A neutral surfactant or reaction product form thereof is present in the emulsion composition in a concentration sufficient to solubilize the reaction product of the saccharide polymer and the fatty acid or fatty acid ester in the aqueous fluid.

[0115] Element 6: The oily material and the emulsifying composition together define an oil-in-water emulsion.

[0116] Element 7: The zwitterionic surfactant is present in the emulsifying composition at a concentration sufficient to promote the formation of an oil-in-water emulsion.

[0117] Element 8: The saccharide polymer comprises a dextrin compound, and the dextrin compound comprises maltodextrin.

[0118] Element 9: The maltodextrin has a dextrose equivalent value of about 3 to about 25.

[0119] Element 10: The molar ratio of fatty acid to saccharide polymer in the reaction product is 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー is about 0.2 or more based on

[0120] Element 11: The saccharide polymer reaction product comprises a fatty acid ester saccharide polymer reaction product.

[0121] Element 12: The neutral surfactant contains a fatty acid alkanolamide.

[0122] Element 13: The fatty acid alkanolamide contains a compound selected from the group consisting of cocamide diethanolamine, cocamide monoethanolamine, cocamide diisopropanolamine, palmitamide diethanolamine, palmitamide monoethanolamine, palmitamide diisopropanolamine, and any combination thereof.

[0123] Element 14A: The oil-in-water emulsion is stable for at least about 1 day.

[0124] Element 14B: The emulsified fluid is stable for at least about one day.

[0125] As non-limiting examples, exemplary combinations applicable to A, A1, A2, and B include: 1, 2, and / or 3, and 4; 1, 2, and / or 3, and 5; 1, 2, and / or 3, and 6; 1, 2, and / or 3, and 7; 1, 2, and / or 3, and 8; 1, 2, and / or 3, and 8 and 9; 1, 2, and / or 3, and 10; 1, 2, and / or 3, and 11; 1, 2, and / or 3, and 12; 1, 2, and / or 3, and 12 and 13; 4 and 5; 4-6; 4 and 6; 4 and 7; 4, 5, and 7; 4 and 8; 4, 8, and 9; 4 and 1 Examples of suitable nucleotide sequences include, but are not limited to, 0;4 and 11;4 and 12;4, 12, and 13;5 and 6;5 and 7;5-7;5 and 8;5, 8, and 9;5 and 10;5 and 11;5 and 12;5, 12, and 13;6 and 7;6 and 8;6, 8, and 9;6 and 10;6 and 11;6 and 12;6, 12, and 13;7 and 8;7-9;7 and 10;7 and 11;7 and 12;7, 12, and 13;8 and 9;8 and 10;8 and 11;8 and 12;8, 12, and 13;10 and 11;10 and 12;10, 12, and 13;11 and 12;11-13; and 12 and 13. Any of 1-13 may be further combined with 14A or 14B, or 14A or 14B may be further combined with any of the aforementioned combinations.

[0126] Further embodiments disclosed herein include:

[0127] A'. Emulsified Fluid. The emulsified fluid comprises: an oily material emulsified with an emulsifying composition, which comprises: an aqueous fluid; a neutral surfactant or a reaction product form thereof; a reaction product of a saccharide polymer and a fatty acid or fatty acid ester, the saccharide polymer comprising a dextran, a dextrin compound or any combination thereof, the reaction product of the saccharide polymer and the fatty acid or fatty acid ester and the reaction product form of the neutral surfactant, if present, formed in the presence of a hydroxide base in the aqueous fluid; and a zwitterionic surfactant.

[0128] B': An emulsion composition. The emulsion composition comprises: an aqueous fluid; a neutral surfactant or a reaction product form thereof; a reaction product of a saccharide polymer and a fatty acid or fatty acid ester, where the saccharide polymer comprises a dextran, a dextrin compound, or any combination thereof, and where the reaction product of the saccharide polymer and the fatty acid or fatty acid ester and the reaction product form of the neutral surfactant, if present, is formed in the presence of a hydroxide base in the aqueous fluid; and a zwitterionic surfactant; where the zwitterionic surfactant is present in an amount, measured by weight, that is greater than the amount of the reaction product of the saccharide polymer.

[0129] A method for emulsifying an aqueous fluid, the method comprising: providing an emulsion composition, the emulsion composition comprising: an aqueous fluid; a neutral surfactant or a reaction product form thereof; a reaction product of a saccharide polymer and a fatty acid or fatty acid ester, the saccharide polymer comprising a dextran, a dextrin compound, or any combination thereof, the reaction product of the saccharide polymer and the fatty acid or fatty acid ester, and the reaction product form of the neutral surfactant, if present, formed in the presence of a hydroxide base in the aqueous fluid; and a zwitterionic surfactant; and contacting the emulsion composition with an oily material to form an emulsion.

[0130] A1': A personal care product containing the emulsified fluid of A' or the emulsified composition of B'.

[0131] A2': An underground treatment fluid containing the emulsified fluid of A' or the emulsified composition of B'.

[0132] Embodiments A', A1', A2', B', and C' may include one or more of the following further embodiments in any combination.

[0133] Element 1': The emulsion composition further contains glycerol.

[0134] Element 2': The reaction product of the saccharide polymer is formed from fatty acid esters, and at least a portion of the glycerol is derived from the fatty acid esters.

[0135] Element 3': The fatty acid ester comprises a glycerol ester containing up to three fatty acids having from about 4 to about 30 carbon atoms.

[0136] Element 4': The oily substance and the emulsifying composition together define an oil-in-water emulsion.

[0137] Element 5': The zwitterionic surfactant is present in an amount, measured on a weight basis, that is greater than the amount of the reaction product of the saccharide polymer.

[0138] Element 6': The zwitterionic surfactant is present in an amount, measured on a weight basis, of about 2:1 or greater relative to the reaction product of the saccharide polymer.

[0139] Element 7': The zwitterionic surfactant is present in an amount, measured on a weight basis, of about 4:1 or greater relative to the reaction product of the saccharide polymer.

[0140] Element 8': The saccharide polymer comprises a dextrin compound, and the dextrin compound comprises maltodextrin.

[0141] Element 9': The molar ratio of fatty acid to saccharide polymer in the reaction product of the saccharide polymer is 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー is about 0.2 or more based on

[0142] Element 10': The molar ratio of fatty acid to saccharide polymer in the reaction product of the saccharide polymer is 脂肪酸もしくは脂肪酸エステル中の脂肪酸 : Mole サッカライドポリマー中のグルコースモノマー Based on this, the range is about 0.2 to about 0.9.

[0143] Element 11': The saccharide polymer reaction product comprises a fatty acid ester saccharide polymer reaction product.

[0144] Element 12': The neutral surfactant contains a fatty acid alkanolamide.

[0145] Element 13': The emulsified fluid is stable for at least about one day.

[0146] As non-limiting examples, exemplary combinations applicable to A', A1', A2', B', and C' include, but are not limited to: 1' and 5'; 1', and 6' or 7'; 1' and 8'; 1', and 9' or 10'; 1' and 12'; 1' and 13'; 4' and 5'; 4', and 6' or 7'; 4' and 8'; 4', and 9' or 10'; 4' and 12'; 4' and 13'; 5', 6', or 7', and 8; 5', 6', or 7', and 9' or 10'; 5', 6', or 7', and 12'; 8', and 9' or 10'; 8' and 11'; 8' and 12'; 8' and 13'; and 9' or 10', and 12.

[0147] In order to facilitate a further understanding of the disclosure herein, examples of various representative embodiments are set forth below, which should not be construed as limiting or defining the scope of the invention. (Example)

[0148] Example 1: Representative procedure for preparation of maltodextrin reaction products with glycerol esters. 25.00 g of fatty acid alkanolamide surfactant and 10.00 g of KOH (45% active solution) were mixed in water. The reaction mixture was mechanically stirred and heated to 65°C. Soybean oil and 150.0 g of maltodextrin (MALTRIN M100, Grain Processing Corporation, Muscatine, Iowa; DE=9.0-12.0) as a 30% active solution were then added to the reaction mixture. The amount of soybean oil was selected to give a reaction product with an HLB of 12 or 16 upon formation. The amount of water was selected to give a concentration of 5 wt% alkanolamide surfactant, 2.5 wt% fatty acid ester (oil), and 10 wt% maltodextrin based on the total reactants. Once the maltodextrin was dissolved, heating was discontinued and the reaction mixture was stirred until it reached room temperature. The resulting aqueous phase containing the reaction product was used without further treatment in further studies described below. Dextran reaction products may also be formed using similar procedures. Other fatty acid ester and alkanolamide surfactants may be used as well.

[0149] Example 2: Representative procedure for preparation of maltodextrin reaction product with free fatty acids. 25.00 g of fatty acid alkanolamide surfactant and 10.00 g of KOH (45% active solution) were mixed in water. The reaction mixture was mechanically stirred and heated to 65°C. A fatty acid mixture containing saturated fatty acids with lauric and myristic acids as the main components and 150.0 g of maltodextrin (MALTRIN M100, Grain Processing Corporation, Muscatine, Iowa; DE=9.0-12.0) as a 30% active solution was then added to the reaction mixture. The amount of fatty acid mixture was selected to give an HLB of 12 or 16. The amount of water was selected to give an alkanolamide surfactant concentration of 5 wt%, fatty acid concentration of 2.5 wt%, and maltodextrin concentration of 10 wt%, based on the total reactants. Once the maltodextrin was dissolved, heating was discontinued and the reaction mixture was stirred until it reached room temperature. The resulting aqueous phase containing the reaction product was used without further treatment in further studies described below. Dextran reaction products may also be formed using similar procedures. Other fatty acid ester and alkanolamide surfactants may be used as well.

[0150] Preparation of Emulsion Compositions. The reaction products prepared as above were either tested for emulsification performance as is or further mixed with zwitterionic surfactant to form emulsion compositions. Samples were diluted with 4% KCl or water after the addition of zwitterionic surfactant. Emulsion performance was determined by mixing the reaction products or emulsion compositions formed therefrom and then shaking with a given amount of oily substance. After emulsifying the oily substance, the stability of the emulsion was monitored over time, usually for at least overnight, but often over several days or weeks. For emulsions that remained stable over the observation period, a few drops of the emulsion were added to water or the oily substance itself to examine the emulsion properties. Oil-in-water emulsions remained dispersed when added to water and did not undergo phase separation, but phase separation occurred when these types of emulsions were added to oily substances. Table 1 below summarizes the samples tested and the results obtained.

[0151] [Table 1]

[0152] a Cocamidopropyl Hydroxysultaine, 50% Active Solution, Glycerin Free (Southern Chemical) b Cocamidopropyl Hydroxysultaine, 50% active solution (Southern Chemical) c Cocamidopropyl Betaine, 35-40% active solution (Southern Chemical) d Cocamidopropyl Hydroxysultaine, 50% active solution (Southern Chemical)

[0153] The 120K brine had the following composition (each component in g / L): CaCl2 (16.540), NaCl (103.730), MgCl2 (4.230), NaHCO3 (0.830), BaCl2 (0.180), Na2SO4 (0.740), SrCl2 (0.180), and FeCl3 (0.030).

[0154] The Brookfield viscosity of selected soybean oil emulsions was measured at room temperature (25°C). Soybean oil itself exhibited a Brookfield viscosity of 15 cP (63 spindle, 20 rpm). Unstable emulsions that separated within a few hours tended to exhibit Brookfield viscosity values ​​in the range of about 20-100 cP. In contrast, stable emulsions exhibited Brookfield viscosity values ​​in the range of 3000-6000 cP.

[0155] In addition to the aforementioned tests, three anionic surfactants, three neutral surfactants, and one cationic surfactant were tested for their emulsification performance with soybean oil in water and 120K brine. The following compositions were tested: a) 1% by volume surfactant, 1% by volume reaction product of Example 2, 18% by volume 120K brine, and 80% by volume soybean oil, and b) 0.5% by volume surfactant, 0.5% by volume reaction product of Example 2, 19% by volume deionized water, and 80% by volume soybean oil. None of the alternative surfactants produced stable emulsions in 120K brine, and only the cationic surfactant showed evidence of successful emulsification in deionized water.

[0156] Unless otherwise indicated, all numerical values ​​expressing quantities and the like in the specification and the associated claims should be understood to be 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 embodiments of the 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.

[0157] One or more exemplary embodiments incorporating various features are presented herein. For clarity, not all features of a physical implementation are described or shown in this application. It is understood that in developing a physical embodiment incorporating an embodiment of the present invention, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government-related, and other constraints that vary from implementation to implementation and from time to time. Although the developer's efforts may be time-consuming, such efforts would be routine for one of ordinary skill in the art and having the benefit of this disclosure.

[0158] Although various systems, compositions, means, and methods are described herein in terms of "containing" various components or steps, the systems, compositions, means, and methods can also "consist essentially of" or "consist of" the various components and steps.

[0159] As used herein, the phrase "at least one of" preceding a series of items, along with the terms "and" or "or" separating any items, modifies the list as a whole and not each member (i.e., each item) of the list. The phrase "at least one of" allows for a meaning including at least one of any of the items, and / or at least one of any combination of the items, and / or at least one of each of the items. By way of example, the phrase "at least one of A, B, and C" or "at least one of A, B, or C" refers, respectively, to A only, B only, or C only; any combination of A, B, and C; and / or at least one of each of A, B, and C.

[0160] Thus, the disclosed systems, compositions, means, and methods are well adapted to achieve the objects and advantages mentioned, as well as those inherent therein. The specific embodiments disclosed above are illustrative only, as the teachings of the disclosure may be modified and implemented in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Moreover, no limitations are intended to the details of construction or design shown herein, other than as set forth in the following claims. It is therefore apparent that the specific exemplary embodiments disclosed above may be altered, combined, or modified, and all such variations are deemed to be within the scope of the present disclosure. The systems, compositions, means, and methods illustratively disclosed herein may be suitably practiced in the absence of any element not specifically disclosed herein and / or any appropriate element disclosed herein. Although the systems, compositions, means, and methods are described in terms that "contain," "include," or "comprise" various components or steps, the systems, means, and methods may also "consist essentially of" or "consist of" the various components and steps. All of the values ​​and ranges disclosed above may vary to some extent. Whenever a numerical range with a lower limit and an upper limit is disclosed, any numerical value contained within that range and any contained range is specifically disclosed. In particular, all ranges of values ​​disclosed herein (in the form of "about a to about b", or equivalently "about a to b", or equivalently "about a to b") should be understood to represent all numerical values ​​and ranges encompassed within the broader range of values. Also, the terms in the claims have their obvious ordinary meanings unless expressly and unambiguously defined by the patent owner. Moreover, the indefinite article "a" or "an" used in the claims is defined herein to mean one or more than one of the elements it introduces. In the event of any discrepancy in the use of a word or term in this specification and in one or more patents or other documents that may be incorporated herein by reference, the definition consistent with this specification should be adopted.

Claims

1. The emulsion composition comprises an oily substance emulsified in an emulsion composition, the emulsion composition comprising: aqueous fluid; Neutral surfactants or reaction product forms thereof; a reaction product of a saccharide polymer and a fatty acid or a fatty acid ester, wherein the saccharide polymer comprises a dextran, a dextrin compound, or any combination thereof, and wherein the reaction product of the saccharide polymer and the fatty acid or the fatty acid ester, and the reaction product form of the neutral surfactant, if present, is formed in the presence of a hydroxide base in the aqueous fluid; and Zwitterionic surfactants; containing Emulsified fluid.

2. The emulsified fluid of claim 1 , wherein the emulsion composition further comprises glycerol.

3. 3. The emulsified fluid of claim 2, wherein the reaction product of the saccharide polymer is formed from a fatty acid ester and at least a portion of the glycerol is derived from the fatty acid ester.

4. 10. The emulsified fluid of claim 1, wherein the oily substance and the emulsifying composition collectively define an oil-in-water emulsion.

5. 10. The emulsified fluid of claim 1, wherein the zwitterionic surfactant is present in an amount, measured by weight, that is greater than the amount of the reaction product of the saccharide polymer.

6. 6. The emulsified fluid of claim 5, wherein the zwitterionic surfactant is present in an amount of about 2:1 or greater relative to the reaction product of the saccharide polymer, measured by weight.

7. 2. The emulsified fluid of claim 1, wherein the saccharide polymer comprises a dextrin compound, and the dextrin compound comprises maltodextrin.

8. 10. The emulsified fluid of claim 1, wherein the reaction product of the saccharide polymer comprises a fatty acid ester saccharide polymer reaction product.

9. The emulsified fluid of claim 1 , wherein the neutral surfactant comprises a fatty acid alkanolamide.

10. A subsurface treatment fluid or personal care product containing the emulsified fluid of claim 1.

11. aqueous fluid; Neutral surfactants or reaction product forms thereof; a reaction product of a saccharide polymer and a fatty acid or a fatty acid ester, wherein the saccharide polymer comprises a dextran, a dextrin compound, or any combination thereof, and the reaction product of the saccharide polymer and the fatty acid or the fatty acid ester, and the reaction product form of the neutral surfactant, if present, is formed in the aqueous fluid in the presence of a hydroxide base; and Zwitterionic surfactants; Contains the zwitterionic surfactant is present in an amount, measured by weight, that is greater than the amount of the reaction product of the saccharide polymer; Emulsifying composition.

12. 12. The emulsion composition of claim 11, wherein the zwitterionic surfactant is present in an amount of about 2:1 or greater relative to the reaction product of the saccharide polymer, measured by weight.

13. The emulsion composition according to claim 11, further comprising glycerol.

14. 14. The emulsion composition of claim 13, wherein the reaction product of the saccharide polymer is formed from a fatty acid ester and at least a portion of the glycerol is derived from the fatty acid ester.

15. 12. The emulsion composition of claim 11, wherein the saccharide polymer comprises a dextrin compound, and the dextrin compound comprises maltodextrin.

16. The emulsion composition according to claim 11, wherein the neutral surfactant comprises a fatty acid alkanolamide.

17. A subsurface treatment fluid or personal care product containing the emulsified composition of claim 11.

18. Providing an emulsion composition, said emulsion composition comprising: aqueous fluid; Neutral surfactants or reaction product forms thereof; a reaction product of a saccharide polymer and a fatty acid or a fatty acid ester, wherein the saccharide polymer contains a dextran, a dextrin compound, or any combination thereof, and the reaction product of the saccharide polymer and the fatty acid or the fatty acid ester, and the reaction product form of the neutral surfactant, if present, is formed in the presence of a hydroxide base in the aqueous fluid; and Zwitterionic surfactants; providing an emulsion composition comprising: and, contacting the emulsified composition with an oily substance to form an emulsion; A method comprising:

19. 20. The method of claim 18, wherein the oily substance and the emulsifying composition collectively define an oil-in-water emulsion.

20. 20. The method of claim 18, wherein the emulsion composition further comprises glycerol.

21. 21. The method of claim 20, wherein the reaction product of the saccharide polymer is formed from a fatty acid ester and at least a portion of the glycerol is derived from the fatty acid ester.

22. 20. The method of claim 18, wherein the saccharide polymer comprises a dextrin compound, and the dextrin compound comprises maltodextrin.

23. 20. The method of claim 18, wherein the neutral surfactant comprises a fatty acid alkanolamide.

24. 20. The method of claim 18, wherein the zwitterionic surfactant is present in an amount, measured by weight, that is greater than the amount of the reaction product of the saccharide polymer.

25. 25. The method of claim 24, wherein the zwitterionic surfactant is present in an amount of about 2:1 or greater relative to the reaction product of the saccharide polymer, measured by weight.

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