Alkoxylated (hydroxyalkyl)aminophenol polymer and method of use

Abstract

Polymers formed by the condensation of bis(hydroxycarbyl)-aminophenol compounds with aldehydes are disclosed. The condensation polymers include one or more repeating units having a bis(hydroxycarbyl)amino functional group. The hydroxyl group of the bis(hydroxycarbyl)amino functional group is available for further condensation with an epoxide, such as ethylene oxide, to yield a polyalkoxylated polymer. The polymers are useful as polymerization inhibitors, polymerization retarders, surfactants, or combinations thereof in one or more industrial systems.

Description

[Technical Field]

[0001] The present invention generally relates to polymer compositions based on the condensation of phenol compounds and aldehydes, and alkoxylated adducts thereof. [Background technology]

[0002] Polymer compounds are used throughout industry to assist people in achieving important manufacturing and processing objectives. Benefits in industrial processes, such as corrosion inhibition, biofilm formation inhibition, microbial growth inhibition, rheological modification, emulsification, demulsification, tackification, plasticization, defoaming, flocculation, and coagulation, are achieved by implementers using various polymer compounds. Therefore, polymer surfactants, emulsifiers, biofilm inhibitors, biocides, rheological modifiers, anticorrosive agents, emulsion disruptors, fuel dehazing agents, asphaltene dispersants, defoaming additives, flocculants / coagulants, etc., are commonly available in industry to enhance one or more industrial processes or to help achieve one or more industrial manufacturing, processing, transportation, or storage objectives.

[0003] An industrially important class of polymers is the phenol-aldehyde polymer, which includes prepolymers and cured resins (collectively, "phenol polymers" or "phenol resins"). Phenols are synthesized by condensing phenol monomers, such as phenol, resorcinol, bisphenol A, alkylphenols, and / or mixtures thereof, with aldehydes such as formaldehyde. The industrially useful form of phenol is the phenol prepolymer. Phenol prepolymers are commercially available as aqueous dispersions containing the partial reaction products of one or more phenol monomers and formaldehyde. In such forms, the prepolymer is relatively stable in aqueous dispersions. Since formaldehyde is mainly present in solution as a dynamic equilibrium of methylene glycol oligomers, the concentration of any reactive form of "free" formaldehyde present in the prepolymer formulation depends on temperature and pH. Commercially available phenolic prepolymers include Novalac and Resol.

[0004] Novalac is a phenol prepolymer dispersion with a formaldehyde-to-phenol monomer molar ratio of less than 1. Curing is achieved using heat, along with the addition of an aldehyde or formaldehyde donor (such as hexamethylenetetramine) in some embodiments, using an acid or base catalyst. Examples of suitable Novalac curing catalysts include oxalic acid, hydrochloric acid, and sulfonic acid. The prepolymer units are primarily linked by methylene and / or ether groups via methylation of phenol monomers with formaldehyde in a reactive form. Resol is a phenol prepolymer dispersion having a formaldehyde-to-phenol monomer ratio greater than 1 (e.g., about 1.5). Resol is cured after drying using heat and a base catalyst.

[0005] To form a phenol prepolymer dispersion, phenol monomers, aldehydes, water, and a catalyst are mixed in desired amounts and heated, for example, to about 50°C to 100°C or about 60°C to 80°C to form a prepolymerized dispersion. In embodiments, the prepolymer is crosslinked by heating to about 120°C, forming methylene and dibenzyl ether crosslinks through the exclusion of both the dispersed water and the water formed by the polycondensation reaction. As a result, a stable three-dimensional cured network is obtained. The final crosslinking step yields a phenol resin with industrially recognized characteristics such as excellent hardness, thermal stability, and chemical impermeability.

[0006] Alkylphenol-based phenols, or "alkylphenols," are structurally similar to phenols formed from phenols and / or resorcinols, and are synthesized using any of the aforementioned processes in which alkylphenols are used instead of, or in combination with, phenols, resorcinols, etc. The alkylphenol monomers used to synthesize alkylphenols are typically 4-alkylphenols, such as 4-nonylphenol, where the nonyl moiety is linear or branched. Alkylphenol prepolymers and resins have improved solubility in hydrocarbon solvents compared to their non-alkylated counterparts. Industrially, alkylphenols are used to construct green tack and impart adhesive strength to rubber adhesives, are useful as modifiers for rubber materials such as butyl rubber and chloroprene rubber, and impart improved oil resistance, heat resistance, chemical resistance, and weather resistance to rubber products such as belts, treads, hoses, and vehicle tires.

[0007] The alkylphenol monomer used in the majority of industrial alkylphenols is nonylphenol, which is often more accurately described as highly branched C9 4-alkylphenol. Nonylphenol-formaldehyde condensation polymers offer a preferred solubility profile and cost-effective combination for industrial use. The cost-effectiveness of nonylphenol monomers is due to the historically widespread industrial adoption of ethoxylated phenol surfactants, which are highly effective nonionic surfactants. However, nonylphenol and other alkylphenols are restricted in many countries due to the degradation products of their ethoxylated adducts in the environment. Nonylphenol is now recognized as an endocrine disruptor and heteroestrogen in humans and aquatic animals. Therefore, nonylphenol ethoxylates are being replaced in many international markets by other surfactants, such as alkanol ethoxylates. Similarly, there is a need in industry to replace alkylphenols, as it is generally desirable to eliminate the use of alkylphenols, especially nonylphenol. [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] The development of environmentally friendly monomers that can be usefully used to form polymers with novel and desirable properties remains a continuing need in the industry. Furthermore, there is a need in the industry to provide alternatives to alkylphenols, including both prepolymers and resins. [Means for solving the problem]

[0009] Polyalkoxylated polymers and compositions containing them are described herein. The polyalkoxylated polymers are polyalkoxylated (hydroxyalkyl)aminophenol polymers comprising polyalkoxylated repeating units having the following structure: [ka] In the formula, R

[0010] and R 2 are -(CR 7 R 8 ) n (CHOR 9 )(CH2) p (O) q R 10 wherein R 3 is [R 11 O] x H, R 4 and R 5 are independently H, C1 - C 22 alkyl, or -[R 11 O] x H, R 6 is H, alkyl, aryl, benzyl, or aralkyl optionally substituted with an alkyl group, an alkoxy group, or a hydroxyl group, R 7 and R 8 are independently H or alkyl, R 9 is H or -[R 11 O] x H, R 10 is a C1 - C 24 linear, branched, or cyclic alkyl, aryl, or aralkyl, each R 11 is independently -CH2 - CH2 -, -CH(CH3)-CH2 -, -CH2 - CH2 - CH2 -, -CH2 - CH2 - CH2 - CH2 -, or -CH(C6H6)-CH2 -, n is an integer from 1 to 12, p is 0 or an integer from 1 to 12, q is 0 or 1, each x is independently an integer from 2 to 1000.

[0010] In an embodiment, R 4 and R<sh 5 are H. In an embodiment, R 7 and R 8is H. In the embodiment, n, p, and q are 1. In the embodiment, R 10 is selected from n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-hexyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, or 2-ethylhexyl. In embodiments, R 6 H is H.

[0011] In the embodiment, at least one R 11 is -CH2-CH2-. In the embodiment, at least one R 11 This is -CH(CH3)-CH2-. In the embodiment, each R 11 is -CH2-CH2-. In the embodiment, each R 11 This is -CH(CH3)-CH2-. In the embodiment, -[R 11 O] x H is characterized by an alkylene oxide functional group. In some embodiments, -[R 11 O] x H is characterized by a copolymer alkylene oxide functional group. In some embodiments of the copolymer alkylene oxide functional group, each R 11 is either -CH2-CH2- or -CH(CH3)-CH2-. In some embodiments, the copolymer alkylene oxide functional group is a block copolymer alkylene oxide functional group. In embodiments, each x is between 2 and 100.

[0012] In the embodiment, the polyalkoxylated polymer is a crosslinked polyalkoxylated polymer network having 1 to 1,000 total polyalkoxylated repeating units having one or more of the structures described above, or having at least one, in the embodiment, more than 1,000 total polyalkoxylated repeating units.

[0013] In embodiments, a method for decomposing an emulsion in an industrial process stream includes adding one or more polyalkoxylated polymers to an industrial process stream containing, essentially having, or consisting of an emulsion to form a treated process stream. Industrial process streams suitably treated by the addition of one or more polyalkoxylated HCAP resins include emulsions of crude oil and wash water formed during crude oil refining, and manufacturing process streams formed during the synthesis, refining, and / or transport of ethylenically unsaturated or "vinyl" compounds such as butadiene, styrene, and acrylic acid. In embodiments, one or more polyalkoxylated polymers are added to or present in the treated industrial process stream in concentrations of 0.1 ppm to 10,000 ppm.

[0014] Other subjects and characteristics are, in part, self-evident, and some are shown below. [Modes for carrying out the invention]

[0015] This disclosure provides references to preferred embodiments, but those skilled in the art will recognize that modifications may be made in form and detail without departing from the spirit and scope of the invention. Various embodiments are described in detail with reference to the drawings, where similar reference numerals in some figures represent similar parts and assemblies. References to various embodiments do not limit the scope of the claims appended herein. Furthermore, no examples described herein are intended to be limiting, but merely to describe some of the many possible embodiments of the claims appended herein.

[0016] definition

[0017] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art. In case of any conflict, the definitions in this document shall prevail. Methods and materials similar to or equivalent to those described herein may be used in carrying out or testing the present invention, but preferred methods and materials are described below. All publications, patent applications, patents, and other references referred to herein are incorporated in their entirety by reference. The materials, methods, and examples disclosed herein are illustrative and not intended to limit the scope of this invention.

[0018] As used herein, the terms “comprise,” “include,” “having,” “has,” “can,” and “contain,” and their variations, are intended to be unrestricted transitional phrases, terms, or words that do not preclude the possibility of additional actions or structures. The singular forms “a,” “and,” and “the” include multiple referents unless the context clearly indicates otherwise. This disclosure also contemplates other embodiments that “comprising,” “consisting of,” and “consisting essentially of” the embodiments or elements presented herein, whether expressly described or not.

[0019] As used herein, the terms “optional” or “optional” mean that the events or circumstances described thereafter may occur but are not required, and that such descriptions include both cases in which the events or circumstances occur and cases in which they do not occur.

[0020] Where used herein, the term “about” modifies the amount, concentration, volume, process temperature, process time, yield, flow rate, pressure, and similar values, as well as ranges, of components in a composition, for example, when describing embodiments of this disclosure, refers to variations in numerical quantities that may arise, for example, from typical measurement and handling procedures used to produce a compound, composition, concentrate, or formulation; from accidental errors in these procedures; from differences in the manufacture, source, or purity of the starting materials or components used to carry out the method; and from similar approximation considerations. The term “about” also includes different quantities due to the degradation of a formulation having a particular initial concentration or mixture, and different quantities due to mixing or processing a formulation having a particular initial concentration or mixture. Where modified by the term “about,” the claims appended herein include these quantities and their equivalents. Furthermore, where “about” is used to describe a range of values, unless specifically limited by context, for example, “about 1 to 5” means “1 to 5,” “about 1 to about 5,” “1 to about 5,” and “about 1 to 5.”

[0021] As used herein, the term “substantially” means “essentially from” as the term is interpreted in U.S. Patent Law, and includes “consisting of” as the term is interpreted in U.S. Patent Law. For example, a solution that “substantially” does not contain a particular compound or material may not contain that compound or material, or may contain small amounts of that compound or material present due to unintended contamination, side reactions, or incomplete purification, etc. “Small amounts” may be trace amounts, immeasurable amounts, amounts that do not impair value or property, or any other amounts as provided in the context. A composition that “substantially” has the provided list of components may consist only of those components, or may have trace amounts of any other components present, or may have one or more additive components that do not materially affect the properties of the composition. In addition, as used, for example, in describing embodiments of this disclosure, “substantially” modifies the type or amount, characteristics, measurable quantity, method, value, or range of a component in a composition, meaning a variation that does not affect the enumerated composition, characteristics, quantity, method, value, or range in an overall manner, but in a manner that negates the intended composition, characteristics, quantity, method, value, or range. Where modified by the term “substantially,” the claims appended herein include the equivalents as defined herein.

[0022] When used herein, any enumerated range of values ​​should be interpreted as supporting claims that enumerate any subrange having an endpoint that is a real number within the enumerated range, assuming all values ​​within the range. As a hypothetical example, the disclosure herein relating to the range 1–5 shall be deemed to support claims for any of the following ranges: 1–5, 1–4, 1–3, 1–2, 2–5, 2–4, 2–3, 3–5, 3–4, and 4–5.

[0023] Consideration

[0024] Disclosed herein is a polyalkoxylated bis(hydroxycarbyl)aminophenol polymer, which is a polymer compound comprising one or more repeating units containing a condensation product of a bis(hydroxycarbyl)aminophenol polymer (HCAP) resin and an aldehyde, wherein each HCAP repeating unit is polyalkoxylated to contain one or more polyalkylene oxide functional groups.

[0025] The polyalkoxylated HCAP resin contains at least one polyalkoxylated HCAP repeating unit according to the following formula. [ka] In the formula, R 1 and R 2 However, -(CR 7 R 8 ) n (CHOR 9 )(CH2) p (O) q R 10 And, R 3 However, [R 11 O] x H is, R 4 and R 5 However, independently, H, C1~C 22 Alkyl, -[R 11 O] x H, or NR1R2, R 6 However, H, alkyl, aryl, benzyl, or aralkyl is optionally substituted with an alkyl group, alkoxy group, or hydroxyl group. R 7 and R 8 However, independently, it is H or alkyl, R 9 However, H or -[R 11 O] x H is, R 10 However, C1~C 24 These are linear, branched, or cyclic alkyl, aryl, or aralkyl compounds. Each R 11However, independently, they are -CH2-CH2-, -CH(CH3)-CH2-, -CH2-CH2-CH2-, CH2-CH2-CH2-CH2-, or -CH(C6H6)-CH2-, n is an integer between 1 and 12. p is an integer between 0 and 12. q is 0 or 1, Each x is an independent integer between 2 and 1000.

[0026] In this embodiment, R 4 and R 5 H is H. In this embodiment, R 7 and R 8 is H. In the embodiment, n, p, and q are 1. In the embodiment, R 10 The compound is selected from n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-hexyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, or 2-ethylhexyl.

[0027] In this embodiment, R 6 H is H. In this embodiment, R 6 This is CH3. In this embodiment, R 6 is COOH. In the embodiment, R 6 is benzyl. In the embodiment, R 6 teeth, [ka] And, In the formula, R 12 is methyl or ethyl. In the embodiment, R 6 It contains one or two oxygen atoms. In the embodiment, R 6 This includes the ether portion. In the embodiment, R 6 It contains a hydroxyl moiety. In the embodiment, R 6 This includes one or more hydroxyl moieties, one or more ether moieties, or a combination thereof. In embodiments, R 6It includes a crosslinked portion. For example, a bisaldehyde such as glyoxal is used as the aldehyde in the condensation. The bisaldehyde contains two aldehyde functional groups that can condense with the HCAP functional group, and thus, crosslinking of the resulting HCAP polymer can be achieved.

[0028] In an embodiment, at least one R 11 is -CH2-CH2-. In an embodiment, at least one R 11 is -CH(CH3)-CH2-. In an embodiment, each R 11 is -CH2-CH2-. In an embodiment, each R 11 is -CH(CH3)-CH2-. In an embodiment, -[R 11 O] x H is preferably characterized by a polyalkoxylated functional group, an alkylene oxide functional group, a polymeric alkylene oxide functional group, or a polyalkylene oxide functional group. In some embodiments, -[R 11 O] x H is characterized by a copolymeric alkylene oxide functional group. In some embodiments of the copolymeric alkylene oxide functional group, each R 11 is either -CH2-CH2- or -CH(CH3)-CH2-. In an embodiment, the copolymeric alkylene oxide functional group is arranged in an alternating, random, or block configuration. In some embodiments, the copolymeric alkylene oxide functional group is a block copolymeric alkylene oxide functional group. In an embodiment, each x is from 2 to 200.

[0029] In some embodiments, the polyalkoxylated HCAP resin comprises, consists essentially of, or consists of an alternative repeating unit that is a polyalkoxylated HCAP repeating unit having a tertiary amino functional group located in a 1,3-relationship (i.e., meta-) to the phenolic oxygen. Another repeating unit has the following structure.

Chemical formula

[0030] In the embodiments, the polyalkoxylated HCAP resin is an HCAP resin containing alkylene oxide functional groups bonded to each HCAP repeating unit. In the embodiments, the polyalkoxylated HCAP resin contains two alkylene oxide functional groups bonded to each HCAP repeating unit. In the embodiments, the polyalkoxylated HCAP resin contains three alkylene oxide functional groups bonded to each HCAP repeating unit. In the embodiments, the polyalkoxylated HCAP resin contains four or more alkylene oxide functional groups bonded to each HCAP repeating unit. Each alkylene oxide functional group contains at least two alkoxy repeating units and up to 1000 alkoxy repeating units, for example, 2-800, 2-600, 2-400, 2-200, 2-100, 2-80, 2-60, 2-40, 2-20, or 2-10 alkoxy repeating units.

[0031] A method for producing polyalkoxylated HCAP resins comprises forming an HCAP prepolymer from an HCAP compound, converting the HCAP prepolymer into an HCAP resin, and functionalizing the HCAP resin with one or more alkylene oxide functional groups. In embodiments, the HCAP compound is characterized by comprising an aromatic ring compound having a bis(hydroxycarbyl)amino adduct bonded to the ring, at least one hydroxyl group or alkoxyl group (phenol hydroxyl group) bonded to the ring, and at least two hydrogen atoms readily subject to acid or base-catalyzed condensation with an aldehyde bonded to the ring. Thus, in embodiments, the HCAP compound is, for example, phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or two or more thereof. When HCAP compounds are added to an industrial process stream for producing, for example, styrene, isoprene, butadiene, or another ethylenically unsaturated monomer, they are identified as polymerization inhibitors or polymerization retarders in the concurrently pending U.S. Patent Application No. 16 / 860,954. As such, HCAP compounds are suitably used to reduce free radical or oxidation-type polymerization occurring in such industrial process systems.

[0032] HCAP compounds readily undergo condensation polymerization with aldehydes. Therefore, in the embodiments, one or more HCAP compounds are condensed with aldehydes such as formaldehyde (including paraformaldehyde and formalin), acetaldehyde, vanillin, ethyl vanillin, glyoxal, glyoxylic acid, salicylaldehyde, or benzaldehyde to provide a bis(hydroxycarbyl)aminophenol polymer (HCAP polymer) containing one or more HCAP repeating units.

[0033] All embodiments relating to the HCAP repeating units disclosed herein are intended to be freely and without limitation combined as starting materials for forming the polyalkoxylated HCAP resins disclosed herein.

[0034] In some embodiments, the HCAP polymer is a polymer comprising at least one HCAP repeating unit. In some embodiments, the HCAP repeating unit is a repeating unit corresponding to a condensation product of an aldehyde with, for example, phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or two or more bis(hydroxycarbyl)amino adducts thereof. In the embodiment, the HCAP polymer is obtained by condensing one or more HCAP compounds with one or more aldehydes to obtain at least three HCAP repeating units and up to 100 HCAP repeating units, for example, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 HCAP repeating units, or 3-10, 10-20, 20-30, 30-40, 40-50, 50-60, 60-70, 70-80, 8 The HCAP polymer is formed by forming a polymer having 0 to 90 or 90 to 100 HCAP repeating units, or 3 to 90, 3 to 80, 3 to 70, 3 to 60, 3 to 50, 3 to 40, 3 to 30, 3 to 20, 3 to 15, 3 to 10, 3 to 9, 3 to 8, 3 to 7, 3 to 6, or 3 to 5 HCAP repeating units, or 5 to 100, 10 to 100, 20 to 100, 30 to 100, 40 to 100, 50 to 100, 60 to 100, 70 to 100, 80 to 100, or 90 to 100 HCAP repeating units. In some embodiments, the HCAP polymer is formed by condensing an HCAP compound with formaldehyde and another aldehyde such as acetaldehyde or benzaldehyde to form an HCAP polymer having at least 3 repeating units and up to 100 HCAP repeating units.

[0035] In embodiments, the HCAP polymer is an HCAP copolymer. The HCAP copolymer comprises at least one HCAP repeating unit which is a first repeating unit, and a second repeating unit which comprises a condensation product of a phenol compound and an aldehyde selected from the aldehydes listed above, for example, formaldehyde or its equivalent (formalin or paraformaldehyde). The phenol compound is characterized by an aromatic compound having one or more hydroxyl groups directly bonded thereto. Examples of phenol compounds include, but are not limited to, phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, and hydroxyhydroquinone. The HCAP copolymer comprises at least three total repeating units and up to 1000 repeating units, at least one of which is an HCAP repeating unit. In some such embodiments, the HCAP copolymer comprises 1 to 500 HCAP repeating units or 1 to 100 HCAP repeating units.

[0036] The combination of condensation strategies described above is advantageous in providing a broad compositional and structural range of HCAP polymer products. In embodiments, an HCAP repeating unit comprises two hydroxyalkyl moieties and one or more aromatic hydroxyl moieties per repeating unit. In embodiments, an HCAP copolymer comprises at least one HCAP repeating unit. In embodiments, an HCAP homopolymer comprises at least three HCAP repeating units.

[0037] Examples of HCAP polymers, though not limiting, include homopolymers and copolymers containing one or more repeating units (a) to (e). [ka]

[0038] Repeating unit (a) is formed by the reaction of 4-aminophenol with butyl glycidyl ether, followed by condensation with formaldehyde. Repeating unit (b) is formed by the reaction of 4-aminophenol with 1,2-epoxyoctane, followed by condensation with formaldehyde. Repeating unit (c) is formed by the reaction of 4-aminophenol with 2-ethylhexyl glycidyl ether, followed by condensation with benzaldehyde. Repeating unit (d) is formed by the reaction of 4-aminophenol with styrene oxide, followed by condensation with formaldehyde. Repeating unit (e) is formed by mixing 4-aminophenol with C8~C 10 It is formed by reaction with alkylglycidyl ether, followed by condensation with benzaldehyde. In some embodiments, a mixture of C8-C8 is used. 10 Alkylglycidyl ethers are linear C8-C8 ethers. 10 It contains a mixture of alkyl moieties, but in other embodiments, it is a mixture of C8-C 10 Alkylglycidyl ethers are linear and branched C8-C 10 Contains a mixture of alkyl groups.

[0039] The HCAP polymer as defined herein is an HCAP prepolymer or an HCAP resin. In embodiments, the HCAP prepolymer is formed by using the aforementioned process of condensing the aldehyde and phenol content at a mild temperature such as below 100°C to form the HCAP prepolymer. The HCAP prepolymer is then heated to remove condensation water and achieve curing (chain extension and / or crosslinking) to form the HCAP resin. In some embodiments, the aldehyde to total phenol content ratio is selected by the user to form a Novalac-type HCAP prepolymer, and the molar ratio of aldehyde to total phenol content is less than 1. In some embodiments, the aldehyde to total phenol content ratio is selected by the user to form a Resol-type HCAP prepolymer, and the molar ratio of aldehyde to total phenol content is greater than 1. In embodiments, the ratio of total phenol content to aldehyde is selected by the user to be about 1:1. In some embodiments, the molar ratio of aldehyde to total phenol content is about 0.0005:1 to 0.8:1, or about 0.001 to 0.6:1, or about 0.1:1 to 0.4:1, or about 0.2:1 to 0.3:1. In other embodiments, the molar ratio of total phenol content to aldehyde is about 0.0005:1 to 0.8:1, or about 0.001 to 0.6:1, or about 0.1:1 to 0.4:1, or about 0.2:1 to 0.3:1.

[0040] In some embodiments, condensation reactions commonly used in forming phenol aldehyde prepolymers (novalac and resol) or cured phenolic resins are advantageously used herein to form HCAP prepolymers and resins. Specifically, one or more HCAP compounds, or a combination of one or more HCAP compounds and one or more additional aromatic hydroxylated compounds, are selected and combined with one or more aldehydes. Examples of additional aromatic hydroxylated compounds include, but are not limited to, phenols, alkylated phenols, resorcinols, pyrocatechols, hydroquinones, phloroglucinols, hydroxyhydroquinones, lignosulfonic acids, phenol disulfonic acids, and oligomerization sources (such as tannic acid, humic acid, fulvic acid, lignin extracts, and quebraco extracts); and other aromatic hydroxylated compounds. The combination of one or more HCAP compounds and optionally one or more additional aromatic compounds provides a "total phenol content" or number of moles of reactive functional groups available for condensation with aldehydes.

[0041] Accordingly, in the embodiment, a selected amount of total phenol content is combined with a selected amount of one or more aldehydes, the selection of which provides a desired level of polymerization, and the selected acidic or basic curing catalyst is added under conditions of gentle heating, for example, 50°C to 120°C, or about 60°C to 100°C, to obtain a polymer condensation product or prepolymer. In the embodiment, the synthesis of the HCAP prepolymer is carried out in the absence of added water. In the embodiment, the synthesis of the HCAP prepolymer is carried out substantially in the absence of added water, where “substantially” means that enough water is added to the reaction vessel to achieve or enable a reaction such as the depolymerization of paraformaldehyde or formalin to formaldehyde. In the embodiment, the synthesis of the HCAP prepolymer is achieved by adding an acid or basic catalyst to the reaction vessel, along with enough water to dissolve the acid or base and / or deliver it to the reaction vessel.

[0042] In the embodiment, after condensation is complete, the HCAP prepolymer is dispersed in a selected solvent. The HCAP prepolymer is dispersed with a total solid content of 30% to 90% by weight, or 35% to 80% by weight, or about 40% to 70% by weight, or about 50% to 60% by weight, based on the weight of the dispersion.

[0043] The HCAP prepolymer is converted into an HCAP resin by heating the prepolymer dispersion to at least 100°C, for example, 100°C to 180°C, or 120°C to 150°C. The higher temperature at this stage causes the formation of methylene and dibenzyl ether crosslinks via the desorption of water formed by the condensation reaction. In some embodiments, the HCAP prepolymer undergoes chain elongation, crosslinking, or both (collectively "cured") simultaneously with the evaporation of the solvent by coating and evaporative heating, etc., to yield an HCAP resin. In other embodiments, the HCAP prepolymer is cured by heating in a solvent, and the condensation water is removed from the reaction vessel by azeotropy or by the use of molecular sieves or another desiccant.

[0044] After curing, the HCAP prepolymer is converted into an HCAP resin. The HCAP resin is a three-dimensional cured network comprising one or more HCAP repeating units. Each HCAP repeating unit comprises at least two alkanol hydroxyl groups incorporated into the main chain of the HCAP polymer as (hydroxycarbyl)amino moieties. In embodiments, an HCAP repeating unit, or another repeating unit of the HCAP polymer, or a combination thereof, further comprises one or more aromatic (phenolic) hydroxyl moieties. The HCAP hydroxyl moieties incorporated into the main chain of the HCAP polymer can be used for functionalization to impart one or more additional properties to the HCAP resin, or to alter one or more properties of the HCAP resin. Thus, in embodiments, one or more HCAP resins are suitably functionalized by the reaction of alkanol and / or aromatic hydroxyl groups, and one or more adducts bonded thereto are bonded thereto to form a functionalized HCAP resin.

[0045] In one embodiment, one or more HCAP resins are suitably functionalized to produce a polyalkoxylated polymer. In such an embodiment, one or more HCAP resins are suitably functionalized by the reaction of alkanol and / or aromatic hydroxyl groups to form one or more alkoxy groups, thereby forming a polyalkoxylated HCAP polymer or polyalkoxylated HCAP resin. The polyalkoxylated HCAP resin is an HCAP resin having a polyalkylene oxide moiety or a functional group bonded thereto. In one embodiment, the polyalkoxylated HCAP resin has one polyalkylene oxide moiety or functional group bonded to each HCAP repeating unit. In one embodiment, the polyalkoxylated HCAP resin has two or more polyalkylene oxide moieties or functional groups bonded to each repeating unit. In one embodiment, the polyalkoxylated HCAP resin has two or more polyalkylene oxide moieties or functional groups bonded to one HCAP repeating unit. In one embodiment, the polyalkoxylated HCAP resin has two or more polyalkylene oxide moieties or functional groups bonded to each HCAP repeating unit.

[0046] Therefore, in the embodiment, the polyalkoxylated HCAP resin is formed by the reaction of one or more hydroxyl groups of the HCAP resin with one or more alkylene oxides. The polyalkylene oxide portion is a polyether portion covalently bonded to the HCAP resin via one or more oxygen atoms of the HCAP resin hydroxyl groups, containing an alkanolic hydroxyl group, an aromatic hydroxyl group, or both alkanolic and aromatic hydroxyl groups.

[0047] The alkylene oxide preferably used to form the polyalkoxylated HCAP resin is not particularly limited. In the embodiment, the alkylene oxide is ethylene oxide, propylene oxide, butylene oxide, styrene oxide, or a combination of two or more of these. In the embodiment, the alkylene oxide is a mixture of ethylene oxide and propylene oxide. In the embodiment, the alkylene oxide is ethylene oxide.

[0048] In some embodiments, a method for forming a polyalkoxylated HCAP resin involves contacting an alkylene oxide with an HCAP resin containing one of the above HCAP resins under basic conditions to promote ring-opening polymerization (polyalkoxylation) of the alkylene oxide. In some embodiments, the alkylene oxide is liquid when in contact with the HCAP resin. In some embodiments, the alkylene oxide is gaseous when in contact with the HCAP resin. In some embodiments, the gas is applied to the HCAP resin under a pressure above atmospheric pressure, for example, about 7 kPa to 700 kPa, such as 20 kPa to 600 kPa above atmospheric pressure. Such pressure is achieved by enclosing the HCAP resin in a chamber designed and adapted to apply a gas under pressure, such as a pressure vessel available from Paar Instrument Company in Maureen, Illinois, or a similar pressurizable chamber reactor designed and adapted to apply a pressurized gas to the chamber, and adding the alkylene oxide gas to the reactor under a pressure sufficient to initiate and propagate the ring-opening polymerization of the alkylene oxide. In some embodiments, it is not necessary to add heat to initiate and propagate the ring-opening polymerization. In other embodiments, it is desirable to heat the polymer in the reactor to a temperature of, for example, 40°C to 200°C, or for example, 50°C to 180°C.

[0049] In the embodiment, alkylene oxide is contacted with an HCAP resin in a selected molar ratio to form a polyalkoxylated HCAP resin having a desired number and composition of polyalkylene oxide repeating units. In the embodiment, polyalkoxylation occurs at both alkanolic hydroxyl groups and phenolic (aromatic) hydroxyl groups of the HCAP polymer. The polyalkylene oxide chain length is statistically constructed by chain extension initiated by each of the hydroxyl groups of the HCAP polymer backbone. Thus, the number of polyalkylene oxide repeating units is easily targeted by contacting the HCAP resin with a calculated number of moles of alkylene oxide per mole of hydroxyl groups. For example, to obtain 10 ethylene oxide repeating units per hydroxyl group, an HCAP resin containing 1 mole of HCAP repeating units per kg of HCAP resin, where each HCAP repeating unit contains 2 hydroxyl groups, requires contact with 20 moles of alkylene oxide per kg of HCAP resin to produce a polyalkoxylated HCAP resin having 2 polyalkylene oxide moieties bonded to each HCAP repeating unit, further comprising 10 polyalkylene oxide repeating units, or approximately 10 polyalkylene oxide repeating units, or on average, for example, number average 10 polyalkylene oxide repeating units or weight average 10 polyalkylene oxide repeating units.

[0050] In the embodiment, the polyalkoxylated HCAP resin has at least two and as many as 1,000 polyalkylene oxide repeating units per polyalkylene oxide portion, often 2 to 800, 2 to 600, 2 to 400, 2 to 200, 2 to 100, 2 to 50, or 2 to 30 polyalkylene oxide repeating units per polyalkylene oxide portion, or 2 to 25, 2 to 20, 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, 2 to 8, 2 to 6, 4 to 20, 4 to 18, 4 to 16, 4 to 14, or 4 to 12 per polyalkylene oxide portion. , 4-10, 4-8, 2-14, 2-4, 4-6, 6-8, 8-10, 10-12, 12-24, 14-16, 16-18, 18-20, 20-25, or 25-30 polyalkylene oxide repeating units, or the number average or weight average of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 26, 28, 30, 40, 50, 60, 70, 80, 90, 100 or more polyalkylene oxide repeating units per polyalkylene oxide portion. In embodiments, there are two polyalkylene oxide functional groups per functionalized HCAP repeating unit. In embodiments, there are three polyalkylene oxide functional groups per functionalized HCAP repeating unit. In the embodiment, there are four or more polyalkylene oxide functional groups per functionalized HCAP repeating unit, for example, four, five, or even six polyalkylene oxide functional groups per functionalized HCAP repeating unit.

[0051] In embodiments, each polyalkylene oxide functional group present on the polyalkoxylated polymer disclosed herein comprises or consists of copolymer repeating units comprising polyethylene oxide repeating units, polypropylene oxide repeating units, polybutylene oxide repeating units, polystyrene oxide repeating units, or repeating units derived from two or more different alkylene oxides. Copolymer alkylene oxide functional groups include random, alternating, and block copolymer functional groups. For example, in embodiments, the polyalkylene oxide functional group is a polyethylene oxide functional group. In embodiments, the polyalkylene oxide functional group comprises a polyethylene oxide functional group. In some such embodiments, the polyalkylene oxide functional group is a polyethylene oxide-polypropylene oxide copolymer functional group. In some such embodiments, the polyethylene oxide-polypropylene oxide copolymer functional group is a block copolymer functional group comprising one, two, or three polyethylene oxide blocks and one, two, or three polypropylene oxide blocks.

[0052] The inventors have found that the polyalkoxylated HCAP resins described herein are particularly useful as emulsion disruptors for inverting water-in-oil polymer grids in preparations for petroleum materials (such as asphaltenes or pyragas products) encompassed in water, or for, for example, water-based methods (tertiary petroleum recovery) or other underground injection applications.

[0053] Accordingly, compositions comprising polyalkoxylated HCAP resins, and methods for using polyalkoxylated HCAP resins to decompose oil and water emulsions are described herein. In embodiments, polyalkoxylated HCAP resins are used to decompose or otherwise “destroy” emulsions that are formed in some cases during crude oil extraction and / or refining. As used herein, “emulsion” includes water-in-oil emulsions, oil-in-water emulsions, and composite emulsions, and the emulsion includes both petroleum-based oil phases and vegetable-based oil phases. In embodiments, the emulsion includes one or more of crude oil, refined oil, bitumen, condensate, slop oil, distillate oil, fuel, and mixtures thereof.

[0054] Additionally, polyalkoxylated HCAP resins are useful for decomposing emulsions in other industrial process flows, such as manufacturing process flows, and process flows formed during the synthesis, purification, and / or transport of ethylenically unsaturated or "vinyl" compounds such as butadiene, styrene, and acrylic acid. Polyalkoxylated HCAP resins are also useful for decomposing emulsions formed during the synthesis, purification, and / or transport of industrial process flows derived from plant sources, such as biodiesel process flows.

[0055] Therefore, a method for decomposing emulsions present in an industrial process flow involves, essentially consists of, or consists of, applying one or more polyalkoxylated HCAP resins to one or more industrial process flows containing emulsions to form a treated industrial process flow. In embodiments, the treated process flow contains a decomposed emulsion. The decomposed emulsion is a composition having two separate, generally visible phases: an oil phase (or oily phase) and an aqueous phase. The phases appear as an immiscible liquid layer and often have a visible interface between them. In embodiments, phase separation of the treated process flow to form a decomposed emulsion generally occurs after the treated industrial process flow is allowed to stand for a selected period of time, or substantially after it has been allowed to stand for a selected period of time. This time is selected by the operator to be between 10 minutes and 12 hours. The amount of polyalkoxylated HCAP resin applied to the industrial process flow is effective in decomposing the emulsion within it. That is, the treated industrial process stream is an industrial process stream containing, essentially consisting of, or comprising an emulsion, and after the treated industrial process stream is allowed to stand for a selected period of time or substantially standing, it has a sufficient amount of one or more polyalkoxylated HCAP resins dissolved or dispersed therein to form a decomposed process stream, or a decomposed emulsion in the process stream. In embodiments, the aqueous phase of the decomposed process stream contains one or more compounds preferably removed from the oil phase as a result of the treatment of the industrial process stream and the decomposition of the emulsion therein.

[0056] In the embodiment, the amount of polyalkoxylated HCAP resin applied to the industrial process flow to form the treated process flow is based on the weight or volume of the industrial process flow to form the treated industrial process flow, ranging from 0.01 ppm to 10,000 ppm, for example, 0.1 ppm to 8,000 ppm, 0.1 ppm to 6,000 ppm, 0.1 ppm to 4,000 ppm, 0.1 ppm to 2,000 ppm, 0.1 ppm to 1,000 ppm, 0.1 ppm to 500 ppm, 0.1 ppm to 400 ppm, 0.1 ppm pm~300ppm, 0.1ppm~200ppm, 0.1ppm~100ppm, 0.1ppm~50ppm, 0.1ppm~25ppm, 0.1ppm~10ppm, 1ppm~8000ppm, 1ppm~6000ppm, 1ppm~4000p pm, 1ppm~2000ppm, 1ppm~1000ppm, 1ppm~500ppm, 1ppm~400ppm, 1ppm~300ppm, 1ppm~200ppm, 1ppm~100ppm, 1ppm~50ppm, 1ppm~25ppm, 1p pm~10ppm, 5ppm~10ppm, 10ppm~20ppm, 20ppm~30ppm, 30ppm~40ppm, 40ppm~50ppm, 50ppm~60ppm, 60ppm~70ppm, 70ppm~80ppm, 80ppm~90p pm, 90ppm~100ppm, 50ppm~100ppm, 100ppm~200ppm, 200ppm~300ppm, 200ppm~300ppm, 300ppm~400ppm, 400ppm~500ppm, 500ppm~600ppm, These ranges are 700ppm-800ppm, 800ppm-900ppm, 900ppm-1000ppm, 1000ppm-1500ppm, 1500ppm-2000ppm, 2000ppm-2500ppm, 2500ppm-3000ppm, 3000ppm-4000ppm, 4000ppm-5000ppm, 5000ppm-6000ppm, 6000ppm-7000ppm, 7000ppm-8000ppm, 8000ppm-9000ppm, or 9000ppm-10,000ppm.

[0057] In embodiments, to increase the efficiency or ease of applying one or more polyalkoxylated HCAP resins to an industrial process flow, one or more polyalkoxylated HCAP resins are included in a deemulsifier composition useful for delivering a dispersion or solution of polyalkoxylated HCAP resins to an industrial process flow and achieving decomposition of the emulsion therein. Accordingly, a deemulsifier composition comprising one or more polyalkoxylated HCAP resins and a solvent suitable for dissolving or dispersing one or more polyalkoxylated HCAP resins is described herein. In embodiments, the solvent is selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, kerosene, propylene carbonate, glycol ether, paraffinic solvent, and any combination thereof. In embodiments, the alcohol is selected from methanol, ethanol, isopropanol, 2-ethylhexanol, benzyl alcohol, and any combination thereof. In embodiments, the glycol is ethylene glycol or glycol ether (such as ethylene glycol monobutyl ether), or a combination of ethylene glycol and glycol ether.

[0058] In embodiments, the deemulsifier composition further comprises one or more additives. Suitable additives in the deemulsifier composition include corrosion inhibitors, viscosity reducers, friction reducers, scale inhibitors, clay swelling inhibitors, biocides, flow-back aids, surfactants, and / or other chemical additives used in crude oil production, refining, and chemical processing. In embodiments, the deemulsifier composition comprises additional deemulsifiers such as alcohols, fatty acids, fatty amines, glycols, and alkylphenol formaldehyde condensation products. In embodiments, the deemulsifier composition excludes alkylphenol compounds such as nonylphenol or its adducts.

[0059] In embodiments, the deemulsifier composition contains at least 1% and up to 99.9% by weight of polyalkoxylated HCAP resin, for example, 1% to 5% by weight, 1% to 10% by weight, 5% to 10% by weight, 10% to 15% by weight, 15% to 20% by weight, 20% to 25% by weight, 25% to 30% by weight, 30% to 35% by weight, 35% to 40% by weight, 40% to 45% by weight, 45% to 50% by weight, 50% to 55% by weight, 55% to 60% by weight, 60% to 65% by weight, and 65% by weight. The product contains polyalkoxylated HCAP resin in the following proportions: ~70% by weight, 70%~80% by weight, 80%~85% by weight, 85%~90% by weight, 90%~95% by weight, 95%~99.9% by weight, 1%~20% by weight, 20%~40% by weight, 40%~60% by weight, 60%~80% by weight, 80%~99.9% by weight, 10%~30% by weight, 30%~60% by weight, 60%~90% by weight, 90%~99.9% by weight, 1%~50% by weight, or 50%~99.9% by weight.

[0060] Accordingly, in any one or more methods described herein, the polyalkoxylated HCAP resin is added to or applied to the industrial process flow in an "undiluted" state, i.e., as 100% solid, in order to obtain the treated industrial process flow. Additionally, in any one or more methods described herein, the polyalkoxylated HCAP resin is added to or applied to the industrial process flow as a deemulsifier composition. In some such embodiments, the operator may suitably apply or add to the industrial process flow a certain volume or weight of a deemulsifier composition in an amount corresponding to a selected weight of the polyalkoxylated HCAP resin for effective treatment of the industrial process flow.

[0061] In the embodiment, the treated industrial process flow contains at least one polyalkoxylated HCAP resin in an amount effective to obtain the treated industrial process flow. In the embodiment, the effective amount of polyalkoxylated HCAP resin present in or added to the industrial process flow to form the treated industrial process flow depends on the specific industrial process flow, the type of emulsion present in the industrial process flow that requires decomposition, and the amount (by weight or volume) of emulsion in the industrial process flow compared to the total weight or volume of the industrial process flow. In the embodiment, the effective amount of polyalkoxylated HCAP resin added to the industrial process flow is in the range of 0.1 ppm to 10,000 ppm, based on the weight or volume of the industrial process flow, as described above.

[0062] A method for decomposing emulsions in one or more industrial process streams comprises adding one or more polyalkoxylated HCAP resins to an industrial process stream containing, essentially consisting of, or comprising an emulsion in an amount effective for decomposing the emulsion. In embodiments, the treated industrial process stream includes water, such as wash water from a refinery desalination process, an oil source, such as crude oil, and polyalkoxylated HCAP resins. In some such embodiments, the method further comprises an initial step of mixing the water source and the oil source to form an emulsion before adding one or more polyalkoxylated HCAP resins to form a treated emulsion, and a final step of decomposing the treated emulsion. In embodiments, the oil source is crude oil. In embodiments, the water source is residual water, fresh water, distilled water, or water, having less than 0.1% by weight of total dissolved solids in it. "Decomposing a treated emulsion" means allowing an emulsion, such as a treated emulsion, to stand or substantially stand for a selected period of time to form a two-phase industrial process flow from the emulsion, such as a treated emulsion. In embodiments, the period that may elapse is the amount of time that passes before the two phases become visually apparent. The process of decomposing a treated emulsion is not particularly limited in terms of time, but generally the step of letting the treated emulsion stand or substantially stand is about 10 minutes to 12 hours, for example, 30 minutes to 12 hours, 1 hour to 12 hours, 2 hours to 12 hours, 10 minutes to 2 hours, 1 hour to 2 hours, 1 hour to 4 hours, 1 hour to 6 hours, 1 hour to 8 hours, or 1 hour to 10 hours.

[0063] In some embodiments, when an emulsion such as the aforementioned water / oil emulsion is decomposed, a purified oil phase is obtained because, due to close contact between the oil phase and the aqueous phase within the emulsion, a portion, or in some embodiments substantially all, of the water-soluble compounds that are desirable to be removed from the oil phase migrate into the aqueous phase within the emulsion. Subsequently, the decomposition of the emulsion into the oil and aqueous phases is carried out according to well-established chemical separation principles to obtain a purified oil phase and an aqueous phase containing materials such as salts and other water-soluble or hydrophilic compounds and materials obtained from the emulsified oil source.

[0064] Accordingly, in embodiments, one or more polyalkoxylated HCAP resins or demulsifier compositions are suitably added to an industrial process stream containing, essentially consisting of, or comprising an emulsion of an oil source and a water source, either during or after emulsion formation. Alternatively, the polyalkoxylated HCAP resin or demulsifier composition is added to the water source, or the oil source, or both the water source and the oil source, prior to the initial step of mixing the water source and the oil source to form an emulsion. In embodiments, one or more polyalkoxylated HCAP resins are added to an industrial process stream containing, essentially consisting of, or comprising an emulsion of water and crude oil. In embodiments, the emulsion of water and crude oil contains 5% to 50% by weight of water, with the remainder of the emulsion being oil. For example, in the embodiment, the emulsion of water and crude oil contains 5% to 45% by weight, 5% to 40% by weight, 5% to 35% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 15% by weight, or 5% to 10% by weight of water.

[0065] In some embodiments, one or more polyalkoxylated HCAP resins are added to an industrial process flow by injecting a liquid deemulsifier composition, such as a polyalkoxylated HCAP dispersion or solution, into the industrial process flow. In some embodiments, the industrial process flow contains crude oil. The liquid deemulsifier composition comprises at least one polyalkoxylated HCAP resin and a solvent, and in some embodiments, comprises one or more additives, such as the deemulsifier composition additives described above.

[0066] In embodiments, one or more polyalkoxylated HCAP resins are added continuously to an industrial process stream. In embodiments, one or more polyalkoxylated HCAP resins are added semi-continuously to an industrial process stream. In embodiments, one or more polyalkoxylated HCAP resins are added in batches to an industrial process stream. One or more polyalkoxylated HCAP resins of this disclosure can be used in methods for demulsifying water-in-oil emulsions, oil-in-water emulsions, and composite emulsions in various manufacturing and refining processes. Specific examples include, but are not limited to, oilfield production emulsions, refinery desalination emulsions, refined fuel emulsions, and recovered oil emulsions (e.g., crude oil slop, used lubricating oil, and recovered oil in the steel and aluminum industries). For example, in an industrial refinery desalination process, crude oil is mixed with wash water, and the mixture is stirred to form an industrial process stream which is an emulsion. In the emulsion, salts and other contaminants may be dissolved or dispersed in the wash water. Next, the aqueous phase is separated from the emulsion by mixing the emulsion with an effective amount of one or more polyalkoxylated HCAP resins.

[0067] A typical desalination process involves the use of pumps to move incoming crude oil from a storage tank through piping to one or more heat exchangers. Wash water may be injected into the heated oil flow, and this flow may be mixed by an in-line mixing device. The emulsified process flow can flow into an electrostatic desalination vessel, where decomposition and separation of crude oil and water spills occur. Injection of one or more polyalkoxylated HCAP resins into the fluid flow can be carried out at various locations along the desalination process path. Possible injection locations include, but are not limited to, before the crude oil storage tank, at the outlet side of the crude oil storage tank, upstream of the in-line mixer, in the wash water flow, and other possible locations.

[0068] In some embodiments, the industrial process flow is an emulsion containing crude oil and a water source. In embodiments, the water source is residual water, fresh water, or water that, when added to the crude oil, contains less than 0.1% by weight of total dissolved solids.

[0069] In such industrial process flows, the effective amount of polyalkoxylated HCAP resin added to the industrial process flow is based on the volume of oil. For example, the effective amount may be approximately 1 ppm to 3,000 ppm, approximately 1 ppm to 1,000 ppm, approximately 1 ppm to 500 ppm, approximately 1 ppm to 250 ppm, approximately 1 ppm to 200 ppm, approximately 1 ppm to 150 ppm, approximately 1 ppm to 100 ppm, approximately 1 ppm to 50 ppm, or approximately 1 ppm to 25 ppm, based on the volume of oil.

[0070] In one embodiment, the deemulsifier composition is combined with a reverse emulsion disruptor, and the combined composition is added to an industrial process stream that contains, is essentially, or consists of an emulsion. In one embodiment, the emulsion is an emulsion of crude oil and wash water. In another embodiment, the combined composition is added to the emulsion, wash water, and / or oil. In yet another embodiment, the reverse emulsion disruptor is added to the emulsion, wash water, and / or oil separately from the deemulsifier composition.

[0071] In some embodiments, the deemulsifier composition is introduced into the crude oil emulsion by injecting the deemulsifier composition into a subsurface cavity or well. In some embodiments, injecting the deemulsifier composition includes injecting the deemulsifier composition into the crude oil at the wellhead. In some embodiments, injecting the deemulsifier composition is injecting the deemulsifier composition into the crude oil process flow at a selected point between the wellhead and the final oil storage tank. In some embodiments, the deemulsifier composition is injected continuously, semi-continuously, or in batch mode. Injection is generally achieved using an electric or gas pump fluid-connected to the source of the deemulsifier composition. In some embodiments, the addition or injection of the deemulsifier composition is preferably controlled by one or more digital control mechanisms. [Examples]

[0072] experiment

[0073] Example 1

[0074] A 500 mL three-necked round-bottom flask was equipped with a temperature probe, nitrogen inlet, condenser, and magnetic stirrer. Next, 190 g of 2-ethylhexylglycidyl ether was added to the flask. Then, with good stirring, 4-aminophenol was added to the flask. The mixture was heated to 120°C under a nitrogen blanket and stirred for about 1 hour or until the reaction was complete. As the reaction progressed, the formation of a uniform dark amber product was observed. The resulting product was characterized by the following structure, as determined by NMR and ESI-MS. [ka]

[0075] Example 2

[0076] The procedure of Example 1 was repeated using butyl glycidyl ether by 1:1 molar substitution with 2-ethylhexyl glycidyl ether. The polymer product was analyzed by gel permeation chromatography and found to have a weight-average molecular weight of 6996 g / mol and a polydispersity index of 4.9.

[0077] Example 3

[0078] C8~C 10 The procedure of Example 1 was repeated using (average carbon chain length) alkylglycidyl ether in a 1:1 molar substitution with 2-ethylhexylglycidyl ether. The polymer product was analyzed by gel permeation chromatography and found to have a weight-average molecular weight of 6157 g / mol and a polydispersity index of 3.0.

[0079] Example 4

[0080] A Dean-Stark trap with an overhead stirrer, N2 purge, temperature probe, and condenser was fitted to a 1 L four-necked round-bottom flask. Repeating Example 1, the entire resulting product was added to the flask along with 290 g of heavy aromatic naphtha (HAN) and 1.5 g of 50% KOH solution. The overhead stirrer was started with a very slow nitrogen purge (approximately 1 bubble per 5 seconds). The reaction flask was heated to 65°C. Then, 20 g of paraformaldehyde was prepared for addition to the flask. Once a consistent temperature of 65°C was achieved, the first aliquot of paraformaldehyde (approximately 10 g) was added to the flask. A temperature increase of 15°C to 20°C was observed. When the exothermic reaction stopped and the reactor returned to 65°C, the remaining 20 g of paraformaldehyde was added to the flask. A temperature increase of 1°C to 10°C was observed.

[0081] When the exothermic reaction stopped, the set temperature inside the flask was changed from 65°C to 95°C. The flask was then held at 95°C for 3 hours.

[0082] After 3 hours, the flask's set temperature was increased to 180°C, and reflux was observed. Reflux was continued for 3 hours. At the end of the 3-hour reaction period, the heat source was removed, and the flask was allowed to cool overnight. The amount of water removed via the Dean-Stark trap was recorded.

[0083] The polymer product was analyzed by gel permeation chromatography and found to have a weight-average molecular weight of 4574 g / mol and a polydispersity index of 2.2.

[0084] Example 5

[0085] In a 1 L four-necked round-bottom flask, pN,N-di-[1-(2-ethylhexyloxy)-2-hydroxypropyl]aminophenol / formaldehyde resin prepared according to the procedure of Example 1 and potassium hydroxide were added. An overhead stirrer, a Dean-Stark trap with a nitrogen purge and condenser, and a temperature probe were attached to the flask. The nitrogen purge was started at a rate of 1 bubble / second, and the stirrer was started at a moderate speed. The water flow to the condenser was turned on, and the Dean-Stark trap was filled with heavy aromatic naphtha up to the neck. The temperature was set to 150°C and heating was started. Water was distilled from the base catalyst. 5 mL of sample was collected for Karl Fischer water analysis. If the sample contained more than 0.1% water, distillation was continued for 30 minutes and the analysis was repeated. When the sample contained less than 0.1% water, the flask was cooled to 60°C. Once the reaction mixture reached 60°C, the N2 purge was increased.

[0086] Example 6

[0087] 500 g of the reaction mixture from Example 1, containing KOH dissolved in HAN, was transferred to a 1 L Paar pressure reaction vessel (obtained from Paar Instrument Company, Maureen, Illinois). The vessel was closed and purged three times with nitrogen, and then the nitrogen pressure in the flask was set to 5 psi (34 kPa).

[0088] The container was heated to 150°C. Ethylene oxide gas was then added until the pressure inside the container reached 60 psi (414 kPa). The weight of ethylene oxide added to the reactor was recorded. The pressure was observed to decrease inside the container over time. When the pressure reached 10 psi (69 kPa), additional ethylene oxide was added until the pressure again reached 60 psi (414 kPa). The pressure was reduced to 10 psi (69 kPa), and then ethylene oxide was added until the desired amount of ethylene oxide was added and reacted, resulting in a pressure of 60 psi (414 kPa).

[0089] After adding the desired amount of ethylene oxide and allowing the reaction to proceed, a 50 mL sample was taken under safe conditions. This recovered aliquot was recorded, and the amount of ethylene oxide required for the next 1 mole of EO was calculated. When the pressure reached 10 psi, the desired amount of ethylene oxide required to complete the 1 mole addition was added, or it was added until the pressure reached 60 psi. The pressure was reduced, and the process was continued until the desired amount of ethylene oxide had been added and consumed by the reaction. After each pressurization, an aliquot of the polymer was removed from the reactor.

[0090] Example 7

[0091] Formed using the procedure of Example 4, with a weight-average molecular weight (M) of 4574 g / mol. w The amount of resin having a polydispersity index (PDI) of 2.2 was divided into seven parts. Using the procedure of Example 6, a portion of the resin was reacted with 8 to 20 moles of ethylene oxide per mole of monomer repeating units to obtain samples DM-1 to DM-7 shown in Table 1.

[0092] Table 1. Reaction ratios of resins and ethylene oxides in Example 7 for forming demulsifiers DM-1 to DM-7. [Table 1]

[0093] The effectiveness of polyethoxylated HCAP resins DM-1 to DM-7 in demulsifying oil-in-water emulsions was tested using the emulsion decomposition test outlined below.

[0094] Emulsion decomposition test. A water-in-oil emulsion is prepared by blending 5 mL of tap water and 45 mL of crude oil with 10 ppm (active) of a selected deemulsifier. The mixture is blended in a Waring blender at 100% power for 30 seconds to form an emulsion. The emulsion is added to a glass tube and capped with a cap to which an electrode assembly is fixed. The capped tube is placed in a portable electric desalter (PED), which uses constant heating via a heating block designed and fitted to tightly fit the glass tube, and is further adapted to apply voltage to the contents of the tube via the electrode assembly. The PED heating block is preheated to 120°C before inserting the tube into the PED. A 2000-volt electric field is applied to the tube continuously for 2 minutes a total of 6 times during the test, with the voltage being applied for 2 minutes starting at 12, 22, 27, 32, 37, and 42 minutes after insertion of the tube into the PED. During the experiment, the tubes were observed at regular intervals, and the percentage of water coagulation was monitored over time. Here, the percentage of water coagulation refers to the volume of the aqueous layer ("decomposed" water) visually separated from the rest of the tube's contents as a percentage of the total volume of the tube's contents. The total volume of dissolved water and the rate of aqueous layer development were used to compare the performance of deemulsifiers in promoting water coagulation.

[0095] Using the emulsion decomposition test outlined above, deemulsifiers DM-2 to DM-7 were tested using a first crude oil with a crude oil API of 20.27°. Blank emulsions formed from crude oil and without deemulsifiers were also tested. The results are shown in Table 2.

[0096] Table 2. Percentage of water flocculation per unit of time (minutes) for deemulsifiers DM-2 to DM-7, as tested in Example 7. [Table 2]

[0097] As shown in Table 2, the polyalkoxylated HCAP resin either accelerated the decomposition (aggregation) of the entire emulsion after standing for 40 minutes, or in some cases after standing for only 15 minutes, or resulted in a greater degree of aggregation than the emulsion alone. After 40 minutes, DM-2 appeared to have optimal properties for the decomposition of the first crude oil emulsion.

[0098] Example 8

[0099] Using the emulsion decomposition test of Example 7, deemulsifiers DM-1 to DM-6 were tested with a second crude oil having a crude oil API of 36.1°. The results are shown in Table 3.

[0100] Table 3. Percentage of water coagulation per unit of time (minutes) for deemulsifiers DM-1 to DM-6, as tested in Example 8. [Table 3]

[0101] As shown in Table 3, the polyalkoxylated HCAP resin either accelerated the decomposition (aggregation) of the entire emulsion after standing for 30 minutes, or in some cases after standing for only 10 minutes, or resulted in a greater degree of aggregation than the emulsion alone. After 30 minutes, DM-2 appeared to have optimal properties for separating the second crude oil emulsion. Examples of embodiments of the present disclosure are listed in the following items [1] to

[21] . [1] A polymer comprising repeating units having the structure of formula I, formula II, or a combination thereof, [ka] During the ceremony, R 1 and R 2 However, -(CR 7 R 8 ) n (CHOR 9 )(CH 2) p (O) q R 10 And, R 3 However, [R 11 O] x H is, R 4 and R 5 However, independently, H, C 1 ~C 22 Alkyl, -[R 11 O] x H, or -NR 1 R 2 And, R 6 However, H, alkyl, aryl, benzyl, or aralkyl is optionally substituted with an alkyl group, alkoxy group, or hydroxyl group. R 7 and R 8 However, independently, it is H or alkyl, R 9 However, H or -[R 11 O] x H is, R 10 However, C 1 ~C 24 These are linear, branched, or cyclic alkyl, aryl, or aralkyl compounds. Each R 11 However, independently, -CH 2 -CH 2 -, -CH(CH 3 )-CH 2 -, -CH 2 -CH 2 -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 -, or -CH(C 6 H 6 )-CH 2 -and, n is an integer between 1 and 12. p is an integer between 0 and 12. q is 0 or 1, A polymer where each x is an independent integer between 2 and 1000. [2] R 4 and R 5 However, the polymer described in item 1 is H. [3] R 7 and R 8 The polymer described in item 1 or 2, wherein H is present. [4] R 10 The polymer described in any one of items 1 to 3, wherein n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-hexyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, or 2-ethylhexyl. [5] R 6 However, the polymer is H, as described in any one of items 1 to 4. [6] A polymer according to any one of items 1 to 5, wherein n, p, and q are 1. [7] A polymer according to any one of items 1 to 6, comprising 1 to 100 of the aforementioned repeating units. [8] R 4 、R 5 , and R 9 A polymer as described in any one of items 1 to 7, wherein H is and x is an integer between 2 and 20. [9] The polymer according to any one of items 1 to 8, further comprising a second repeating unit containing a condensation product of a phenol compound and an aldehyde.

[10] The polymer according to item 9, wherein the phenol compound is phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or a combination of two or more thereof.

[11] The polymer according to item 9 or 10, wherein the aldehyde is formaldehyde, acetaldehyde, benzaldehyde, vanillin, salicylic acid, glyoxal, glyoxylic acid, or a combination of two or more thereof.

[12] Each R 11 However, -CH 2 -CH 2 -A polymer as described in any one of items 1 through 11.

[13] Each R11 However, -CH 2 -CH 2 -and-CH(CH 3 )-CH 2 - A polymer selected from any one of items 1 to 12.

[14] The polymer according to any one of items 1 to 13, wherein the polymer excludes repeating units having the structure of formula II.

[15] A composition comprising a polymer described in any one of items 1 to 14 and a solvent, wherein the composition comprises 1% to 99.9% by weight of the polymer.

[16] A composition comprising crude oil, washing water, and a polymer described in any one of items 1 to 14 or a composition described in item 15.

[17] A method for processing an industrial process flow, the method comprising adding a polymer according to any one of items 1 to 14 or a composition according to item 15 to the industrial process flow to form a processed industrial process flow.

[18] The method according to item 17, wherein the industrial process flow includes crude oil and wash water.

[19] The method according to item 17 or 18, further comprising allowing the treated industrial process flow to stand for 10 minutes to 12 hours.

[20] The method according to any one of items 17 to 19, wherein the addition is the addition of the polymer described in item 1 in an amount of 0.1 ppm to 10,000 ppm to the industrial process flow.

[21] Use of a polymer described in any one of items 1 to 14 or a composition described in item 15 for decomposing emulsions in industrial process flows.

Claims

1. A polymer comprising repeating units having the structure of formula I, formula II, or a combination thereof, 【Chemistry 1】 During the ceremony, R １ and R ２ are - (CR ７ R ８ ) ｎ (CHOR ９ )(CH ２ ) ｐ (O) ｑ R １０ where R ３ However, [R １１ O] ｘ It is H, R ４ and R ５ However, independently, H and C １ ~C ２２ Alkyl, -[R １１ O] ｘ H, or -NR １ R ２ And, R ６ However, it is H, alkyl, aryl, benzyl, or aralkyl, which are optionally substituted with an alkyl group. R ７ and R ８ However, independently, it is H or alkyl, R ９ However, H or -[R １１ O] ｘ It is H, R １０ However, C １ ~C ２４ These are linear, branched, or cyclic alkyl, aryl, or aralkyl compounds. Each R １１ However, independently, -CH ２ -CH ２ -, -CH(CH ３ ) - CH ２ -ien-CH ２ -CH ２ -CH ２ -ien-CH ２ -CH ２ -CH ２ -CH ２ -, or -CH(C ６ H ６ ) - CH ２ - and n is an integer between 1 and 12. p is an integer from 0 to 12, q is 0 or 1, A polymer in which each x is an independent integer between 2 and 1000.

2. R ４ and R ５ The polymer according to claim 1, wherein H is present.

3. R ７ and R ８ The polymer according to claim 1 or 2, wherein H is present.

4. R １０ The polymer according to any one of claims 1 to 3, wherein the polymer is selected from n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-hexyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, or 2-ethylhexyl.

5. R ６ The polymer according to any one of claims 1 to 4, wherein H is present.

6. The polymer according to any one of claims 1 to 5, wherein n, p, and q are 1.

7. The polymer according to any one of claims 1 to 6, comprising 1 to 100 of the repeating units.

8. R ４ , R ５ , and R ９ The polymer according to any one of claims 1 to 7, wherein x is H and x is an integer from 2 to 20.

9. The polymer according to any one of claims 1 to 8, further comprising a second repeating unit containing a condensation product of a phenol compound and an aldehyde.

10. The polymer according to claim 9, wherein the phenol compound is phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or a combination of two or more thereof.

11. The polymer according to claim 9 or 10, wherein the aldehyde is formaldehyde, acetaldehyde, benzaldehyde, vanillin, salicylic acid, glyoxal, glyoxylic acid, or a combination of two or more thereof.

12. Each R １１ However, -CH ２ -CH ２ - The polymer according to any one of claims 1 to 11.

13. Each R １１ However, -CH ２ -CH ２ - and -CH(CH ３ ) - CH ２ A polymer according to any one of claims 1 to 12, selected from -.

14. The polymer according to any one of claims 1 to 13, wherein the polymer excludes repeating units having the structure of formula II.

15. A composition comprising a polymer according to any one of claims 1 to 14 and a solvent, wherein the composition comprises 1% to 99.9% by weight of the polymer.

16. A composition comprising crude oil, washing water, and the polymer according to any one of claims 1 to 14 or the composition according to claim 15.

17. A method for processing an industrial process flow, the method comprising adding a polymer according to any one of claims 1 to 14 or a composition according to claim 15 to the industrial process flow to form a processed industrial process flow.

18. The method according to claim 17, wherein the industrial process flow includes crude oil and wash water.

19. The method according to claim 17 or 18, further comprising allowing the treated industrial process flow to stand for 10 minutes to 12 hours.

20. The method according to any one of claims 17 to 19, wherein the addition is the addition of the polymer according to claim 1 in an amount of 0.1 ppm to 10,000 ppm to the industrial process flow.

21. Use of the polymer according to any one of claims 1 to 14 or the composition according to claim 15 for decomposing emulsions in industrial process flows.

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