(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 bis(hydroxycarbyl)amino functionality. The polymers are useful as antifouling agents, polymerization inhibitors, rheology modifiers, dehaze agents, polymerization retarders, surfactants, or combinations thereof in one or more industrial process streams.

Description

[Technical Field]

[0001] The present invention generally relates to polymer compositions based on the condensation of phenol compounds and aldehydes. [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, emulsifiers, 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 some 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.

Summary of the Invention

Problems to be Solved by the Invention

[0008] The development of environmentally friendly monomers that are usefully used to form polymers having novel and useful properties is continuously required in the industry. Furthermore, there is a need to provide alternatives to alkylphenols for many applications in which these compounds have found industrial utility.

Means for Solving the Problems

[0009] Bis(hydroxycarbyl)aminophenolic ("HCAP") polymers, compositions comprising HCAP polymers, and methods of using HCAP polymers are described herein. The HCAP polymer comprises HCAP repeating units according to Formula I. <00001​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​H is alkyl, aryl, benzyl, or aralkyl, which is optionally substituted with an alkyl group, alkoxy group, or hydroxyl group, n is an integer from 1 to 12, p is 0 or an integer from 1 to 12, and q is 0 or 1.

[0010] In this embodiment, R 3 H is H. In this embodiment, R 4 and R 5 H is H. In this embodiment, R 6 and R 7 H is H. In this embodiment, R 9 is H. In the embodiment, n, p, and q are 1. In the embodiment, R 8 The compound is n-octyl, isooctyl, n-decyl, isodecyl, n-hexyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-butyl, or 2-ethylhexyl. In embodiments, the HCAP polymer contains 1 to 100 HCAP repeating units. In embodiments, the HCAP repeating unit is a first repeating unit, and the HCAP polymer is an HCAP copolymer further comprising a second repeating unit containing a condensation product of a phenol compound and an aldehyde. In embodiments, the phenol compound is phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or a mixture of two or more thereof.

[0011] In some embodiments, the HCAP polymer comprises HCAP repeating units according to formula II. [ka] In the formulas, R1, R2, R3, R5, and R9 are the same as those in formulas I and II. In some embodiments, the HCAP polymer includes one or more HCAP repeating units according to formula II, and excludes HCAP repeating units according to formula I. In other embodiments, the HCAP polymer includes one or more HCAP repeating units according to formula I, and excludes HCAP repeating units according to formula II. In yet another embodiment, the HCAP polymer may be characterized by including one or more HCAP repeating units according to formula I and one or more HCAP repeating units according to formula II. Thus, in embodiments, the HCAP copolymer includes, essentially consists of, or comprises one or more HCAP repeating units of formula I, II, or a combination thereof. In embodiments, the HCAP copolymer includes one or more HCAP repeating units of formula I, II, or a combination thereof; and one or more additional repeating units including condensation products of phenol compounds and aldehydes. In some such embodiments, one or more HCAP repeating units of formula I, II, or combinations thereof constitute a first repeating unit, and the HCAP copolymer further comprises a second repeating unit comprising a condensation product of a phenol compound and an aldehyde. In embodiments, the phenol compound is phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or a mixture of two or more thereof. In embodiments, the aldehyde is formaldehyde, acetaldehyde, benzaldehyde, vanillin, salicylic acid, glyoxal, glyoxylic acid, or a mixture of two or more thereof.

[0012] In embodiments, the HCAP polymer is an HCAP prepolymer. In embodiments, the HCAP polymer is an HCAP resin. In embodiments, the HCAP resin consists of, is essentially derived from, or includes a stable three-dimensional curing network. The HCAP resin has industrially recognized characteristics such as excellent hardness, thermal stability, and chemical impermeability. In embodiments, the HCAP polymer exhibits polymerization inhibitory or polymerization retardant properties when added to one or more sources of polymerizable species. Such sources include, for example, industrial process flows for producing styrene, isoprene, butadiene, or other ethylenically unsaturated monomers; and petroleum by-products entrained or emulsified in water, including pyrogas, pital, and asphaltene found in productive water and water quench systems in petroleum processing and reaction systems such as pyrolysis or ethylene decomposition systems. In embodiments, the HCAP resin exhibits biofilm inhibitory properties. In embodiments, the HCAP resin exhibits biocidic activity. In embodiments, HCAP resin is a rheological modifier for petroleum-based liquids and compounds dissolved or dispersed in petroleum-based liquids. In embodiments, HCAP resin is an emulsifying disruptor for petroleum materials entrained in water (such as asphaltenes or pyragas products) or for inverting water-in-oil polymer grids in preparations for, for example, water-based methods (tertiary petroleum recovery) or other underground injection applications. In embodiments, HCAP resin is a dehazing agent for fuel compositions including diesel, gasoline, jet fuel, and kerosene.

[0013] Other subjects and characteristics are, in part, self-evident, and some are shown below. [Modes for carrying out the invention]

[0014] 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.

[0015] definition

[0016] 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.

[0017] As used herein, the term “contaminant” means any one or more species present in and that can precipitate from an industrial process stream containing hydrocarbons, water, or mixtures thereof. Known contaminants present in hydrocarbons such as crude oil include asphaltenes, waxes, heavy oil, tar, and aliphatic and aromatic hydrocarbons having a density less than that of water, as well as other dissolved or dispersed organic and inorganic solids. Other known contaminants include by-products of hydrocarbon reaction or hydrocarbon refining processes, including polynuclear aromatic hydrocarbons, coke, oligomers and polymers (formed from the polymerization of vinyl by-products of hydrocarbon processing such as oxidized hydrocarbons, styrene, butadiene, and cyclopentadiene); and materials such as pyrolysis products resulting from the decomposition, aggregation, and / or polymerization of any of the aforementioned or other contaminant species present in an industrial process stream containing hydrocarbons, water, or mixtures thereof.

[0018] As used herein, the term “antifouling agent” means any one or more compounds, or a composition comprising one or more compounds, that are effective in preventing the precipitation of one or more contaminants present in an industrial process flow. The antifouling agent is added to the industrial process flow in an amount effective in preventing, reducing, or delaying the precipitation of one or more contaminants present in or from the industrial process flow. Thus, the antifouling agent has “antifouling properties” with respect to an industrial process flow that is effective in preventing, reducing, or delaying the precipitation of one or more contaminants.

[0019] As used herein, the terms “comprise(s),” “include(s),” “having,” “has,” “can,” and “contain(s),” 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.

[0020] 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.

[0021] Where used herein, the term “about” modifies the amount, concentration, volume, process temperature, process time, yield, flow rate, pressure, and similar values, and 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 amounts due to the degradation of a formulation having a particular initial concentration or mixture, and different amounts 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.”

[0022] 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.

[0023] 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.

[0024] Consideration

[0025] A bis(hydroxycarbyl)aminophenol polymer ("HCAP polymer" or "HCAP resin") is disclosed, which is a polymer compound comprising one or more repeating units, each containing a condensation product of a bis(hydroxycarbyl)aminophenol compound (HCAP compound) and an aldehyde. In embodiments, the HCAP compound has one of the following structures: [ka] In the formula, R 1 and R 2 However, -(CR 6 R 7 ) n (CHOH)(CH2) p (O) q R 8 And R 3 However, H is alkyl, aryl, benzyl, or aralkyl, and R 4 and R 5 However, independently, H, or C1~C 22 Alkyl, -OH, or NR1R2, R 6 and R 7 However, independently, H or alkyl, and R 8 However, C1~C 24 The molecule is linear, branched, or cyclic alkyl, aryl, or aralkyl, where n is an integer from 1 to 12, p is 0 or an integer from 1 to 12, and q is 0 or 1. In the embodiment, R 4 and R 5 One or more of these are H or alkyl, and the HCAP compound is based on 4-aminophenol. In the embodiment, R 4 and R 5 One or more of these are H or -OH, and furthermore, the HCAP compound of formula I is based on an aromatic hydroxylated compound such as 4-aminoresorcinol or phloroglucinol. In the embodiment, R 6 and R 7 is H. In the embodiment, n, p, and q are each 1. In the embodiment, R 8 C4~C 18 It is a linear or branched alkyl group. In some such embodiments, R 8These are n-octyl, isooctyl, n-decyl, isodecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-hexyl, n-butyl, or 2-ethylhexyl.

[0026] In the embodiment, the HCAP compound is a bis(hydroxycarbyl)amino adduct-N(R) bonded to an aromatic ring compound. 1 R 2 The HCAP compound is characterized by comprising an aromatic ring compound having ), at least one hydroxyl group or alkoxyl group (phenolic hydroxyl group) bonded to the aromatic ring compound, and at least two hydrogen atoms readily subject to acid or base-catalyzed condensation with an aldehyde bonded to the aromatic ring compound. Accordingly, in embodiments, the HCAP compound is, for example, a bis(hydroxycarbyl)amino adduct of phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or another phenol compound. All embodiments relating to the HCAP compounds, repeating units, polymers, and copolymers disclosed herein are intended to be freely combined without limitation.

[0027] In some embodiments, HCAP compounds are identified in concurrently pending U.S. Patent Application No. 16 / 860,954 as polymerization inhibitors or polymerization retarders when added to industrial process streams for producing, for example, styrene, isoprene, butadiene, or other ethylenically unsaturated monomers. As such, HCAP compounds are suitably used to reduce free radical or oxidation-type polymerization occurring in such industrial process systems. However, the inventors have found that HCAP compounds are susceptible to condensation polymerization with aldehydes to form polymers having potential polymerization inhibitor, polymerization retarder, or antifouling activity in systems for processing ethylenically unsaturated monomers, or to prevent fouling by polymerizable species in petroleum by-products entrained or emulsified in water, including pyrogas, pital, and asphaltene found in product water and water quench systems in petroleum processing and reaction systems such as pyrolysis or ethylene cracking systems.

[0028] Therefore, in the embodiments, one or more HCAP compounds are condensed with an aldehyde 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. The HCAP repeating unit is defined as bis(hydroxycarbyl)amino adduct-N(R) as defined for the HCAP compound of formula I. 1 R 2 It is characterized by including ). In the embodiment, the HCAP repeating unit corresponds to formula I. [ka] In the formula, R 1 , R 2 , R 3 , R 4 , and R 5 As defined above, R 9 H, alkyl, aryl, benzyl, or aralkyl is optionally substituted with an alkyl group, alkoxy group, or hydroxyl group. All embodiments relating to the HCAP repeating unit are intended to be freely combinable. In the embodiment, R 9 H is H. In this embodiment, R 9 This is CH3. In this embodiment, R 9 is COOH. In the embodiment, R 9 is benzyl. In the embodiment, R 9 teeth, [ka] And, In the formula, R 10 is methyl or ethyl. In the embodiment, R 9 It contains one or two oxygen atoms. In the embodiment, R 9 This includes the ether portion. In the embodiment, R 9contains a hydroxyl moiety. In some embodiments, R 9 contains one or more hydroxyl moieties, one or more ether moieties, or combinations thereof. In an embodiment, R 9 contains a crosslinking moiety. For example, glyoxal (bisaldehyde) is used as the aldehyde. The bisaldehyde contains two aldehyde functional groups that can condense with the HCAP functional group, thus enabling crosslinking of the resulting HCAP polymer. In an embodiment, R 4 and R 5 one or more of are H or -OH, and further, the HCAP repeating unit is based on an aromatic hydroxylated compound such as resorcinol or phloroglucinol.

[0029] In an embodiment of the repeating unit of Formula I, R 3 is H. In an embodiment of the repeating unit of Formula I, R 4 is H. In an embodiment of the repeating unit of Formula I, R 5 is H. In an embodiment of the repeating unit of Formula I, R 6 is H. In an embodiment of the repeating unit of Formula I, R 7 is H. In an embodiment of the repeating unit of Formula I, R 3 R 4 R 5 R 6 and R 7 two or more of are H. In an embodiment of the repeating unit of Formula I, R 3 R 4 R 5 R 6 and R 7 are H.

[0030] Furthermore, in an embodiment of the repeating unit of Formula I, R 6 and R 7 are H, n is 1, and q is 0. In some embodiments of the repeating unit of Formula I, R 8 is a branched-chain alkyl group, an aryl group, or an aralkyl group. In some embodiments of the repeating unit of Formula I, R 8 is C4 - C 24Branched-chain alkyl or C6-C 24 It is aralkyl. In the embodiment, the repeating unit of formula I includes n having a value of 0, 1, or 2. In the embodiment, the repeating unit of formula II includes p having a value of 0, 1, or 2.

[0031] The HCAP repeating unit is -N(R) as shown in equation I. 1 R 2 The HCAP repeating unit is characterized by comprising a bis(hydroxycarbyl)amino adduct defined by ). 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. All embodiments relating to the HCAP repeating units disclosed herein are intended to be freely combined. In embodiments, the HCAP repeating unit is an HCAP repeating unit of formula I. In embodiments, the HCAP polymer comprises one or more HCAP repeating units according to formula I.

[0032] In the embodiment, the HCAP polymer is a polymer containing at least one HCAP repeating unit. 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.

[0033] In embodiments, the HCAP polymer is an HCAP copolymer. In embodiments, 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. In embodiments, the HCAP copolymer comprises a repeating unit according to formula I.

[0001] The combination of the aforementioned condensation strategies is advantageous in providing a broad range of compositions and structures for HCAP polymer condensates. 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. In embodiments, the weight-average molecular weight of the HCAP polymer product is about 200 Da to about 1,000,000 Da, for example, 200 Da to 800,000 Da, 500 Da to 600,000 Da, 1,000 Da to 400,000 Da, 1,000 Da to 200,000 Da, 1,000 Da to 100,000 Da, 1,000 Da to 80,000 The ranges are 0Da, 1,000Da~60,000Da, 1,000Da~40,000Da, 1,000Da~20,000Da, 5,000Da~800,000Da, 5,000Da~600,000Da, 5,000Da~400,000Da, 5,000Da~200,000Da, or 5,000Da~100,000Da.

[0034] The number of HCAP repeating units in a homopolymer or copolymer condensate can be represented by m, where m is an integer or an average value such as a weight average or number average of 1 to 100 for copolymer condensates and 3 to 100 for homopolymer condensates. Thus, exemplary but non-limiting HCAP polymers include homopolymers and copolymers containing one or more repeating units I(a) to I(e). [ka]

[0035] The repeating unit I(a) is formed from the reaction of 4-aminophenol with butyl glycidyl ether, followed by condensation with formaldehyde. The repeating unit I(b) is formed by the reaction of 4-aminophenol with 1,2-epoxyoctane, followed by condensation with formaldehyde. The repeating unit I(c) is formed by the reaction of 4-aminophenol with 2-ethylhexyl glycidyl ether, followed by condensation with benzaldehyde. The repeating unit I(d) is formed by the reaction of 4-aminophenol with styrene oxide, followed by condensation with formaldehyde. The repeating unit I(e) is formed by the reaction of 4-aminophenol with a mixed C8-C 10 alkyl glycidyl ether, followed by condensation with benzaldehyde. In some embodiments, the mixed C8-C 10 alkyl glycidyl ether comprises a mixture of linear C8-C 10 alkyl moieties, while in other embodiments, the mixed C8-C 10 alkyl glycidyl ether comprises a mixture of linear and branched C8-C 10 alkyl moieties.

[0036] In other exemplary but non-limiting embodiments, the HCAP polymer comprises one or more repeating units according to formula II. [Chemical formula] In the formulas, R1, R2, R3, R5, and R9 are the same as those in formulas I and II. In embodiments, the HCAP polymer is an HCAP copolymer comprising one or more repeating units of both formulas I and II. In some embodiments, the HCAP polymer comprises one or more HCAP repeating units according to formula II and excludes HCAP repeating units according to formula I. In other embodiments, the HCAP polymer comprises one or more HCAP repeating units according to formula I and excludes HCAP repeating units according to formula II. In yet another embodiment, the HCAP polymer may be characterized by comprising one or more HCAP repeating units according to formula I and one or more HCAP repeating units according to formula II. Thus, in embodiments, the HCAP copolymer comprises, essentially consists of, or comprises one or more HCAP repeating units of formulas I, II, or combinations thereof. In embodiments, the HCAP copolymer comprises one or more HCAP repeating units of formulas I, II, or combinations thereof; and one or more additional repeating units comprising condensation products of phenol compounds and aldehydes. In some such embodiments, one or more HCAP repeating units of formula I, II, or combinations thereof constitute a first repeating unit, and the HCAP copolymer further comprises a second repeating unit comprising a condensation product of a phenol compound and an aldehyde. In embodiments, the phenol compound is phenol, resorcinol, pyrocatechol, hydroquinone, phloroglucinol, hydroxyhydroquinone, or a mixture of two or more thereof. In embodiments, the aldehyde is formaldehyde, acetaldehyde, benzaldehyde, vanillin, salicylic acid, glyoxal, glyoxylic acid, or a mixture of two or more thereof.

[0037] In embodiments, the synthesis of HCAP compounds is described in concurrently pending U.S. Patent Application No. 16 / 860,954. In embodiments, HCAP is formed by a neat (solvent-free, 100% solid, or 100% active) reaction in a selected molar ratio of an aminophenol compound, such as 4-aminophenol, and a selected epoxy-functional compound (typically, but not always, a glycidyl ether). In embodiments, about 2 moles of the epoxy-functional compound are contacted with about 1 mole of the aminophenol compound. In other embodiments, an excess molar amount of the epoxy-functional compound is used in the reaction.

[0038] In some embodiments, the synthesis of HCAP compounds is achieved by contacting an aminophenol compound and an epoxy-functional compound at a temperature of 50°C to 200°C, where contact is achieved by one or more of the following methods: excluding air or substantially excluding air, heating, stirring, adding one of the two reagents dropwise to the other, in a batch or continuous manner. In some embodiments, substantially excluding air is achieved by covering or sparging the reaction vessel with an inert gas such as Ar or N2. In some embodiments, the synthesis of HCAP is facilitated by further including a solvent, such as a petroleum-based solvent, in an amount up to 100% by volume, based on the mass or volume of the combined reagents. In some embodiments, water is substantially excluded from the synthesis in such a way that no additional water is added to the reaction vessel.

[0039] In the embodiment, an HCAP compound is synthesized and optionally isolated by purification (e.g., by recrystallization and / or evaporation of the solvent), then condensed with an aldehyde to form an HCAP prepolymer, which is converted into an HCAP resin. In the embodiment, one or more HCAP repeating units of the HCAP resin are HCAP repeating units of formula I or II or a combination thereof. The HCAP resin is an HCAP homopolymer or HCAP copolymer as described above.

[0040] Therefore, the HCAP polymer or polymer product is defined herein as either an HCAP prepolymer or an HCAP resin. In embodiments, the HCAP prepolymer is formed by 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.

[0041] In some embodiments, condensation reactions commonly used in forming phenol aldehyde prepolymers (novalac and resol) or cured phenol resins are advantageously used herein to form HCAP prepolymers and HCAP resins, including copolymer prepolymers and / or 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.

[0042] Therefore, 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 mild heating conditions, for example, 50°C to 120°C, or about 60°C to 100°C, to obtain a polymer condensation product or prepolymer. Suitable curing catalysts include sodium hydroxide, sulfuric acid, potassium hydroxide, triethylamine, oxalic acid, p-toluenesulfonic acid, p-dodecylbenzenesulfonic acid, methanesulfonic acid, dioctyl sulfosuccinate, or curing catalyst resins (such as resins sold by Georgia Pacific Corporation (Atlanta, GA) under the trade name RESI-CAT®, such as GP® 012G23 RESI-CAT®). The acid or base catalyst is added to the reaction vessel in conventional amounts, for example, 10 ppm to 7% by weight based on the weight of the reaction mixture, for example, 10 ppm to 200 ppm, 200 ppm to 500 ppm, 500 ppm to 1000 ppm, 1000 ppm to 2000 ppm, 2000 ppm to 0.5% by weight, 0.5% to 1% by weight, 1% to 2% by weight, 2% to 5% by weight, 5% to 7% by weight, 10 ppm to 1000 ppm, 10 ppm to 1% by weight, 100 ppm to 1% by weight, or 1000 ppm to 1% by weight based on the weight of the reaction mixture.

[0043] In the embodiments, the synthesis of the HCAP prepolymer is preferably carried out in an inert solvent. A mild temperature can be used to initially react the aldehyde with the HCAP compound and any other aromatic hydroxylated compounds present, so aromatic naphtha, paraffinic solvents, or heavy aromatic naphtha can be used as solvents. Based on the total mass of the aldehyde and the HCAP compound, a petroleum-based aromatic or paraffinic solvent, or a fractional or single-compound petroleum-based solvent, such as xylene, is favorably used as a mediator for the condensation reaction in an amount of 25% to 75% by volume, for example, 30% to 75% by volume, or 40% to 75% by volume, or 50% to 75% by volume, or 60% to 75% by volume, or 70% to 75% by volume, or 25% to 70% by volume, or 25% to 60% by volume, or 25% to 50% by volume, or 25% to 40% by volume, or 25% to 30% by volume.

[0044] In the embodiments, the synthesis of the HCAP prepolymer is carried out in the absence of added water. In the embodiments, 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 embodiments, the synthesis of the HCAP prepolymer is achieved by adding an acid or base catalyst to the reaction vessel, along with enough water to dissolve the acid or base and / or deliver it to the reaction vessel.

[0045] In some embodiments, after condensation is complete, the HCAP prepolymer is dispersed in a selected solvent. The selected solvent is preferably a hydrocarbon solvent or a mixture thereof having a boiling point above 100°C. The HCAP prepolymer is dispersed in the solvent with a total solid content of 30% to 90% by weight, or 35% to 80% by weight, or about 40% to 70 wt%, or about 50% to 60% by weight, based on the weight of the dispersion. The HCAP prepolymer is suitably 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 "curing") simultaneously with the evaporation of the solvent, such as by coating and evaporative heating, 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.

[0046] HCAP resins are stable, three-dimensional curing networks. HCAP resins possess industrially recognized characteristics such as excellent hardness, thermal stability, and chemical impermeability. In embodiments, HCAP resins exhibit antifouling properties when added to one or more sources of polymerizable species. Such sources include, in various embodiments, industrial process flows for producing styrene, isoprene, butadiene, or other ethylenically unsaturated monomers; as well as petroleum by-products entrained or emulsified in water, including pyrogas, pital, and asphaltene found in the water-generated water and water-quenching systems of petroleum processing and reaction systems such as pyrolysis or ethylene decomposition systems. In embodiments, HCAP resins exhibit biofilm-inhibiting properties or biocide activity. In embodiments, HCAP resins are rheological modifiers for petroleum-based liquids and compounds dissolved or dispersed in petroleum-based liquids. In embodiments, HCAP resins are useful as emulsifying agents for water-in-oil polymer grid inversion in preparations for petroleum materials (such as asphaltenes or pyro-gas products) encompassed in water, or for, for example, water-based methods (tertiary petroleum recovery) or other underground injection applications. In embodiments, HCAP resins are useful as dehazing agents for fuel compositions including diesel, gasoline, jet fuel, and kerosene.

[0047] The HCAP resins described herein comprise one or more HCAP repeating units. Each HCAP repeating unit comprises at least two alkanolic 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 alkanolic and / or aromatic hydroxyl groups, and one or more adducts bonded thereto are bonded thereto to form a functionalized HCAP resin.

[0048] In embodiments, one or more HCAP resins are suitably combined with one or more additional components to provide an HCAP composition. Thus, in embodiments, the HCAP composition comprises, essentially consists of, or comprises one or more HCAP resins and one or more additional components. In embodiments, the one or more additional components comprises, essentially consists of, or comprises a solvent. In embodiments, the solvent is selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ether, or any combination thereof. In some embodiments, the alcohol is selected from methanol, ethanol, isopropanol, 2-ethylhexanol, benzyl alcohol, or any combination thereof. In some embodiments, the glycol is ethylene glycol or glycol ether (such as ethylene glycol monobutyl ether), or any combination thereof. In some embodiments, the HCAP composition excludes alkylphenols and / or alkylphenol alkoxylates.

[0049] In some embodiments, one or more additional components present in or added to the HCAP compositions disclosed herein include one or more corrosion inhibitors, viscosity reducers, friction reducers, scale inhibitors, clay swelling inhibitors, biocides, dispersants, backflow aids, emulsifiers, emulsifier disruptors, hydrogen sulfide scavengers, hydrate inhibitors, pH modifiers, surfactants, and / or other chemical additives known to those skilled in the art of crude oil production, refining, and chemical processing.

[0050] In embodiments, the HCAP composition comprises, based on the total weight of the composition, one or more HCAP polymers in an amount of at least 5% by weight and up to 99.9% by weight, and one or more additional components in an amount of 0.01% to 95% by weight, for example, 0.01% to 90% by weight, 0.01% to 80% by weight, 0.01% to 70% by weight, 0.01% to 60% by weight, 0.01% to 50% by weight, 0.01% to 40% by weight, 0.01% to 30% by weight, 0.01% to 20% by weight, 0.01% to 10% by weight, 0.01% to 5% by weight, 0.01% to 4% by weight, 0.01% to 3% by weight, 0.01% to 2% by weight, 0.01% to 1% by weight, or 0.01% to 0.1% by weight of the total of the one or more additional components. One or more additional components are suitably mixed with one or more HCAP resins in any order to obtain the HCAP composition.

[0051] In accordance with the foregoing disclosure, one or more HCAP resins, or compositions comprising one or more HCAP resins, may be usefully added to one or more industrial process flows to provide one or more benefits to the industrial process flows compared to the same industrial process flows in which the one or more HCAP resins are absent. Such benefits include obtaining one or more of the following properties or effects: antifouling, antipolymerization, flow modification, biofilm suppression, biocidal activity, cloud removal, emulsion disruption, and increased yield in tertiary oil recovery.

[0052] Therefore, in the embodiments, one or more HCAP resins, or compositions comprising one or more HCAP resins, are suitably added to industrial process flows containing one or more contaminants, and the HCAP resins have antifouling properties when added thereto. In the embodiments, the contaminants include or are essentially composed of asphaltenes, waxes, or combinations thereof, and the compositions comprising one or more HCAP resins, or one or more HCAP resins having one or more additional components, are effective as antifouling agents when added to industrial process flows. In some embodiments, the compositions comprising one or more HCAP resins, or one or more HCAP resins having one or more additional components, are suitably added to industrial process flows containing or are essentially composed of one or more polymerizable species. In the embodiments, the polymerizable species comprises one or more of styrene, isoprene, butadiene, or other ethylenically unsaturated monomers, and the compositions comprising HCAP resins, or HCAP resins having one or more additional components, acquire antifouling properties when added thereto. The antifouling properties of one or more HCAP resins prevent one or more contaminants from settling on one or more surfaces present in an industrial processing system used in manufacturing or processing operations performed against an industrial process flow, such as the surfaces of metal pipes, pumps, heating or cooling devices, and other parts and surfaces of the industrial processing system that come into contact with the industrial process flow during manufacturing or processing.

[0053] In some embodiments, an industrial process stream containing one or more contaminants contains, is essentially composed of, or consists of one or more hydrocarbon compounds. In some such embodiments, one or more hydrocarbon compounds are crude oil or are present in crude oil. In some embodiments, an industrial process stream containing one or more contaminants is crude oil. In other embodiments, an industrial process stream containing one or more contaminants is a reaction product or refined petroleum product resulting from one or more industrial processes carried out on the industrial process stream, prior to the addition of one or more HCAP resins or compositions containing one or more HCAP resins to the industrial process stream.

[0054] In some embodiments, where an industrial process stream containing one or more contaminants contains, is essentially, or consists of one or more hydrocarbon compounds, the contaminants are waxes. Petroleum waxes are generally solid or semi-solid, crystalline or semi-crystalline C2 waxes that are naturally present in crude oil and in some of its refining or reaction products. 20 ~C 50 The hydrocarbons are hydrocarbons. The antifouling properties of one or more HCAP resins prevent one or more waxes present in the industrial treatment flow from settling on one or more surfaces present in the industrial hydrocarbon treatment system, such as metal pipes, pumps, heating equipment surfaces, and other parts and surfaces that come into contact with the one or more waxes present in the industrial treatment flow. The antifouling properties of one or more HCAP resins prevent the settling of one or more waxes present in the industrial treatment flow during batch storage and transport of the industrial treatment flow, for example, during storage and transport of the industrial treatment flow in metal or plastic containment vessels. Storage or transport containment vessels are any containers or vessels used to store or transport crude oil or hydrocarbons or mixtures thereof, and include, but are not limited to, storage tanks, railcars, tank trucks, ships, barges, or pipelines.

[0055] In embodiments, an industrial process stream containing one or more fouling substances contains, is essentially derived from, or consists of generated water. In embodiments, an industrial process stream containing one or more fouling substances contains, is essentially derived from, or consists of quench water. The quench water and generated water are industrial process streams containing one or more petroleum by-products encompassed, dispersed, or emulsified in water, the one or more by-products being Pygas, Pytar, asphalten, or mixtures thereof. Quench water is placed in a water quench system for petroleum processing and reaction systems, such as pyrolysis or ethylene decomposition systems, in which the addition of one or more HCAP resins, or a composition containing one or more HCAP resins, to the quench water makes it effective as an antifouling agent compared to the same quench water without the one or more HCAP resins. The antifouling properties of one or more HCAP resins prevent one or more fouling substances from settling on one or more surfaces present in the water quench system, such as metal pipes, pumps, heating devices, and other parts and surfaces of the water quench system in contact with one or more fouling substances. The generated water, also called "connate," is natural water obtained during the petroleum recovery process along with crude oil, and contains one or more petroleum by-products encompassed therein, often including 0.1% and 30% by weight of total dissolved solids dispersed therein, and in some embodiments further including materials such as organic and inorganic debris and salts (including calcium salts).

[0056] In embodiments, the HCAP resin is a rheological modifier for industrial process flows, comprising, essentially, or consisting of a petroleum-based liquid and a compound dissolved or dispersed in the petroleum-based liquid. Therefore, when one or more HCAP resins, or a composition comprising one or more HCAP resins with one or more additional components, is added in an effective amount to such an industrial process flow, the HCAP resins reduce or eliminate the increase in viscosity of the petroleum-based liquid during storage, i.e., over time, compared to the same industrial process flow without the presence of the HCAP resins. In embodiments, the HCAP resin is a dehazing agent for industrial process flows, comprising, essentially, or consisting of a fuel composition comprising diesel, gasoline, jet fuel, and kerosene. Therefore, when one or more HCAP resins, or a composition comprising one or more HCAP resins having one or more additional components, is added in an effective amount to such an industrial process flow, the one or more HCAP resins reduce or eliminate the loss of transparency and the occurrence of clouding observed in the fuel composition during storage, i.e., over time, compared to the same industrial process flow in which the one or more HCAP resins are absent.

[0057] In some embodiments, one or more HCAP resins, or compositions containing one or more HCAP resins, are continuously added to an industrial process flow, such as one of the aforementioned industrial process flows. In some embodiments, one or more HCAP resins, or compositions containing one or more HCAP resins, are added intermittently or semi-continuously to an industrial process flow, such as one of the aforementioned industrial process flows. In some embodiments, one or more HCAP resins, or compositions containing one or more HCAP resins, are added in batches to an industrial process batch, which is one or more distinct volumes of one or more of the aforementioned industrial process flows. In some embodiments, the amount of composition applied to a selected industrial process flow over a selected unit time is fixed. In other embodiments, the amount of composition applied to a selected industrial process flow over a selected unit time is variable.

[0058] In the embodiment, one or more HCAP resins are suitably added to an industrial process flow, such as one of the aforementioned industrial process flows, in an amount ranging from 0.1 ppm to 10,000 ppm based on the volume of the industrial process flow. In the embodiment, one or more HCAP resins are suitably added to an industrial process flow, such as one of the aforementioned industrial process flows, in an amount ranging from 0.1 ppm to 10,000 ppm based on the weight of the industrial process flow. In the embodiment, an HCAP composition containing one or more HCAP resins is suitably added to an industrial process flow, such as one of the aforementioned industrial process flows, in an amount corresponding to one or more HCAP resins ranging from 0.1 ppm to 10,000 ppm, based on the volume or weight of the industrial process flow. In any of these embodiments, one or more HCAP resins are present in concentrations of 0.1 ppm to 10,000 ppm, 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 250 ppm, 0.1 ppm to 100 ppm, 0.1 ppm to 50 ppm, 0.1 ppm to 40 ppm, 0.1 ppm to 30 ppm, 0.1 ppm to 20 ppm, and 0.1 ppm to 20 ppm, based on the volume of the industrial process flow or the weight of the industrial process flow. It is suitably added to industrial process flows, such as any of the aforementioned industrial process flows, in amounts of ppm~10 ppm, 0.1 ppm~5 ppm, 0.1 ppm~1 ppm, 1 ppm~10,000 ppm, 1 ppm~8,000 ppm, 1 ppm~6,000 ppm, 1 ppm~4,000 ppm, 1 ppm~2,000 ppm, 1 ppm~1,000 ppm, 1 ppm~500 ppm, 1 ppm~250 ppm, 1 ppm~100 ppm, 1 ppm~50 ppm, 1 ppm~40 ppm, 1 ppm~30 ppm, 1 ppm~20 ppm, 1 ppm~10 ppm, or 1 ppm~5 ppm.

[0059] In accordance with the above, one or more HCAP resins are included in the treated industrial process flow composition. The treated industrial process flow comprises one or more HCAP resins, and the industrial process flow comprises contaminants. In the embodiment, the industrial process flow comprises, is essentially composed of, or consists of hydrocarbons. In the embodiment, the processed industrial process flow contains one or more HCAP resins ranging from about 0.1 ppm to about 10,000 ppm, based on either the volume or weight of the processed process flow, for example, based on either the volume or weight of the processed process flow, 0.1 ppm to 10,000 ppm, 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 250 ppm, 0.1 ppm to 100 ppm, 0.1 ppm to 50 ppm, 0.1 ppm to The HCAP resin comprises one or more HCAP resins in concentrations of 40 ppm, 0.1 ppm to 30 ppm, 0.1 ppm to 20 ppm, 0.1 ppm to 10 ppm, 0.1 ppm to 5 ppm, 0.1 ppm to 1 ppm, 1 ppm to 10,000 ppm, 1 ppm to 8,000 ppm, 1 ppm to 6,000 ppm, 1 ppm to 4,000 ppm, 1 ppm to 2,000 ppm, 1 ppm to 1,000 ppm, 1 ppm to 500 ppm, 1 ppm to 250 ppm, 1 ppm to 100 ppm, 1 ppm to 50 ppm, 1 ppm to 40 ppm, 1 ppm to 30 ppm, 1 ppm to 20 ppm, 1 ppm to 10 ppm, or 1 ppm to 5 ppm. In some embodiments, the processed industrial process flow is placed within an industrial processing system.

[0060] In some embodiments, the treated industrial process flow is stable at temperatures of approximately 20°C to 400°C, meaning that the HCAP resin does not substantially decompose or undergo substantial thermochemical transformation within the described temperature range when subjected to industrial processes requiring these temperatures. In some embodiments, the treated industrial process flow is placed within an industrial processing system and then subjected to temperatures of 20°C to 400°C. That is, the treated industrial process flow is in contact with the industrial processing system while being subjected to it, and the antifouling properties of the HCAP resin are not reduced or substantially reduced. "Substantially not reduced" means that the antifouling properties of the HCAP resin subjected to temperatures up to 400°C are reduced by less than 10% by using any measurement method known to those skilled in the art to measure the fouling of the industrial processing system based on the initial antifouling properties.

[0061] In the embodiments, the HCAP resin or HCAP composition, or both, is thermally stable under conditions commonly used or encountered in hydrocarbon process flows. Therefore, in the embodiments, one or more HCAP resins or HCAP compositions are added to one or more hydrocarbon process flows before subjecting the treated hydrocarbon process flow to one or more thermally difficult processes, such as hydrogenation. The HCAP resins retain their antifouling properties during hydrocarbon processing at temperatures of approximately 20°C to 400°C. Furthermore, the HCAP resins are hydrolyzably stable and resistant to hydrolysis even at temperatures above 100°C, making them suitable for use in hydrocarbon process flows containing liquid water or water vapor.

[0062] In the embodiments, an industrial process flow treated according to either of the uses or applications described above receives a reduction of at least 20% in contamination (precipitation of contaminants or wax) and a reduction of about 100% in contamination compared to the corresponding industrial process flow (i.e., the untreated process flow), for example, a reduction of 30% to 100% in contamination compared to the industrial processing system surface in contact with the corresponding untreated industrial process flow, or a reduction of 40% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, 90% to 100%, or 95% to 100% in measurable contamination on the industrial processing system surface in contact with the treated industrial process flow.

[0063] In embodiments, contamination reduction may be determined by the following tests: A selected volume of treated industrial process flow is added to hexane or heptane, and the diluted and treated industrial process flow is left at approximately 20°C for 2 hours. Any precipitate formed in the diluted and treated industrial process flow is measured by volume and reported as a percentage of the precipitate observed in a control sample, which is the corresponding untreated industrial process flow, similarly diluted with hexane or heptane. Contamination may be measured as the relative increase in the amount of precipitate obtained from the diluted and treated industrial process flow at the end of the 2-hour period, compared to the retention of solids in the untreated industrial process flow over the same period. Contamination may also be measured as the relative decrease in the weight or volume of precipitate resulting from a selected contact period of the treated industrial process flow in or placed within an industrial process system, compared to the same contact period between the industrial process system and the corresponding untreated industrial process flow.

[0064] In some embodiments, the treated industrial process flow is added to or placed within an industrial process system, the system includes an internal surface, and the treated hydrocarbon flow is in fluid contact with the internal surface. In embodiments, the internal surface includes, essentially consists of, or comprises a metal. In embodiments, the industrial process system includes items for extracting hydrocarbon products from underground reservoirs, for transporting one or more hydrocarbon products from a first location to a second location, or for separating, purifying, treating, separating, distilling, reacting, metering, heating, cooling, or housing one or more hydrocarbon products. [Examples]

[0065] experiment

[0066] Example 1

[0067] 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]

[0068] Example 2

[0069] 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.

[0070] Example 3

[0071] 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.

[0072] Example 4

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] Example 5

[0078] A 1 L four-necked round-bottom flask was packed with pN,N-di-[1-(2-ethylhexyloxy)-2-hydroxypropyl]aminophenol / formaldehyde resin prepared according to the procedure of Example 1 and potassium hydroxide. 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. When the reaction mixture reached 60°C, the N2 purge was increased.

[0079] Example 6

[0080] The procedure of Example 1 was repeated using 2-ethylhexylglycidyl ether or another alkylglycidyl ether in a 1:1 molar substitution thereof to prepare polymer resins AD-1 to AD-6 shown in Table 1. The resins were analyzed by gel permeation chromatography, and the weight-average molecular weight and polydispersity index of the resins are reported in Table 1.

[0081] Table 1. Weight-average molecular weight and polydispersity index of resins AD-1 to AD-6 in Example 7. [Table 1]

[0082] Next, resins AD-1 to AD-6 were tested for their effectiveness as asphaltene dispersants. The desired result of such tests is that when the resin is mixed with crude (unrefined) oil products containing dispersed asphaltene material, there is little to no precipitation of the asphaltene material. Solid precipitation from crude oil mixtures predicts the relative fouling behavior in petroleum process flows. Therefore, since the tests used actual crude oil materials, a blank (without dispersant) and conventional industrial asphaltene dispersants were tested in parallel to demonstrate the comparative effectiveness of resins AD-1 to AD-6 in preventing precipitation.

[0083] Therefore, to test each resin, 100 μL of crude oil with an API specific gravity of 20.3° was filled into a 15 mL graduated conical centrifuge tube, to which 10 ppm by weight of the resin (active substance) was added, and then 10 mL of n-heptane was added to the tube. The tube was then thoroughly mixed by hand until all the oil appeared to be dispersed. The test tubes were then placed in a test tube rack at ambient room temperature and left for 2 hours, after which the volume of the precipitate in the test tubes was recorded. The observed volume of the precipitate in each centrifuge tube after 2 hours is reported in Table 2.

[0084] In addition to testing each of the resins AD-1 to AD-6 using the procedure described above, a blank (without dispersant) was prepared for comparison, and two conventional industrial asphaltene dispersants were also tested for comparison purposes by adding 10 ppm by weight of the active substance, as reported by the manufacturer of formulations EC3019C and EC3238A, obtained from Ecolab Inc. (St. Paul, MN). The observed volume of each precipitate in the centrifuge tube after 2 hours is reported in Table 2.

[0085] Table 2. Observed volume of precipitate formed in 10 mL of test formulations containing AD-1 to AD-6. [Table 2]

[0086] Compared to commercially available asphaltene dispersants, resins AD-2, AD-3, AD-4, AD-5, and AD-6 were found to be equally or more effective in preventing precipitation, and AD-1 was equally or more effective than the commercially available asphaltene dispersant EC3238A. 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] In the formula, R 1 and R 2 However, -(CR 6 R 7 ) n (CHOH)(CH 2 ) p (O) q R 8 And R 3 However, H is alkyl, aryl, benzyl, or aralkyl, and R 4 and R 5 However, independently, H, or C 1 ~C 22 Alkyl, -OH, or NR 1 R 2 And R 6 and R 7 However, independently, H or alkyl, and R 8 However, C 1 ~C 24 R is a linear, branched, or cyclic alkyl, aryl, or aralkyl group. 9 A polymer in which H is alkyl, aryl, benzyl, or aralkyl, which is optionally substituted with an alkyl group, alkoxy group, or hydroxyl group, n is an integer from 1 to 12, p is 0 or an integer from 1 to 12, and q is 0 or 1. [2] R 3 However, the polymer described in item 1 is H. [3] R 4 and R 5 The polymer described in item 1 or 2, wherein H is present. [4] R 6 and R 7 However, the polymer is H, as described in any one of items 1 to 3. [5] R 9 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] R 8 The polymer according to any one of items 1 to 6, wherein the compound is n-octyl, isooctyl, n-decyl, isodecyl, n-hexyl, n-butyl, or 2-ethylhexyl. [8] A polymer according to any one of items 1 to 7, comprising 1 to 100 of the aforementioned repeating units. [9] The polymer according to any one of items 1 to 8, further comprising additional repeating units containing condensation products of phenol compounds and aldehydes.

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

[12] The polymer according to any one of items 1 to 11, wherein the polymer does not contain repeating units having the structure of formula II.

[13] A composition comprising a polymer described in any one of items 1 to 12, and a solvent selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ether, or any combination thereof.

[14] The composition according to item 13, further comprising one or more corrosion inhibitors, viscosity reducers, friction reducers, scale inhibitors, clay swelling inhibitors, biocides, dispersants, backflow aids, emulsifiers, emulsifiers, hydrogen sulfide scavengers, hydrate inhibitors, pH modifiers, or surfactants.

[15] The composition according to item 13 or 14, wherein the composition comprises 5% to 99.9% by weight of the polymer.

[16] A method for preventing contamination in an industrial process flow, the method comprising adding a polymer according to any one of items 1 to 12, or a composition according to any one of items 13 to 15, in a concentration of 0.1 ppm to 10,000 ppm, to the industrial process flow.

[17] The method according to item 16, wherein the industrial process flow is a crude oil process flow or contains one or more polymerizable species.

[18] A processed industrial process flow, A polymer according to any one of items 1 to 12 or a composition according to any one of items 13 to 15, A treated industrial process stream containing a mixture of contaminants and an industrial process stream containing contaminants.

[19] The treated industrial process stream described in item 18, wherein the contaminating substance includes asphaltene or wax.

[20] An industrial process system comprising an industrial process flow described in item 18 or 19, which is located within the system and is in fluid contact with a surface therein.

[21] Use of a polymer described in any one of items 1 to 12 or a composition described in any one of items 13 to 15 as an antifouling agent 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】 Wherein, R ９ , ２４ and R ２ are - (CR ６ R ７ ) ｎ (CHOH)(CH ２ ) ｐ (O) ｑ R ８ and R ３ is H, alkyl, aryl, benzyl, or aralkyl, R ４ [[ID=2&]]and R ５ are independently H, or C １ ~C ２２ alkyl, -OH, or NR １ R ２ wherein, when R ４ of Formula I is NR １ R ２ , R ４ of Formula II is not NR １ R ２ and R ６ and R ７ are independently H or alkyl, R ８ is a straight-chain, branched-chain, or cyclic alkyl, aryl, or aralkyl of C １ ~C ２４ , R ９ is H, alkyl, aryl, benzyl, or aralkyl optionally substituted with an alkyl group, n is an integer from 1 to 12, p is 0 or an integer from 1 to 12, q is 0 or 1, a polymer.

2. R ３ The polymer according to claim 1, wherein H is present.

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

4. R ６ and R ７ The polymer according to any one of claims 1 to 3, wherein H is present.

5. R ９ 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. R ８ The polymer according to any one of claims 1 to 6, wherein the polymer is n-octyl, isooctyl, n-decyl, isodecyl, n-hexyl, n-butyl, or 2-ethylhexyl.

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

9. The polymer according to any one of claims 1 to 8, further comprising additional repeating units 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 mixture 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 mixture of two or more thereof.

12. The polymer according to any one of claims 1 to 11, wherein the polymer does not contain repeating units having the structure of formula II.

13. A composition comprising a polymer according to any one of claims 1 to 12, and a solvent selected from toluene, heavy aromatic naphtha, xylene, glycol, water, alcohol, ethylene glycol, ethylene glycol monobutyl ether, kerosene, propylene carbonate, glycol ether, or any combination thereof.

14. The composition according to claim 13, further comprising one or more corrosion inhibitors, viscosity reducers, friction reducers, scale inhibitors, clay swelling inhibitors, biocides, dispersants, backflow aids, emulsifiers, emulsifiers, hydrogen sulfide scavengers, hydrate inhibitors, pH modifiers, or surfactants.

15. The composition according to claim 13 or 14, wherein the composition comprises 5% by weight to 99.9% by weight of the polymer.

16. A method for preventing contamination in an industrial process flow, the method comprising adding to the industrial process flow a polymer according to any one of claims 1 to 12, or a composition according to any one of claims 13 to 15, in an amount of 0.1 ppm to 10,000 ppm.

17. The method according to claim 16, wherein the industrial process flow is a crude oil process flow or comprises one or more polymerizable species.

18. A processed industrial process flow, A polymer according to any one of claims 1 to 12 or a composition according to any one of claims 13 to 15, A treated industrial process stream containing a mixture of contaminants and an industrial process stream containing contaminants.

19. The treated industrial process flow according to claim 18, wherein the contaminating substance comprises asphaltene or wax.

20. An industrial process system comprising an industrial process flow according to claim 18 or 19, which is located within the system and is in fluid contact with a surface therein.

21. Use of the polymer according to any one of claims 1 to 12 or the composition according to any one of claims 13 to 15 as an antifouling agent in industrial process flows.

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