Biocide composition
阅读说明：本技术 杀生物剂组合物 (Biocide composition ) 是由 维克托·凯亚斯勒 杰弗里·凯莱布·克拉克 卡里耶·凯勒-舒尔茨 布赖恩·迈克尔·贝内特 于 2014-07-31 设计创作，主要内容包括：本申请公开了杀生物剂组合物。所述组合物可用于与原油和天然气的生产、运输、存储和分离相关的应用。本申请还公开了使用所述组合物的方法,特别是在与原油和天然气的生产、运输、存储和分离相关的应用中使用所述组合物的方法。(Disclosed herein are biocide compositions. The compositions are useful in applications related to the production, transportation, storage, and separation of crude oil and natural gas. Also disclosed are methods of using the compositions, particularly in applications related to the production, transportation, storage, and separation of crude oil and natural gas.)
1. A biocide composition comprising:
an imidazoline compound;
a quaternary amine; and
phosphorus (P)
wherein the imidazoline compound has formula (I),
R1is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-Ci7H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen;
the phosphorus
wherein the quaternary amine is a benzalkonium salt represented by the formula:
wherein n is 8,10, 12, 14, 16 or 18; and X is Cl, Br or I.
2. The composition of claim 1, further comprising a demulsifier.
3. The composition of claim 2, wherein the demulsifier is selected from the group consisting of dodecylbenzylsulfonic acid (DDBSA), the sodium salt of xylenesulfonic acid (NAXSA), epoxidized and propoxylated compounds, anionic, cationic and nonionic surfactants, and resins, phenolic and epoxy resins, and combinations thereof.
4. A method of controlling microbial proliferation in a system for the production, transportation, storage and separation of crude oil and natural gas, the method comprising contacting the system with an effective amount of a composition according to any one of claims 1 to 3.
Technical Field
The present disclosure relates generally to biocides, and more particularly to biocides comprising imidazolines (e.g., acrylated imidazolines), quaternary amines, and phosphides
Background
Oilfield systems suffer from increased risks associated with microbial control, including: h2S production, Microbiologically Influenced Corrosion (MIC) and biofouling. When MIC is suspected in the system, the main area of interest becomes a biofilm or sessile organism on the surface of the pipeline. Within the industry, it is generally recognized that in order to effectively control bacteria within the system, in addition to providing sufficient planktonic kill (planktonic kill), one should focus on minimizing biofilm regrowth kinetics after treatment (sessile control). Albeit tetrakis- (hydroxymethyl) phosphonium
Disclosure of Invention
In one aspect, a biocide composition is disclosed comprising: an imidazoline compound; seasonAn amine; and phosphorus
The imidazoline compound has the formula (I),
wherein
R1、R4And R5Each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,
the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle are each independently unsubstituted or substituted at each occurrence with 1 to 3 substituents independently selected from halogen, -COR6、-CO2R7、-SO3R8、-PO3H2、-CON(R9)(R10)、-OR11and-N (R)12)(R13)；
R2Is a group derived from a fatty acid;
R3selected from groups derived from unsaturated acids;
R6、R7、R8、R9、R10and R11Each independently at each occurrence is selected from the group consisting of hydrogen, alkyl, and alkenyl;
R12and R13Each occurrence independently selected from hydrogen, alkyl, -COR14、-CO2R15-alkyl-COR16and-alkyl-CO2R17(ii) a And is
R14、R15、R16And R17Each occurrence is independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
For compounds of formula (I), R1May be unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
For compounds of formula (I), R1May be a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
For compounds of formula (I), R1May be a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or absent; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
Furthermore, the imidazoline compound can have formula (II),
wherein
R1、R4And R5Each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,
the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle are each independently unsubstituted or substituted at each occurrence with 1 to 3 substituents independently selected from halogen, -COR6、-CO2R7、-SO3R8、-PO3H2、-CON(R9)(R10)、-OR11and-N (R)12)(R13)；
R2Is a group derived from a fatty acid;
R3and RxEach independently selected from groups derived from unsaturated acids;
R6、R7、R8、R9、R10and R11Each independently at each occurrence is selected from the group consisting of hydrogen, alkyl, and alkenyl;
R12and R13Each occurrence independently selected from hydrogen, alkyl, -COR14、-CO2R15-alkyl-COR16and-alkyl-CO2R17(ii) a And is
R14、R15、R16And R17Each occurrence is independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
For the compound of formula (2), R1May be unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; rxis-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
For formula (2)) In the compound of (1), R1May be a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; rxis-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
For the compound of formula (2), R1May be a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or absent; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; rxis-CH2CH2CO2ReWherein R iseIs hydrogen, C1-C6-alkyl, or ReIs absent; r4Is hydrogen; and R is5Is hydrogen.
Furthermore, the imidazoline compound can have a structure of formula (III),
wherein
R1、R4And R5Each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,
the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle are each independently unsubstituted or substituted at each occurrence with 1 to 3 substituents independently selected from halogen, -COR6、-CO2R7、-SO3R8、-PO3H2、-CON(R9)(R10)、-OR11and-N (R)12)(R13)；
R2Is a group derived from a fatty acid;
R6、R7、R8、R9、R10and R11Each independently at each occurrence is selected from the group consisting of hydrogen, alkyl, and alkenyl;
R12and R13Each occurrence independently selected from hydrogen, alkyl, -COR14、-CO2R15-alkyl-COR16and-alkyl-CO2R17(ii) a And is
R14、R15、R16And R17Each occurrence is independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
For the compound of formula (3), R1May be unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
For the compound of formula (3), R1May be a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
For the compound of formula (3), R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or absent; r2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
The quaternary amine may have the formula
[N+R5aR6aR7aR8a][X-]
Wherein
R5a、R6a、R7aAnd R8aEach independently selected from substituted or unsubstituted C1-C18-an alkyl group; and is
X is C, Br or I.
For quaternary amines, R5a、R6a、R7aAnd R8aMay each be independently selected from unsubstituted C1-C18Alkyl radical, C1-C18-hydroxyalkyl and benzyl.
The quaternary amine can be selected from tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, phenyltrimethylammonium chloride, phenyltriethylammonium chloride, cetylbenzyldimethylammonium chloride, hexadecyltrimethylammonium chloride, and dimethyl C12-16Alkyl benzyl ammonium chloride, monomethyl di-C12-16-alkylbenzyl quaternary ammonium chloride, benzyl triethanolamine quaternary ammonium chloride, benzyl dimethylaminoethanolamine quaternary ammonium chloride, cocoalkyldimethylbenzyl ammonium chloride, and combinations thereof.
Phosphorus (P)
In addition, phosphorus
In addition, phosphorus
The composition may further comprise a demulsifier. The demulsifier may be selected from dodecylbenzylsulfonic acid (DDBSA), sodium salts of xylene sulfonic acid (NAXSA), epoxidized and propoxylated compounds, anionic, cationic and nonionic surfactants, and resins (phenolic and epoxy resins), and combinations thereof.
The composition may further comprise one or more additional components, each component independently selected from the group consisting of corrosion inhibitors, solvents, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, gas hydrate inhibitors, biocides, pH modifiers, and surfactants.
In another aspect, a method of controlling biofouling is disclosed, the method comprising providing to a system an effective amount of a composition of the present invention. The method may include controlling proliferation of microorganisms in a system for production, transportation, storage, and separation of crude oil and natural gas. The method may include controlling the proliferation of microorganisms in a system used in a coal-fired process (coal-fired process), wastewater treatment, farm, slaughterhouse, landfill (land-fill), municipal wastewater plant, coal coking process (coal-fired process), or biofuel process.
Also described herein are compounds, compositions, methods, and processes.
Drawings
Figure 1 depicts the biocidal activity of a composition comprising a quaternary amine and an imidazoline.
FIG. 2 depicts compositions comprising imidazolines, quaternary amines and phosphorus
FIG. 3 depicts compositions comprising different ratios of imidazoline, quaternary amine, and phosphorus
Fig. 4 depicts an emulsion trend study.
Fig. 5A, 5B and 5C depict corrosion rates versus concentration for V08, THPS and glutaraldehyde.
Detailed Description
Disclosed herein are biocide compositions, methods of use of the compositions, and processes for their preparation. The composition comprises at least one imidazoline compound, at least one quaternary amine, and at least one phosphorus
The composition is particularly useful for controlling the proliferation of microorganisms in equipment used for the production, transportation, storage and separation of crude oil and natural gas. The compositions kill planktonic and sessile microorganisms and provide enhanced biofilm kinetic regrowth control (sessile control). The compositions are effective against conventional oilfield microorganisms (e.g., sulfate reducing bacteria and acid producing bacteria), including genera such as vibrio thiolyticus (Desulfovibrio), microbium thiolyticus (Desulfomicrobium), Shewanella (Shewanella), Clostridium (Clostridium), and Pseudomonas (Pseudomonas). Thus, the compositions reduce the required biocide treatment rate and frequency compared to biocides currently on the market.
1. Definition of terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control. Although preferred methods and materials are described below, methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.
As used herein, the terms "comprising," "including," "containing," "having," "may," and variants thereof refer to open transition phrases, terms, or words that do not exclude the possibility of additional acts or structures. Unless the context clearly indicates otherwise, an object modified by no quantitative term includes plural objects. The present disclosure also contemplates other embodiments that "comprise," consist of, "and" consist essentially of the embodiments or elements shown herein, whether or not explicitly stated.
The term "suitable substituent" as used herein is intended to mean a chemically acceptable functional group, preferably a moiety that does not eliminate the activity of the compounds of the present invention. Such suitable substituents include, but are not limited to: halogen groups, perfluoroalkyl groups, perfluoroalkoxy groups, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, oxo groups, mercapto groups, alkylthio groups, alkoxy groups, aryl or heteroaryl groups, aryloxy or heteroaryloxy groups, aralkyl or heteroarylalkyl groups, aralkyloxy or heteroarylalkoxy groups, HO- (C ═ O) -groups, heterocyclic groups, cycloalkyl groups, amino groups, alkylamino and dialkylamino groups, carbamoyl groups, alkylcarbonyl groups, alkoxycarbonyl groups, alkylaminocarbonyl groups, dialkylaminocarbonyl groups, arylcarbonyl groups, aryloxycarbonyl groups, alkylsulfonyl groups and arylsulfonyl groups. One skilled in the art will appreciate that many substituents may be substituted with additional substituents.
The term "alkyl" as used herein refers to a straight or branched chain hydrocarbon group, preferably a hydrocarbon group having from 1 to 32 carbon atoms (i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31, or 32 carbons). Alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl. The alkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkenyl" as used herein refers to a straight or branched chain hydrocarbon group, preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31 or 32 carbons, and having one or more carbon-carbon double bonds. Alkenyl groups include, but are not limited to: vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, 2-methyl-1-propenyl, 1-butenyl and 2-butenyl. The alkenyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkynyl" as used herein refers to a straight or branched hydrocarbon group preferably having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 39, 30, 31 or 32 carbons and having one or more carbon-carbon triple bonds. Alkynyl groups include, but are not limited to: ethynyl, propynyl and butynyl. The alkynyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkoxy," as used herein, refers to an alkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.
The term "aryl" as used herein means a monocyclic, bicyclic or tricyclic aromatic group, such as phenyl, naphthyl, tetrahydronaphthyl, indanyl and the like; which is optionally substituted with one or more suitable substituents as defined above, preferably 1 to 5 suitable substituents.
The term "aralkyl" as used herein, means an aryl group attached to the parent molecular moiety through an alkyl group. An aralkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "arylalkyl," as used herein, refers to an alkylaryl group attached to the parent molecular moiety through an alkyl group. The alkyl aralkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The terms "carbonyl", "(C ═ O)" or "-C (O) -" (as used in phrases such as alkylcarbonyl, alkyl- (C ═ O) -or alkoxycarbonyl) refer to a linker > C ═ O moiety attached to a second moiety such as an alkyl or amino group (i.e., amide group). Alkoxycarbonylamino (i.e. alkoxy (C ═ O) -NH-) refers to an alkyl carbamate group. Carbonyl is also defined herein equivalently as (C ═ O). Alkylcarbonylamino refers to a group such as acetamide.
The term "cycloalkyl" as used herein refers to a monocyclic, bicyclic, or tricyclic carbocyclic group (e.g., cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclopentenyl, cyclohexenyl, bicyclo [2.2.1] heptyl, bicyclo [3.2.1] octyl, and bicyclo [5.2.0] nonyl, and the like); optionally containing 1 or 2 double bonds. The cycloalkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above, preferably 1 to 5 suitable substituents.
The term "cycloalkylalkyl" as used herein, means a cycloalkyl group attached to the parent molecular moiety through an alkyl group. The cycloalkylalkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkylcycloalkylalkyl" as used herein refers to a cycloalkylalkyl group substituted with one or more alkyl groups. The alkylcycloalkylalkyl group can be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "halo" or "halogen" as used herein refers to a fluoro, chloro, bromo, or iodo group.
The term "heteroaryl" as used herein refers to a monocyclic, bicyclic or tricyclic aromatic heterocyclic group containing one or more heteroatoms (e.g., 1 to 3 heteroatoms) selected from O, S and N in the ring. Heteroaryl groups include, but are not limited to: pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, thienyl, furyl, imidazolyl, pyrrolyl, thienyl, and the like,
The term "heteroarylalkyl" as used herein, means a heteroaryl group attached to the parent molecular moiety through an alkyl group. Heteroarylalkyl may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkylheteroarylalkyl" as used herein refers to a heteroarylalkyl group substituted with one or more alkyl groups. The alkylheteroarylalkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "heterocycle" or "heterocyclyl" as used herein refers to a monocyclic, bicyclic or tricyclic group containing 1 to 4 heteroatoms selected from N, O, S (O)n、P(O)n、PRzNH or NRzWherein R iszAre suitable substituents. The heterocyclic group optionally contains 1 or 2 double bonds. Heterocyclic groups include, but are not limited to: azetidinyl, tetrahydrofuryl, imidazolidinyl, pyrrolidinyl, piperidinyl, piperazinyl, piperidinyl, piperazinyl, and the like,
The term "heterocyclylalkyl" as used herein, means a heterocyclic group attached to the parent molecular moiety through an alkyl group. The heterocyclylalkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "alkylheterocyclylalkyl" as used herein refers to a heterocyclylalkyl group substituted with one or more alkyl groups. The alkyl heterocyclylalkyl group may be unsubstituted or substituted with one or more suitable substituents as defined above.
The term "hydroxy" as used herein refers to an-OH group.
The term "oxo" as used herein refers to a doubly bonded oxygen (═ O) group, where the bonding partner is a carbon atom. Such a group may also be considered a carbonyl group.
The term "acrylate" as used herein refers to a material resulting from the michael addition of acrylic acid and an imidazoline. The addition of this chemical moiety to the imidazoline increases its water solubility, enabling it to reach metal surfaces submerged below the water layer.
The term "TOFA" as used herein refers to tall oil fatty acid, which is a distillation product derived from trees and comprises a fatty acid having CAS number 61790-12-3, C17H31-35A mixture of COOH. It is a mixture of oleic acid, linoleic acid, and saturated fatty acids (e.g., about 46% oleic acid, about 41% linoleic acid, about 4% stearic acid, and about 9% other acids) as the major components.
The term "decyl" as used herein means-C10H21Alkyl, also known as "decanoyl".
The term "dodecyl" as used herein means-C12H25Alkyl, also known as "lauryl".
The term "hexadecyl" as used herein means-C16H33Alkyl groups, also known as "palmityl".
The term "hexyl" as used herein means-C6H13Alkyl, also known as "hexanoyl".
The term "octadienyl" as used herein means cis, cis-9, 12-octadecadienyl, also known as "linoleyl".
The term "octadecenyl" as used herein means cis-9-octadecenyl, also referred to as "oleyl".
The term "octadecyl" as used herein means-C18H37Alkyl, also known as "stearyl".
The term "octyl" as used herein means-C8H17Alkyl, also known as "octanoyl".
The term "tetradecyl" as used herein means-C14H29Alkyl, also known as "myristyl".
The term "myristoleic acid" or "(Z) -tetradec-9-enoic acid" as used herein means
The term "palmitoleic acid" or "(Z) -hexadec-9-enoic acid" as used herein means
The term "sapienic acid" or "(Z) -hexadec-6-enoic acid" as used herein means
The term "oleic acid" or "(Z) -octadec-9-enoic acid" as used herein means
The term "elaidic acid" or "(E) -octadec-9-enoic acid" as used herein means
The term "vaccenic acid" or "(E) -octadec-11-enoic acid" as used herein means
The term "linoleic acid" or "(9Z, 12Z) -octadeca-9, 12-dienoic acid" as used herein means
The term "linolenic acid" or "(9E, 12E) -octadeca-9, 12-dienoic acid" as used herein means
The term "alpha-linolenic acid" or "(9Z, 12Z, 15Z) -octadeca-9, 12, 15-trienoic acid" as used herein means
The term "arachidonic acid" or "(5Z, 8Z,11Z,14Z) -eicosa-5, 8,11, 14-tetraenoic acid" as used herein means
The term "eicosapentaenoic acid" or "(5Z, 8Z,11Z,14Z,17Z) -eicosa-5, 8,11,14, 17-pentaenoic acid" as used herein means
The term "erucic acid" or "(Z) -docosal-13-enoic acid" as used herein means
The term "docosahexaenoic acid" or "(4Z, 7Z, 10Z,13Z,16Z,19Z) -docosahexa-4, 7,10,13,16, 19-hexa-enoic acid" as used herein means
The term "hexadecatrienoic acid" or "(7Z, 10Z, 13Z) -hexadec-7, 10, 13-trienoic acid" as used herein refers to
The term "linoleic acid" or "(6Z, 9Z,12Z, 15Z) -octadeca-6, 9,12, 15-tetraenoic acid" as used herein means
The term "timnodonic acid" or "(11Z, 14Z,17Z) -eicosa-11, 14, 17-trienoic acid" as used herein refers to
The term "eicosatetraenoic acid" or "(5Z, 8Z,11Z,14Z,17Z) -eicosa-5, 8,11,14, 17-pentaenoic acid" as used herein means
The term "heneicosapentaenoic acid" or "(6Z, 9Z,12Z,15Z, 18Z) -heneicosapentaenoic acid" as used herein refers to
The term "Sprocochloric acid" or "(7Z, 10Z,13Z,16Z,19Z) -docosapentaenoic acid" as used herein means
The term "docosahexaenoic acid" or "(4Z, 7Z, I0Z,13Z,16Z) -docosapentaenoic acid (docosapentaenoic acid)" as used herein means
The term "(9Z, 12Z,15Z,18Z,21Z) -tetracosanoic-9, 12,15,18, 21-pentaenoic acid" as used herein means
The term "nicotinic acid" or "(6Z, 9Z,12Z,15Z,18Z,21Z) -tetracosenic-6, 9,12,15,18, 21-hexaenoic acid" as used herein means
The term "gamma-linolenic acid" or "(6Z, 9Z,12Z) -octadeca-6, 9, 12-trienoic acid" as used herein refers to
The term "eicosadienoic acid" or "(11Z, 14Z) -eicosa-11, 14-dienoic acid" as used herein refers to
The term "dihomo-gamma-linolenic acid" or "(8Z, 11Z,14Z) -eicosa-8, 11, 14-trienoic acid" as used herein refers to
The term "docosadienoic acid" or "(13Z, 16Z) -docosadienoic acid" as used herein refers to
The term "arachidonic acid" or "(7Z, 10Z,13Z, 16Z) -docosatetraenoic acid" as used herein means
The term "tetracosatetraenoic acid" or "(9Z, 12Z,15Z,18Z) -tetracosatetraenoic-9, 12,15, 18-tetraenoic acid" as used herein means
The term "(6Z, 9Z,12Z,15Z, 18Z) -tetracosanoic-6, 9,12,15, 18-pentaenoic acid" as used herein means
The term "(Z) -eicosa-11-enoic acid" as used herein means
The term "eicosapentaenoic acid" or "(Z) -eicosa-13-enoic acid" as used herein means
The term "mead acid" or "(5Z, 8Z, 11Z) -eicosa-5, 8, 11-trienoic acid" as used herein refers to
The term "nervonic acid" or "(Z) -tetracosen-15-enoic acid" as used herein means
The term "rumenic acid" or "(9Z, 11E) -octadeca-9, 11-dienoic acid" as used herein means
The term "α -octadecatrienoic acid" or "(8E, 10E,12Z) -octadeca-8, 10, 12-trienoic acid" as used herein means
The term "beta-octadecatrienoic acid" or "(8E, 10E,12E) -octadeca-8, 10, 12-trienoic acid" as used herein means
The term "orchid acid" or "(8E, 10Z, 12E) -octadeca-8, 10, 12-trienoic acid"
The term "alpha-eleostearic acid" or "(9Z, 11E, 13E) -octadeca-9, 11, 13-trienoic acid" as used herein means
The term "beta-eleostearic acid" or "(9E, 11E, 13E) -octadeca-9, 11, 13-trienoic acid" as used herein means
The term "catalpic acid" or "(9E, 11E,13Z) -octadeca-9, 11, 13-trienoic acid" as used herein means
The term "punicic acid" or "(9Z, 11E,13Z) -octadec-9, 11, 13-trienoic acid" as used herein refers to
The term "ru-melenic acid" or "(9E, 11Z, 15E) -octadeca-9, 11, 15-trienoic acid" as used herein means
The term "α -stearidonic acid" or "(9Z, 11E, 13E, 15Z) -stearidonic-9, 11, 13, 15-tetraenoic acid" as used herein means
The term "beta-stearidonic acid" or "(9E, 11E, 13E, 15E) -stearin-9, 11, 13, 15-tetraenoic acid" as used herein means
The term "primary color pentaenoic acid" or "(5Z, 8Z, 10E,12E, 14Z) -eicosa-5, 8,10, 12, 14-pentaenoic acid" as used herein refers to
The term "pinolenic acid" or "(5Z, 9Z,12Z) -octadeca-5, 9, 12-trienoic acid" as used herein means
The term "podocarpic acid" or "(5Z, 11Z,14Z) -eicosa-5, 11, 14-trienoic acid" as used herein refers to
The term "propionic acid" as used herein means CH3CH2COOH。
The term "butyric acid" as used herein refers to CH3(CH2)2COOH。
The term "pentanoic acid" as used herein refers to CH3(CH2)3COOH。
The term "hexanoic acid" as used herein means CH3(CH2)4COOH。
The term "heptanoic acid" as used herein refers to CH3(CH2)5COOH。
The term "octanoic acid" as used herein means CH3(CH2)6COOH。
The term "nonanoic acid" as used herein means CH3(CH2)7COOH。
The term "decanoic acid" as used herein means CH3(CH2)8COOH。
The term "undecanoic acid" as used herein refers to CH3(CH2)9COOH。
The term "lauric acid" as used herein means CH3(CH2)10COOH。
The term "tridecanoic acid" as used herein refers to CH3(CH2)11COOH。
The term "myristic acid" as used herein means CH3(CH2)12COOH。
The term "pentadecanoic acid" as used herein means CH3(CH2)13COOH。
The term "palmitic acid" as used herein means CH3(CH2)14COOH。
The term "heptadecanoic acid" as used herein refers to CH3(CH2)15COOH。
The term "stearic acid" as used herein refers to CH3(CH2)16COOH。
The term "nonadecanoic acid" as used herein refers to CH3(CH2)17COOH。
The term "eicosanoic acid" as used herein refers to CH3(CH2)18COOH。
The term "heneicosanoic acid" as used herein refers to CH3(CH2)19COOH。
The term "behenic acid" as used herein means CH3(CH2)20COOH。
The term "tricosanoic acid" as used herein refers to CH3(CH2)21COOH。
The term "lignoceric acid" as used herein means CH3(CH2)22COOH。
The term "pentacosanic acid" as used herein refers to CH3(CH2)23COOH。
The term "cerotic acid" as used herein refers to CH3(CH2)24COOH。
The term "heptacosanoic acid" as used herein refers to CH3(CH2)25COOH。
The term "montanic acid" as used herein refers to CH3(CH2)26COOH。
The term "nonacosanoic acid" as used herein refers to CH3(CH2)27COOH。
The term "melissic acid" as used herein means CH3(CH2)28COOH。
The term "hentriacid" as used herein refers to CH3(CH2)29COOH。
The term "laccaic acid" as used herein refers to CH3(CH2)30COOH。
The term "pediculic acid" as used herein means CH3(CH2)31COOH。
The term "gadoleic acid" as used herein refers to CH3(CH2)32COOH。
The term "ceroplastic acid" as used herein refers to CH3(CH2)33COOH。
The term "triacylglycerol" as used herein refers to CH3(CH2)34COOH。
2. Composition comprising a metal oxide and a metal oxide
The compositions disclosed herein comprise an imidazoline compound, a quaternary amine, and phosphorus
The composition may comprise an imidazoline compound, a quaternary amine, phosphorus
In addition, the composition may comprise an imidazoline compound, a quaternary amine, a phosphorus
In addition, the composition may comprise an imidazoline compound, a quaternary amine, a phosphorus
In addition, the composition may comprise an imidazoline compound, a quaternary amine, a phosphorus
In addition, the composition may comprise an imidazoline compound, a quaternary amine, a phosphorus
In addition, the composition may comprise an imidazoline compound, a quaternary amine, a phosphorus
a. Imidazoline compounds
The compositions disclosed herein comprise at least one imidazoline compound. The imidazoline compound can have formula (I), (1I), or (III),
wherein
R1、R4And R5Each independently selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle,
the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, and heterocycle are each independently unsubstituted or substituted at each occurrence with 1 to 3 substituents independently selected from halogen, -COR6、-CO2R7、-SO3R8、-PO3H2、-CON(R9)(R10)、-OR11and-N (R)12)(R13)；
R2Is a group derived from a fatty acid;
R3and RxEach independently selected from groups derived from unsaturated acids;
R6、R7、R8、R9、R10and R11Each independently at each occurrence is selected from the group consisting of hydrogen, alkyl, and alkenyl;
R12and R13Each occurrence independently selected from hydrogen, alkyl, -COR14、-CO2R15-alkyl-COR16and-alkyl-CO2R17(ii) a And is
R14、R15、R16And R17Each occurrence is independently selected from the group consisting of hydrogen, alkyl, and alkenyl.
For these imidazolines, when R ═ H and the carboxylic acid moiety is deprotonated, the R group of the carboxylic acid moiety may be absent. For example, when R is12And/or R13Is a deprotonated carboxylic acid moiety (e.g., when R12is-CH2CH2CO2-is (a)15And/or R17May not be present.
For imidazoline compounds, R1May be an unsubstituted alkyl group. For example, R1May be unsubstituted C1-C10Alkyl (e.g. methyl, ethyl, propyl (e.g. n-propyl, isopropyl), butyl (e.g. n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g. n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-butyl, 3-pentyl), hexyl, heptyl, octyl, nonyl or decyl). In addition, R1May be unsubstituted C2-C10-an alkyl group. For these imidazoline compounds, R1May be unsubstituted C2-C8-an alkyl group. In addition, R1May be unsubstituted C2-C6-an alkyl group. Preferably, R1Is propyl, butyl or hexyl.
For these imidazolines, R1Is a substituted alkyl group. For example, R1Is substituted C1-C10Alkyl, substituted C2-C10Alkyl, substituted C2-C8-alkyl or substituted C2-C6-an alkyl group. In addition, R1Is C substituted by one substituent1-C10Alkyl radical, C2-C10Alkyl radical, C2-C8-alkyl or C2-C6-alkyl, said substituent being selected from-COR6、-CO2R7、-SO3R8、-PO3H2、-CON(R9)(R10)、-OR11and-N (R)12)(R13) Wherein R is6、R7、R8、R9、R10、R11、R12And R13As defined above. More specifically, R1Is C substituted by one substituent2-C6-alkyl, said substituent being selected from-N (R)12)(R13) Wherein R is12And R13Each independently selected from hydrogen, alkyl, -COR14、-CO2R15-alkyl-COR16and-alkyl-CO2R17Wherein R is14、R15、R16And R17As defined above. In addition, R1Is C substituted by one substituent2-C6-alkyl, said substituent being selected from-N (R)12)(R13) Wherein R is12And R13Each independently selected from hydrogen and C2-C6-alkyl, -COR14、-CO2R15、-C2-C6-alkyl-COR16and-C2-C6-alkyl-CO2R17Wherein R is14、R15、R16And R17Selected from hydrogen and C1-C34-an alkyl group. For these imidazolines, R1Is a straight chain C substituted by one substituent2-C6-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each independently selected from hydrogen, -COR14、-CO2R15、-C2-C6-alkyl-COR16and-C2-C6-alkyl-CO2R17Wherein R is14、R15、R16And R17Selected from hydrogen and C1-C34-an alkyl group. For example, R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31. In addition, R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen.
For the imidazolines of formulas (I), (II) and (III), R2Is C4-C34-alkyl or C4-C34-alkenyl. For example, R2Is- (CH)2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)6CH3、-(CH2)7CH3、-(CH2)8CH3、-(CH2)9CH3、-(CH2)10CH3、-(CH2)11CH3、-(CH2)12CH3、-(CH2)13CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)17CH3、-(CH2)18CH3、-(CH2)19CH3、-(CH2)20CH3、-(CH2)21CH3、-(CH2)22CH3、-(CH2)23CH3、-(CH2)24CH3、-(CH2)25CH3、-(CH2)26CH3、-(CH2)27CH3、-(CH2)28CH3、-(CH2)29CH3、-(CH2)30CH3、-(CH2)31CH3、-(CH2)32CH3、-(CH2)33CH3、-(CH2)34CH3、-(CH2)2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CH(CH2)7CH3、-(CH2)3CH＝CHCH2CH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CH(CH2)4CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)3CH＝CHCH＝CHCH＝CHCH＝CHCH＝CH(CH2)4CH3、-(CH2)4CH＝CH(CH2)8CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)6CH＝CHCH＝CHCH＝CH(CH2)4CH3、-(CH2)6CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CH(CH2)3CH3、-(CH2)7CH＝CH(CH2)5CH3、-(CH2)7CH＝CH(CH2)7CH3、-(CH2)7CH＝CHCH＝CHCH＝CH(CH2)3CH3、-(CH2)7CH＝CHCH＝CH(CH2)5CH3、-(CH2)7CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH＝CHCH2CH2CH＝CHCH2CH3、-(CH2)7CH＝CHCH＝CHCH＝CHCH＝CHCH2CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)9CH＝CH(CH2)5CH3、-(CH2)9CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)9CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)9CH＝CH(CH2)7CH3、-(CH2)11CH＝CH(CH2)5CH3、-(CH2)11CH＝CH(CH2)7CH3、-(CH2)11CH＝CHCH2CH＝CH(CH2)4CH3Or- (CH)2)13CH＝CH(CH2)7CH3。
For imidazolines, R2May be a group derived from a saturated fatty acid or an unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to: butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laccaic acid, pediculosic acid, gemc acid, ceroplastic acid, and hexacosanoic acid. Suitable unsaturated fatty acids include, but are not limited to: myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, linoleic acid, tricosanoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, Spragic acid, docosapentaenoic acid, (9Z,12Z,15Z,18Z,21Z) -tetracosenic-9, 12,15,18, 21-pentaenoic acid, nicotinic acid, gamma-linolenic acid, eicosadienoic acid, dihomo-gamma-linolenic acid, docosadienoic acid, aleic acid, tetracosenic acid, (6Z,9Z,12Z,15Z, 18Z) -tetracosenic-6, 9,12,15,18-pentaenoic acid, (Z) -eicosa-11-enoic acid, miridonic acid, erucic acid, nervonic acid, rumenic acid, alpha-octadecatrienoic acid, beta-octadecatrienoic acid, orcidic acid, alpha-eleostearic acid, beta-eleostearic acid, catalpic acid, punicic acid, RUMIANENoic acid, alpha-octadecatetraenoic acid, beta-octadecatetraenoic acid, primary color pentaenoic acid, pinolenic acid, and rohepanoic acid. Preferably, R2Derived from coconut oil, tallow, or Tall Oil Fatty Acids (TOFA).
For imidazolines, R3is-C (R)aRb)-C(RcRd)-CO2ReWherein R isa、Rb、RcAnd RdEach independently selected from hydrogen (-H), halogen and alkyl, and wherein ReIs hydrogen (-H) or alkyl. For example, R3is-C (R)aRb)-C(RcRd)-CO2ReWherein R isa、Rb、RcAnd RdEach independently selected from hydrogen (-H), halogen and C1-C6-alkyl, and wherein ReIs hydrogen (-H) or C1-C6-an alkyl group. In addition, R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H) or C1-C6-an alkyl group. In addition, when R is3Is a deprotonated carboxylic acid moiety (e.g., when R3is-CH2CH2CO2 -In time), ReMay not be present.
For the imidazoline, R3May be derived from acrylic acid. Suitable acrylic acids include, but are not limited to: acrylic acid, methacrylic acid, 2-ethacrylic acid, 2-propylacrylic acid, and 2- (trifluoromethyl) acrylic acid. For example, R3Can be derived from acrylic acid (H)2C＝CHCO2H)。
The imidazolines of formula (I), (II) or (III) may have Rx，Rxis-C (R)aRb)-C(RcRd)-CO2ReWherein R isa、Rb、RcAnd RdEach independently selected from hydrogen (-H), halogen and alkyl, and wherein ReIs hydrogen (-H) or alkyl. In addition, RxCan be-C (R)aRb)-C(RcRd)-CO2ReWherein R isa、Rb、RcAnd RdEach independently selected from hydrogen (-H), halogen and C1-C6-alkyl, and wherein ReIs hydrogen (-H) or C1-C6-an alkyl group. Furthermore, Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H) or C1-C6-an alkyl group. In addition, when R isxIs a deprotonated carboxylic acid moiety (e.g., when Rxis-CH2CH2CO2 -In time), ReMay not be present.
For the imidazolines described herein, RxMay be derived from acrylic acid. Suitable acrylic acids include, but are not limited to: acrylic acid, methacrylic acid, 2-ethacrylic acid, 2-propylacrylic acid, and 2- (trifluoromethyl) acrylic acid. For example, RxCan be derived from acrylic acid (H)2C＝CHCO2H)。
The imidazolines of formula (I), (II) or (III) may have R4And R5，R4And R5Each independently is unsubstituted C1-C10Alkyl (e.g. methyl, ethyl, propyl (e.g. n-propyl, isopropyl), butyl (e.g. n-butyl, isobutyl, tert-butyl, sec-butyl), pentyl (e.g. n-pentyl, isopentyl, tert-pentyl, neopentyl, sec-pentyl, 3-pentyl), hexyl, heptyl, octyl, nonyl or decyl) or hydrogen. In addition, R4And R5May each independently be unsubstituted C1-C6Alkyl or hydrogen. Preferably, R4And R5Each is hydrogen (-H).
The imidazolines of formula (I), (II) or (III) may have R6、R7、R8、R9、R10And R11，R6、R7、R8、R9、R10And R11Each independently at each occurrence is selected from the group consisting of hydrogen, unsubstituted alkyl, and unsubstitutedAlkenyl groups of (a). For example, R6、R7、R8、R9、R10And R11May be independently selected at each occurrence from hydrogen, unsubstituted C1-C34Alkyl and unsubstituted C2-C34-alkenyl. In addition, R6、R7、R8、R9、R10And R11May be independently selected at each occurrence from hydrogen, unsubstituted C1-C10Alkyl and unsubstituted C2-C10-alkenyl.
In addition, R6、R7、R8、R9、R10And R11May be independently selected at each occurrence from hydrogen and a group derived from a fatty acid.
For the imidazoline compound, R12And R13Can be independently selected from hydrogen and C at each occurrence1-C10-alkyl, -COR14、-CO2R15、-C1-C10-alkyl-COR16and-C1-C10-alkyl-CO2R17. In addition, R12And R13May be independently selected at each occurrence from hydrogen, unsubstituted C1-C10-alkyl, -COR14、-CO2R15、-C1-C10-alkyl-COR16and-C1-C10-alkyl-CO2R17。
For the imidazoline, R14、R15、R16And R17May be independently selected at each occurrence from hydrogen, unsubstituted alkyl, and unsubstituted alkenyl. In addition, R14、R15、R16And R17May be independently selected at each occurrence from hydrogen, unsubstituted C1-C34Alkyl and unsubstituted C2-C34-alkenyl. Furthermore, R14、R15、R16And R17May be independently selected at each occurrence from hydrogen, unsubstituted C1-C10Alkyl and unsubstituted C2-C10-alkenyl. In addition, when the carboxylic acid moiety is deprotonated, R15And/or R17May not be present.
The imidazoline compound can have R14、R15、R16And R17，R14、R15、R16And R17Each occurrence is independently selected from hydrogen and a group derived from a fatty acid. In addition, R14、R15、R16And R17Can be independently selected from hydrogen and C at each occurrence4-C34-alkyl and C4-C34-alkenyl. Furthermore, R14、R15、R16And R17May be independently selected at each occurrence from hydrogen, - (CH)2)3CH3、-(CH2)4CH3、-(CH2)5CH3、-(CH2)6CH3、-(CH2)7CH3、-(CH2)8CH3、-(CH2)9CH3、-(CH2)10CH3、-(CH2)11CH3、-(CH2)12CH3、-(CH2)13CH3、-(CH2)14CH3、-(CH2)15CH3、-(CH2)16CH3、-(CH2)17CH3、-(CH2)18CH3、-(CH2)19CH3、-(CH2)20CH3、-(CH2)21CH3、-(CH2)22CH3、-(CH2)23CH3、-(CH2)24CH3、-(CH2)25CH3、-(CH2)26CH3、-(CH2)27CH3、-(CH2)28CH3、-(CH2)29CH3、-(CH2)30CH3、-(CH2)31CH3、-(CH2)32CH3、-(CH2)33CH3、-(CH2)34CH3、-(CH2)2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CH(CH2)7CH3、-(CH2)3CH＝CHCH2CH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CH(CH2)4CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)3CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)3CH＝CHCH＝CHCH＝CHCH＝CHCH＝CH(CH2)4CH3、-(CH2)4CH＝CH(CH2)8CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)4CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)5CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)6CH＝CHCH＝CHCH＝CH(CH2)4CH3、-(CH2)6CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CH(CH2)3CH3、-(CH2)7CH＝CH(CH2)5CH3、-(CH2)7CH＝CH(CH2)7CH3、-(CH2)7CH＝CHCH＝CHCH＝CH(CH2)3CH3、-(CH2)7CH＝CHCH＝CH(CH2)5CH3、-(CH2)7CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH＝CHCH2CH2CH＝CHCH2CH3、-(CH2)7CH＝CHCH＝CHCH＝CHCH＝CHCH2CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)7CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)9CH＝CH(CH2)5CH3、-(CH2)9CH＝CHCH2CH＝CH(CH2)4CH3、-(CH2)9CH＝CHCH2CH＝CHCH2CH＝CHCH2CH3、-(CH2)9CH＝CH(CH2)7CH3、-(CH2)11CH＝CH(CH2)5CH3、-(CH2)11CH＝CH(CH2)7CH3、-(CH2)11CH＝CHCH2CH＝CH(CH2)4CH3And- (CH)2)13CH＝CH(CH2)7CH3。
For the imidazolines of formulas (I), (II) and (III), R14、R15、R16And R17Can be independently selected at each occurrence from hydrogen, a group derived from a saturated fatty acid, and a group derived from an unsaturated fatty acid. Suitable saturated fatty acids include, but are not limited to: butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, arachic acid, heneicosanoic acid, behenic acid, tricosanoic acid, lignoceric acid, pentacosanoic acid, cerotic acid, heptacosanoic acid, montanic acid, nonacosanoic acid, melissic acid, hentriacontanoic acid, laccaic acid, pediculosic acid, gemc acid, ceroplastic acid, and hexacosanoic acid. Suitable unsaturated fatty acids include, but are not limited to: myristoleic acid, palmitoleic acid, hexadecenoic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolenic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, hexadecatrienoic acid, linoleic acid, eicosatrienoic acid, eicosatetraenoic acid, heneicosapentaenoic acid, Sprocryic acid, docosapentaenoic acid, (9Z,12Z,15Z,18Z,21Z) -tetracosenic-9, 12,15,18, 21-pentaenoic acid, nicotinic acid, gamma-linolenic acid, eicosadienoic acid, dihomo-gamma-linolenic acid, docosadienoic acid, elaidic acid, tetracosenoic acid, (6Z,9Z,12Z,15Z, 18Z) -tetracosenic-6, 9,12,15, 18-pentaenoic acid, (Z) -eicosa-1.1-enoic acid, miridonic acid, erucic acid, nervonic acid, rumenic acid, alpha-octadecatrienoic acid, beta-octadecatrienoic acid, orchidic acid, alpha-eleostearic acid, beta-eleostearic acid, catalpic acid, punicic acid, taomicenic acid, alpha-octadecatetraenoic acid, beta-octadecatetraenoic acid, eicosapentaenoic acid, pinolenic acid, and rohanopine acid. In addition, R14、R15、R16And R17Each occurrence is independently hydrogen or a group derived from coconut oil, tallow, or Tall Oil Fatty Acid (TOFA).
Preferably, the imidazoline is a compound of formula (I), wherein R is1Is unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
Alternatively, the imidazoline is a compound of formula (I) wherein R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
Furthermore, imidazolines are compounds of the formula (I), in which R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or is absent (e.g. R)12is-C2-alkyl-CO2-)；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
Furthermore, imidazolines are compounds of the formula (II), in which R1Is unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)xis-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
The imidazoline can be a compound of formula (II) wherein R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)xis-CH2CH2(CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
The imidazoline can be a compound of formula (II) wherein R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or is absent (e.g. R)12is-C2-alkyl-CO2 -)；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)xis-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
The imidazoline can be a compound of formula (III) wherein R1Is unsubstituted C2-C6-an alkyl group; r2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
The imidazoline can be a compound of formula (III) wherein R1Is substituted by a substituentSubstituted straight chain C2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
The imidazoline can be a compound of formula (III) wherein R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or is absent (e.g. R)12is-C2-alkyl-CO2 -)；R2is-C17H35、-C17H33or-C17H31；R4Is hydrogen; and R is5Is hydrogen.
Whether or not explicitly described, it is to be understood that formula (I), formula (II), and formula (III) are each intended to encompass tautomeric forms, racemic forms, enantiomeric forms, diastereomeric forms, zwitterionic forms, and salt forms of the formula (I). When R is3And/or RxWhen derived from acrylic acid, the imidazoline may be present in zwitterionic form.
The imidazoline compound can be present in the composition in an amount of 1 to 50 weight%, 2 to 40 weight%, 3 to 30 weight%, 4 to 20 weight%, 5 to 17 weight%, 6 to 16 weight%, 7 to 15 weight%, 8 to 14 weight%, 9 to 13 weight%, or 10 to 12 weight%, based on the total weight of the composition. The imidazoline compound may comprise about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, or about 20 wt% of the composition, based on the total weight of the composition. The composition may comprise about 11 wt% imidazoline compound, based on the total weight of the composition. The composition may comprise l1 wt% of imidazoline compound based on the total weight of the composition.
b. Quaternary amines
The compositions disclosed herein comprise quaternary amines. Suitable quaternary amines include, but are not limited to: alkyl, hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts.
Suitable alkyl, hydroxyalkyl, alkylaryl, arylalkyl or arylamine quaternary salts include those of the formula [ N+R5aR6aR7aR8a][X-]Those alkylaryl, arylalkyl, and arylamine quaternary salts of (a), wherein R5a、R6a、R7aAnd R8aContaining 1 to 18 carbon atoms and X is Cl, Br or I. For quaternary amines, R5a、R6a、R7aAnd R8aMay each be independently selected from alkyl (e.g., C)1-C18Alkyl), hydroxyalkyl (e.g. C)1-C18Hydroxyalkyl) and aralkyl (e.g., benzyl). Monocyclic aromatic amine salts or polycyclic aromatic amine salts with alkyl or alkylaryl halides include those of the formula [ N+R5aR6aR7aR8a][X-]A salt of, wherein R5a、R6a、R7aAnd R8aContaining 1 to 18 carbon atoms and X is Cl, Br or I.
Suitable quaternary ammonium salts include, but are not limited to: tetramethylammonium chloride, tetraethylammonium chloride, tetrapropylammonium chloride, tetrabutylammonium chloride, tetrahexylammonium chloride, tetraoctylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, phenyltrimethylammonium chloride, phenyltriethylammonium chloride, cetylbenzyldimethylammonium chloride, cetyltrimethylammonium chloride, dimethyl alkylbenzyl quaternary ammonium compounds, monomethyl dialkyl benzyl quaternary ammonium compounds, trimethyl benzyl quaternary ammonium compounds, and trialkyl benzyl quaternary ammonium compounds, wherein the alkyl group can contain from about 1 to about 24 carbon atoms, from about 10 to about 24 carbon atomsAbout 18 carbon atoms or about 12 to about 16 carbon atoms, such as, for example, C12-16Benzyl dimethyl ammonium chloride. Suitable quaternary ammonium compounds (quats) include, but are not limited to: trialkyl, dialkyl, dialkoxyalkyl, monoalkoxy, benzyl and imidazoline
The quaternary amine may be an ammonium benzalkonium salt represented by the formula:
wherein n is 8,10, 12, 14, 16 or 18; and X is Cl, Br or I.
The quaternary amine may be a mixture of benzalkonium salts where n is 8,10, 12, 14, 16, and 18.
The quaternary amine may be a mixture of benzalkonium salts where n is 12, 14, 16, and 18.
The quaternary amine may be a mixture of benzalkonium salts, where n is 12, 14, and 16.
The quaternary amine may be a mixture of benzalkonium salts, where n is 12, 14, 16, and 18, and X is Cl.
The quaternary amine can be a mixture of benzalkonium salts, where n is 12, 14, and 16, and X is Cl.
The quaternary amine may be an alkylpyridine
wherein R is9aIs an alkyl, aryl or aralkyl group, wherein the alkyl group has from 1 to about 18 carbon atoms and B is Cl, Br or I. Wherein, these are changed intoThe compound being an alkylpyridine
The quaternary amine can be present in the composition in an amount of 0.1 wt% to 80 wt%, 1 wt% to 40 wt%, 5 wt% to 35 wt%, 10 wt% to 30 wt%, 15 wt% to 25 wt%, 16 wt% to 24 wt%, 17 wt% to 23 wt%, 18 wt% to 22 wt%, or 19 wt% to 21 wt%, based on the total weight of the composition. The quaternary amine comprises about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, about 20 wt%, about 21 wt%, about 22 wt%, about 23 wt%, about 24 wt%, about 25 wt%, about 26 wt%, about 27 wt%, about 28 wt%, about 29 wt%, about 30 wt%, about 31 wt%, about 32 wt%, about 33 wt%, about 34 wt%, or about 35 wt% of the composition, based on the total weight of the composition. The quaternary amine is present in an amount of about 20 wt% or about 21 wt%, based on the total weight of the composition. The quaternary amine is present in an amount of 20.5 wt% based on the total weight of the composition.
The composition may comprise from 5 wt% to 35 wt% of a quaternary amine comprising C12Benzyldimethylammonium chloride (e.g. 4 to 20 wt. -%, based on the total weight of the composition), C14Benzyldimethylammonium chloride (e.g. 1 to 10 wt. -%, based on the total weight of the composition), C16Benzyldimethylammonium chloride (e.g. 0.1 to 5 wt% based on the total weight of the composition) and C18Benzyldimethylammonium chloride (e.g., 0.5 wt.% or less based on the total weight of the composition). The composition may comprise about 20 wt% or about 21 wt% of a quaternary amine comprising C12Benzyldimethylammonium chloride (e.g. 14.5 wt. -%, based on the total weight of the composition), C14Benzyldimethylammonium chloride (e.g. 5 wt. -%, based on the total weight of the composition), C16Benzyldimethylammonium chloride (e.g. 1 wt% based on the total weight of the composition) and C18Benzyldimethylammonium chloride (e.g., 0.2 wt.% or less based on the total weight of the composition).
c. Phosphorus (P)
The compositions disclosed herein comprise at least one phosphorus
Based on the total weight of the composition, phosphorus
d. Demulsifier
The compositions disclosed herein may comprise a demulsifier (also known as a demulsifier). Suitable demulsifiers include, but are not limited to: dodecylbenzylsulfonic acid (DDBSA), sodium salt of xylenesulfonic acid (NAXSA), epoxylated and propoxylated compounds, anionic, cationic and nonionic surfactants, and resins, such as polyalkylene oxides, vinyl polymers, polyamines, polyamides, phenolic resins, and silicone polyethers. The demulsifier may be a vinyl polymer, for example: polymers of acrylic acid with tert-butyl phenol, formaldehyde, maleic anhydride, propylene oxide and ethylene oxide (CAS registry number 178603-70-8).
The demulsifier may be present in an amount from 0.1 to 30, from 0.5 to 10, or from 1 to 5 weight percent based on the total weight of the composition. The demulsifier comprises about 1 wt%, about 2 wt%, about 3 wt%, about 4 wt%, or about 5 wt% of the composition, based on the total weight of the composition. The composition comprises about 2 wt% or about 3 wt% of the demulsifier based on the total weight of the composition. The composition contained 2.6 wt% of a demulsifier based on the total weight of the composition.
e. Synergist
The compositions disclosed herein may comprise a synergistic component. Suitable synergist compounds include, but are not limited to: thioglycolic acid, 3' -dithiodipropionic acid, thiosulphate, thiourea, 2-mercaptoethanol, L-cysteine and tert-butylthiol. The synergist compound may be 2-mercaptoethanol.
The synergist may be present in an amount of 0.01 to 10 wt%, 0.1 to 8 wt%, 0.5 to 7 wt%, 1 to 6 wt%, 2 to 5 wt%, or 3 to 4 wt%, based on the total weight of the composition. The synergist may comprise about 0.5 wt%, about 1 wt%, about 1.5 wt%, about 2.0 wt%, about 2.5 wt%, about 3.0 wt%, about 3.5 wt%, about 4.0 wt%, about 4.5 wt%, about 5.0 wt%, about 5.5 wt%, or about 6.0 wt% of the composition, based on the total weight of the composition. The composition may comprise about 3.5 wt% of the synergist based on the total weight of the composition. The composition may comprise 3.5 wt% of the synergist based on the total weight of the composition.
f. Solvent(s)
The compositions disclosed herein may comprise a solvent. Suitable solvents include, but are not limited to: alcohols, hydrocarbons, ketones, ethers, aromatics, amides, nitriles, sulfoxides, esters, glycol ethers, aqueous systems, and combinations thereof. The solvent may be water, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, or xylene. Representative polar solvents suitable for formulation of the composition include: water, brine, seawater, alcohols (including straight or branched chain aliphatic alcohols such as methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols and derivatives (ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone, diisobutyl ketone), N-methylpyrrolidone (NMP), N-dimethylformamide, etc. Representative non-polar solvents suitable for formulation of the composition include aliphatic solvents such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel oil, and the like; aromatic solvents such as toluene, xylene, heavy aromatic naphtha, fatty acid derivatives (acids, esters, amides), and the like.
The solvent may be methanol, isopropanol, 2-ethylhexanol, or combinations thereof. Additionally, the solvent can be methanol, isopropanol, 2-ethylhexanol, water, or combinations thereof.
The compositions of the present invention may comprise from 0% to 99%, from 1% to 98%, from 10% to 80%, from 20% to 70%, from 30% to 60%, or from 40% to 55% by weight of one or more solvents, based on the total weight of the composition.
The compositions of the present invention may comprise about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight of one or more solvents, based on the total weight of the composition. The compositions of the present invention comprise about 40% of one or more alcoholic solvents and about 15% water. The composition of the present invention may comprise about 40% of a methanol/isopropanol mixture and about 15% water. The composition of the invention may comprise 40% of a methanol/isopropanol mixture and 14.9% of water.
The compositions of the present invention optionally comprise one or more additional additives. Suitable additives include, but are not limited to: corrosion inhibitors, asphaltene inhibitors, paraffin inhibitors, scale inhibitors, emulsifiers, water clarifiers, dispersants, hydrogen sulfide scavengers, gas hydrate inhibitors, biocides, pH modifiers, and surfactants.
g. Corrosion inhibitors
Suitable corrosion inhibitors for inclusion in the composition include, but are not limited to: monoalkyl, dialkyl or trialkyl or alkylaryl phosphates; a phosphate ester of hydroxylamine; phosphate esters of polyhydric alcohols; and monomeric or oligomeric fatty acids.
Suitable monoalkyl, dialkyl and trialkyl phosphates and alkylaryl phosphates and phosphates of monoethanolamine, diethanolamine and triethanolamine typically contain from 1 to about 18 carbon atoms. Preferred monoalkyl, dialkyl and trialkyl phosphates, alkylaryl or arylalkyl phosphates are obtained by reacting C3-C18Fatty alcohol and pentoxidePhosphorus reaction prepared by the reaction of phosphorus. The ester groups of the phosphate intermediate were exchanged with triethyl phosphate, which resulted in a broader distribution of alkyl phosphate. Alternatively, the phosphate esters may be prepared by mixing with a mixture of alkyl diesters, low molecular weight alkyl alcohols or glycols. The low molecular weight alkyl alcohol or diol preferably comprises C6To C10An alcohol or a diol. In addition, phosphate esters of polyhydric alcohols containing one or more 2-hydroxyethyl groups and salts thereof, and hydroxylamine phosphate obtained by reacting polyphosphoric acid or phosphorus pentoxide with hydroxylamine (e.g., diethanolamine or triethanolamine) are preferred.
The corrosion inhibitor may be a monomeric fatty acid or an oligomeric fatty acid. It is preferably C14-C22Saturated and unsaturated fatty acids and dimer, trimer and oligomer products obtained by polymerizing one or more of such fatty acids.
h. Asphaltene inhibitors
Suitable asphaltene inhibitors include, but are not limited to: aliphatic sulfonic acids, alkylaryl sulfonic acids, aryl sulfonates, lignosulfonates, alkylphenol/aldehyde resins and similar sulfonated resins, polyolefin esters, polyolefin imides, polyolefin esters with alkyl, alkylene phenyl or alkylene pyridyl functionality, polyolefin amides with alkyl, alkylene phenyl or alkylene pyridyl functionality, polyolefin imides with alkyl, alkylene phenyl or alkylene pyridyl functionality, alkenyl/vinyl pyrrolidone copolymers, graft polymers of polyolefins with maleic anhydride or vinyl imidazole, hyperbranched polyester amides, polyalkoxylated asphaltenes, amphoteric fatty acids, alkyl succinates, sorbitan monooleates, and polyisobutylene succinic anhydride.
i. Paraffin inhibitor
Suitable paraffin inhibitors include, but are not limited to, paraffin crystal modifiers (crystal modifiers) and dispersant/crystal modifier combinations. Suitable paraffin wax crystal modifiers include, but are not limited to, alkyl acrylate copolymers, alkyl acrylate-vinylpyridine copolymers, ethylene-vinyl acetate copolymers, maleic anhydride ester copolymers, branched polyethylenes, naphthalene, anthracene, microcrystalline wax, and/or asphaltene. Suitable dispersants include, but are not limited to, dodecylbenzene sulfonate, alkoxylated alkylphenols, and alkoxylated alkylphenol resins.
j. Anti-scaling agent
Suitable anti-fouling agents include, but are not limited to: salts of phosphates, phosphoric acids, phosphonates, phosphonic acids, polyacrylamides, acrylamido-methylpropane sulfonate/acrylic acid copolymer (AMPS/AA), phosphinite maleic acid copolymer (PHOS/MA), and polymaleic acid/acrylic acid/acrylamido-methylpropane sulfonate terpolymer (PMA/AMPS).
k. Emulsifier
Suitable emulsifiers include, but are not limited to: carboxylic acid salts, products of acylation reactions between carboxylic acids or carboxylic acid anhydrides and amines, alkyl, acyl and amide derivatives of sugars (alkyl-sugar emulsifiers).
Water purifying agent
Suitable water purifying agents include, but are not limited to, inorganic metal salts such as alum, aluminum chloride, and aluminum chlorohydrate, or organic polymers such as acrylic-based polymers, acrylamide-based polymers, polymeric amines, polymeric alkanolamines, polymeric thiocarbamates, and cationic polymers such as diallyldimethylammonium chloride (DADMAC).
m. dispersing agent
Suitable dispersants include, but are not limited to: aliphatic phosphonic acids having from 2 to 50 carbons, such as hydroxyethyldiphosphonic acid and aminoalkylphosphonic acids, for example polyaminomethylene phosphonic acid esters having from 2 to 10N atoms, for example carrying at least one methylene phosphonic acid group per N atom; examples of the latter are ethylenediamine tetra (methylene phosphonate), diethylenetriamine penta (methylene phosphonate) and triamine-and tetramine-polymethylene phosphonates having 2 to 4 methylene groups between each N atom, at least 2 of the number of methylene groups in each phosphonate being different. Other suitable dispersants include lignin or lignin derivatives such as lignosulfonates and naphthalene sulfonic acids and derivatives.
Hydrogen sulfide scavenger
Suitable additional hydrogen sulfide scavengers include, but are not limited to: oxidizing agents (e.g., inorganic peroxides such as sodium peroxide or chlorine dioxide), aldehydes (e.g., aldehydes of 1 to 10 carbons such as formaldehyde or glutaraldehyde or (meth) acrolein), triazines (e.g., monoethanolamine triazine, monomethylamine triazine, and triazines from various amines or mixtures thereof), and glyoxal.
Gas hydrate inhibitors
Suitable gas hydrate inhibitors include, but are not limited to: thermodynamic Hydrate Inhibitors (THI), Kinetic Hydrate Inhibitors (KHI) and anti-agglomerants (AA). Suitable thermodynamic hydrate inhibitors include, but are not limited to: NaCl salt, KCI salt, CaCl2Salt, MgCI2Salt, NaBr2Salts, formates (e.g., potassium formate), polyols (e.g., glucose, sucrose, fructose, maltose, lactose, gluconate, monoethylene glycol, diethylene glycol, triethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, monobutylene glycol, dibutylene glycol, tributylene glycol, glycerol, diglycerol, triglycerol and sugar alcohols (e.g., sorbitol, mannitol), methanol, propanol, ethanol, glycol ethers (e.g., diethylene glycol monomethyl ether, ethylene glycol monobutyl ether), and alkyl or cyclic esters of alcohols (e.g., ethyl lactate, butyl lactate, methyl ethyl benzoate) Lactams (e.g., polyvinylcaprolactam, polyvinyllactam), pyrrolidones (e.g., polyvinylpyrrolidones of various molecular weights), surfactants (e.g., fatty acid salts, ethoxylated alcohols, propoxylated alcohols, sorbitol esters, ethoxylated sorbitol esters, polyglycerol esters of fatty acids, alkyl glucosides, alkyl polyglucosides, alkyl sulfates, alkyl sulfonates, alkyl ester sulfonates, alkyl aromatic sulfonates, alkyl betaines, alkyl amido betaines), hydrocarbyl dispersants (e.g., lignosulfonates, iminodisuccinates, polyaspartates), amino acids, and proteins.
Biocides
Suitable additional biocides include, but are not limited to: oxidizing biocides and non-oxidizing biocides. Suitable non-oxidizing biocides include, for example, aldehydes (e.g., formaldehyde, glutaraldehyde and acrolein), amine compounds (e.g., quaternary amine compounds and cocodiamine (cocodiamine)), halide compounds (e.g., bronopol and 2-2-dibromo-3-nitrilopropionamide (DBNPA)), sulfide compounds (e.g., isothiazolones, carbamates and metronidazole) and quaternary phosphonium compounds
q.pH modifier
Suitable pH modifiers include, but are not limited to: alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal carbonates, alkaline earth metal bicarbonates, and mixtures or combinations thereof. Exemplary pH modifiers include NaOH, KOH, Ca (OH)2、CaO、Na2CO3、KHCO3、K2CO3、NaHCO3MgO and Mg (OH)2。
r. surfactant
Suitable surfactants include, but are not limited to: anionic surfactants, cationic surfactants, zwitterionic surfactants, and nonionic surfactants. Anionic surfactants include alkyl aryl sulfonates, olefin sulfonates, paraffin sulfonates, alcohol sulfates, alcohol ether sulfates, alkyl carboxylates and alkyl ether carboxylates, as well as alkyl and ethoxy alkyl phosphate esters, and mono-and dialkyl sulfosuccinates and sulfosuccinamates. Cation(s)The surfactant includes alkyl trimethyl quaternary ammonium salt, alkyl dimethyl benzyl quaternary ammonium salt, dialkyl dimethyl quaternary ammonium salt and imidazoline
The surfactant may be a quaternary ammonium compound, an amine oxide, an ionic surfactant or a nonionic surfactant, or a combination thereof. Suitable quaternary amine compounds include, but are not limited to: alkyl benzyl ammonium chloride, benzyl coconut oil alkyl (C)12-C18) Dimethyl ammonium chloride, di-cocoalkyl (C)12-C18) Dimethyl ammonium chloride, ditallowdimethyl ammonium chloride, di (hydrogenated tallow alkyl) dimethyl quaternary ammonium methyl chloride, methyl bis (2-hydroxyethyl cocoalkyl (C)12-C18) Quaternary ammonium chloride, dimethyl (2-ethyl) tallow ammonium methyl sulfate, n-dodecylbenzyl dimethyl ammonium chloride, n-octadecylbenzyl dimethyl ammonium chloride, n-dodecyltrimethyl ammonium sulfate, soya alkyl trimethyl ammonium chloride and hydrogenated tallow alkyl (2-ethylhexyl) dimethyl quaternary ammonium methyl sulfate.
s. additional Components
The compositions made according to the present invention may also contain additional functional agents or additives that provide beneficial properties. Those skilled in the art will appreciate that additional agents or additives will vary depending upon the particular composition being manufactured and its intended use.
Alternatively, the composition does not comprise any additional agents or additives.
3. Synthesis of
The compounds and compositions of the present invention may be better understood in conjunction with the following synthetic schemes and methods which illustrate the means by which the compounds may be prepared.
Scheme 1
As shown in scheme 1, the compound of formula (1) can be prepared by reacting imidazoline of formula (2) with acrylic acid of formula (3), wherein R is1、R2、R3、R4、R5、Ra、Rb、RcAnd ReAs defined above. The imidazoline of formula (2) can be prepared by reacting a diamine, such as Ethylenediamine (EDA), Diethylenetriamine (DETA), or triethylenetetramine (TETA), with a long chain fatty acid, such as Tall Oil Fatty Acid (TOFA). The compounds of formula (3) incorporated into representative reaction schemes typically comprise α, β -unsaturated carboxylic fatty acids and their amide and ester derivatives; unsaturated sulfonic and phosphonic fatty acids; and combinations thereof. The compound of formula (3) may be selected from substituted and unsubstituted α, β -unsaturated carboxylic fatty acids having from 3 to about 11 carbon atoms and amide and ester derivatives thereof, or salts thereof; substituted and unsubstituted α, β -unsaturated fatty acids having 2 to about 11 carbon atoms or salts thereof; and combinations thereof.
For scheme 1, R4、R5、Ra、Rb、RcAnd ReEach is hydrogen. Furthermore, R1Is C2-C10Alkyl radical, C2-C8-alkyl or C2-C6-an alkyl group; and R is4、R5、Ra、Rb、RcAnd ReEach is hydrogen. In addition, R1Is C2-C10Alkyl radical, C2-C8-alkyl or C2-C6-an alkyl group; r2Is C17A group; and R is4、R5、Ra、Rb、RcAnd ReEach is hydrogen. Likewise, R1Is C2-C10Alkyl radical, C2-C8-alkyl or C2-C6-an alkyl group; r2Is a group derived from coconut oil, tallow, or Tall Oil Fatty Acid (TOFA); and R is4、R5、Ra、Rb、RcAnd ReEach is hydrogen.
Scheme 2
As shown in scheme 2, the compound of formula (4) can be prepared by reacting imidazoline of formula (2) with acrylic acid of formula (3), wherein R is1、R2、R3、Rx、R4、R5、Ra、Rb、RcAnd ReAs defined above.
For scheme 2, R4、R5、Ra、Rb、RcAnd ReEach is hydrogen. Furthermore, R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12Is hydrogen and R13is-COR14Wherein R is14is-C17H35、-C17H33or-C17H31；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)xis-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen. In addition, R1Is a straight chain C substituted by one substituent2-alkyl, said substituent being terminal-N (R)12)(R13) Wherein R is12And R13Each is-C2-alkyl-CO2R17Wherein R is17Is hydrogen or is absent (e.g. R)12is-C2-alkyl-CO2 -)；R2is-C17H35、-C17H33or-C17H31；R3is-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)3is-CH2CH2CO2 -)；Rxis-CH2CH2CO2ReWherein R iseIs hydrogen (-H), C1-C6-alkyl, or ReIs absent (e.g. R)xis-CH2CH2CO2 -)；R4Is hydrogen; and R is5Is hydrogen.
The imidazolines useful in the compositions of the present invention may also be commercially available.
The compounds may be further modified, for example by manipulation of substituents. These operations may include, but are not limited to: reduction, oxidation, organometallic cross-coupling, alkylation, acylation and hydrolysis reactions, as is well known to those skilled in the art. In some cases, the order in which the foregoing reaction schemes are carried out may be varied to facilitate the reaction or to avoid undesirable reaction products.
4. Application method
The compositions of the present invention may be used in any industry where it is desirable to control biological deposition and/or inhibit corrosion at a surface. The compositions may preferably be used as biocides in oil and gas applications. By treating a gas stream or a liquid stream with an effective amount of the composition of the present invention, the composition can provide significant planktonic kill and enhanced biofilm control by retarding the kinetics of biofilm regrowth.
The composition may be used in a water system, a condensate/oil system/gas system, or any combination thereof.
The compositions may be applied to gases or liquids produced or used in the production, transportation, storage and/or separation of crude oil or natural gas.
The compositions can be applied to gas streams used or produced in coal burning processes, such as coal burning power plants.
The composition may be applied to gases or liquids produced or used in wastewater treatment, farms, slaughterhouses, landfills, municipal wastewater plants, coal coking processes, or biofuel processes.
The fluid to which the composition may be added may be an aqueous medium. The aqueous medium may comprise water, a gas and optionally a liquid hydrocarbon. The fluid that may be introduced into the composition may be a liquid hydrocarbon. The liquid hydrocarbon may be any type of liquid hydrocarbon including, but not limited to: crude oil, heavy oil, processed resids, asphalts, coker oil, coker gas oil, fluid catalytic cracker feedstock, gas oil, naphtha, fluid catalytic cracking slurry, diesel fuel, fuel oil, jet fuel, gasoline, and kerosene. The fluid or gas may be a refined hydrocarbon product.
The fluid or gas treated with the composition of the present invention may be at any selected temperature, such as ambient or elevated temperature. The fluid (e.g., liquid hydrocarbon) or gas may be at a temperature of about 40 ℃ to about 250 ℃. The fluid or gas may be at a temperature of-50 ℃ to 300 ℃,0 ℃ to 200 ℃,10 ℃ to 100 ℃, or 20 ℃ to 90 ℃.
The present composition may be added to the fluid at various levels of water cut (water cut). For example, the water content may be 0% to 100% volume/volume (v/v), 1% to 80% v/v, or 1% to 60% v/v. The fluid may be an aqueous medium comprising various salinity levels. The salinity of the fluid may be 0% to 25%, about 1% to 24%, or about 10% to 25% weight/weight (w/w) of the Total Dissolved Solids (TDS).
The fluid or gas to which the composition of the present invention is added is contained and/or exposed to many different types of devices. For example, the fluid or gas may be contained in a device that transports the fluid or gas from one point to another, such as an oil and/or gas pipeline. The unit can be part of an oil and/or gas refinery, such as a pipeline, separation vessel, dehydration unit, or gas pipeline. The fluid may be contained in and/or exposed to equipment used in oil extraction and/or production (e.g., a wellhead). The apparatus may be part of a coal fired power plant. The device may be a scrubber (e.g., a wet flue gas desulfurizer, a spray dryer absorber, a dry sorbent injector, a spray tower, a contact tower, or a bubble cap tower, etc.). The device may be a cargo ship, a storage vessel, a collection tank or a pipe connected to a tank, vessel or processing unit. The fluid or gas may be contained in a water system, a condensate/oil system/gas system, or any combination thereof.
The compositions of the present invention may be introduced into a fluid or gas by any suitable method for ensuring dispersion in a fluid or gas. The inhibitor composition is added at a point upstream of the flow line where corrosion protection is desired. Mechanical devices (e.g., chemical syringe pumps, tee tubes, injection fittings, atomizers, tubes, etc.) can be used to inject the composition. The compositions of the present invention may be incorporated with or without one or more additional polar or non-polar solvents, depending on the application and requirements. The composition of the invention can be pumped into the oil and/or gas line using a central line (umbilical line). The composition may be delivered to a selected fluid using a capillary injection system. The composition may be introduced into a liquid and mixed. The composition may be injected into the gas stream as an aqueous or non-aqueous solution, mixture or slurry. The fluid or gas may be passed through an absorber column containing a compound or composition of the invention.
The composition may be applied to a fluid or gas to provide any selected concentration. In fact, the present compositions are typically added to a flow line to provide an effective treatment amount of the composition of from about 0.01 to about 10,000 ppm. The composition may be applied to a fluid or gas to provide from about 1 part per million (ppm) to about 1,000,000ppm, from about 1ppm to about 100,000ppm, from about 10ppm to about 75,000ppm, from about 10ppm to about 10,000ppm, from about 50ppm to about 10,000ppm, or from about 1ppm to about 1,000ppm00ppm to about 500ppm total active (e.g., imidazoline, quaternary amine, phosphorus)
The composition may be applied continuously, in batches, or a combination thereof. The dosage of the composition may be continuous.
The composition dosage may be intermittent (i.e., batch processing).
The composition dosage may be continuous/maintenance and/or intermittent.
Dosage rates for continuous processing are typically from about 10ppm to about 500ppm or from about 10ppm to about 200 ppm.
Dosage rates for batch processing are typically from about 10ppm to about 10,000 ppm.
The composition can be applied to a pipeline as a pill to provide a high dose (e.g., 10,000ppm) of the composition.
The flow line in which the composition is used may have a flow rate of 0 ft/sec to 100 ft/sec or 0.1 ft/sec to 50 ft/sec. In some cases, the composition may be formulated with water for addition to a flow line.
The composition may provide 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 100% planktonic kill. After a 4 hour contact period with the biocide composition, the composition can provide 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6%, 99.7%, 99.8%, 99.9%, or 100% planktonic kill in a dynamic flow cycling test.
The dynamic flow loop can be characterized by a test system that: a selected volume of fluid (e.g., 1.5 liters) is maintained continuously circulating over a 1018 carbon steel bio-cylinder (biostud) (e.g., at the 6 o' clock position of the modified Robbin apparatus). A test fluid may be pumped through the system at a selected rate (e.g., about 3.1 gallons per minute), which allows microorganisms and solids to deposit on the bio-cartridge. ATP may be used to quantitatively monitor the health of a microbial population (e.g., weekly) during the growth phase of a biofilm (e.g., 7 weeks). After the establishment of mature biofilms is completed, a study of biocide efficacy can begin. During the study, solid and fluid samples may be collected at predetermined intervals (e.g., 4 hours, 24 hours, 72 hours, or 120 hours) before and after biocide treatment. Baseline readings (e.g., solid and fluid samples) may be obtained prior to adding biocide to the single flow loop. To investigate how quickly the biofilm can regrow after a batch biocide treatment, all of the biocide treated fluid in each flow loop can be removed from the system and untreated production fluid added back to the system. Additional solid samples (e.g., cartridges) can be removed at selected time intervals (e.g., 24 hours, 48 hours, and 72 hours or 120 hours) after the addition of new fluid to determine how quickly the biofilm can regrow to its pre-treated size.
The compounds, compositions, methods and processes of this invention will be better understood by reference to the following examples, which are intended to illustrate and not to limit the scope of the invention.
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