Ionic compounds derived from polyamines, compositions thereof, and methods of preparing the same

Abstract

Disclosed herein are multiply charged cationic or anionic compounds, methods for preparing the same, and articles or compositions comprising the same. The disclosed multiply charged cationic or anionic compounds are derived from polyamines via two reactions: an aza-Michael addition reaction with an activated olefin having an ionic group and a ring-opening reaction with an epoxide. The activated olefin has one of the following formulas: (1), (2), or (3), the epoxide is (4), and X is NH or O. #imgabs0#

Description

[0001] This application is a divisional application of PCT international patent application PCT / US2019 / 048451 with an application date of August 28, 2019, which entered the Chinese national phase, with Chinese patent application No. 201980053830.1 and the invention name being “Multiple charged ionic compounds derived from polyamines, their compositions and preparation methods thereof”.

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority under 35 U.S.C. §119 to provisional application serial number 62 / 724,357, filed on August 29, 2018, which is incorporated herein by reference in its entirety. Technical Field

[0004] The present disclosure generally relates to the field of multiply charged molecules and methods for their manufacture. Specifically, the present disclosure relates to a novel class of modified polyamines comprising both cationic or anionic groups and nonionic groups attached to their nitrogen atoms. The disclosed compounds can be used alone or in combination with other chemicals in various applications as soil control agents, antimicrobial agents, disinfectants, fabric softeners, antistatic agents, corrosion inhibitors, foaming agents, flotation traps, dispersants, surfactant-assisted enhanced oil recovery (EOR), cleaning agents, and the like. Background Art

[0005] Water systems, including industrial water systems, are used for many different purposes. Any water system, including its equipment and water, is susceptible to microbial contamination and scaling. Scaling or deposition of any organic or inorganic material can occur even in industrial water systems treated with the best water treatment programs currently available. If a water system is not cleaned or treated regularly, it will become severely scaled.

[0006] Scaling occurs due to microbial contamination and subsequent microbial and / or biofilm growth. The sources of microbial contamination in industrial water systems are numerous and can include, but are not limited to, airborne contamination, makeup water, process leaks, and improperly cleaned equipment. Scaling-causing microorganisms can establish their microbial communities on any wettable or semi-wettable surface in a water system. Evaporative cooling water systems are particularly susceptible to scaling.

[0007] Scaling can negatively impact water systems, particularly industrial water systems. For example, heavy mineral scale (inorganic material) will accumulate on any water-contacting surface, and any scale, in turn, provides an ideal environment for microbial and / or biofilm growth. If scaling or biofilm growth is allowed to proceed in a water system, the system may suffer from reduced operational efficiency, premature equipment failure, and increased health risks associated with microbial scaling and / or biofilm growth.

[0008] When microbial communities develop on surfaces, exopolymeric substances secreted by the microorganisms contribute to biofilm formation. These biofilms are complex ecosystems that establish a means for concentrating nutrients and providing protection for microbial growth, so biofilms can accelerate scale formation, corrosion, and other scaling processes. Biofilms not only contribute to reduced efficiency in water systems, but they also provide an excellent environment for microbial proliferation and for the production of dangerous Legionella bacteria. Therefore, it is important to minimize biofilms and other scaling processes as much as possible to minimize the health risks associated with Legionella and other waterborne pathogens.

[0009] A variety of methods have been developed to clean or remove biofilms and the microorganisms associated with them. While cleaning and removing biofilms is necessary, a better approach is to prevent or reduce scaling or biofilm formation or growth, thereby reducing the need to remove or remove the biofilm. Cleaning or removing biofilms typically requires operational interruption and the introduction of other chemicals. One method of preventing or reducing scaling and / or biofilm formation or growth is to treat the water system with a scaling control composition reagent or scaling control composition. For example, corrosion inhibitors and / or scaling control composition reagents are typically added to upstream oil and gas production fluids to protect carbon steel pipelines and infrastructure from corrosion and biofilm growth.

[0010] Quaternary ammonium compounds have been used as corrosion inhibitors and scale control agents for many years. Quaternary ammonium compounds are an important subclass of surfactants because they have unique properties. The main difference between quaternary ammonium compounds and other surfactants is their unique structure. Quaternary ammonium compounds are mainly composed of two parts: a hydrophobic group (e.g., a long alkyl group) and a quaternary ammonium salt group. The unique positive charge of ammonium plays a key role in the surface or between different components of the surfactant and the biofilm, such as electrostatic interaction. However, the quaternary ammonium compounds used for this purpose are generally diquaternary ammonium species or species quaternized with benzyl chloride, which are known to have great hazards. In addition, government regulations require that any water containing a single quaternary compound be released into the environment.

[0011] It is therefore an object of the present disclosure to develop a method for efficiently and effectively preparing novel compounds for controlling scale in water systems.

[0012] Another object of the present disclosure is to use the novel compounds in articles, products and / or compositions.

[0013] These and other objects, advantages and features of the present disclosure will become apparent from the following description taken in conjunction with the claims set forth herein. Summary of the Invention

[0014] Disclosed herein are novel compounds, methods for preparing the disclosed compounds, and articles or compositions comprising the disclosed compounds. More specifically, the disclosed compounds are multiply charged cationic or anionic compounds comprising multiple positive or negative charges and nonionic groups within a single molecule of varying sizes. The disclosed compounds are derived from water-soluble polyamines or polyethyleneimines.

[0015] In one aspect, disclosed herein is a multiply charged compound having one of the following general formulas: NA2-[R 10 '] n -NA2, (RNA) n -RNA2, NA2-(RNA) n -RNA2 or NA2-(RN(R')) n -RNA2, where R 10 ' is an unsubstituted or substituted straight or branched C2-C 10 Alkylene or a combination thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkyl, RNAB, RNARNAB or RN(RNAB)2; n can be 2 to 1,000,000; A is H, or H, combination of

[0016] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) ; Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the compound is a compound having 1, 2, 3 or more group and at least one A cationic compound with multiple charges or one, two, three or more group and at least one Anionic compounds with multiple charges.

[0017] In another aspect, disclosed herein is a multiply charged compound derived from a polyamine by reacting the polyamine with an activated olefin and an epoxide, wherein the activated olefin has one of the following formulas:

[0018] and the epoxide is

[0019] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) ; Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the polyamine and the activated olefin undergo an aza Michael Addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0020] In another aspect, disclosed herein is a method of preparing a compound disclosed herein or a salt thereof.

[0021] In yet another aspect, provided herein are articles, products, or compositions comprising one or more compounds disclosed herein.

[0022] The foregoing summary is illustrative only and is not intended to be limiting in any way. In addition to the illustrative aspects, embodiments, and features described above, further aspects, embodiments, and features of the present technology will become apparent to those skilled in the art from the following drawings and detailed description, which show and describe illustrative embodiments of the present technology. Accordingly, the drawings and detailed description should be regarded as illustrative in nature and not limiting in any way. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 An exemplary general reaction scheme is shown for generating multiply charged cationic compounds first by a ring-opening reaction between a linear polyethyleneimine and an epoxide, followed by an aza-Michael addition reaction with an activated olefin (α,β-unsaturated carbonyl compound).

[0024] Figure 2 An exemplary alternative general reaction scheme is shown for generating multiply charged cationic compounds first by an aza-Michael addition reaction between a linear polyethyleneimine and an α,β-unsaturated carbonyl compound, followed by a ring-opening reaction with an epoxide.

[0025] Figure 3 Shown is an exemplary general reaction scheme for generating multiply charged cationic compounds by reacting branched polyethyleneimines with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening reactions and aza-Michael addition reactions, respectively.

[0026] Figure 4 A general reaction scheme is shown for generating multiply charged cationic compounds by reacting linear polyethyleneimines with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening reactions and aza-Michael addition reactions, respectively.

[0027] Various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings, wherein like reference numerals represent like parts throughout the several views. Reference to various embodiments does not limit the scope of the present disclosure. The figures shown herein are not intended to limit the various embodiments according to the present disclosure, but are presented for illustrative purposes only. DETAILED DESCRIPTION

[0028] Disclosed herein are novel compounds, methods for preparing the compounds disclosed herein, and articles or compositions comprising the compounds disclosed herein. More specifically, disclosed are multiply charged cationic or anionic compounds derived from polyamines, activated olefins, and epoxides via aza-Michael addition reactions and ring-opening reactions. Methods for synthesizing such compounds are also disclosed.

[0029] The embodiments of the present disclosure are not limited to specific compositions and methods of use that can be varied and understood by those skilled in the art. It should be further understood that all terms used herein are only used for the purpose of describing specific embodiments and are not intended to be limited in any manner or scope. For example, unless the content clearly indicates otherwise, the singular forms "a", "an", and "the" as used in this specification and the appended claims may include plural indicators. In addition, all units, prefixes, and symbols may be expressed in the form accepted by the SI.

[0030] Numerical ranges described in this specification include values within the defined ranges. Throughout this disclosure, various aspects of the disclosure may be presented in range format. It should be understood that the use of range format is for convenience and brevity only and should not be construed as a fixed limitation on the scope of the disclosure. Therefore, the description of a range should be considered to have specifically disclosed all possible subranges and individual values within the range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0031] In order to make it easier to understand the present disclosure, some terms are first defined. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the embodiments of the present disclosure relate. Many methods and materials similar to, modified or equivalent to those described herein can be used in the practice of the embodiments of the present disclosure without undue experimentation, and preferred materials and methods are described herein. When describing and claiming embodiments of the present disclosure, the following terms will be used according to the definitions set forth below.

[0032] As used herein, the term "about" refers to variations in numerical quantities that can occur, for example, due to typical measurement and liquid handling procedures used to make concentrates or use solutions in the real world; due to errors in these procedures; due to differences in the manufacture, source, or purity of the ingredients used to prepare the composition or perform the method; etc. The term "about" also encompasses amounts that differ due to different equilibrium conditions of the composition resulting from a particular initial mixture. Whether or not modified by the term "about," the claims encompass equivalents to the quantities.

[0033] As used herein, "substituted" refers to an organic group (e.g., as defined below (e.g., alkyl)) in which one or more bonds to a hydrogen atom contained therein are replaced with a bond to a non-hydrogen or non-carbon atom. Substituted groups also include groups in which one or more bonds to one or more carbons or one or more hydrogens are replaced with one or more bonds to a heteroatom (including double or triple bonds). Thus, unless otherwise indicated, a substituted group is substituted with one or more substituents. A substituted group may be substituted with 1, 2, 3, 4, 5, or 6 substituents.

[0034] Substituted cyclic groups include rings and ring systems in which bonds to hydrogen atoms are replaced with bonds to carbon atoms. Thus, substituted cycloalkyl, aryl, heterocyclyl and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl and alkynyl groups as defined herein.

[0035] As used herein, the term "alkyl" refers to a saturated hydrocarbon having one or more carbon atoms, including straight-chain alkyl groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.), cycloalkyl groups (or "cycloalkyl" or "alicyclic" or "carbocyclyl") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl groups substituted with alkyl groups (e.g., alkyl-substituted cycloalkyl groups and cycloalkyl-substituted alkyl groups).

[0036] Unless otherwise specified, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl." As used herein, the term "substituted alkyl" refers to an alkyl group having substituents replacing one or more hydrogens on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halide, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxy, phosphate, phosphonate, phosphinate, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl and ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamide, nitro, trifluoromethyl, cyano, azido, heterocyclic, alkylaryl or aromatic (including heteroaromatic).

[0037] In certain embodiments, the alkyl group of substitution may include heterocyclic radicals. As used herein, term "heterocyclic radical (heterocyclic group) " includes a closed ring structure similar to a carbocyclic group, wherein the one or more carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur or oxygen. Heterocyclic radicals may be saturated or unsaturated. Exemplary heterocyclic radicals include but are not limited to aziridine, oxirane (epoxide, oxirane), thioethane (epoxy sulfide), dioxirane, azetidine, oxetane, thietane, dioxetane, dithietane, dithietene, azetidine, pyrrolidine, pyrroline, oxetane, dihydrofuran and furan.

[0038] Alkenyl or alkene is a straight chain, branched or cycloalkyl group having two to about 30 carbon atoms, and further comprises at least one double bond. In certain embodiments, alkenyl has 2 to about 30 carbon atoms, or generally has 2 to 10 carbon atoms. Alkenyl can be substituted or unsubstituted. For the double bond in alkenyl, the configuration of the double bond can be trans or cis configuration. Alkenyl can be substituted similarly to alkyl.

[0039] Alkynyl is a straight chain, branched or cycloalkyl group having two to about 30 carbon atoms and further comprising at least one triple bond. In certain embodiments, alkynyl has 2 to about 30 carbon atoms, or typically has 2 to 10 carbon atoms. Alkynyl can be substituted or unsubstituted. Alkenyl can be substituted similarly to alkyl or alkenyl.

[0040] As used herein, the terms "alkylene," "cycloalkylene," "alkynylides," and "alkenylene," alone or as part of another substituent, refer to a divalent radical derived from an alkyl, cycloalkyl, or alkenyl group, respectively, as exemplified by -CH2CH2CH2-. For alkylene, cycloalkylene, alkynylene, and alkenylene, no orientation of the attached group is implied.

[0041] As used herein, the term "ester" refers to an 30 COOR 31 Group. R 30 alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylene, alkylene or heterocyclylene, absent, substituted or unsubstituted as defined herein. 31 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.

[0042] As used herein, the term "amine" (or "amino") refers to an -R 32 NR 33 R 34 Group. R32 alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylene, alkylene or heterocyclylene, absent, substituted or unsubstituted as defined herein. 33 and R 34 and R is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.

[0043] As used herein, the term "amine" also refers to an independent compound. When an amine is a compound, it can be composed of R 32 'NR 33 'R 34 ' group is represented by the formula, wherein R 32 '、R 33 ' and R 34 and R is independently hydrogen, or a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.

[0044] As used herein, the term "alcohol" refers to an -R 35 OH group. R 35 Absent, substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylenealkylene or heterocyclylene as defined herein.

[0045] As used herein, the term "carboxylic acid" refers to a -R 36 COOH group. 36 Absent, substituted or unsubstituted alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylenealkylene or heterocyclylene as defined herein.

[0046] As used herein, the term "ether" refers to an -R 37 OR 38 Group. R 37 alkylene, cycloalkylene, alkenylene, alkynylene, arylene, aralkylene, heterocyclylene, alkylene or heterocyclylene, absent, substituted or unsubstituted as defined herein. 38 is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.

[0047] As used herein, the term "solvent" refers to any inorganic or organic solvent. The solvent can be used as a reaction solvent or carrier solvent in the disclosed method or article, product or composition. Suitable solvents include, but are not limited to, oxygenated solvents such as lower alkanols, lower alkyl ethers, glycols, aryl glycol ethers and lower alkyl glycol ethers. Examples of other solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol and butanol, isobutanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, mixed ethylene glycol-propylene glycol ethers, ethylene glycol phenyl ether and propylene glycol phenyl ether. Water is also a solvent. Solvents used herein can be composed of a single solvent or a mixture of many different solvents.

[0048] Glycol ethers include, but are not limited to, diethylene glycol n-butyl ether, diethylene glycol n-propyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol tert-butyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol propyl ether, dipropylene glycol tert-butyl ether, ethylene glycol butyl ether, ethylene glycol propyl ether, ethylene glycol ethyl ether, ethylene glycol methyl ether, ethylene glycol methyl ether acetate, propylene glycol n-butyl ether, propylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, tripropylene glycol methyl ether and tripropylene glycol n-butyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, etc. or mixtures thereof.

[0049] Acids

[0050] The compositions or methods disclosed herein can comprise an acid. However, in some embodiments, the compositions disclosed herein do not contain an acid.

[0051] Typically, the acid used in the present disclosure comprises organic acids and inorganic acids. Organic acids include, but are not limited to glycolic acid (glycolic acid), formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride and benzoic acid. Organic acids also comprise dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid and terephthalic acid. Combinations of these organic acids can also be used. Inorganic acids include, but are not limited to mineral acids, such as phosphoric acid, sulfuric acid, sulfamic acid, methylsulfuric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid and nitric acid. Inorganic acids can be used alone, in combination with one or more other inorganic acids, or in combination with one or more organic acids. Acid generators can be used to form suitable acids, comprising, for example, generators such as potassium fluoride, sodium fluoride, lithium fluoride, ammonium fluoride, ammonium bifluoride, sodium silicon fluoride, etc.

[0052] Examples of particularly suitable acids in the methods or compositions disclosed herein include inorganic and organic acids. Exemplary inorganic acids include phosphoric acid, phosphonic acid, sulfuric acid, sulfamic acid, methylsulfuric acid, hydrochloric acid, hydrobromic acid, hydrofluoric acid, and nitric acid. Exemplary organic acids include glycolic acid (glycolic acid), citric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid. Organic dicarboxylic acids such as oxalic acid, maleic acid, fumaric acid, adipic acid, and terephthalic acid can also be used.

[0053] Alkalinity source or base

[0054] The disclosed preparation methods or compositions may include using an effective amount of an alkalinity source or base as a catalyst or ingredient. The alkalinity source or base further includes one or more basic compounds. The alkalinity source can be added to the reaction mixture in the form of a solid, liquid, or solution.

[0055] Generally, an effective amount of an alkalinity source is considered to be an amount that provides a reaction mixture with a pH of at least about 8. When the pH of the solution is between about 8 and about 10, it can be considered mildly alkaline, and when the pH is greater than about 12, the solution can be considered caustic.

[0056] The alkalinity source can comprise alkali metal carbonate, alkaline metal hydroxide, alkaline metal silicate, alkaline metal silicate or its mixture. Suitable metal carbonate that can be used comprises, for example, sodium carbonate or potassium carbonate, bicarbonate, sesquicarbonate or its mixture. Suitable alkali metal hydroxide that can be used comprises, for example, sodium hydroxide, lithium hydroxide or potassium hydroxide. Examples of useful alkaline metal silicates comprise sodium silicate or potassium silicate (MO:SiO2 ratio is 2.4 to 5:1, M represents alkali metal) or metasilicate. Silicate can be prepared by mixing hydroxide and silicate. The alkalinity source can also comprise metal borate, such as sodium borate or potassium borate etc.

[0057] The alkalinity source may also include ethanolamine, urea sulfate, amines, amine salts, and quaternary ammonium. The simplest cationic amines, amine salts, and quaternary ammonium compounds may be schematically depicted as follows:

[0058]

[0059] wherein R represents a long alkyl chain, R', R", and R'" may be a long alkyl chain or a smaller alkyl group or an aryl group or hydrogen, and X represents an anion.

[0060] In some embodiments, the preparation method does not contain a source of alkalinity because the reactants contain a primary amine or primary amine group to catalyze the reaction. In some embodiments, the compositions disclosed herein do not contain a source of alkalinity.

[0061] polyamines

[0062] The polyamine may have, but is not limited to, the general formula NH2-[R 10 '] n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2 or H2N-(RN(R')) n -RNH2, where R 10 ' is an unsubstituted or substituted straight or branched C2-C 10 Alkylene or a combination thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 alkyl, RNH2, RNHRNH2 or RN(RNH2)2; and n can be 2 to 1,000,000. The monomers in the polyamine, such as the R or R' groups, can be the same or different. In the present disclosure, polyamine refers to both small molecule polyamines when n is 1 to 9 and polymeric polyamines when n is 10 to 1,000,000.

[0063] Small molecule polyamines include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, and tris(2-aminoethyl)amine.

[0064] Other possible polyamines include Huntsman's Monoamines, diamines and triamines. These highly versatile products contain primary amino groups attached to the ends of a polyether backbone typically based on propylene oxide (PO), ethylene oxide (EO) or a mixture of the two oxides. The amines comprise a family of polyetheramines consisting of monoamines, diamines, and triamines based on a core polyether backbone structure. Amines also include high conversion and polyetheramines based on polytetramethylene glycol (PTMEG). These The average molecular weight of the amine (M w ) is from about 130 to about 4,000.

[0065] The polyamines used in the present disclosure can be polyamine derivatives or modified polyamines in which one or more NH protons (but not all) in the polyamine are replaced by unsubstituted or substituted groups. For example, alkyl polyamines containing one or more alkyl groups attached to nitrogen atoms can be used to produce the multiply charged cationic polyamines disclosed herein. In these PEI derivatives, only some of the primary NH2 or secondary NH protons are replaced by other aprotic groups, and the remaining NH2 or NH protons can still react with Michael acceptors, such as activated olefins containing hydrophilic (ionic) groups, via aza-Michael addition reactions.

[0066] One class of polymeric polyamines includes polyethyleneimine (PEI) and its derivatives. Polyethyleneimine (PEI) or polyethylenimine is a polymer with repeating units of CH2CH2NH, and its general formula is NH2(CH2CH2NH) n -CH2CH2NH2, where n can be from 2 to 10 5 The molecular weight of the repeating monomer in PEI (M w ) is 43.07, and the nitrogen-carbon ratio is 1:2.

[0067] PEI derivatives include ethoxylated / propylated PEI, polyquaternium PEI, polyglycerol quaternium PEI, and other PEI derivatives, salts, or mixtures thereof. The molar mass of the polyethyleneimine including the modified polyethyleneimine can vary from about 800 g / mol to about 2,000,000 g / mol. For example, HP20 is an alkoxylated PEI product. In these PEI derivatives, only some of the primary NH2 or secondary NH2 protons are replaced by functional groups, and the remaining NH2 or NH2 protons are still available to react with Michael acceptors, such as activated olefins or α,β-unsaturated compounds containing hydrophilic (ionic) groups.

[0068] PEI and its derivatives can be linear, branched, or dendritic. Linear polyethyleneimine contains all secondary amines, in contrast to branched PEI, which contains primary, secondary, and tertiary amino groups. Fully branched dendritic forms also exist and contain primary and tertiary amino groups. Images of unmodified linear, branched, and dendritic PEI are shown below.

[0069]

[0070]

[0071] PEI derivatives are typically obtained by replacing one or more protons on the nitrogen atom with different groups. One such PEI derivative is ethoxylated and propoxylated PEI, in which polyethyleneimine is derivatized with ethylene oxide (EO) and / or propylene oxide (PO) side chains. Ethoxylation of PEI can increase the solubility of PEI.

[0072] PEI is produced on an industrial scale. Various commercial polyethyleneimines are available, including, for example, those sold under the trade names Those sold by BASF include, for example FG, G. PR 8515, WF, G 20 / 35 / 100, HF, P. PS, PO 100, PN50 / 60 and SK. The average molecular weight (M) of these PEI w ) are about 800, about 1,300, about 2,000, about 5,000, about 25,000, about 1,300 / 2,000 / 5,000, about 25,000, about 750,000, about 750,000, about 1,000,000 and about 2,000,000, respectively.

[0073] Two commonly used average values for the molecular weight of a polymer are the number average molecular weight (M) and n ) and weight average molecular weight (M w ). The polydispersity index (D) represents the molecular weight distribution of the polymer. Mn=(∑n i M i ) / ∑n i 、M w =(∑n i M i 2 ) / ∑n i M i and D=M w / M n , where the index i represents the number of different molecular weights present in the sample, and n i is of molar mass M i For polymers, M n and M w Usually different. For example, by GPC, the M n Can be about 10,000, and through LS, M w It can be about 25,000.

[0074] Light scattering (LS) can be used to measure the M wAnother easy way to measure the molecular weight of a sample or product is gel permeation chromatography (GPC). GPC is an analytical technique that separates molecules in a polymer by size and provides a molecular weight distribution of the material. GPC is sometimes also called size exclusion chromatography (SEC). This technique is commonly used to analyze the molecular weight of a polymer. n and M w Both.

[0075] These commercially available and exemplary polyethyleneimines are soluble in water and can be used as anhydrous polyethyleneimines and / or in aqueous solutions or methoxypropanol (e.g., for PO 100) is obtained from the modified polyethyleneimine provided in.

[0076] PEI and its derivatives have found many applications that are generally derived from their polycationic properties. Due to the presence of amine groups, PEI can be protonated with acids to form PEI salts from the surrounding medium, thereby producing products that are partially or completely ionized depending on the pH. For example, about 73% of PEI is protonated at pH 2, about 50% of PEI is protonated at pH 4, about 33% of PEI is protonated at pH 5, about 25% of PEI is protonated at pH 8, and about 4% of PEI is protonated at pH 10. Typically, PEI can be purchased in its protonated or unprotonated form in both aqueous and anhydrous conditions. The charge (cationic) density of commercial PEI is about 16-17 meq / g (milliequivalents per gram) at pH 13.

[0077] The counterion of each protonated nitrogen center is in balance with the anion of the acid obtained during neutralization. Examples of protonated PEI salts include, but are not limited to, PEI-hydrochloride, PEI-sulfate, PEI-nitrate, PEI-acetate, PEI fatty acid salts, and the like. In fact, any acid can be used to protonate PEI, thereby resulting in the formation of the corresponding PEI salt compound.

[0078] Suitable polyethyleneimines useful in the present disclosure may contain mixtures of primary, secondary, and tertiary amine substituents or mixtures of different average molecular weights. The mixture of primary, secondary, and tertiary amine substituents may be in any ratio, including, for example, a ratio of about 1:1:1 to about 1:2:1, with branching every 3 to 3.5 nitrogen atoms along the chain segment. Alternatively, suitable polyethyleneimine compounds may be primarily one of the primary, secondary, or tertiary amine substituents.

[0079] The polyamines that can be used to prepare the multiply charged cationic or anionic compounds disclosed herein can have a wide range of average molecular weights. Different multiply charged cationic or anionic compounds with characteristic average molecular weights can be produced by selecting different starting small molecule polyamines, polymeric PEIs, or mixtures thereof. By controlling the size of the polyamine or PEI and the degree of modification of the α,β-unsaturated compound and the epoxide, multiply charged cationic or anionic compounds with similar average molecular weights and multiple cationic or multiple anionic charges can be produced. Due to this characteristic, different multiply charged cationic or anionic compounds can be produced and used for a wider range of applications using unmodified polyamines or PEIs.

[0080] Specifically, the average molecular weight (M) of the polyamines that can be used to prepare the modified polyamines disclosed herein is w ) is about 60-200, about 100-400, about 100-600, about 600-5,000, about 600-800, about 800-2,000, about 800-5,000, about 100-2,000,000, about 100-25,000, about 600-25,000, about 800-25,000, about 600-750,000, about 800-750,000, about 25,000-750,000, about 750,000-2,0 00,000, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 1,000, about 1,500, about 2,000, about 3,000, about 5,000, about 8,000, about 10,000, about 15,000, about 20,000, about 50,000, about 100,000, about 250,000, about 500,000, about 1,000,000, about 2,000,000, or any value therebetween.

[0081] In one aspect, disclosed herein is a multiply charged compound having one of the following general formulas: NA2-[R 10 '] n -NA2, (RNA) n -RNA2, NA2-(RNA) n -RNA2 or NA2-(RN(R')) n -RNA2, where R 10 ' is an unsubstituted or substituted straight or branched C4-C 10 Alkylene or a combination thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n can be 2 to 1,000,000; A is H, combination of; or H, combination of

[0082] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) ; Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the compound is a compound having 1, 2, 3 or more group and at least one A cationic compound with multiple charges or one, two, three or more group and at least one Anionic compounds with multiple charges.

[0083] In some embodiments, A is In some other embodiments, A is In yet other embodiments, A is

[0084] In some embodiments, the multiply charged compound is NA2-[R 10 '] n -NA2. In some other embodiments, the multiply charged compound is (RNA) n-RNA2. In yet other embodiments, the multiply charged compound is NA2-(RNA) n -RNA2. In other embodiments, the multiply charged compound is NA2-(RN(R')) n -RNA2.

[0085] In some embodiments, R 7 is H. In some other embodiments, R 7 is a C1-C4 alkyl group. In yet other embodiments, R 8 It is C 12 -C 20 alkyl.

[0086] In another aspect, disclosed herein is a multiply charged compound derived from a polyamine by reacting the polyamine with an activated olefin and an epoxide, wherein the activated olefin has one of the following formulas:

[0087] and the epoxide is

[0088] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) ; Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k-O-alkyl, wherein k is an integer from 1 to 30; wherein the polyamine and the activated olefin undergo an aza-Michael addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0089] The multiply charged cationic or anionic compounds disclosed herein are derived from polyamines by aza-Michael addition reactions of the polyamines with activated olefins having ionic groups, such as α,β-unsaturated carbonyl compounds, and ring-opening reactions of the polyamines with epoxides.

[0090] The two reactions to produce the polyamines of the disclosed compounds can be sequential or simultaneous, for example as Figure 1 、 Figure 2 and Figure 3 The figure illustrates a general scheme of structures and reactions for producing the disclosed multiply charged cation or anion compounds, shown in three different ways.

[0091] Figure 1 An exemplary general reaction scheme is shown for generating multiply charged cationic compounds first by a ring-opening reaction between a linear polyethyleneimine and an epoxide, followed by an aza-Michael addition reaction with an activated olefin, such as an α,β-unsaturated carbonyl compound having a cationic group. Figure 2 An exemplary alternative general reaction scheme is shown for generating multiply charged cationic compounds first by an aza-Michael addition reaction between a linear polyethyleneimine and an α,β-unsaturated carbonyl compound, followed by a ring-opening reaction with an epoxide. Figure 3 Shown is an exemplary general reaction scheme for generating multiply charged cationic compounds by reacting branched polyethyleneimines with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening reactions and aza-Michael addition reactions, respectively.

[0092] exist Figure 1 、 Figure 2 and Figure 3 wherein k, l, m, n, o or p is an integer from 1 to 100; X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl; R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR 4 R 5 R6(+) or its salt; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl or benzyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30.

[0093] Figure 1 、 Figure 2 and Figure 3 Structures V and VI in Figure 1 depict generalized reaction products. In Structures V and VI, all secondary and primary amine groups in the polyethyleneimine react with the epoxide and the α,β-unsaturated carbonyl compound, resulting in no secondary amine groups remaining. It is possible that some secondary or primary amine groups in the disclosed multiply charged ionic compounds do not react completely with the epoxide or activated olefin, but instead remain as primary or secondary amine groups in the multiply charged ionic compound or its salt.

[0094] In some embodiments, R 7 is H. In some other embodiments, R 7 is CH3. In yet other embodiments, R 7 It is a C2-C4 alkyl group.

[0095] In some embodiments, R 8 It is C1-C 30 In some other embodiments, R 8 is a C8-C4 alkyl group. In yet other embodiments, R 8 It is C8-C 20 alkyl.

[0096] In some embodiments, R 8 Yes - (CH2) k -O-alkyl, wherein k is an integer from 1 to 30 and the alkyl group is C1-C 30 alkyl.

[0097] In some embodiments, the polyamine is NH2-[R 10 '] n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2 or H2N-(RN(R')) n -RNH2, where R 10 ' is an unsubstituted or substituted straight or branched C2-C 10Alkylene or a combination thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 alkyl, RNH2, RNHRNH2 or RN(RNH2)2; and n can be 2 to 1,000,000. The monomers in the polyamine, such as the R or R' groups, can be the same or different. In the present disclosure, polyamine refers to both small molecule polyamines when n is 1 to 9 and polymeric polyamines when n is 10 to 1,000,000.

[0098] In other words, a multiply charged ionic compound may have the formula: NA2-[R 10 '] n -NA2, (RNA) n -RNA2, NA2-(RNA) n -RNA2 or NA2-(RN(R')) n -RNA2, etc., where R 10 ' is an unsubstituted or substituted straight or branched C4-C 10 Alkylene; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n can be 2 to 1,000,000; A is H, combination of; or H, wherein X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+); Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0099] In some embodiments, A is positively charged and nonionic In some other embodiments, A is negatively charged and nonionic

[0100] In some embodiments, at least two of the primary NH2 protons are At least one of the primary NH2 or secondary NH is replaced by and the remaining primary NH2 protons remain. In some embodiments, at least two of the primary NH2 protons are replaced by At least one of the primary NH2 or secondary NH is replaced by and the remaining primary NH2 protons are retained. In other embodiments, all primary NH2 protons are replaced by In some embodiments, some of the primary NH2 and secondary NH protons are replaced by

[0101] In some embodiments, all primary NH2 and some secondary NH protons are replaced by However, the compounds disclosed herein are compounds having 1, 2, 3 or more group and at least one A cationic compound with multiple charges or one, two, three or more group and at least one Anionic compounds with multiple charges.

[0102] In some embodiments, R 2 is H. In some embodiments, R 2is CH3. In yet other embodiments, R 2 It is CH3CH3, CH2CH2CH3 or CH(CH3)2.

[0103] In some embodiments, Y is -NR4R5R6 (+) In some other embodiments, Y is -NR4R5R6 (+) , and R 4 、R 5 and R 6 is independently CH3. In yet other embodiments, Y is -NR4R5R6 (+) , and R 4 and R 5 are independently CH3, and R 6 It is C6-C 12 In some other embodiments, Y is -NR4R5R6 (+) , and R 4 and R 5 are independently CH3, and R 6 It is -CH2-C6H6.

[0104] In some embodiments, Y is -NR4R5R6 (+) , and the counterion of Y is any negatively charged ion or species. In some other embodiments, the counterion of Y is selected from the group consisting of chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, carbonate, bicarbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, and combinations thereof.

[0105] In some embodiments, Y' is -COOH or a salt thereof. In other embodiments, Y' is -SO3H, -OSO3H or a salt thereof. In still other embodiments, Y' is -PO3H, -OPO3H or a salt thereof.

[0106] In some embodiments, when Y is an anionic group, the negatively charged countersite ion is Li + 、Na + , K + NH3 + , quaternary ammonium, etc.

[0107] In some embodiments, R 3 is CH2. In some other embodiments, R 3 is CH2CH2. In some other embodiments, R 3 is C(CH3)2. In yet other embodiments, R 3 It is an unsubstituted straight chain and saturated C1-C30 In some embodiments, R 3 It is an unsubstituted straight chain and unsaturated C1-C 30 Alkylene.

[0108] In some embodiments, R 3 It is a straight chain C8-C 18 In some other embodiments, R 3 It is a branched C8-C 20 Alkyl, alkenyl or alkynyl.

[0109] In some embodiments, the polyamine is of the formula -[RNH] n - linear, branched or dendritic macromolecular polyamine, wherein R is -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 alkylene or combinations thereof, and n is an integer from 3, 4, 5, 6, 7-9, or 10 to 1,000,000.

[0110] In some embodiments, the polyamine is of the formula (RNH) n -RNH2 linear, branched or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 alkylene or a combination thereof, and n can be 2 to 1,000,000. In some embodiments, R is the same in each monomer. In other embodiments, R can be different from monomer to monomer.

[0111] In some other embodiments, the polyamine has the general formula H2N-(RNH) n -RNH2 linear, branched or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 alkylene or a combination thereof, and n can be 2 to 1,000,000. In some embodiments, R is the same in each monomer. In other embodiments, R can be different from monomer to monomer.

[0112] In yet other embodiments, the polyamine has the general formula H2N-(RN(R')) n -RNH2 linear, branched or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 alkyl, RNH2, RNHRNH2, or RN(RNH2)2; and n can be 2 to 1,000,000. In some embodiments, R or R' is the same in each monomer. In other embodiments, R or R' can be different from monomer to monomer.

[0113] In some embodiments, the polyamine is a polyamine having the general formula NH2-[R 10 '] n -NH2 polyamines, where R 10 ' is an unsubstituted or substituted straight or branched C4-C 10 alkylene or combinations thereof, and n is 3, 4, 5, 6, 7-9, or 10 to 1,000,000.

[0114] In some embodiments, the polyamine is Huntsman One or more polyamines selected from the group consisting of:

[0115] In some embodiments, the polyamine comprises an alkyleneamine comprising ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, tris(2-aminoethyl)amine, or mixtures thereof.

[0116] In other embodiments, the polyamine is a mixture of monoamines, diamines, and triamines with a polyether backbone or with a polyether backbone based on propylene oxide (PO), ethylene oxide (EO), or a mixture of the two oxides.

[0117] In some embodiments, the polyamine is an unmodified polyamine. In other embodiments, the polyamine is a modified polyamine.

[0118] In yet other embodiments, the polyamine is an ethoxylated polyamine, a propylated polyamine, a polyamine with a polyquaternium salt, a polyamine with a polyglycerol, or a combination thereof.

[0119] In yet other embodiments, the polyamine is a linear, branched or dendritic macromolecular polyethyleneimine. In other embodiments, the polyamine comprises only primary and secondary amine groups. In certain embodiments, the polyamine comprises only primary, secondary and tertiary amine groups. In other embodiments, the polyamine comprises only primary and tertiary amine groups.

[0120] In some embodiments, the polyamine is a single compound. In other embodiments, the polyamine is a mixture of two or more different polyamines, wherein the different polyamines have different molecular weights, different structures, or both.

[0121] In some embodiments, the average molecular weight (M w ) is from about 60 to about 2,000,000 Da. In other embodiments, the average molecular weight (M) of the polyamine is from about 60 to about 2,000,000 Da. w ) is from about 60 to about 5,000 Da. In yet other embodiments, the average molecular weight (M) of the polyamine is from about 60 to about 5,000 Da. w ) is about 60 to about 25,000 Da.

[0122] In some embodiments, the average molecular weight (M w ) is about 60-200, about 100-400, about 100-600, about 600-5,000, about 600-800, about 800-2,000, about 800-5,000, about 100-2,000,000, about 100-25,000, about 600-25,000, about 800-25,000, about 600-750,000, about 800-750,000, about 25,000-750,000, about 750,000-2,0 00,000, about 100, about 200, about 300, about 400, about 500, about 600, about 700, about 800, about 1,000, about 1,500, about 2,000, about 3,000, about 5,000, about 8,000, about 10,000, about 15,000, about 20,000, about 50,000, about 100,000, about 250,000, about 500,000, about 1,000,000, about 2,000,000, or any value therebetween.

[0123] In some embodiments, the polyamine has an average molecular weight (M w ) is from about 130 to about 4,000 diamine or triamine.

[0124] In some embodiments, the compound is derived from a mixture of linear polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC). In other embodiments, the compound is derived from a mixture of linear polyethyleneimine and [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC).

[0125] In other embodiments, the multiply charged cationic compound is derived from a mixture of branched polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC). In other embodiments, the compound is derived from a mixture of linear polyethyleneimine and [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC).

[0126] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethyleth-1-ammonium methyl sulfate (DMAEA-MSQ).

[0127] In other embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), or a mixture thereof.

[0128] In some other embodiments, the activated olefin is 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium methyl sulfate (DMAEA-MSQ), or a mixture thereof.

[0129] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid, itaconic acid, maleic acid, 3-(allyloxy)-2-hydroxypropane-1-sulfonate or a salt thereof or a mixture thereof.

[0130] In other embodiments, the activated olefin is vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

[0131] In some embodiments, the epoxide is an alkyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, 1,2-epoxyalkane, 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof. In other embodiments, the epoxide is an alkyl glycidyl ether or 1,2-epoxyalkane. In still other embodiments, the epoxide is hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, or a mixture thereof. In other embodiments, the epoxide is 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof.

[0132] In yet other embodiments, when the activated olefin contains an anionic group that can carry a negative charge at alkaline pH, the negatively charged positive counterion includes but is not limited to alkali metal ions, Li + 、Na + , K + NH4 + , quaternary ammonium ions, etc.

[0133] In some embodiments, the compound is derived from epoxide, (3-acrylamidopropyl)trimethylammonium chloride (APTAC), and the average molecular weight (M w ) is about 1,300 polyethyleneimine, average molecular weight (M w ) is about 5,000 polyethyleneimine, average molecular weight (M w ) is about 25,000 polyethyleneimine or average molecular weight (M w ) is a product of polyethyleneimine of about 750,000.

[0134] It will be appreciated that when n is greater than 2, the compound may be a mixture of more than two cationic compounds that differ from each other in the exact position of the NH substitution.

[0135] In some embodiments, the average molecular weight (M) of the multiply charged cationic or anionic compound is w ) is about 100 to about 2,000,000 Da. In other embodiments, the average molecular weight (M) of the multiply charged cationic or anionic compound is about 100 to about 2,000,000 Da. w ) is about 100 to about 50,000 Da. In yet other embodiments, the average molecular weight (M) of the multiply charged cationic or anionic compound is about 100 to about 50,000 Da. w ) is about 100 Da to about 600 Da, about 100 Da to about 1,000 Da, about 100 Da to about 1,400 Da, about 100 Da to about 3,000 Da, about 100 Da to about 5,500 Da, or about 100 Da to about 10,000 Da, about 100 Da to about 20,000 Da, about 100 Da to about 30,000 Da, or about 100 Da to about 40,000 Da.

[0136] In some embodiments, the multiply charged cationic compound has at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 positive charges. In other embodiments, the compound has 10 to 1,000 positive charges, or any value therebetween.

[0137] In some embodiments, the multiply charged cationic compound has at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, at least 9, or at least 10 negative charges. In other embodiments, the compound has 10 to 1,000 positive charges, or any value in between.

[0138] In some embodiments, the compound or modified compound is soluble or dispersible in water.

[0139] Aza-Michael addition reaction and epoxide ring-opening reaction

[0140] The multiply charged cationic or anionic compounds disclosed herein are derived from an aza-Michael addition reaction between a polyamine and a Michael acceptor (such as an activated olefin or an α,β-unsaturated carbonyl compound containing a hydrophilic (ionic) group) and from a ring-opening reaction between a polyamine and an epoxide. The aza-Michael addition reaction and the ring-opening reaction can occur sequentially or simultaneously. In some embodiments, the reaction product of the aza-Michael addition reaction is further derived from a ring-opening reaction of an epoxide. Alternatively, the multiply charged cationic or anionic compounds disclosed herein are derived from a ring-opening reaction between a polyamine and an epoxide, and the product of the ring-opening reaction is then reacted with a Michael acceptor, such as an activated olefin or an α,β-unsaturated carbonyl compound containing a hydrophilic (ionic) group, by an aza-Michael addition reaction between the products.

[0141] Aza-Michael addition reactions occur when a fatty amine group comes into contact with an unsaturated hydrocarbon moiety (e.g., a carbon-carbon double bond) adjacent to an electron-withdrawing group (e.g., a carbonyl, cyano, or nitro group). Specifically, Michael additions are reactions between nucleophiles and activated olefin and alkyne functional groups, where the nucleophile adds across a carbon-carbon multiple bond adjacent to an electron-withdrawing and resonance-stabilized activating group (e.g., a carbonyl group). The Michael addition nucleophile is referred to as a "Michael donor," the activated electrophilic olefin is referred to as a "Michael acceptor," and the reaction product of the two components is referred to as a "Michael adduct." Examples of Michael donors include, but are not limited to, amines, thiols, phosphines, carbanions, and alkoxides. Examples of Michael acceptors include, but are not limited to, acrylates, alkyl methacrylates, acrylonitrile, acrylamide, maleimides, cyanoacrylates, and vinyl sulfones, vinyl ketones, nitroethylene, α,β-unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridine, azo compounds, β-ketoacetylenes, and acetylenic esters.

[0142] As used herein, "activated olefin" refers to a substituted olefin in which at least one of the double-bonded carbons has a conjugated electron-withdrawing group. Examples of activated olefins include, but are not limited to, α,β-unsaturated carbonyl compounds (e.g., CH2=CHCO-NH-CH3, alkyl-CH=CH-CO-alkyl, CH2=CH2C(O)-O-CH3), CH2=CH-COOH, CH2=CH(CH3)-COOH, CH2=CH-SO3H, and the like.

[0143] The aza-Michael addition reaction can be catalyzed by a strong acid or a strong base. In some cases, some ionic liquids can serve as both a reaction medium and a catalyst. Preferred catalysts for the aza-Michael addition reaction used to synthesize the disclosed compounds are bases. Exemplary base catalysts can be hydroxides and amines. Because the reaction used to synthesize the disclosed compounds uses polyamines, the polyamines themselves can serve as catalysts for the reaction. In such embodiments, no additional catalyst is required, or the additional catalyst is optional. Other preferred catalysts include amidine bases and guanidine bases.

[0144] The use of solvent and / or diluent in the reaction is optional. When using solvent, various non-acidic solvents are suitable, such as water, ether (for example, tetrahydrofuran (THF)), aromatic hydrocarbons (for example, toluene and xylene), alcohol (for example, n-butanol) etc. Since the synthesis process is relatively insensitive to solvent, the reaction can use a variety of solvents. When using solvent (or diluent), the scope of loading level can be as low as about 10wt-% to as high as about 80wt-% and higher. The solvent loading level can be 0wt-%, about 1wt-% to about 10wt-%, about 10wt-% to about 20wt-%, about 20wt-% to about 30wt-%, about 30wt-% to about 40wt-%, about 40wt-% to about 50wt-%, about 50wt-% to about 60wt-%, about 60wt-% to about 70wt-%, about 70wt-% to about 80wt-%, about 1wt-% to about 10wt-%. About 20 wt-%, about 20 wt-% to about 40 wt-%, about 40 wt-% to about 60 wt-%, about 60 wt-% to about 80 wt-%, about 40 wt-% to about 70 wt-%, about 5 wt-%, about 15 wt-%, about 25 wt-%, about 35 wt-%, about 45 wt-%, about 55 wt-%, about 65 wt-%, about 75 wt-%, or any value therebetween in the final reaction mixture.

[0145] Typically, the reaction can be carried out at a temperature within a wide temperature range. The range of reaction temperature can be from about 0°C to about 150°C, more preferably from about 50°C to about 80°C. The contact temperature can be from about 10°C to about 140°C, from about 20°C to about 130°C, from about 30°C to about 120°C, from about 40°C to about 110°C, from about 50°C to about 100°C, from about 60°C to about 90°C, from about 70°C to about 80°C, from about 0°C to about 20°C, from about 20°C to about 40°C, from about 40°C to about 60°C, from about 60°C to about 80°C, from about 80°C to about 100°C, from about 100°C to about 120°C, from about 120°C to about 150°C, from about 5°C, about 25°C, about 45°C, about 65°C, about 85°C, about 105°C, about 125°C, about 145°C or any value therebetween. The reaction temperature may be approximately the same from the start of the reaction to the end of the reaction, and the reaction temperature may be changed from one temperature to another as the reaction proceeds.

[0146] Reaction times for the synthesis of the compounds disclosed herein can vary widely, depending on factors such as the reaction temperature, the potency and amount of the catalyst, the presence or absence of a diluent (solvent), etc. Preferred reaction times can be from about 0.5 hours to about 48 hours, from about 1 hour to 40 hours, from about 2 hours to 38 hours, from about 4 hours to about 36 hours, from about 6 hours to about 34 hours, from about 8 hours to about 32 hours, from about 10 hours to about 30 hours, from about 12 hours to about 28 hours, from about 14 hours to 26 hours, from about 16 hours to 24 hours, from about 18 hours to 20 hours, from about 1 hour to 8 hours, from 8 hours to 16 hours, from 8 hours to about 24 hours, from about 2 hours, from about 4 hours, from about 6 hours, from about 8 hours, from about 10 hours, from about 14 hours, from about 16 hours, from about 18 hours to 24 hours, from about 18 hours to 20 hours, from about 1 hour to 8 hours, from about 8 hours to 16 hours, from about 8 hours to about 24 hours, from about 2 hours, from about 4 hours, from about 6 hours, from about 8 hours, from about 10 hours, from about 14 hours, from about 16 hours, from about 18 hours, from about 24 hours, from about 30 hours, from about 36 hours, or any value therebetween.

[0147] The ring-opening reaction of epoxides with amines is also known in the art. The ring-opening reaction can be carried out at a temperature of about -20°C to about 200°C in the presence of a catalyst, base, or acid. In some embodiments, the ring-opening reaction is carried out in the absence of a catalyst, base, or acid. In other embodiments, the ring-opening reaction is carried out at a temperature of about 100°C to about 150°C; at different temperatures for the aza-Michael addition reaction; or in the presence of different catalysts, bases, or acids.

[0148] When one mole of polyamine and specified moles (two or more moles) of activated olefin, epoxide and the two are mixed together at the above temperature for a sufficient time, both aza-Michael addition and ring-opening reactions for synthesizing the disclosed compounds can be completed.

[0149] It was found that aza-Michael addition reaction and epoxide ring-opening reaction can be used to synthesize the disclosed compounds without using elevated temperatures greater than 200° C. and elevated pressures greater than normal atmospheric pressure, and with high yields (greater than 98%).

[0150] The process of two reactions can usually be monitored by ESI-MS and / or NMR spectrum to monitor the consumption of monomer. The reaction product can be purified or separated by HPLC or other methods known to those skilled in the art. For carrying out complete reaction, the formed product can be separated by removing the solvent or by precipitating in a non-polar solvent opposite to the reaction medium. For reaction in water, the formed product is precipitated out from the aqueous reaction mixture. Higher pressure can accelerate the reaction. Usually, if the reaction is carried out at room temperature with a suitable catalyst, the product yield of the reaction can exceed 98%, in some embodiments within 16 hours.

[0151] Preparation method

[0152] In another aspect, disclosed herein is a method for preparing a compound or a salt thereof, wherein the method comprises reacting a polyamine with The epoxide is contacted with an activated olefin (Michael acceptor) having an ionic group according to one of the following formulae:

[0153]

[0154] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) , Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; and R 4 、R 5 and R 6 Independently C1-C 10 Alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k-O-alkyl, wherein k is an integer from 1 to 30; wherein the polyamine and the activated olefin undergo an aza-Michael addition reaction; the polyamine and the epoxide undergo a ring-opening reaction; and wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0155] In some embodiments of the disclosed methods, the polyamine is NH2-[R 10 '] n -NH2, (RNH) n -RNH2, H2N-(RNH) n -RNH2、H2N-(RN(R')) n -RNH2 or a mixture thereof, wherein R 10 ' is an unsubstituted or substituted straight or branched C2-C 10 Alkylene or a combination thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkylene or a combination thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted linear or branched C4-C 10 Alkyl, RNH2, RNHRNH2 or RN(RNH2)2, and n can be 2 to 1,000,000.

[0156] In some embodiments, the activated olefin is

[0157]

[0158] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR4R5R6 (+) , and R 4 、R 5 and R 6 Independently C1-C 10 alkyl.

[0159] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethyleth-1-ammonium methyl sulfate (DMAEA-MSQ), or a mixture thereof.

[0160] In some embodiments, Y is -NR4R5R6 (+) , and the counterion of Y is any negatively charged ion or species. In other embodiments, the counterion of Y is chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, carbonate, bicarbonate, hydrogen oxalate, hydrogen sulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

[0161] In some other embodiments of the disclosed methods, the activated olefin is

[0162]

[0163] Where X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl or alkynyl; R 2 ' is H, CH3 or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y';m is an integer from 2 to 4;R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y 'is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; and R 4 、R 5 and R 6 Independently C1-C 10 alkyl.

[0164] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinylsulfonic acid, vinylphosphonic acid, or mixtures thereof.

[0165] In other embodiments, the activated olefin is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 3-(allyloxy)-2-hydroxypropane-1-sulfonate, or a mixture thereof.

[0166] In yet other embodiments, when the activated olefin contains an anionic group that can carry a negative charge at alkaline pH, the negatively charged positive counterion includes but is not limited to alkali metal ions, Li + 、Na + , K + NH4 + , quaternary ammonium ions, etc.

[0167] In some embodiments, R 7 is H. In some other embodiments, R 7 is CH3. In yet other embodiments, R 7 It is a C2-C4 alkyl group.

[0168] In some embodiments, R 8 It is C1-C 30 In some other embodiments, R 8 is a C8-C4 alkyl group. In yet other embodiments, R 8 It is C8-C 20 alkyl.

[0169] In some embodiments, R 8 Yes - (CH2) k -O-alkyl, wherein k is an integer from 1 to 30 and the alkyl group is C1-C 30 alkyl.

[0170] In some embodiments, the epoxide is an alkyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, 1,2-epoxyalkane, 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof. In other embodiments, the epoxide is an alkyl glycidyl ether or 1,2-epoxyalkane. In still other embodiments, the epoxide is hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, or a mixture thereof. In other embodiments, the epoxide is 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof.

[0171] In some embodiments of the disclosed method, the contacting step is carried out in the presence of a reaction solvent. The reaction solvent can be any inorganic solvent or organic solvent commonly used in chemical synthesis. The reaction solvent used in the disclosed method can be introduced into the reaction between the polyamine and the activated olefin containing a cationic or anionic group, and between the polyamine and the epoxide by any means known to those skilled in the art. For example, the solvent can be added to a container or vessel before, simultaneously with, or after the addition of the polyamine or activated olefin or both to react with one or both reactants.

[0172] In some embodiments, the reaction solvent is water, methanol, ethanol, propanol, ethylene glycol, PEG or a mixture thereof. In other embodiments, the reaction solvent is water.

[0173] In some other embodiments of the disclosed methods, the contacting step is performed in the presence of a catalyst, a base, or an acid. The catalyst, base, or acid can be introduced into the reaction between the polyamine and the activated olefin by any means known to those skilled in the art.

[0174] In some embodiments, the contacting step is carried out in the absence of any additional base or alkalinity source. In other embodiments, the contacting step is carried out in the presence of an alkalinity source. In other embodiments, the contacting step is carried out in the presence of an organic base (such as an alkanolamine). In yet other embodiments, the contacting step is carried out in the presence of an alkali metal hydroxide, a carbonate, an imidazole / pyridine base or a combination thereof (such as NaOH, Na2CO3, aminoethylpyridine, aminopropylimidazole or a combination thereof). In other embodiments, the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide. In some embodiments, the catalyst base is an amidine base or a guanidine base or a mixture thereof. In other embodiments, the catalyst is an ionic liquid, such as 1,8-diazabicyclo[5.4.0]-undec-7-ene-8-acetate, for reaction under solvent-free conditions at room temperature.

[0175] In yet other embodiments of the disclosed methods, the contacting step is performed in the presence of an acid. In other embodiments, the contacting step is performed in the presence of a catalyst. The catalyst can be any one or more catalysts known to those skilled in the art for use in Michael addition reactions.

[0176] In yet other embodiments of the disclosed methods, the contacting step is performed in the absence of a catalyst, base, or acid. In other embodiments, the contacting step is performed in the absence of an alkali metal hydroxide, carbonate, silicate, metasilicate, imidazole / pyridyl base, or all thereof. In some embodiments, the contacting step is performed in the absence of a base.

[0177] In some embodiments, the contacting step is a two-step process, first between the polyamine and the activated olefin, and then between the product and the epoxide. In other embodiments, the contacting step is a two-step process, first between the polyamine and the epoxide and then between the product and the activated olefin. In yet other embodiments, the contacting step is a single step in which the polyamine contacts both the epoxide and the activated olefin. When the contacting step is a two-step process, the two steps can be carried out at two differential temperatures ranging from about -20°C to about 200°C. In some embodiments, the contacting step with the activated olefin is carried out at a temperature of about 20°C to about 120°C. In other embodiments, the contacting step with the epoxide is carried out at a temperature of about 100°C to about 150°C.

[0178] In yet another aspect, provided herein are articles, products, or compositions comprising one or more compounds disclosed herein.

[0179] In some embodiments, the article, product, or composition further comprises a carrier solvent or vehicle. As used herein, a "carrier solvent" or vehicle is a solvent or solvent system in which a disclosed compound can be uniformly and stably distributed.

[0180] As used herein, "stable" means that the compounds disclosed herein do not precipitate or separate from the carrier solvent or other ingredients in the composition within about 1 hour, about 1 hour to about 12 hours, about 12 hours, about 1 day, about 5 days, about 10 days, about 20 days, about 1 month, about 1 month to about 1 year, or about 1 year to about 2 years after the compounds disclosed herein and the carrier solvent or any other ingredients are uniformly mixed.

[0181] In other embodiments, the carrier is water, an organic solvent, or a mixture thereof. In some embodiments, the article, product, or composition further comprises an organic solvent. In other embodiments, the article, product, or composition further comprises an organic solvent and water.

[0182] In some embodiments, the organic solvent is an alcohol, a hydrocarbon, a ketone, an ether, an alkylene glycol, a glycol ether, an amide, a nitrile, a sulfoxide, an ester, or any combination thereof. In other embodiments, the organic solvent is an alcohol, an alkylene glycol, an alkylene glycol alkyl ether, or a combination thereof. In still other embodiments, the organic solvent is methanol, ethanol, propanol, isopropyl alcohol, butanol, isobutyl alcohol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[0183] In some embodiments, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, 2-ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, methylene glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, ethyl ether, propylene carbonate, or N-methylpyrrolidone.

[0184] In some embodiments, the article, product or composition may further include an additional surfactant. The additional surfactant is a nonionic, semi-nonionic, anionic, cationic, amphoteric, zwitterionic, Gemini, dicationic, dianionic surfactant or a combination thereof.

[0185] In some embodiments, the article, product, or composition is a solid. In other embodiments, the article, product, or composition is a liquid.

[0186] As used herein, the term "substantially free" refers to a composition that is completely devoid of a component or has a component in an amount so small that the component does not affect the performance of the composition. The component may be present as an impurity or as a contaminant and should be less than 0.5 wt-%. In another embodiment, the amount of the component is less than 0.1 wt-%, and in yet another embodiment, the amount of the component is less than 0.01 wt-%.

[0187] As used herein, the terms "weight percent," "wt-%," "percent by weight," "wt%," and variations thereof refer to the concentration of a substance, i.e., the weight of the substance divided by the total weight of the composition and multiplied by 100. It should be understood that, as used herein, "percent," "%," and the like are intended to be synonymous with "weight percent," "wt-%," and the like.

[0188] The methods and compositions of the present disclosure may comprise, consist essentially of, or consist of the components and ingredients of the disclosed compositions or methods, as well as other ingredients described herein. As used herein, "consisting essentially of" means that the methods and compositions may include additional steps, components, or ingredients, but only if the additional steps, components, or ingredients do not materially alter the basic and novel features of the claimed methods and compositions.

[0189] Examples

[0190] The embodiments of the present disclosure are further defined in the following non-limiting examples. Although these examples indicate certain embodiments of the present disclosure, they are provided for illustration only. From the above discussion and these examples, those skilled in the art can determine the essential characteristics of the present disclosure and, without departing from its spirit and scope, can make various changes and modifications to the embodiments of the present disclosure to make them suitable for various uses and conditions. Therefore, in addition to those shown and described herein, those skilled in the art will understand the various modifications of the embodiments of the present disclosure based on the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

[0191] Example 1

[0192] General scheme for the synthesis of exemplary compounds

[0193] The general synthetic reaction scheme for preparing the multiply charged cationic or anionic compounds disclosed herein is Figure 4 In this general scheme, linear polyethyleneimine is used as a representative polyamine. The hydrogen on the nitrogen of the linear polyethyleneimine is replaced by a cationic group via an aza-Michael addition reaction and by a hydrophobic group via an epoxide ring-opening reaction. Different compositions can be produced by varying the amounts of the ionic monomer and the hydrophobic alkyl epoxide.

[0194] exist Figure 4 In which k is an integer from 1 to 100; X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 Alkyl; R 3 Absent or unsubstituted linear or branched C1-C 30 Alkylene; Y is -NR 4 R 5 R 6(+) or its salt; R 4 、R 5 and R 6 Independently C1-C 10 alkyl or benzyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30.

[0195] The progress of the reaction can be monitored by ESI-MS and / or NMR spectroscopy to monitor the consumption of the cationic monomer and epoxide. The reaction can be stopped when approximately >98% of the monomer and epoxide are consumed. Aqueous or alcoholic solutions of multiply charged cationic or anionic compounds can be used "as is" for application testing.

[0196] In the above scheme, water and / or isopropanol can be used as solvent. However, the use of solvent and / or diluent is optional in the reaction. When using solvent, various non-acidic solvents are suitable, such as acetonitrile, ether (for example, tetrahydrofuran (THF)), other alcohols (for example, methanol, ethanol, n-butanol, ethylene glycol, PEG or mixture) etc.

[0197] In the above scheme, no additional catalyst is required. Because the reactions used to synthesize the disclosed multiply charged cationic or anionic compounds utilize polyamines, the polyamines themselves can serve as (base) catalysts for both reactions. However, additional catalysts are optional. The aza-Michael addition reaction and the ring-opening reaction used to synthesize the disclosed multiply charged cationic or anionic compounds can also be catalyzed by strong acids or strong bases.

[0198] In the above scheme, the reaction can be carried out at a temperature of about 50°C to about 130°C. However, the reaction temperature may range from about 20°C to about 150°C, more preferably from about 50°C to about 100°C.

[0199] In the above scheme, the synthesis is achieved in two steps. However, the disclosed multiply charged cationic or anionic compounds can be synthesized in a one-pot step by reacting polyamines with ionic monomers and epoxides simultaneously via a tandem Michael addition and ring-opening reaction.

[0200] Example 2

[0201] Synthesis of DETA / 2EHGE (1:2) adduct

[0202] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar, 2-ethylhexyl glycidyl ether (2-EHGE, 55 g) was added. Diethylenetriamine (DETA, 15 g) was then added to the well-stirred reaction mixture. The reaction temperature was raised to 130° C. and stirred for 3 hours or until the reaction was complete.

[0203] Example 3

[0204] TEPA / C 12 -C 14 Synthesis of Alkyl Glycidyl Ether (1:3) Adducts

[0205] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar, add ERISYS TM GE8(C 12 -C 14Alkyl glycidyl ether, CAS No. 68609-97-2, 132 g). Triethylenepentamine (TEPA, 98%, 30 g) was then added to the well-stirred reaction mixture. The reaction temperature was raised to 130°C and stirred for 3 hours or until the reaction was complete.

[0206] Example 4

[0207] TEPA / C 12 -C 14 Synthesis of Alkyl Glycidyl Ether (1:2) Adducts

[0208] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar, add ERISYS TM GE8(C 12 -C 14 Alkyl glycidyl ether, CAS No. 68609-97-2, 120 g). Triethylenepentamine (TEPA, 98%, 40 g) was then added to the well-stirred reaction mixture. The reaction temperature was raised to 130°C and stirred for 3 hours or until the reaction was complete.

[0209] Example 5

[0210] Synthesis of Ethylamine E-100 / APTAC (1:2.5) Adduct

[0211] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar, polyethyleneamine E-100 (50 g) was added. (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 121 g) and water (20 g) were then added to the flask. The resulting mixture was stirred at 80° C. overnight. As the reaction proceeded to completion, the mixture became a clear, pale yellow solution.

[0212] Example 6

[0213] Synthesis of Exemplary Multiply Charged Cationic Compounds

[0214] To a 250 mL, three-necked, round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar was added the compound of Example 1 (DETA / 2EHGE 1:2 adduct, 21.5 g). (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 34 g) and water were then added to the flask. The resulting suspension was stirred at 70°C overnight or until complete consumption of the APTAC was achieved. As the reaction proceeded to completion, the suspension became a clear, pale yellow solution.

[0215] Example 7

[0216] Synthesis of Exemplary Multiply Charged Anionic Compounds

[0217] To a 250 mL, three-necked, round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar was added the compound of Example 2 (DETA / 2EHGE 1:2 adduct, 21.5 g). A solution of 2-acrylamido-2-methyl-1-propanesulfonic acid sodium salt (NaAMPS, 58%, 49 g) and water (6 g) were then added to the flask. The resulting suspension was stirred at 70° C. overnight or until complete consumption of the NaAMPS was achieved. As the reaction proceeded to completion, the suspension became a clear, pale yellow solution.

[0218] Example 8

[0219] Synthesis of Exemplary Multiply Charged Cationic Compounds

[0220] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, a condenser, and a magnetic stirring bar, the compound of Example 3 (TEPA / C 12 -C 14 alkyl glycidyl ether, 1:3 adduct, 35.6 g) and isopropyl alcohol (36 g). (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 24 g) was then added to the flask. The resulting mixture was stirred at 70°C overnight or until complete consumption of the APTAC was achieved. As the reaction proceeded to completion, the suspension became a clear, dark amber solution.

[0221] Example 9

[0222] Synthesis of Exemplary Multiply Charged Anionic Compounds

[0223] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, a condenser, and a magnetic stirring bar, the compound of Example 3 (TEPA / C 12 -C 14 alkyl glycidyl ether, 1:3 adduct, 40 g) and isopropyl alcohol (26 g). 2-Acrylamido-2-methyl-1-propanesulfonic acid sodium salt solution (NaAMPS, 58%, 46 g) and water (31 g) were then added to the flask. The resulting solution was stirred at 70°C overnight or until complete consumption of the NaAMPS was achieved. As the reaction proceeded to completion, the mixture became a clear, light yellow solution.

[0224] Example 10

[0225] Synthesis of Exemplary Multiply Charged Cationic Compounds

[0226] To a 250 mL three-necked round-bottom flask equipped with a temperature probe, a condenser, and a magnetic stirring bar, the compound of Example 4 (TEPA / C 12 -C 14 alkyl glycidyl ether, 1:2 adduct, 33.62 g) and isopropyl alcohol (50 g). (3-Acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 31 g) was then added to the flask. The resulting mixture was stirred at 70°C overnight or until complete consumption of the APTAC was achieved. As the reaction proceeded to completion, the suspension became a clear, dark amber solution.

[0227] Example 11

[0228] Synthesis of multiply charged cationic compounds / surfactants

[0229] To a 250 mL three-necked round bottom flask equipped with a temperature probe, condenser and magnetic stirring bar was added the compound of Example 5 (ethyleneamine E-100 / APTAC 1:2.5 adduct, 74%, 50 g). TM GE 8(C 12 -C 14 Alkyl glycidyl ether, CAS No. 68609-97-2, 41.5 g) and isopropyl alcohol (40 g) were added to the flask. The resulting mixture was stirred at 90° C. overnight or until the reaction was complete.

[0230] Example 12

[0231] Synthesis of multiply charged cationic compounds

[0232] To a 250 mL three-necked round bottom flask equipped with a temperature probe, condenser and magnetic stirring bar was added the compound of Example 5 (ethyleneamine E-100 / APTAC 1:2.5 adduct, 74%, 63 g). TM GE 8(C 12 -C 14 Alkyl glycidyl ether, CAS No.: 68609-97-2, 34.2 g) and isopropyl alcohol (40 g) were added to the flask. The resulting mixture was stirred at 90° C. overnight or until the reaction was complete.

[0233] Example 13

[0234] One-pot synthesis of exemplary multiply charged cationic compounds

[0235] ERISYS was added to a 500 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. TM GE8(C12 -C 14 alkyl glycidyl ether, CAS No. 68609-97-2, 110 g), triethylenepentamine (TEPA, 99%, 25 g), (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 108 g) and isopropyl alcohol (80 mL). The resulting mixture was stirred at 90° C. overnight or until the reaction was complete, as determined by consuming APTAC and ERISYS TM As indicated by GE 8. As the reaction proceeded to completion, the mixture became a clear amber solution.

[0236] Example 14

[0237] One-pot synthesis of exemplary multiply charged cationic compounds

[0238] To a 500 mL three-necked round-bottom flask equipped with a temperature probe, a condenser, and a magnetic stir bar, 2-ethylhexyl glycidyl ether (98%, 93 g), triethylenetetramine (TETA, 60%, 29.8 g), (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 67 g), and isopropanol (50 mL) were added. The resulting mixture was stirred at 90° C. overnight or until the reaction was complete, as indicated by the consumption of APTAC and 2-ethylhexyl glycidyl ether. As the reaction proceeded to completion, the mixture became a clear amber solution.

[0239] Example 15

[0240] One-pot synthesis of exemplary multiply charged anionic compounds

[0241] To a 500 mL three-necked round-bottom flask equipped with a temperature probe, a condenser, and a magnetic stir bar, 2-ethylhexyl glycidyl ether (98%, 77 g), diethylenetriamine (DETA, 99%, 14 g), acrylamido-2-methyl-1-propanesulfonic acid sodium salt solution (NaAMPS, 58%, 160 g), and isopropyl alcohol (80 mL) were added. The resulting mixture was stirred at 90° C. overnight or until the reaction was complete, as indicated by the consumption of NaAMPS and 2-ethylhexyl glycidyl ether. As the reaction proceeded to completion, the mixture became a dark yellow solution.

[0242] The disclosure being thus described, it will be obvious that the disclosure may be varied in many ways. Such variations are not to be regarded as a departure from the spirit and scope of the disclosure, and all such modifications are intended to be included within the scope of the following claims.

[0243] The above specification provides a description of novel compounds, their synthesis and uses, and compositions, products or articles of manufacture comprising the disclosed compounds. Since many embodiments can be made without departing from the spirit and scope of the disclosure, the disclosure resides in the claims.

Claims

1. A compound comprising: Compounds derived from polyamines by reaction thereof with activated olefins and epoxides, wherein: The activated olefin has the formula: The epoxide is X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 alkyl, alkenyl or alkynyl; R 3 Absent or unsubstituted linear or branched C1-C 30 alkylene; Y is -NR 4 R 5 R 6(+) ; R 4 、R 5 and R 6 Independently C1-C 10 alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the polyamine and the activated olefin undergo an aza Michael addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

2. The compound according to claim 1, wherein the polyamine is (i) having the general formula -[RNH] n - linear, branched or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C2-C 10 alkylene or a combination thereof, and n is an integer from 2, 3, 4, 5, 6, 7, 8, 9 or 10 to 1,000,000; (ii) having the general formula H2N-(RNH) n -RNH2 linear polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C2-C 10 alkylene or a combination thereof, and n is an integer from 2, 3, 4, 5, 6, 7, 8, 9 or 10 to 1,000,000; or (iii) having the general formula H2N-(RN(R')) n -RNH2 linear polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C2-C 10 Alkylene or a combination thereof, R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C2-C 10 alkyl, RNH2, RNHRNH2 or RN(RNH2)2, and n is an integer from 2, 3, 4, 5, 6, 7, 8, 9 or 10 to 1,000,000.

3. The compound of claim 1, wherein the polyamine is a polyalkyleneimine, including ethyleneimine, propyleneimine, buteneimine, penteneimine, hexeneimine, heptenimine, or a combination thereof.

4. The compound of claim 1, wherein the polyamine is an alkyleneamine comprising ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, polyethyleneimine, tris(2-aminoethyl)amine, or a combination thereof.

5. The compound according to claim 1, wherein the polyamine is a mixture of monoamines, diamines and triamines with a polyether backbone or with a polyether backbone based on propylene oxide (PO), ethylene oxide (EO) or a mixture of the two oxides.

6. The compound of claim 1, wherein the polyamine is a linear, branched or dendritic macromolecular polyethyleneimine.

7. The compound of claim 1, wherein the polyamine comprises (i) only primary and secondary amine groups, (ii) only primary, secondary, and tertiary amine groups, or (iii) only primary and tertiary amine groups.

8. The compound of claim 1, wherein the polyamine is a single compound or a mixture of two or more different polyamines, wherein the different polyamines have different molecular weights, different structures, or the different polyamines have different molecular weights and different structures.

9. The compound of claim 1, wherein the polyamine has an average molecular weight of 60 Da to 2,000,000 Da.

10. The compound according to claim 1, wherein X is NH or O, and R 2 It is H or CH3.

11. The compound of claim 1, wherein Y is (i)-NR 4 R 5 R 6(+) , and R 4 、R 5 and R 6 are independently CH3; (ii) -NR 4 R 5 R 6(+) , R 4 and R 5 are independently CH3, and R 6 It is C2-C 12 Aromatic alkyl; (iii) -NR 4 R 5 R 6(+) , R 4 and R 5 are independently CH3, and R 6 is -CH2-C6H6 or (iv) -NR 4 R 5 R 6(+) , and the counterion of Y is chloride, bromide, fluoride, iodide, acetate, aluminate, cyanate, cyanide, dihydrogen phosphate, dihydrogen phosphite, formate, bicarbonate, bioxalate, bisulfate, hydroxide, nitrate, nitrite, thiocyanate, or a combination thereof.

12. The compound according to claim 1, wherein R 3 is CH2, -CH2CH2-, -CH2CH2CH2-, -C(CH3)2-, unsubstituted straight chain and saturated C1-C 20 Alkylene, unsubstituted straight chain and unsaturated C1-C 20 Alkylene, straight chain C8-C 18 Alkyl, alkenyl or alkynyl, or branched C8-C 20 Alkyl, alkenyl or alkynyl.

13. The compound according to claim 1, wherein (i) R 8 is H and R 7 It is C1-C 30 Alkyl; (ii) R 8 It is C1-C 30 Alkyl and R 7 is H, CH3 or C2-C4 alkyl; or (iii) R 8 It is C4-C 30 Alkyl or C8-C 20 alkyl.

14. The compound of claim 1, wherein the epoxide is an alkyl glycidyl ether, butyl glycidyl ether, hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, tetradecyl glycidyl ether, 1,2-epoxyalkane, 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, and wherein the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacrylamido)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl chloride quaternary ammonium salt (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethyleth-1-ammonium methyl sulfate (DMAEA-MSQ).

15. The compound of claim 1, wherein the compound is a mixture of at least two modified polyamine compounds derived from the same polyamine, activated olefin, and epoxide, or wherein the compound is a mixture of at least two modified polyamine compounds derived from different polyamines and the same activated olefin and epoxide.

16. The compound according to claim 1, wherein the average molecular weight (M) of the compound w ) ranges from 100 Da to 2,000,000 Da.

17. The compound of claim 1, wherein the compound has at least 10, 15, 20, or 30 positive (or cationic) charges; at least 2, 3, 4, 5, 6, 7, or 8 positive charges; at least 10, 15, 20, or 30 negative (anionic) charges; or at least 4, 5, 6, 7, or 8 negative (anionic) charges.

18. The compound according to claim 1, wherein the compound has one of the following general formulas: NA2-[R 10 '] n -NA2, (RNA) n -RNA2, NA2-(RNA) n -RNA2 or NA2-(RN(R')) n -RNA2, where: R 10 ' is an unsubstituted or substituted straight or branched C4-C 10 alkylene or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 alkylene or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n is 2 to 1,000,000; A is H, combination of; X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 alkyl, alkenyl or alkynyl; R 3 Absent or unsubstituted linear or branched C1-C 30 alkylene; Y is -NR 4 R 5 R 6(+) ; R 4 、R 5 and R 6 Independently C1-C 10 alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the compound has 1, 2, 3 or more group and at least one A cationic compound with multiple charges.

19. The compound according to claim 1, wherein the compound is derived from linear polyethyleneimine and 2-acrylamido-2-methyl-1-propanesulfonic acid and C 12 -C 14 Alkyl glycidyl ether.

20. The compound of claim 1, wherein the compound is derived from branched polyethyleneimine and 2-ethylhexyl glycidyl ether and (3-acrylamidopropyl)trimethylammonium chloride (APTAC).

21. A method for synthesizing the modified polyamine compound according to any one of claims 1 to 20, the method comprising: contacting a polyamine with an activated olefin and an epoxide to produce a multiply charged cationic or anionic compound; wherein the activated olefin has the formula: The epoxide is X is NH or O; R 2 is H, CH3 or unsubstituted straight or branched C2-C 10 alkyl, alkenyl or alkynyl; R 3 Absent or unsubstituted linear or branched C1-C 30 alkylene; Y is -NR 4 R 5 R 6(+) ; R 4 、R 5 and R 6 Independently C1-C 10 alkyl; R 7 is H or alkyl; and R 8 is an alkyl group or -(CH2) k -O-alkyl, wherein k is an integer from 1 to 30; wherein the polyamine and the activated olefin undergo an aza-Michael addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; wherein the compound is a multiply charged cationic compound having 1, 2, 3 or more positive charges from the activated olefin and at least one nonionic group from the epoxide or a multiply charged anionic compound having 1, 2, 3 or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

22. The method of claim 21, wherein the contacting step is performed in the presence of a reaction solvent.

23. The method of claim 22, wherein the reaction solvent is water, methanol, ethanol, propanol, ethylene glycol, PEG or a mixture thereof.

24. The method of claim 21, wherein the contacting step is performed in the presence of a catalyst, a base, or an acid.

25. The method of claim 21, wherein the contacting step is performed in the absence of a base.

26. The method of claim 21, wherein the contacting step is performed in the presence of an organic base.

27. The method of claim 21, wherein the contacting step is performed in the presence of a hydroxide, an alkali metal hydroxide, an alkaline metal hydroxide, a metal carbonate, an imidazole, a pyridine base, an amidine base, a guanidine base, or a combination thereof.

28. The method of claim 21, wherein the contacting step is performed in the presence of benzyltrimethylammonium hydroxide.

29. A composition comprising one or more modified polyamine compounds according to any one of claims 1 to 20.

30. The composition of claim 29, further comprising a carrier solvent comprising water, an alcohol, an alkylene glycol, an alkylene glycol alkyl ether, or a combination thereof.

31. The composition of claim 30, wherein the carrier solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

32. The composition of claim 29, wherein the composition is a solid or a liquid.

33. The composition of claim 29, further comprising a surfactant, wherein the surfactant is a nonionic surfactant, a semi-nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a mixture thereof.

34. The composition of claim 33, wherein the surfactant is a zwitterionic surfactant, a Gemini surfactant, a dicationic surfactant, a dianionic surfactant, or a mixture thereof.

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