Ionic compounds derived from polyamines, compositions thereof and methods of making thereof

Abstract

The present application relates to ionic compounds derived from polyamines, compositions thereof, and processes for their preparation. Disclosed herein are cationic or anionic compounds having a plurality of charges, methods of making the same, and articles or compositions including the same. The disclosed multi-charged cationic or anionic compounds are derived from a polyamine through 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 the following formula. The epoxide is an epoxide.

Description

[0001] This application is a divisional application of Chinese patent application No. 202310374200.2, filed on August 28, 2019, entitled "Ionic compounds derived from polyamines, compositions thereof and methods thereof", which in turn is a divisional application of Chinese patent application No. 201980053830.1, filed on August 28, 2019, which entered the Chinese national phase of PCT international patent application PCT / US2019 / 048451, entitled "Ionic compounds with multiple charges derived from polyamines, compositions thereof and methods thereof".

[0002] Cross-references to related applications

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

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

[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 deposits of any organic or inorganic material can occur even in industrial water systems treated with the best available water treatment procedures. Without regular cleaning or treatment, water systems will become severely scaled.

[0006] Scaling occurs due to microbial contamination and subsequent microbial and / or biofilm growth. Industrial water systems have numerous sources of microbial contamination, which may 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 of the water system. Evaporative cooling water systems are particularly prone to scaling.

[0007] Scaling has negative impacts on water systems, especially industrial water systems. For example, severe mineral scale (inorganic material) accumulates on any water-contact surfaces, and any scale provides an ideal environment for the growth of microorganisms and / or biofilms. If scaling or biofilm growth can occur in a water system, the system may suffer from reduced operating efficiency, premature equipment failure, and increased health-related risks associated with microbial scaling and / or biofilm growth.

[0008] When microbial communities develop on a surface, the exopolymers secreted by the microorganisms contribute to biofilm formation. These biofilms are complex ecosystems that establish mechanisms for nutrient concentration and provide protection for microbial growth; therefore, biofilms can accelerate scale formation, corrosion, and other scaling processes. Biofilms not only contribute to reduced water system efficiency but also provide an excellent environment for microbial proliferation and the production of dangerous Legionella bacteria. Therefore, it is important to minimize biofilm formation and other scaling processes as much as possible to minimize health-related risks associated with Legionella and other waterborne pathogens.

[0009] Various methods have been developed to clean or remove biofilms and biofilm-associated microorganisms. While cleaning and removing biofilms is necessary, a better approach is to prevent or reduce scaling or biofilm formation or growth, thus reducing the need for biofilm removal. Cleaning or removing biofilms typically requires operational interruption and the introduction of additional chemicals. One method to prevent or reduce scaling and / or biofilm formation or growth is to treat water systems with scaling control compositions or scaling control formulations. For example, corrosion inhibitors and / or scaling control compositions are often 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 for many years as corrosion inhibitors and scale control agents. They belong to an important subclass of surfactants due to their unique properties. The main difference between quaternary ammonium compounds and other surfactants lies in their unique structure. Quaternary ammonium compounds are primarily 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 crucial role in the interaction between surfactants and biofilm surfaces or between different components, such as electrostatic interactions. However, quaternary ammonium compounds used for this purpose are often bis-quaternary ammonium species or species quaternized with benzyl chloride, which are known to be highly hazardous. Furthermore, government regulations prohibit the release of any water containing a single quaternary compound into the environment.

[0011] Therefore, the purpose of this disclosure is to develop a method for the efficient and effective preparation of novel compounds for controlling scaling in water systems.

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

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

[0014] This document discloses novel compounds, methods for preparing the disclosed compounds, and articles or compositions comprising the disclosed compounds. More specifically, the disclosed compounds are multi-charged cationic or anionic compounds comprising multiple positive or negative charges and nonionic groups within unimolecular molecules of various sizes. The disclosed compounds are derived from water-soluble polyamines or polyethyleneimine.

[0015] In one aspect, this paper discloses a compound with multiple charges 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' It is an unsubstituted or substituted straight or branched C2-C chain. 10 Alkyl groups or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl group, RNAB, RNARNAB, or RN(RNAB)2; n can be from 2 to 1,000,000; A is H, Combinations; or H, The combination

[0016] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6(+) Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; wherein the compound has 1, 2, 3 or more alkyl groups. Group and at least one Cationic compounds with multiple charges or having one, two, three or more groups. Group and at least one Anionic compounds with multiple charges in their functional groups.

[0017] On the other hand, this document discloses a compound with multiple charges derived from the polyamine via a reaction of 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 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6 (+) Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k-O-alkyl, where 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 cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0020] On the other hand, a method for preparing the disclosed compound or a salt thereof is disclosed herein.

[0021] On another aspect, this document provides articles, products, or compositions that include one or more compounds disclosed herein.

[0022] The present invention specifically discloses the following embodiments:

[0023] 1. A compound comprising:

[0024] Compounds derived from polyamines through their reaction with activated olefins and epoxides, wherein:

[0025] The activated olefin has one of the following formulas:

[0026]

[0027] The epoxide is

[0028] X is NH or O;

[0029] R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl groups;

[0030] R 2' It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -

[0031] CH2COOH, Y', or -(CH2) m -Y', where m is an integer from 2 to 4;

[0032] R 3 There is no or no straight or branched C1-C chain. 30 Alkylene;

[0033] Y is -NR4R5R6 (+);

[0034] Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof;

[0035] R 4 R 5 and R 6 Independently, it is C1-C 10 alkyl;

[0036] R 7 It is H or alkyl; and

[0037] R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30;

[0038] The polyamine and the activated olefin undergo an aza-Michael addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction.

[0039] The compound is a cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0040] 2. The compound according to Embodiment 1, wherein the polyamine is (i) having the general formula -[RNH] n - linear, branched, or dendritic macromolecular polyamines, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 (i) An alkylene group 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 polyamines, where R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 Alkylene or combinations 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 polyamines, where R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 Alkyl groups or combinations thereof, where R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain 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.

[0041] 3. The compound according to Embodiment 1, wherein the polyamine is a polyalkylene imine, including ethyleneimine, propyleneimine, buteneimine, penteneimine, hexeneimine, heptenimine, or combinations thereof.

[0042] 4. The compound according to Embodiment 1, wherein the polyamine is an alkyleneamine, including ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalineheptamine, polyethyleneimine, tri(2-aminoethyl)amine, or combinations thereof.

[0043] 5. The compound according to embodiment 1, wherein the polyamine is a monoamine, diamine, or triamine mixed with a polyether backbone or with a polyether backbone based on propylene oxide (PO), ethylene oxide (EO), or a mixture of both oxides.

[0044] 6. The compound according to Embodiment 1, wherein the polyamine is a linear, branched, or dendritic macromolecular polyethyleneimine.

[0045] 7. The compound according to any one of embodiments 1 to 6, 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.

[0046] 8. The compound according to any one of embodiments 1 to 7, 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 both.

[0047] 9. The compound according to any one of embodiments 1 to 8, wherein the polyamine has an average molecular weight of about 60 Da to about 2,000,000 Da or about 60 Da to about 25,000 Da.

[0048] 10. The compound according to any one of embodiments 1 to 9, wherein X is NH or O, and R 2 It is H or CH3.

[0049] 11. The compound according to any one of embodiments 1 to 10, wherein Y is (i)-NR 4 R 5 R 6(+) And R 4 R 5 and R 6 Independently, it is CH3; (ii)-NR 4 R 5 R 6(+) R 4 and R 5 Independently, it is CH3, and R 6 It is C2-C 12 Aromatic alkyl groups; (iii)-NR 4 R 5 R 6(+) R 4 and R 5 Independently, it is CH3, and R 6 It is -CH2-C6H6 or (iv)-NR 4 R 5 R 6(+) And the counter ions of Y are chloride ions, bromide ions, fluoride ions, iodide ions, acetate ions, aluminate ions, cyanate ions, cyanide ions, dihydrogen phosphate ions, dihydrogen phosphite ions, formate ions, bicarbonate ions, hydrogen oxalate ions, hydrogen sulfate ions, hydroxide ions, nitrate ions, nitrite ions, thiocyanate ions, or combinations thereof.

[0050] 12. The compound according to any one of embodiments 1 to 10, wherein Y' is -COOH or a salt thereof, -SO3H or a salt thereof, or -PO3H or a salt thereof.

[0051] 13. The compound according to any one of embodiments 1 to 12, wherein R 3 It 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 groups, or branched C8-C groups 20 Alkyl, alkenyl, or ynyl.

[0052] 14. The compound according to any one of embodiments 1 to 13, wherein (i) R 8 It is H and R 7 It is C1-C 30 Alkyl; (ii)R 8 It is C1-C 30 Alkyl and R 7It is H, CH3 or C2-C4 alkyl; or (iii) R 8 It is C4-C 30 Alkyl or C8-C 20 alkyl.

[0053] 15. The compound according to any one of embodiments 1 to 14, 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-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl quaternary ammonium chloride (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium sulfate methyl ester (DMAEA-MSQ), or 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MSQ).

[0054] 16. The compound according to any one of embodiments 1 to 15, wherein the activated olefin is acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), itaconic acid, maleic acid, or 3-(allyloxy)-2-hydroxypropane-1-sulfonate.

[0055] 17. The compound according to any one of embodiments 1 to 15, wherein the activated olefin is vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

[0056] 18. The compound according to any one of embodiments 1 to 15, wherein Y' is an anionic group and the counterion is Li + Na + K + NH3 + Or quaternary ammonium.

[0057] 19. The compound according to any one of embodiments 1 to 18, 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 different polyamines and at least two modified polyamine compounds derived from the same activated olefin and epoxide.

[0058] 20. The compound according to any one of embodiments 1 to 19, wherein the average molecular weight (M) of the compound is... wThe range is approximately 100 Da to approximately 2,000,000 Da, approximately 100 Da to approximately 200,000 Da, or approximately 100 Da to approximately 5,500 Da.

[0059] 21. The compound according to any one of embodiments 1 to 20, wherein the compound has at least 10, 15, 20 or 30 positive (or cation) 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.

[0060] 22. The compound according to embodiment 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:

[0061] R 10' It is an unsubstituted or substituted straight or branched C4-C 10 Alkylenes or combinations thereof;

[0062] R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-

[0063] C 10 Alkylenes or combinations thereof;

[0064] R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-

[0065] C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n can be from 2 to 1,000,000;

[0066] A is H. Combinations; or H,

[0067] The combination;

[0068] X is NH or O;

[0069] R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl groups;

[0070] R 2' It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -

[0071] CH2COOH, Y', or -(CH2) m -Y'; m is an integer from 2 to 4; R 3 Straight-chain C1-C that is absent or unsubstituted 30 Alkylene;

[0072] R 3 There is no or no straight or branched C1-C chain. 30 Alkylene;

[0073] Y is -NR4R5R6 (+) ;

[0074] Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof;

[0075] R 4 R 5 and R 6 Independently, it is C1-C 10 alkyl;

[0076] R 7 It is H or alkyl; and

[0077] R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30;

[0078] The compound is one, two, three or more Group and at least one Cationic compounds with multiple charges or having one, two, three or more groups. Group and at least one Anionic compounds with multiple charges in their functional groups.

[0079] 23. The compound according to embodiment 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.

[0080] 24. The compound according to embodiment 1, wherein the compound is derived from branched polyethyleneimine and 2-ethylhexyl glycidyl ether and (3-acrylamidopropyl)trimethylammonium chloride (APTAC).

[0081] 25. A method for synthesizing a modified polyamine compound according to any one of embodiments 1 to 24, the method comprising:

[0082] Polyamines are contacted with activated olefins and epoxides to generate cationic or anionic compounds with multiple charges;

[0083] The activated olefin said therein has one of the following formulas:

[0084]

[0085] The epoxide is

[0086] X is NH or O;

[0087] R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl groups;

[0088] R 2' It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -

[0089] CH2COOH, Y', or -(CH2) m -Y'; m is an integer from 2 to 4;

[0090] R 3 There is no or no straight or branched C1-C chain. 30 Alkylene;

[0091] Y is -NR4R5R6 (+) ;

[0092] Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof;

[0093] R 4 R 5 and R 6 Independently, it is C1-C 10 alkyl;

[0094] R 7 It is H or alkyl; and

[0095] R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30;

[0096] The polyamine and the activated olefin undergo a azirmickle addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction;

[0097] The compound is a cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0098] 26. The method according to embodiment 25, wherein the contacting step is carried out in the presence of a reaction solvent.

[0099] 27. The method according to embodiment 26, wherein the reaction solvent is water, methanol, ethanol, propanol, ethylene glycol, PEG, or a mixture thereof.

[0100] 28. The method according to any one of embodiments 25 to 27, wherein the contact step is carried out in the presence of a catalyst, a base, or an acid.

[0101] 29. The method according to any one of embodiments 25 to 27, wherein the contact step is performed without alkali.

[0102] 30. The method according to any one of embodiments 25 to 27, wherein the contacting step is carried out in the presence of an organic base.

[0103] 31. The method according to any one of embodiments 25 to 27, wherein the contact step is carried out in the presence of hydroxide, alkali metal hydroxide, basic metal hydroxide, metal carbonate, imidazole, pyridine base, amidine, guanidine base, or a combination thereof.

[0104] 32. The method according to any one of embodiments 25 to 27, wherein the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide.

[0105] 33. An article, product, or composition comprising one or more modified polyamine compounds according to any one of embodiments 1 to 24.

[0106] 34. The article, product, or composition according to embodiment 33 further includes a carrier solvent, said carrier solvent including water, alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof.

[0107] 35. The article, product, or composition according to embodiment 34, wherein the carrier solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[0108] 36. The article, product, or composition according to any one of embodiments 33 to 35, wherein the article, product, or composition is a solid or a liquid.

[0109] 37. The article, product, or composition according to any one of embodiments 33 to 36, further comprising a surfactant, said surfactant being a nonionic, semi-nonionic, cationic, anionic, amphoteric, zwitterionic, gemini, dicationic, dianionic surfactant, or a mixture thereof.

[0110] The foregoing overview is illustrative only and is not intended to be limiting in any way. Other aspects, embodiments, and features of the invention will become apparent to those skilled in the art from the accompanying drawings and detailed description of the illustrative embodiments shown and described below. Therefore, the drawings and detailed description should be considered illustrative in nature and not limiting in any way. Attached Figure Description

[0111] Figure 1 An exemplary general reaction scheme is shown to produce a multi-charged cationic compound first by a ring-opening reaction between linear polyethyleneimine and an epoxide, and then by an aza-Michael addition reaction with an activated olefin (α,β-unsaturated carbonyl compound).

[0112] Figure 2 An exemplary alternative general reaction scheme is shown, which first generates a multi-charged cationic compound via an aza-Michael addition reaction between a linear polyethyleneimine and an α,β-unsaturated carbonyl compound, and then via a ring-opening reaction with an epoxide.

[0113] Figure 3 An exemplary general reaction scheme is shown to generate multi-charged cationic compounds by reacting branched polyethyleneimine with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening and aza-Michael addition reactions, respectively.

[0114] Figure 4 A general reaction scheme is shown to produce multi-charged cationic compounds by reacting linear polyethyleneimine with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening and aza-Michael addition reactions, respectively.

[0115] Various embodiments of the present disclosure will be described in detail with reference to the accompanying drawings, in which the same reference numerals denote the same parts throughout the various views. References to the various embodiments do not limit the scope of the present disclosure. The figures illustrated herein are not intended to limit the various embodiments according to the present disclosure, but are presented for illustrative purposes. Detailed Implementation

[0116] This document discloses novel compounds, methods for preparing the disclosed compounds, and articles or compositions including the disclosed compounds. More specifically, it discloses multi-charged cationic or anionic compounds derived from polyamines, activated alkenes, and epoxides via aza-Michael addition and ring-opening reactions. Methods for synthesizing such compounds are also disclosed.

[0117] The embodiments disclosed herein are not limited to specific compositions and methods of use that may vary and be understood by those skilled in the art. It should further be understood that all terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting in any way or scope. For example, unless otherwise expressly indicated, the singular forms “a,” “an,” and “the” as used in this specification and the appended claims may include plural indicators. Furthermore, all units, prefixes, and symbols may be represented in a form acceptable to them.

[0118] The numerical ranges described in this specification include values ​​within the defined ranges. Throughout this disclosure, various aspects of this disclosure may be presented in a range format. It should be understood that the use of a range format is merely for convenience and brevity and should not be construed as a fixed limitation on the scope of this disclosure. Therefore, the description of a range should be considered as having specifically disclosed all possible subranges within the range as well as individual numerical values ​​(e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0119] To facilitate a clearer understanding of this disclosure, certain terms are defined first. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art as relating to the embodiments of this disclosure. Many similar, modified, or equivalent methods and materials to those described and used herein can be used in the practice of embodiments of this disclosure without requiring excessive experimentation; preferred materials and methods are described herein. In describing and claiming embodiments of this disclosure, the following terms will be used in accordance with the definitions set forth below.

[0120] As used herein, the term "about" refers to a change in numerical quantity that can occur, for example, through typical measurement and liquid handling procedures used in the production of concentrates or the use of solutions in the real world; through errors in these procedures; through differences in the manufacture, origin, or purity of the ingredients used to prepare the composition or perform the method; etc. The term "about" also covers amounts that differ due to different equilibrium conditions resulting from a particular initial mixture. Whether or not modified by the term "about," the claims contain quantitative equivalents.

[0121] As used herein, “substituted” means an organic group (as defined below, e.g., alkyl) in which one or more bonds to a hydrogen atom contained therein are replaced by bonds 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 by one or more bonds to a heteroatom (including double or triple bonds). Therefore, unless otherwise stated, a substituted group is substituted by one or more substituents. A substituted group may be substituted by one, two, three, four, five, or six substituents.

[0122] Substituted cyclic groups comprise rings and ring systems in which bonds to hydrogen atoms are replaced with bonds to carbon atoms. Therefore, substituted cycloalkyl, aryl, heterocyclic, and heteroaryl groups may also be substituted with substituted or unsubstituted alkyl, alkenyl, and alkynyl groups as defined herein.

[0123] As used herein, the term "alkyl (alkyl / alkyl groups)" 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 "alicyclo" or "carbocyclo") (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc.), branched alkyl groups (e.g., isopropyl, tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkyl groups (e.g., alkyl-substituted cycloalkyl and cycloalkyl-substituted alkyl groups).

[0124] Unless otherwise stated, the term "alkyl" includes both "unsubstituted alkyl" and "substituted alkyl". As used herein, the term "substituted alkyl" refers to an alkyl group having one or more substituents on one or more carbons of the hydrocarbon backbone. Such substituents may include, for example, alkenyl, alkynyl, halogen, hydroxyl, alkyl carbonyloxy, aryl carbonyloxy, alkoxy carbonyloxy, aryloxy, aryloxy carbonyloxy, carboxylic acid ester, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, amino carbonyl, alkylamino carbonyl, dialkylamino carbonyl, alkyl thiocarbonyl, alkoxy, phosphate ester, phosphonic acid, phosphonite, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino and alkylarylamino), acylamino (including alkyl carbonylamino, aryl carbonylamino, carbamoyl and urea), imino, mercapto, alkyl thio, aryl thio, thiocarboxylic acid ester, sulfate ester, alkyl sulfinyl, sulfonate, aminosulfonyl, sulfonamide, nitro, trifluoromethyl, cyano, azide, heterocyclic, alkyl aryl or aromatic (including heteroaromatic).

[0125] In some embodiments, the substituted alkyl group may comprise a heterocyclic group. As used herein, the term "heterocyclic group" comprises a closed-ring structure similar to a carbocyclic group, wherein one or more carbon atoms in the ring are elements other than carbon, such as nitrogen, sulfur, or oxygen. Heterocyclic groups may be saturated or unsaturated. Exemplary heterocyclic groups include, but are not limited to, aziridine, ethylene oxide (epoxide, ethylene oxide), cyclothioethane (cyclosulfide), diethylene oxide, aziridine, oxobutane, thiobutane, dioxobutane, dithiobutane, dithiocyclobutene, aziridine, pyrrolidine, pyrrololine, oxopentane, dihydrofuran, and furan.

[0126] An alkenyl or alkene is a straight-chain, branched, or cycloalkyl group having two to about 30 carbon atoms and further comprising at least one double bond. In some embodiments, the alkenyl group has 2 to about 30 carbon atoms, or typically has 2 to 10 carbon atoms. The alkenyl group can be substituted or unsubstituted. The double bond in the alkenyl group can be in a trans or cis configuration. The alkenyl group can be substituted similarly to alkyl groups.

[0127] The alkynyl group is a straight-chain, branched, or cycloalkyl group having two to about 30 carbon atoms, and further comprises at least one triple bond. In some embodiments, the alkynyl group has 2 to about 30 carbon atoms, or typically has 2 to 10 carbon atoms. The alkynyl group can be substituted or unsubstituted. The alkenyl group can be substituted similarly to the alkyl or alkenyl group.

[0128] As used herein, the terms “alkylene,” “cycloalkylene,” “alkynylides,” and “alkenylene,” alone or as part of another substituent, refer to a divalent group derived from an alkyl, cycloalkyl, or alkenyl group, as exemplified by -CH2CH2CH2-. For alkylene, cycloalkylene, alkynylides, and alkenylene, the orientation of the linking group is not implied.

[0129] As used herein, the term "ester" refers to -R 30 COOR 31 Group. R 30 There are no substituted or unsubstituted alkylene, cycloalkylene, alkenylene, ynylene, arylene, arylalkylene, heterocyclic alkylene, or heterocyclic groups as defined herein. R 31 It is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic alkyl or heterocyclic group as defined herein.

[0130] As used herein, the term "amine" (or "amino group") refers to -R 32 NR 33 R 34 Group. R32 There are no substituted or unsubstituted alkylene, cycloalkylene, alkenylene, ynylene, arylene, arylalkylene, heterocyclic alkylene, or heterocyclic groups as defined herein. R 33 and R 34 Independently hydrogen, or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic alkyl or heterocyclic as defined herein.

[0131] As used herein, the term "amine" also refers to a standalone compound. When an amine is a compound, it can be derived from R... 32' NR 33' R 34' The formula is used to represent the group, where R 32' R 33' and R 34 Independently hydrogen, or substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic alkyl or heterocyclic as defined herein.

[0132] As used herein, the term "alcohol" refers to -R 35 OH group. R 35 There are no substituted or unsubstituted alkylene, cycloalkylene, alkenylene, ynylene, arylene, arylalkylene, heterocyclic alkylene or heterocyclic groups as defined herein.

[0133] As used herein, the term "carboxylic acid" refers to -R 36 COOH group. R 36 There are no substituted or unsubstituted alkylene, cycloalkylene, alkenylene, ynylene, arylene, arylalkylene, heterocyclic alkylene or heterocyclic groups as defined herein.

[0134] As used herein, the term "ether" refers to -R 37 OR 38 Group. R 37 There are no substituted or unsubstituted alkylene, cycloalkylene, alkenylene, ynylene, arylene, arylalkylene, heterocyclic alkylene, or heterocyclic groups as defined herein. R 38 It is a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, alkynyl, aryl, aralkyl, heterocyclic alkyl or heterocyclic group as defined herein.

[0135] As used herein, the term "solvent" means any inorganic or organic solvent. Solvents may be used as reaction solvents or carrier solvents in the disclosed methods or articles, products, or compositions. Suitable solvents include, but are not limited to, oxygen-containing 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 ethers, and propylene glycol phenyl ethers. Water is also a solvent. Solvents used herein may consist of a single solvent or a mixture of many different solvents.

[0136] 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 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.

[0137] Acids

[0138] The compositions or methods disclosed herein may contain acids. However, in some embodiments, the compositions disclosed herein do not contain acids.

[0139] Generally, the acids used in this disclosure include 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, hexanoic acid, gluconic acid, itaconic acid, trichloroacetic acid, urea hydrochloride, and benzoic acid. Organic acids also include 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 may also be used. Inorganic acids include, but are not limited to, mineral acids, such as phosphoric acid, sulfuric acid, aminosulfonic acid, methylsulfonic 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-forming agents can be used to form suitable acids, including, for example, potassium fluoride, sodium fluoride, lithium fluoride, ammonium fluoride, ammonium bifluoride, sodium fluoride, etc.

[0140] 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, citric acid, lactic acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic 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, may also be used.

[0141] Alkalinity source or alkali

[0142] The disclosed preparation methods or compositions may include using an effective amount of an alkalinity source or base as a catalyst or component. The alkalinity source or base may further include one or more basic compounds. The alkalinity source may be added to the reaction mixture in solid, liquid, or solution form.

[0143] Generally, the effective amount of an alkalinity source should be considered as the amount that provides a reaction mixture with a pH of at least about 8. A solution with a pH between about 8 and about 10 can be considered mildly alkaline, and a solution with a pH greater than about 12 can be considered caustic.

[0144] Alkalinity sources can comprise alkali metal carbonates, basic metal hydroxides, basic metal silicates, basic metal silicates, or mixtures thereof. Suitable metal carbonates that can be used include, for example, sodium carbonate or potassium carbonate, bicarbonates, sesquicarbonates, or mixtures thereof. Suitable alkali metal hydroxides that can be used include, for example, sodium hydroxide, lithium hydroxide, or potassium hydroxide. Examples of useful basic metal silicates include sodium silicate or potassium silicate (M₂O:SiO₂ ratio of 2.4 to 5:1, where M represents an alkali metal) or metasilicates. Silicates can be prepared by mixing hydroxides and silicates. Alkalinity sources can also comprise metal borates, such as sodium borate or potassium borate.

[0145] Alkalinity sources can also include ethanolamine, urea sulfate, amines, amine salts, and quaternary ammonium compounds. The simplest cationic amines, amine salts, and quaternary ammonium compounds can be schematically described as follows:

[0146]

[0147] Wherein, R represents a long alkyl chain, R', R” and R”’ can be long alkyl chains or smaller alkyl or aryl or hydrogen, and X represents an anion.

[0148] In some embodiments, the preparation method does not contain a basicity source because the reactants contain primary amines or primary amine groups to catalyze the reaction. In some embodiments, the compositions disclosed herein do not contain a basicity source.

[0149] Polyamine

[0150] Polyamines can have, but are 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' It is an unsubstituted or substituted straight or branched C2-C chain. 10 Alkyl groups or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNH2, RNHRNH2, or RN(RNH2)2; and n can be from 2 to 1,000,000. The monomers in the polyamine, such as R or R' groups, can be the same or different. In this 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.

[0151] Small molecule polyamines include, but are not limited to, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimaline heptamine, and tri(2-aminoethyl)amine.

[0152] Other possible polyamines include those from Huntsman. 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 both oxides. Amines include the polyetheramine family, which consists of monoamines, diamines, and triamines based on the core polyether backbone structure. Amines also include high-conversion polyether amines based on polybutanediol (PTMEG). These The average molecular weight of amines (M) w The number ranges from approximately 130 to approximately 4,000.

[0153] The polyamines used in this disclosure can be polyamine derivatives or modified polyamines, wherein one or more (but not all) NH protons in the polyamine are substituted with unsubstituted or substituted groups. For example, alkyl polyamines containing one or more alkyl groups attached to a nitrogen atom can be used to generate the multi-charged cationic polyamines disclosed herein. In these PEI derivatives, only some of the primary NH2 or secondary NH protons are substituted with other aprotic groups, and the remaining NH2 or NH protons can still react with Michael acceptors, such as activated alkenes containing hydrophilic (ionic) groups, via aza-Michael addition reactions.

[0154] One class of polymeric polyamines includes polyethyleneimine (PEI) and its derivatives. Polyethyleneimine (PEI), or polyaziridine, is a polymer having repeating units of CH2CH2NH, and its common formulation is NH2(CH2CH2NH). n -CH2CH2NH2, where n can be 2 to 10 5 The molecular weight (M) of repeating monomers in PEI w The value was 43.07, and the nitrogen-to-carbon ratio was 1:2.

[0155] PEI derivatives include ethoxylated / propylated PEI, polyquaternary ammonium salt PEI, polyglycerol quaternary ammonium salt PEI, and other PEI derivatives, salts, or mixtures thereof. The molar mass of polyethyleneimine containing modified polyethyleneimine can range 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 primary NH2 or secondary NH protons are replaced by functional groups, and the remaining NH2 or NH protons can still react with Michael acceptors, such as activated alkenes or α,β-unsaturated compounds containing hydrophilic (ionic) groups.

[0156] PEI and its derivatives can be linear, branched, or dendritic. Linear polyethyleneimine contains all secondary amines, unlike branched PEI which contains primary, secondary, and tertiary amines. Fully branched dendritic forms also exist and contain primary and tertiary amines. Figures of unmodified linear, branched, and dendritic PEI are shown below.

[0157]

[0158]

[0159] PEI derivatives are typically obtained by substituting one or more protons on a nitrogen atom with different groups. One such PEI derivative is ethoxylated and propoxylated PEI, in which polyethyleneimine is derived from ethylene oxide (EO) and / or propylene oxide (PO) side chains. Ethoxylation of PEI can increase its solubility.

[0160] PEI is produced on an industrial scale. A variety of commercially available polyethyleneimines are available, including, for example, those marketed under trade names. Those sold by (BASF), including, 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 PEIs w The figures are approximately 800, approximately 1,300, approximately 2,000, approximately 5,000, approximately 25,000, approximately 1,300 / 2,000 / 5,000, approximately 25,000, approximately 750,000, approximately 750,000, approximately 1,000,000 and approximately 2,000,000.

[0161] Two commonly used average values ​​for the molecular weight of polymers are number-average molecular weight (M). n ) and weight-average molecular weight (M w The polydispersity index (D) represents the molecular weight distribution of a 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 exponent i represents the number of different molecular weights present in the sample, and n i It has a molar mass M i The total number of moles. For polymers, M n and M w They are usually different. For example, via GPC, the M of PEI compounds... n It can be approximately 10,000, and via LS, M w It can be approximately 25,000.

[0162] Light scattering (LS) can be used to measure the M of polymer samples. 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 the 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 polymers. n and M w Both.

[0163] These commercially available and exemplary polyethyleneimines are water-soluble and can be used as anhydrous polyethyleneimine and / or in aqueous solution or methoxypropanol (as for...). The modified polyethyleneimine provided in PO 100 was obtained.

[0164] PEI and its derivatives have found numerous applications, often derived from their polycationic properties. Due to the presence of amino groups, PEI can be protonated with acid to form PEI salts from the surrounding medium, resulting in products that are partially or fully ionized depending on the pH. For example, approximately 73% of PEI is protonated at pH 2, approximately 50% at pH 4, approximately 33% at pH 5, approximately 25% at pH 8, and approximately 4% at pH 10. Typically, PEI can be purchased in both aqueous and anhydrous forms, either protonated or unprotonated. The charge (cation) density of commercial PEI is approximately 16-17 meq / g (milliequivalents per gram) at pH 13.

[0165] Each protonated nitrogen center maintains equilibrium with the anion of the acid acquired during neutralization. Examples of protonated PEI salts include, but are not limited to, PEI-hydrochloride, PEI-sulfate, PEI-nitrate, PEI-acetate, and PEI fatty acid salts. In fact, any acid can be used to protonate PEI, resulting in the formation of the corresponding PEI salt compound.

[0166] Suitable polyethyleneimines for use in this disclosure may contain mixtures or mixtures of primary, secondary, and tertiary amine substituents. 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, wherein branching occurs every 3 to 3.5 nitrogen atoms along the chain segment. Alternatively, suitable polyethyleneimine compounds may be predominantly one of the primary, secondary, or tertiary amine substituents.

[0167] The polyamines used to prepare the multi-charged cationic or anionic compounds disclosed herein can have a wide range of average molecular weights. Different multi-charged cationic or anionic compounds with characteristic average molecular weights can be generated 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 with α,β-unsaturated compounds and epoxides, multi-charged cationic or anionic compounds with similar average molecular weights and multiple cationic or anionic charges can be produced. Due to this characteristic, different multi-charged cationic or anionic compounds can be generated and used for a wider range of applications using unmodified polyamines or PEIs.

[0168] Specifically, the average molecular weight (M) of the polyamines that can be used to prepare the modified polyamines disclosed herein is [missing information]. w The figures are approximately 60-200, 100-400, 100-600, 600-5,000, 600-800, 800-2,000, 800-5,000, 100-2,000,000, 100-25,000, 600-25,000, 800-25,000, 600-750,000, 800-750,000, 25,000-750,000, and 750,000-2,000. 00,000, approximately 100, approximately 200, approximately 300, approximately 400, approximately 500, approximately 600, approximately 700, approximately 800, approximately 1,000, approximately 1,500, approximately 2,000, approximately 3,000, approximately 5,000, approximately 8,000, approximately 10,000, approximately 15,000, approximately 20,000, approximately 50,000, approximately 100,000, approximately 250,000, approximately 500,000, approximately 1,000,000, approximately 2,000,000 or any value in between.

[0169] In one respect, this paper discloses a multicharged 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' It is an unsubstituted or substituted straight or branched C4-C 10 Alkyl groups or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n can be from 2 to 1,000,000; A is H, Combinations; or H, The combination

[0170] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6 (+) Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; wherein the compound has 1, 2, 3 or more alkyl groups. Group and at least one Cationic compounds with multiple charges or having one, two, three or more groups. Group and at least one Anionic compounds with multiple charges in their functional groups.

[0171] In some embodiments, A is In some other embodiments, A is... In some other embodiments, A is

[0172] In some embodiments, the multicharged compound is NA2-[R 10' ] n -NA2. In some other embodiments, the multicharged compound is (RNA). n-RNA2. In some other embodiments, the multicharged compound is NA2-(RNA). n -RNA2. In some other embodiments, the multicharged compound is NA2-(RN(R')). n -RNA2.

[0173] In some embodiments, R 7 It is H. In some other embodiments, R 7 It is a C1-C4 alkyl group. In some other embodiments, R 8 It is C 12 -C 20 alkyl.

[0174] On the other hand, this document discloses a compound with multiple charges derived from the polyamine via a reaction of the polyamine with an activated olefin and an epoxide, wherein the activated olefin has one of the following formulas:

[0175] And the epoxide is

[0176] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6 (+) Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k-O-alkyl, where 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 cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0177] The multi-charged cations or anions disclosed herein are derived from polyamines through aza-Michael addition reactions of polyamines with activated olefins having ionic groups, such as α,β-unsaturated carbonyl compounds, and through ring-opening reactions of polyamines with epoxides.

[0178] The two reactions that produce the polyamine of the disclosed compound can be sequential or simultaneous, for example, as... Figure 1 , Figure 2 and Figure 3 The figure illustrates three different approaches, showcasing a general scheme for the structures and reactions that produce publicly disclosed cationic or anionic compounds with multiple charges.

[0179] Figure 1 An exemplary general reaction scheme is shown, which first involves a ring-opening reaction between linear polyethyleneimine and an epoxide, and then a azirro-Michael addition reaction with an activated olefin, such as an α,β-unsaturated carbonyl compound having a cationic group, to produce a cationic compound. Figure 2 An exemplary alternative general reaction scheme is shown, which first generates a multi-charged cationic compound via an aza-Michael addition reaction between a linear polyethyleneimine and an α,β-unsaturated carbonyl compound, and then via a ring-opening reaction with an epoxide. Figure 3 An exemplary general reaction scheme is shown to generate multi-charged cationic compounds by reacting branched polyethyleneimine with both epoxides and α,β-unsaturated carbonyl compounds via ring-opening and aza-Michael addition reactions, respectively.

[0180] exist Figure 1 , Figure 2 and Figure 3 In this context, k, l, m, n, o, or p are integers from 1 to 100; X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl; R 3 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR 4 R 5 R6(+) or its salt; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl or benzyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30.

[0181] Figure 1 , Figure 2 and Figure 3 Structures V and VI in the diagram depict the generalized reaction products. In structures V and VI, all secondary and primary amine groups in polyethyleneimine react with epoxides and α,β-unsaturated carbonyl compounds, thus leaving no secondary amine groups. It is possible that in the disclosed multi-charged ionic compounds, some secondary or primary amine groups do not react completely with the epoxide or activated alkene, but remain as primary or secondary amine groups in the multi-charged ionic compound or its salt.

[0182] In some embodiments, R 7 It is H. In some other embodiments, R 7 It is CH3. In some other embodiments, R 7 It is a C2-C4 alkyl group.

[0183] In some embodiments, R 8 It is C1-C 30 Alkyl group. In some other embodiments, R 8 It is a C8-C4 alkyl group. In some other embodiments, R 8 It is C8-C 20 alkyl.

[0184] In some embodiments, R 8 It is -(CH2) k -O-alkyl, where k is an integer from 1 to 30 and the alkyl group is C1-C2. 30 alkyl.

[0185] 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' It is an unsubstituted or substituted straight or branched C2-C chain. 10Alkyl groups or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNH2, RNHRNH2, or RN(RNH2)2; and n can be from 2 to 1,000,000. The monomers in the polyamine, such as R or R' groups, can be the same or different. In this 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.

[0186] In other words, ionic compounds with multiple charges can have the formula: NA2-[R 10' ] n -NA2, (RNA) n -RNA2, NA2-(RNA) n -RNA2 or NA2-(RN(R')) n -RNA2, etc., of which R 10' It is an unsubstituted or substituted straight or branched C4-C 10 Alkylene; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNA2, RNARNA2 or RN(RNA2)2; n can be from 2 to 1,000,000; A is H, Combinations; or H, The combination of , where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6 (+)Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; wherein the compound is a cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0187] In some embodiments, A is positively charged. nonionic In some other embodiments, A is negatively charged. nonionic

[0188] In some embodiments, at least two of the primary NH2 protons are... Substitution, at least one of primary NH2 or secondary NH is replaced The primary NH2 protons are replaced; and the remaining primary NH2 protons are retained. In some embodiments, at least two of the primary NH2 protons are replaced. Substitution, at least one of primary NH2 or secondary NH is replaced The primary NH2 protons are replaced; and the remaining primary NH2 protons are retained. In some other embodiments, all primary NH2 protons are... Substitution. In some embodiments, some primary NH2 and secondary NH protons are replaced.

[0189] Substitution. In some embodiments, all primary NH2 and some secondary NH protons are replaced. Substitution. However, the compounds disclosed herein are those having one, two, three, or more substitutions. Group and at least one Cationic compounds with multiple charges or having one, two, three or more groups. Group and at least one Anionic compounds with multiple charges in their functional groups.

[0190] In some embodiments, R 2 It is H. In some embodiments, R 2It is CH3. In some other embodiments, R 2 It is CH3CH3, CH2CH2CH3 or CH(CH3)2.

[0191] In some embodiments, Y is -NR4R5R6 (+) In some other embodiments, Y is -NR4R5R6 (+) And R 4 R 5 and R 6 Independently, it is CH3. In some other embodiments, Y is -NR4R5R6. (+) And R 4 and R 5 Independently, it is CH3, and R 6 It is C6-C 12 Aromatic alkyl group. In some other embodiments, Y is -NR4R5R6. (+) And R 4 and R 5 Independently, it is CH3, and R 6 It is -CH2-C6H6.

[0192] In some embodiments, Y is -NR4R5R6 (+) Furthermore, the counterion of Y is any negatively charged ion or species. In 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.

[0193] 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.

[0194] In some embodiments, when Y is an anionic group, the counter-position ion of the negative charge is Li. + Na + K + NH3 + Quaternary ammonium compounds, etc.

[0195] In some embodiments, R 3 It is CH2. In some other embodiments, R 3 It is CH2CH2. In some other embodiments, R 3 It is C(CH3)2. In some other embodiments, R 3 It is an unsubstituted linear chain and saturated C1-C30 Alkylene. In some embodiments, R 3 It is an unsubstituted linear and unsaturated C1-C chain. 30 Alkylene.

[0196] In some embodiments, R 3 It is a straight-chain C8-C 18 Alkyl, alkenyl, or ynyl. In some other embodiments, R 3 It is a C8-C branch. 20 Alkyl, alkenyl, or ynyl.

[0197] In some embodiments, the polyamine has the general formula -[RNH]. n - linear, branched, or dendritic macromolecular polyamines, wherein R is -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkylenes or combinations thereof, and n is an integer from 3, 4, 5, 6, 7-9 or 10 to 1,000,000.

[0198] In some embodiments, the polyamine has the general formula (RNH). n -RNH2 is a linear, branched, or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C. 10 Alkylenes or combinations thereof, and n can be from 2 to 1,000,000. In some embodiments, R is the same in each monomer. In other embodiments, R may vary depending on the monomer.

[0199] In some other embodiments, the polyamine has the general formula H2N-(RNH). n -RNH2 is a linear, branched, or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C. 10 Alkylenes or combinations thereof, and n can be from 2 to 1,000,000. In some embodiments, R is the same in each monomer. In other embodiments, R may vary depending on the monomer.

[0200] In some other embodiments, the polyamine has the general formula H2N-(RN(R')). n -RNH2 is a linear, branched, or dendritic macromolecular polyamine, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C. 10Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNH2, RNHRNH2, or RN(RNH2)2; and n can be from 2 to 1,000,000. In some embodiments, R or R' is the same in each monomer. In other embodiments, R or R' may vary depending on the monomer.

[0201] In some embodiments, polyamines are those having the general formula NH2-[R] 10' ] n -NH2 polyamines, of which R 10' It is an unsubstituted or substituted straight or branched C4-C 10 Alkylenes or combinations thereof, and n is 3, 4, 5, 6, 7-9 or 10 to 1,000,000.

[0202] In some embodiments, polyamines are from Huntsman Corporation. One or more of the following polyamines.

[0203] In some embodiments, the polyamine includes alkyleneamines, which include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimalin, polyethyleneimine, tri(2-aminoethyl)amine, or mixtures thereof.

[0204] 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 both oxides.

[0205] In some embodiments, the polyamine is an unmodified polyamine. In other embodiments, the polyamine is a modified polyamine.

[0206] In some other embodiments, the polyamine is an ethoxylated polyamine, a propylated polyamine, a polyamine having a polyquaternary ammonium salt, a polyamine having polyglycerol, or a combination thereof.

[0207] In some other embodiments, the polyamine is a linear, branched, or dendritic macromolecular polyethyleneimine. In some other embodiments, the polyamine includes only primary and secondary amine groups. In some embodiments, the polyamine includes only primary, secondary, and tertiary amine groups. In some other embodiments, the polyamine includes only primary and tertiary amine groups.

[0208] 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.

[0209] In some embodiments, the average molecular weight (M) of the polyamine w The average molecular weight (M) of the polyamine is approximately 60 to approximately 2,000,000 Da. In some other embodiments, the average molecular weight (M) of the polyamine is... w The average molecular weight (M) of the polyamine is approximately 60 to approximately 5,000 Da. In some other embodiments, the average molecular weight (M) of the polyamine is... w The value ranges from approximately 60 to approximately 25,000 Da.

[0210] In some embodiments, the average molecular weight (M) of the polyamine w The figures are approximately 60-200, 100-400, 100-600, 600-5,000, 600-800, 800-2,000, 800-5,000, 100-2,000,000, 100-25,000, 600-25,000, 800-25,000, 600-750,000, 800-750,000, 25,000-750,000, and 750,000-2,000. 00,000, approximately 100, approximately 200, approximately 300, approximately 400, approximately 500, approximately 600, approximately 700, approximately 800, approximately 1,000, approximately 1,500, approximately 2,000, approximately 3,000, approximately 5,000, approximately 8,000, approximately 10,000, approximately 15,000, approximately 20,000, approximately 50,000, approximately 100,000, approximately 250,000, approximately 500,000, approximately 1,000,000, approximately 2,000,000 or any value in between.

[0211] In some embodiments, the polyamine is an average molecular weight (M). w It is a diamine or triamine with a concentration of approximately 130 to approximately 4,000.

[0212] In some embodiments, the compound is a mixture derived from linear polyethyleneimine and (3-acrylamidopropyl)trimethylammonium chloride (APTAC). In other embodiments, the compound is a mixture derived from linear polyethyleneimine and [3-(methacrylamidopropyl)propyl]trimethylammonium chloride (MAPTAC).

[0213] In some other embodiments, the multi-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-(methacrylamidopropyl)propyl]trimethylammonium chloride (MAPTAC).

[0214] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl quaternary ammonium chloride (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium sulfate methyl ester (DMAEA-MSQ).

[0215] In some other embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacrylamidopropyl)propyl]trimethylammonium chloride (MAPTAC), or a mixture thereof.

[0216] In other embodiments, the activated olefin is 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl quaternary ammonium chloride (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium sulfate methyl ester (DMAEA-MSQ), or a mixture thereof.

[0217] 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.

[0218] In some other embodiments, the activated olefin is vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

[0219] 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 a 1,2-epoxyalkane. In still other embodiments, the epoxide is a hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, or a mixture thereof. In still other embodiments, the epoxide is a 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof.

[0220] In other embodiments, when the activated olefin contains anionic groups that can carry a negative charge at alkaline pH, the negatively charged counterions include, but are not limited to, alkali metal ions, Li... + Na + K + NH4 + Quaternary ammonium ions, etc.

[0221] In some embodiments, the compound is derived from epoxide, (3-acrylamidopropyl)trimethylammonium chloride (APTAC), and respectively from an average molecular weight (M). w The molecular weight of polyethyleneimine is approximately 1,300, and the average molecular weight (M) is... w Polyethyleneimine has an average molecular weight of approximately 5,000 and an average molecular weight of approximately 5,000. w The molecular weight of polyethyleneimine is approximately 25,000 or the average molecular weight (M). w It is a product of approximately 750,000 polyethyleneimine.

[0222] It should be understood that when n is greater than 2, the compound can be a mixture of more than two cationic compounds, which differ from each other in the exact position of NH substitution.

[0223] In some embodiments, the average molecular weight (M) of a cation or anion compound carrying multiple charges w The average molecular weight (M) of the multi-charged cationic or anionic compounds is approximately 100 to approximately 2,000,000 Da. w The average molecular weight (M) is approximately 100 to approximately 50,000 Da. In some other embodiments, the average molecular weight (M) of the multi-charged cationic or anionic compounds is... w The values ​​are approximately 100 Da to approximately 600 Da, approximately 100 Da to approximately 1,000 Da, approximately 100 Da to approximately 1,400 Da, approximately 100 Da to approximately 3,000 Da, approximately 100 Da to approximately 5,500 Da, or approximately 100 Da to approximately 10,000 Da, approximately 100 Da to approximately 20,000 Da, approximately 100 Da to approximately 30,000 Da, or approximately 100 Da to approximately 40,000 Da.

[0224] In some embodiments, the cationic compound carrying multiple charges 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 between the positive charges.

[0225] In some embodiments, the cationic compound carrying multiple charges 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 between the positive and negative charges.

[0226] In some embodiments, the compound or modified compound is soluble or dispersible in water.

[0227] Aza-Michael addition reaction and ring-opening reaction of epoxides

[0228] The multi-charged cationic or anionic compounds disclosed herein are derived from azira-Michael addition reactions between polyamines and Michael acceptors (such as activated alkenes or α,β-unsaturated carbonyl compounds containing hydrophilic (ionic) groups) and from ring-opening reactions between polyamines and epoxides. The azira-Michael addition and ring-opening reactions can occur sequentially or simultaneously. In some embodiments, the reaction product of the azira-Michael addition reaction is further derived from the ring-opening reaction of the epoxide. Alternatively, the multi-charged cationic or anionic compounds disclosed herein are derived from the ring-opening reaction between polyamines and epoxides, and the product of said ring-opening reaction then reacts with a Michael acceptor, such as an activated alkene or an α,β-unsaturated carbonyl compound containing a hydrophilic (ionic) group, via an azira-Michael addition reaction between the products.

[0229] Aliphatic amine groups undergo azirro-Michael addition reactions when they come into contact with an unsaturated hydrocarbon moiety (e.g., a carbon-carbon double bond) adjacent to an electron-withdrawing group (such as a carbonyl, cyano, or nitro group). Specifically, Michael addition is a reaction between a nucleophile and an activated alkene or alkyne functional group, where the nucleophile adds via a carbon-carbon multiple bond adjacent to an electron-withdrawing and resonance-stabilized activated group (such as a carbonyl group). The Michael addition nucleophile is called the "Michael donor," the activated electrophilic alkene is called the "Michael acceptor," and the reaction product of the two components is called the "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, maleimide, cyanoacrylates, vinyl sulfones, vinyl ketones, nitroethylene, α,β-unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinylpyridine, azo compounds, β-ketoacetylenes, and acetylene esters.

[0230] As used herein, “activated olefin” refers to a substituted olefin in which at least one of the carbon atoms in the double bond has a conjugated electron-withdrawing group. Examples of activated olefins include, but are not limited to, α,β-unsaturated carbonyl compounds (such as CH2=CHCO-NH-CH3, alkyl-CH=CH-CO-alkyl, CH2=CH2C(O)-O-CH3), CH2=CH-COOH, CH2=CH(CH3)-COOH, CH2=CH-SO3H, etc.

[0231] Aza-Michael addition reactions can be catalyzed by strong acids or strong bases. In some cases, certain ionic liquids can serve as both reaction media and catalysts. A preferred catalyst for the aza-Michael addition reaction used to synthesize the disclosed compounds is a base. Exemplary base catalysts can be hydroxides and amines. Because the reaction used to synthesize the disclosed compounds uses polyamines, the polyamines themselves can act as catalysts. In such embodiments, no additional catalyst is required, or an additional catalyst is optional. Other preferred catalysts include amidines and guanidines.

[0232] The use of solvents and / or diluents in the reaction is optional. When using solvents, a variety of non-acidic solvents are suitable, such as water, ethers (e.g., tetrahydrofuran (THF)), aromatic hydrocarbons (e.g., toluene and xylene), alcohols (e.g., n-butanol), etc. Since the synthetic process is relatively insensitive to solvents, a wide range of solvents can be used in the reaction. When using solvents (or diluents), the loading levels can range from as low as about 10 wt% to as high as about 80 wt% and above. Solvent loading levels can be 0 wt%, about 1 wt% to about 10 wt%, about 10 wt% to about 20 wt%, about 20 wt% to about 30 wt%, about 30 wt% to about 40 wt%, about 40 wt% to about 50 wt%, about 50 wt% to about 60 wt%, about 60 wt% to about 70 wt%, about 70 wt% to about 80 wt%, about 1 wt% to... About 20 wt% to about 40 wt% to about 60 wt% to about 80 wt% to about 70 wt% to about 5 wt% to about 15 wt% to about 25 wt% to about 35 wt% to about 45 wt% to about 55 wt% to about 65 wt% to about 75 wt% or any value between these values ​​and the final reaction mixture.

[0233] Typically, the reaction can be carried out over a wide temperature range. The reaction temperature can range 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, from about 25°C, from about 45°C, from about 65°C, from about 85°C, from about 105°C, from about 125°C, from about 145°C, or any value between these ranges. The reaction temperature can remain roughly the same from start to finish, and the reaction temperature can change from one temperature to another during the reaction.

[0234] The reaction times for the synthesis of the compounds disclosed herein can vary widely, depending on factors such as reaction temperature, the potency and amount of catalyst, and the presence or absence of a diluent (solvent). Preferred reaction times can be from about 0.5 hours to about 48 hours, from about 1 hour to about 40 hours, from about 2 hours to about 38 hours, from about 4 hours to about 36 hours, from 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, from about 24 hours, from about 30 hours, from about 36 hours, or any value between these values.

[0235] The ring-opening reaction of epoxides with amines is also known in the prior art. The ring-opening reaction can be carried out at temperatures from about -20°C to about 200°C and in the presence of a catalyst, base, or acid. In some embodiments, the ring-opening reaction is carried out without a catalyst, base, or acid. In other embodiments, the ring-opening reaction is carried out at temperatures from about 100°C to about 150°C; different temperatures for the azirmickle addition reaction; and in the presence of different catalysts, bases, or acids.

[0236] When one mole of polyamine and a specified mole (two or more moles) of activated olefin, epoxide, and both are mixed together at the above temperature for a sufficient time, both the aza-Michael addition and ring-opening reactions used to synthesize the disclosed compound can be completed.

[0237] It was discovered that the azirmickle addition reaction and the ring-opening reaction of the epoxide can be used to synthesize the disclosed compound without the need for higher temperatures (above 200 °C) and higher pressures (above normal atmospheric pressure), and with high yields (greater than 98%).

[0238] The progress of both reactions can typically be monitored by ESI-MS and / or NMR spectroscopy to detect monomer consumption. Reaction products can be purified or separated by HPLC or other methods known to those skilled in the art. For complete reactions, the formed products can be separated by removing the solvent or by precipitation in a nonpolar solvent opposite to the reaction medium. For reactions in water, the formed products are precipitated from the aqueous reaction mixture. Higher pressures can accelerate the reaction. Typically, if the reaction is carried out at room temperature with a suitable catalyst, the product yield can exceed 98%, and in some examples within 16 hours.

[0239] Preparation method

[0240] On the other hand, a method for preparing a compound or a salt thereof is disclosed herein, wherein the method comprises reacting a polyamine with... The epoxide and the activated olefin (Michael acceptor) having an ionic group according to one of the following formulas are in contact:

[0241]

[0242] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 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, it is C1-C 10 Alkyl; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k-O-alkyl, where 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 cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

[0243] In some embodiments of the disclosed method, 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' It is an unsubstituted or substituted straight or branched C2-C chain. 10 Alkyl groups or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl groups or combinations thereof; R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C4-C 10 Alkyl, RNH2, RNHRNH2 or RN(RNH2)2, and n can be from 2 to 1,000,000.

[0244] In some embodiments, the activated olefin is

[0245]

[0246] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 3 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR4R5R6 (+) And R 4 R 5 and R 6 Independently, it is C1-C 10 alkyl.

[0247] In some embodiments, the activated olefin is (3-acrylamidopropyl)trimethylammonium chloride (APTAC), [3-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl quaternary ammonium chloride (DMAEA-BCQ), 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium sulfate methyl ester (DMAEA-MSQ), or a mixture thereof.

[0248] In some embodiments, Y is -NR4R5R6 (+) Furthermore, 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.

[0249] In some other embodiments of the disclosed method, the activated olefin is

[0250]

[0251] Where X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl, alkenyl, or ynyl; R 2' It 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 There is no or no straight or branched C1-C chain. 30 Alkylene; Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; and R 4 R 5 and R 6 Independently, it is C1-C 10 alkyl.

[0252] In some embodiments, the activated olefin is acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

[0253] In some other embodiments, the activated olefin is 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 3-(allyloxy)-2-hydroxypropane-1-sulfonate, or a mixture thereof.

[0254] In other embodiments, when the activated olefin contains anionic groups that can carry a negative charge at alkaline pH, the negatively charged counterions include, but are not limited to, alkali metal ions, Li... + Na + K + NH4 + Quaternary ammonium ions, etc.

[0255] In some embodiments, R 7 It is H. In some other embodiments, R 7 It is CH3. In some other embodiments, R 7 It is a C2-C4 alkyl group.

[0256] In some embodiments, R 8 It is C1-C 30 Alkyl group. In some other embodiments, R 8 It is a C8-C4 alkyl group. In some other embodiments, R 8 It is C8-C 20 alkyl.

[0257] In some embodiments, R 8 It is -(CH2) k -O-alkyl, where k is an integer from 1 to 30 and the alkyl group is C1-C2. 30 alkyl.

[0258] 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 a 1,2-epoxyalkane. In still other embodiments, the epoxide is a hexyl glycidyl ether, octyl glycidyl ether, dodecyl glycidyl ether, or a mixture thereof. In still other embodiments, the epoxide is a 1,2-epoxytetradecane, 1,2-epoxydodecane, or 1,2-epoxyoctane, or a mixture thereof.

[0259] In some embodiments of the disclosed methods, the contact step is carried out in the presence of a reaction solvent. The reaction solvent can be any inorganic or organic solvent commonly used in chemical synthesis. The reaction solvent used in the disclosed methods can be introduced into the reactions between polyamines and activated olefins containing cationic or anionic groups, and between polyamines and epoxides, in any manner 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.

[0260] 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.

[0261] In other embodiments of the disclosed method, the contact step is carried out in the presence of a catalyst, base, or acid. The catalyst, base, or acid can be introduced into the reaction between the polyamine and the activated olefin in any manner known to those skilled in the art.

[0262] In some embodiments, the contact step is carried out in the absence of any additional base or alkalinity source. In other embodiments, the contact step is carried out in the presence of an alkalinity source. In other embodiments, the contact step is carried out in the presence of an organic base (such as an alkanolamine). In still other embodiments, the contact 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, aminopropylimidazolium, or a combination thereof). In other embodiments, the contact step is carried out in the presence of benzyltrimethylammonium hydroxide. In some embodiments, the catalyst base is an amidine or 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 the reaction under solvent-free conditions at room temperature.

[0263] In other embodiments of the disclosed method, the contact step is carried out in the presence of an acid. In other embodiments, the contact step is carried out in the presence of a catalyst. The catalyst may be any one or more catalysts known to those skilled in the art for Michael addition reactions.

[0264] In other embodiments of the disclosed method, the contact step is carried out without a catalyst, base, or acid. In other embodiments, the contact step is carried out without alkali metal hydroxides, carbonates, silicates, metasilicates, imidazole / pyridinium bases, or all of them. In some embodiments, the contact step is carried out without a base.

[0265] 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 still other embodiments, the contacting step is a single step in which both the polyamine and the epoxide and the activated olefin come into contact. When the contacting step is a two-step process, the two steps can be performed at two temperature differences ranging from about -20°C to about 200°C. In some embodiments, the contacting step with the activated olefin is performed at a temperature ranging from about 20°C to about 120°C. In other embodiments, the contacting step with the epoxide is performed at a temperature ranging from about 100°C to about 150°C.

[0266] On another aspect, this document provides articles, products, or compositions that include one or more compounds disclosed herein.

[0267] In some embodiments, the article, product, or composition further includes a carrier solvent or carrier. As used herein, a "carrier solvent" or carrier is a disclosed solvent or solvent system in which a compound can be uniformly and stably distributed.

[0268] As used herein, “stable” means that the compound disclosed herein does not precipitate or separate from the carrier solvent or other components of 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 compound disclosed herein is uniformly mixed with the carrier solvent or any other components.

[0269] In some 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 some other embodiments, the article, product, or composition further comprises an organic solvent and water.

[0270] In some embodiments, the organic solvent is an alcohol, hydrocarbon, ketone, ether, alkylene glycol, glycol ether, amide, nitrile, sulfoxide, ester, or any combination thereof. In other embodiments, the organic solvent is an alcohol, alkylene glycol, alkylene glycol alkyl ether, or a combination thereof. In still other embodiments, the organic solvent is methanol, ethanol, propanol, isopropanol, butanol, isobutanol, monoethylene glycol, ethylene glycol monobutyl ether, or a combination thereof.

[0271] 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-propanediol, 1,3-propanediol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel oil, toluene, xylene, heavy aromatic naphtha, cyclohexanone, diisobutyl ketone, diethyl ether, propylene carbonate, and N-methylpyrrolidone.

[0272] In some embodiments, the article, product, or composition may further include additional surfactants. These additional surfactants are nonionic, semi-nonionic, anionic, cationic, amphoteric, zwitterionic, gemini, dicationic, dianionic surfactants, or combinations thereof.

[0273] In some embodiments, the article, product, or composition is a solid. In other embodiments, the article, product, or composition is a liquid.

[0274] As used herein, the term "substantially free" means that the composition is completely lacking in a component or that it is present in such a small amount that the component does not affect the properties of the composition. A component may be present as an impurity or 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%.

[0275] As used herein, the terms “weight percent,” “wt-%,” “percent by weight,” “weight %,” and their variations refer to the concentration of a substance, which is 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, “percentage,” “%,” etc., are intended to be synonymous with “weight percent,” “wt-%,” etc.

[0276] The methods and compositions disclosed herein may include, consist essentially of, or be composed of the components and ingredients of the disclosed composition or method, 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, provided that such additional steps, components, or ingredients do not materially alter the essential and novel characteristics of the claimed methods and compositions.

[0277] Example

[0278] Embodiments of this disclosure are further defined in the following non-limiting examples. While these examples indicate certain embodiments of this disclosure, they are given merely for illustrative purposes. From the foregoing discussion and these examples, those skilled in the art can determine the essential characteristics of this disclosure, and various changes and modifications can be made to the embodiments of this disclosure to suit various uses and conditions without departing from its spirit and scope. Therefore, in addition to those shown and described herein, various modifications to the embodiments of this disclosure will become apparent to those skilled in the art based on the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

[0279] Example 1

[0280] General scheme for synthesizing exemplary compounds

[0281] The general synthetic reaction scheme for preparing the multi-charged cationic or anionic compounds disclosed herein is: Figure 4 In this general approach, linear polyethyleneimine is used as a representative polyamine. The hydrogen atom on the nitrogen of 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.

[0282] exist Figure 4 In this context, k is an integer from 1 to 100; X is NH or O; R 2 It is H, CH3, or unsubstituted straight or branched C2-C 10 Alkyl; R 3 There is no or no straight or branched C1-C chain. 30 Alkylene; Y is -NR 4 R 5 R 6(+) or its salt; R 4 R 5 and R 6 Independently, it is C1-C 10 Alkyl or benzyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30.

[0283] The progress of the reaction can be monitored by ESI-MS and / or NMR spectroscopy to detect the consumption of cationic monomers and epoxides. The reaction can be stopped when approximately >98% of the monomers and epoxides have been consumed. Aqueous or alcoholic solutions of multi-charged cationic or anionic compounds can be used "as-is" for application testing.

[0284] In the above scheme, water and / or isopropanol can be used as solvents. However, the use of solvents and / or diluents in the reaction is optional. When using solvents, various non-acidic solvents are suitable, such as acetonitrile, ethers (e.g., tetrahydrofuran (THF)), other alcohols (e.g., methanol, ethanol, n-butanol, ethylene glycol, PEG, or mixtures thereof).

[0285] In the above scheme, no additional catalyst is required. Because the reactions used to synthesize the disclosed multi-charged cationic or anionic compounds employ polyamines, the polyamines themselves can act as (base) catalysts for both reactions. However, additional catalysts are optional. The aza-Michael addition and ring-opening reactions used to synthesize the disclosed multi-charged cationic or anionic compounds can also be catalyzed by strong acids or strong bases.

[0286] 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 can range from about 20°C to about 150°C, more preferably from about 50°C to about 100°C.

[0287] In the above scheme, the synthesis is achieved through a two-step reaction. However, the disclosed cationic or anionic compounds with multiple charges can be synthesized in a one-step, one-pot reaction by simultaneously reacting polyamines with ionic monomers and epoxides via a tandem Michael addition and ring-opening reaction.

[0288] Example 2

[0289] Synthesis of DETA / 2EHGE (1:2) adduct

[0290] Add 2-ethylhexyl glycidyl ether (2-EHGE, 55 g) to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then add diethylenetriamine (DETA, 15 g) to the well-stirred reaction mixture. Raise the temperature of the reaction to 130 °C and stir for 3 hours or until the reaction is complete.

[0291] Example 3

[0292] TEPA / C 12 -C 14 Synthesis of alkyl glycidyl ether (1:3) adduct

[0293] Add ERISYS to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. TM GE8(C 12 -C 14Alkyl glycidyl ether (CAS No.: 68609-97-2, 132 g). Then triethylenepentamine (TEPA, 98%, 30 g) was 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.

[0294] Example 4

[0295] TEPA / C 12 -C 14 Synthesis of alkyl glycidyl ether (1:2) adduct

[0296] Add ERISYS to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. TM GE8(C 12 -C 14 Alkyl glycidyl ether (CAS No.: 68609-97-2, 120 g). Then triethylenepentamine (TEPA, 98%, 40 g) was 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.

[0297] Example 5

[0298] Synthesis of the Ethyleneamine E-100 / APTAC (1:2.5) adduct

[0299] Polyvinylamine E-100 (50 g) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 121 g) and water (20 g) were added to the flask. The resulting mixture was stirred overnight at 80 °C. As the reaction proceeded to completion, the mixture became a clear, pale yellow solution.

[0300] Example 6

[0301] Synthesis of exemplary cationic compounds with multiple charges

[0302] The compound of Example 1 (DETA / 2EHGE 1:2 adduct, 21.5 g) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 34 g) and water were added to the flask. The resulting suspension was stirred overnight at 70 °C or until the APTAC was completely consumed. As the reaction proceeded to completion, the suspension became a clear, pale yellow solution.

[0303] Example 7

[0304] Synthesis of anionic compounds with multiple charges

[0305] The compound of Example 2 (DETA / 2EHGE 1:2 adduct, 21.5 g) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then, a solution of sodium 2-acrylamido-2-methyl-1-propanesulfonate (NaAMPS, 58%, 49 g) and water (6 g) were added to the flask. The resulting suspension was stirred overnight at 70 °C or until the NaAMPS was completely consumed. As the reaction proceeded to completion, the suspension became a clear, pale yellow solution.

[0306] Example 8

[0307] Synthesis of exemplary cationic compounds with multiple charges

[0308] The compound of Example 3 (TEPA / C) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. 12 -C 14 Alkyl glycidyl ether (1:3 adduct, 35.6 g) and isopropanol (36 g). Then (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 24 g) was added to the flask. The resulting mixture was stirred at 70 °C overnight or until the APTAC was completely consumed. As the reaction proceeded to completion, the suspension became a clear, deep amber solution.

[0309] Example 9

[0310] Synthesis of anionic compounds with multiple charges

[0311] The compound of Example 3 (TEPA / C) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. 12 -C 14 Alkyl glycidyl ether (1:3 adduct, 40 g) and isopropanol (26 g). Then, a solution of sodium 2-acrylamido-2-methyl-1-propanesulfonate (NaAMPS, 58%, 46 g) and water (31 g) were added to the flask. The resulting solution was stirred overnight at 70 °C or until the NaAMPS was completely consumed. As the reaction proceeded to completion, the mixture became a clear, pale yellow solution.

[0312] Example 10

[0313] Synthesis of exemplary cationic compounds with multiple charges

[0314] The compound of Example 4 (TEPA / C) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. 12 -C 14 Alkyl glycidyl ether (1:2 adduct, 33.62 g) and isopropanol (50 g). Then (3-acrylamidopropyl)trimethylammonium chloride (APTAC, 75%, 31 g) was added to the flask. The resulting mixture was stirred at 70 °C overnight or until the APTAC was completely consumed. As the reaction proceeded to completion, the suspension became a clear, deep amber solution.

[0315] Example 11

[0316] Synthesis of cationic compounds / surfactants with multiple charges

[0317] The compound of Example 5 (ethyleneamine E-100 / APTAC 1:2.5 adduct, 74%, 50 g) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then ERISYS was added. TM GE 8(C 12 -C 14 Alkyl glycidyl ether (CAS No.: 68609-97-2, 41.5 g) and isopropanol (40 g) were added to the flask. The resulting mixture was stirred at 90°C overnight or until the reaction was complete.

[0318] Example 12

[0319] Synthesis of cationic compounds with multiple charges

[0320] The compound from Example 5 (ethyleneamine E-100 / APTAC 1:2.5 adduct, 74%, 63 g) was added to a 250 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Then ERISYS was added. TM GE 8(C 12 -C 14 Alkyl glycidyl ether (CAS No.: 68609-97-2, 34.2 g) and isopropanol (40 g) were added to the flask. The resulting mixture was stirred at 90°C overnight or until the reaction was complete.

[0321] Example 13

[0322] Exemplary one-pot synthesis of cationic compounds with multiple charges

[0323] Add ERISYS 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 isopropanol (80 mL). The resulting mixture was stirred at 90 °C overnight or until the reaction was complete, as indicated by the consumption of APTAC and ERISYS. TM As indicated by GE 8. As the reaction proceeds to completion, the mixture becomes a clear amber solution.

[0324] Example 14

[0325] Exemplary one-pot synthesis of cationic compounds with multiple charges

[0326] Add 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) to a 500 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Stir the resulting mixture at 90 °C overnight or until the reaction is complete, as indicated by the consumption of APTAC and 2-ethylhexyl glycidyl ether. As the reaction proceeds to completion, the mixture becomes a clear amber solution.

[0327] Example 15

[0328] Exemplary one-pot synthesis of anionic compounds with multiple charges

[0329] Add 2-ethylhexyl glycidyl ether (98%, 77 g), diethylenetriamine (DETA, 99%, 14 g), sodium acrylamide-2-methyl-1-propanesulfonate solution (NaAMPS, 58%, 160 g), and isopropanol (80 mL) to a 500 mL three-necked round-bottom flask equipped with a temperature probe, condenser, and magnetic stir bar. Stir the resulting mixture at 90 °C overnight or until the reaction is complete, as indicated by the consumption of NaAMPS and 2-ethylhexyl glycidyl ether. As the reaction proceeds to completion, the mixture becomes a deep yellow solution.

[0330] As will be apparent from the description herein, this disclosure can be modified in many ways. Such modifications are not considered to depart from the spirit and scope of this disclosure, and all such modifications are intended to be included within the scope of the appended claims.

[0331] The above description provides a description of novel compounds, their synthesis and uses, and compositions, products, or articles comprising the disclosed compounds. Because many embodiments may be made without departing from the spirit and scope of this disclosure, this disclosure is attributed to the claims.

Claims

1. A compound comprising: Compounds derived from polyamines through their reaction with activated olefins and epoxides, wherein: The activated olefin has the following formula: The epoxide is R 2' It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y', where m is an integer from 2 to 4; Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; The polyamine and the activated olefin undergo a azirmickle addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; The compound is a cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three 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 polyamines, wherein R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 (i) An alkylene group 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 polyamines, where R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 Alkylene or combinations 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 polyamines, where R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain or branched C2-C 10 Alkyl groups or combinations thereof, where R' is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight-chain 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 according to claim 1, wherein the polyamine is a polyalkylene imine, including ethyleneimine, propyleneimine, buteneimine, penteneimine, hexeneimine, heptenimine, or combinations thereof.

4. The compound according to claim 1, wherein the polyamine is an alkyleneamine, including ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexadecimaleneheptamine, polyethyleneimine, tris(2-aminoethyl)amine, or combinations thereof.

5. The compound according to claim 1, wherein the polyamine is a monoamine, diamine, or triamine mixed with a polyether backbone or with a polyether backbone based on propylene oxide (PO), ethylene oxide (EO), or a mixture of both oxides.

6. The compound according to 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 Y' is -COOH or a salt thereof, -SO3H or a salt thereof, or -PO3H or a salt thereof.

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

12. The compound according to 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-(methacryloylamino)propyl]trimethylammonium chloride (MAPTAC), 2-(acryloyloxy)-N,N,N-trimethylethylammonium chloride (DMAEA-MCQ), N,N-dimethylaminoethyl acrylate benzyl quaternary ammonium chloride (DMAEA-BCQ), or 2-(methacryloyloxy)-N,N,N-trimethylethyl-1-ammonium sulfate methyl ester (DMAEA-MSQ).

13. The compound according to claim 1, wherein the activated olefin is acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), itaconic acid, maleic acid, or 3-(allyloxy)-2-hydroxypropane-1-sulfonate.

14. The compound of claim 1, wherein the activated olefin is vinyl sulfonic acid, vinyl phosphonic acid, or a mixture thereof.

15. The compound according to claim 1, wherein Y' is an anionic group and the counterion is Li. + Na + K + NH3 + Or quaternary ammonium.

16. 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 different polyamines and at least two modified polyamine compounds derived from the same activated olefin and epoxide.

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

18. The compound according to claim 1, wherein the compound has at least 10, 15, 20 or 30 positive (or cation) 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.

19. 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' It is an unsubstituted or substituted straight or branched C4-C 10 Alkylenes or combinations thereof; R is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH(CH3)CH2-, unsubstituted or substituted straight or branched C4-C. 10 Alkylenes 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. The combination; R 2’ It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y', where m is an integer from 2 to 4; Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H, or a salt thereof; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; The compound is one, two, three or more Group and at least one A cationic compound with multiple charges on its functional groups.

20. The compound of 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.

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

22. A method for synthesizing a modified polyamine compound according to any one of claims 1 to 21, the method comprising: Polyamines are contacted with activated olefins and epoxides to generate cationic or anionic compounds with multiple charges; The activated olefin has the following formula: The epoxide is R 2' It is H, CH3, or unsubstituted or substituted straight or branched C1-C 10 Alkyl, alkenyl, alkynyl, -COOH, -CH2COOH, Y' or -(CH2) m -Y', where m is an integer from 2 to 4; Y' is -COOH, -SO3H, -PO3H, -OSO3H, -OPO3H or a salt thereof; R 7 It is H or alkyl; and R 8 It is an alkyl group or -(CH2). k -O-alkyl, where k is an integer from 1 to 30; The polyamine and the activated olefin undergo a azirmickle addition reaction, and the polyamine and the epoxide undergo a ring-opening reaction; The compound is a cationic compound having one, two, three or more positive charges from the activated olefin and at least one nonionic group from the epoxide, or an anionic compound having one, two, three or more negative charges from the activated olefin and at least one nonionic group from the epoxide.

23. The method of claim 22, wherein the contacting step is carried out in the presence of a reaction solvent.

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

25. The method of claim 22, wherein the contacting step is carried out in the presence of a catalyst, a base, or an acid.

26. The method of claim 22, wherein the contacting step is performed without alkali.

27. The method of claim 22, wherein the contacting step is carried out in the presence of an organic base.

28. The method of claim 22, wherein the contacting step is carried out in the presence of a hydroxide, an alkali metal hydroxide, a basic metal hydroxide, a metal carbonate, an imidazole, a pyridine base, an amidine, a guanidine base, or a combination thereof.

29. The method of claim 22, wherein the contacting step is carried out in the presence of benzyltrimethylammonium hydroxide.

30. A composition comprising one or more modified polyamine compounds according to any one of claims 1 to 21.

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

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

33. The composition of claim 30, wherein the composition is a solid or a liquid.

34. The composition of claim 30, further comprising a surfactant, said surfactant being a nonionic surfactant, a semi-nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, or a mixture thereof.

35. The composition of claim 34, wherein the surfactant is an amphoteric surfactant, a gemini surfactant, a dicationic surfactant, a dianionic surfactant, or a mixture thereof.

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