Charge balancing polymers for industrial water applications

Abstract

Compositions comprising a charge balancing polymer are disclosed. The composition comprises a compound of formula (I): wherein E is a repeating unit remaining after polymerization of an ethylenically unsaturated compound; r1 is H or lower (C1-C4) alkyl; g is-CH2 <-> or-CHCH3 <->; r2 is-(CH2-CH2-O) n-, or-(CH2-CH2-O) n or-(CH2-CH (OH)-CH2) n, where n is in the range of about 1 to 100; x is SO3 or-O-; z is H or a water-soluble cationic moiety; f is a repeating unit having formula (II) wherein R4 is H or a lower (C1-C4) alkyl group, R5 is a hydroxyl-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a nonionic hydroxyl group-containing monomer selected from the group consisting of PEG-OH having 1 to 10 repeating units, etc. Wherein c and d are positive integers; and e is a non-negative integer.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to U.S. Provisional Patent Application No. 63 / 435,536, filed on December 27, 2022, which is incorporated herein by reference in its entirety. Technical Field

[0003] The disclosed technology relates to polymer compositions useful as deposit control agents and corrosion inhibitors in water treatment processes. More specifically, the disclosed technology relates to charge-balanced copolymers of ethylenically unsaturated monomers incorporating monomers containing nonionic hydroxyl groups. Background Art

[0004] Corrosion and scale formation problems and the resulting effects have plagued industrial water systems for many years. For example, scale tends to accumulate on the inner walls of various water systems (such as boiler systems and cooling systems) and thereby greatly reduce the operating efficiency of the system.

[0005] Deposits in pipelines, heat exchange equipment, and the like can arise from several causes. For example, the precipitation of calcium carbonate, calcium sulfate, and calcium phosphate in water systems causes these fouling compounds to accumulate along or around metal surfaces in contact with the water circulating in the system. This can severely hinder the heat transfer function of a particular system.

[0006] Corrosion, on the other hand, is the degradative electrochemical reaction of a metal with its environment. Simply put, it's the reversion of a refined metal to its natural state. For example, iron ore is iron oxide. Iron ore is refined into steel. When steel corrodes, it forms iron oxide, which, if left unattended, can cause the metal to fail or become damaged, shutting down a particular water system until necessary repairs can be made.

[0007] Typically, the formation of calcium sulfate, calcium phosphate, and calcium carbonate in cooling water systems has been shown to be detrimental to the overall efficiency of the cooling water system. Furthermore, with the prevalence of cooling treatments that use high levels of orthophosphate to promote passivation of metal surfaces in contact with the system water, it has become critical to control calcium phosphate crystallization so that relatively high levels of orthophosphate can be maintained in the system to achieve the desired passivation without causing scaling or hindering heat transfer functions that are typically caused by calcium phosphate deposition.

[0008] Silica (SiO2) is present in most natural waters. When these waters circulate in cooling towers, the silica level increases and often reaches a level where precipitation of silica species occurs. Sometimes precipitation occurs by polymerization of the silica itself, thereby producing silica gel. For this purpose, relatively high SiO2 concentrations are required, typically greater than about 200 ppm. However, when certain cations are present, silica species can precipitate at much lower concentrations. Cations that promote silica precipitation include, but are not limited to, Al2O3, MgO4, and MgO5. 3+ Mg 2+ 、Zn 2+ and Fe 3+ Aluminum is very insoluble in water and readily precipitates under cooling water conditions. When aluminum enters the cooling system (e.g., due to carryover), it can cause serious precipitation problems. One such problem is the precipitation of phosphate species that may be present as corrosion inhibitors. Such precipitates can be problematic due to both sedimentation and corrosion effects.

[0009] Conventional treatment procedures involve the use of various dispersants, salts and corrosion inhibitors to prevent corrosion and scale formation. Large amounts of active materials and / or blends are often required, leading to complex feeding and control strategies. Industrial polymers commonly used as salts and corrosion inhibitors in these treatment procedures include anionic vinyl monomers (acrylic acid, maleic acid, etc.). When the anionic charge of these monomers is that of a weak acid such as a carboxylic acid, the monomers chelate and become active towards cationic metals in industrial waters. The use of sulfonic acid groups imparts dispersing and calcium phosphate inhibition properties and reduces activity towards calcite. To date, there are few examples of polymers or single molecules active for inhibiting and dispersing metal silicates.

[0010] In addition, fully charged industrial polymers are usually focused on suppressing a salt or suppressing and dispersing a salt. This requires feeding multiple active substances to handle multiple salts and other conditions in these industrial water applications. Usually, operating conditions are designed to manipulate the supersaturation of salts (particularly metal silicates). Fully charged polymers usually have limited corrosion characteristics, and other active substances (phosphates, phosphonates and / or metal salts) need to be fed separately. Usually all these active substances are incompatible in concentrated formulations, resulting in the need for multiple feed sources. More general industrial polymers are needed. Summary of the Invention

[0011] The disclosed technology provides charge-balanced copolymers of ethylenically unsaturated monomers incorporating monomers containing nonionic hydroxyl groups.

[0012] Various aspects of the present disclosure relate to a composition comprising a charge-balancing polymer having Formula I:

[0013]

[0014] wherein E is the repeating unit remaining after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n or –(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO3 or -O-; Z is H or a water-soluble cationic moiety; and F is a repeating unit having formula II

[0015]

[0016] wherein R4 is H or a lower (C1-C4) alkyl group, R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units, etc.; wherein c and d are positive integers; and e is a non-negative integer.

[0017] In various aspects, the ethylenically unsaturated compound is one or more of a carboxylic acid or a sulfonic acid.

[0018] In various aspects, the composition can further comprise a polymer having Formula III:

[0019]

[0020] wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

[0021] Various aspects of the present disclosure further relate to a method of preventing the formation and deposition of corrosion and fouling-generating species on a surface exposed to an aqueous system, the method comprising adding to the aqueous system an effective amount of a charge-balancing polymer comprising an ethylenically unsaturated monomer and a monomer comprising a nonionic hydroxyl group.

[0022] In various aspects of the disclosed method, the method comprises adding to the aqueous system an effective amount of a charge-balancing polymer having Formula I:

[0023]

[0024] wherein E is the remaining repeating unit after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n, wherein n is in the range of about 1 to 100; X is SO3 or -O-; Z is H or a water-soluble cationic moiety; and F is a repeating unit having formula II

[0025]

[0026] wherein R4 is H or a lower (C1-C4) alkyl group, R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units, etc.; wherein c and d are positive integers; and e is a non-negative integer.

[0027] In various aspects of the disclosed method, the ethylenically unsaturated compound is one or more of a carboxylic acid or a sulfonic acid.

[0028] In various aspects of the disclosed method, the method further comprises adding an effective amount of a polymer having formula III:

[0029]

[0030] wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

[0031] In various aspects of the disclosed methods, the charge balancing polymer is added in combination with at least one or more topping agents. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Those skilled in the art will understand that the drawings described below are for illustration purposes only and are not intended to limit the scope of the present invention in any way.

[0033] Figure 1 The maximum calcite saturation of the disclosed charge-balancing polymer embodiments is demonstrated compared to polymaleic acid (PMA) or polyacrylic acid (PAA) polymers used alone.

[0034] Figure 2A Calcite dispersion on low-temperature (low-T) surfaces after treatment with charged SO3 copolymers is demonstrated.

[0035] Figure 2B demonstrated calcite dispersion on low-T surfaces treated with polymaleic acid copolymer.

[0036] Figure 2C and 2D Calcite dispersion on hot and low-T surfaces is shown, respectively, after treatment with examples of the disclosed charge-balancing polymers.

[0037] Figure 3The maximum MgSiO 3 saturation in water samples treated with examples of the charge-balancing polymers of the present disclosure is demonstrated.

[0038] Figure 4A The corrosion control properties of embodiments of the charge-balancing polymers of the present disclosure are demonstrated.

[0039] Figure 4B The corrosion control properties of a control program including PMA copolymer and aluminum are demonstrated.

[0040] Figure 5 The corrosion control properties of embodiments of the charge-balancing polymers of the present disclosure are demonstrated.

[0041] Figure 6A Calcite dispersion on low-T surfaces after treatment with charged SO3 copolymers is demonstrated.

[0042] Figure 6B demonstrated calcite dispersion on low-T surfaces treated with polymaleic acid copolymer.

[0043] Figures 6C-6E Calcite dispersion on hot and low-T surfaces is demonstrated after treatment with examples of the disclosed charge-balancing polymers.

[0044] Figures 7A-7B The corrosion control properties of embodiments of the disclosed charge-balancing polymers on mild steel (LCS) surfaces are demonstrated.

[0045] Figure 7C The corrosion control properties of embodiments of the disclosed charge-balancing polymers on an Admiralty Diameter (ADM) surface are demonstrated.

[0046] Figures 8A-8C The corrosion control properties of embodiments of the disclosed charge-balancing polymers on LCS surfaces are demonstrated.

[0047] Figure 8D The corrosion control properties of embodiments of the disclosed charge-balancing polymers on ADM surfaces are demonstrated. DETAILED DESCRIPTION

[0048] Approximate language as used herein in the entire specification and claims can be applied to modify any quantitative representation that can be changed in a permissible manner without causing its related basic function to change. Therefore, the value modified by one or more terms, such as "about (about)" is not limited to the specified exact value. In at least some cases, approximate terms may correspond to the precision of the instrument used to measure the value. Range limitations can be combined and / or interchangeable, and unless the context or language indicates otherwise, such ranges are determined and include all sub-ranges described herein. Except in the operating examples or when otherwise indicated, all numerals or expressions related to the amount of a component, reaction conditions, monomer ratio, polymer molecular weight (Mw) etc. used in the specification and claims should be understood to be modified by the term "about" in all cases.

[0049] “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or the material is present and instances where it does not occur or the material is not present.

[0050] As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," or any other variations thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0051] The singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0052] The disclosed technology provides compositions and methods of using charge-balanced copolymers comprising ethylenically unsaturated monomers that incorporate monomers containing nonionic hydroxyl groups.

[0053] It has been found that the compositions disclosed herein exhibit universal properties not found in conventional fully charged polymers. By incorporating monomers with nonionic hydroxyl groups, the overall charge of the polymer backbone (e.g., acrylic acid) is reduced relative to anionic analogs. Without being bound by theory, by reducing the charge on the polymer backbone, the polymer may be able to better rearrange itself to interact with various salt surfaces. When the carboxylic acid groups are coordinated with metal cations, the hydroxyl groups provide solvation. Alternatively, they can better stabilize the hydrophobic chelating core compared to homopolymers having only anionic carboxylic acid groups. The addition of hydroxyl groups can further allow for interaction with salt colloids, which can promote interaction with silicates and metal oxides (suspended solids).

[0054] In various aspects, the resulting charge-balancing polymers can exhibit improved properties in at least one or more of calcite inhibition and dispersion, metal silicate inhibition and dispersion, calcium and metal phosphate tolerance, metal fluorides, metal sulfates, mixtures of metal salt colloids, clay and iron dispersion, and metal corrosion properties. In addition, these charge-balancing polymers can be further formulated with a variety of active materials, including but not limited to salt inhibitors, microbial (MB) control agents, and metal salt inhibitors (zinc, aluminum, tin, iron, manganese, molybdenum, lanthanide and actinide metals, silicates, etc.).

[0055] As used herein, the term "effective amount" refers to any amount of the charge-balancing polymers of the present disclosure that is effective in inhibiting and / or preventing the formation and deposition of corrosion and fouling species in industrial water systems.

[0056] As used herein, the term "Mw" refers to the weight average molecular weight (Mw) of a polymer. It should be understood that polymers encompass a wide range of Mw values ​​and can be characterized by other acceptable Mw analyses. It should be further understood that Mw values ​​can vary due to reaction conditions and the use and amount of chain transfer agents.

[0057] In various aspects of the disclosed technology, compositions comprising charge-balancing polymers are disclosed, the polymers comprising ethylenically unsaturated compounds and monomers comprising nonionic hydroxyl groups. In various aspects, suitable monomers comprising nonionic hydroxyl groups include, but are not limited to, allyloxy monomers such as 3-allyloxy-1,2-propylene glycol, ethylene glycol vinyl ether, diethylene glycol monoallyl ether, allyl-poly(ethylene glycol), 1,4-butanediol vinyl ether, 2-allyloxyethanol, diethylene glycol vinyl ether, 7-octene-1,2-diol, 3,4-dihydroxy-1-butene, trimethylolpropane allyl ether; allyl PEG-OH monomers having any number of PEG repeating units, including 2-allyloxyethanol, etc.; protected alcohols such as those used in polyvinyl alcohol synthesis; and alcohol esters with vinyl carboxylic acid monomers, including hydroxyethyl methacrylate, hydroxypropyl acrylate, etc.

[0058] In various aspects, the composition can include a charge-balanced copolymer or terpolymer having the structure of Formula I:

[0059]

[0060] wherein E is the remaining repeating unit after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100 or about 1 to 20; X is selected from SO3 or -O-; Z is H or any water-soluble cationic moiety that counters the valence of the anionic group X, including but not limited to Na, K, Ca or NH4; F, when present, is a repeating unit having formula II:

[0061]

[0062] In Formula II, X and Z are the same as in Formula I. R4 is H or a lower (C1-C4) alkyl group, and R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units.

[0063] About the E of formula I, it can be included in the repeating unit obtained after the polymerization of carboxylic acid, sulfonic acid, phosphonic acid or its amide form or its mixture.Exemplary compounds include but are not limited to the repeating unit remaining after the polymerization of the following: acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrenesulfonic acid, vinylsulfonic acid, isopropenylphosphonic acid, vinylphosphonic acid, vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid etc. and its mixture.In some respects, the water-soluble salt form of these acids can be used.In some respects, more than one type of monomeric unit E can be present in the polymer of the present disclosure.

[0064] In various aspects, the subscripts c, d, and e in Formula I are the molar ratios of the monomer repeat units. In some aspects, the subscripts c and d are positive integers, while the subscript e is a non-negative integer. In some aspects, c and d are integers of 1 or greater, while e can be 0, 1, 2, etc.

[0065] In some aspects, the compositions of the present disclosure may include a charge-balancing polymer having the structure of Formula Ia:

[0066]

[0067] Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n ranges from about 1 to 100; X is -O-; and Z is H or a water-soluble cationic moiety; wherein c and d are positive integers.

[0068] In various aspects, the molar ratio c:d ranges from 30:1 to 1:20, or about 15:1 to 1:10, or 5:1 to 1:5, or 5:1 to 1:1, or 3:1 to 1:1.

[0069] In other aspects, the compositions of the present disclosure may include a charge-balancing polymer having the structure of Formula Ib:

[0070]

[0071] Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO 3 ; and Z is H or a water-soluble cationic moiety; wherein c, d, and e are positive integers.

[0072] In various aspects, the molar ratio of c:d:e can range from about 300:10:1 to 1:1:300.

[0073] In various aspects, the composition can further comprise a polymer having Formula III:

[0074]

[0075] wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

[0076] In various aspects, the polymerization of the copolymers and / or terpolymers of the present disclosure can be carried out according to solution, emulsion, micellar or dispersion polymerization techniques. In various aspects, the synthesis of the polymers can be carried out in aqueous or non-aqueous media (including organic solvent media). Conventional polymerization initiators such as persulfates, peroxides and azo-type initiators can be used. Polymerization can also be initiated by radiation or ultraviolet mechanisms. Chain transfer agents such as sodium hypophosphite, sodium metabisulfite or sodium bisulfite; alcohols including isopropyl alcohol or allyl alcohol; amines or mercapto compounds can be used to adjust the molecular weight of the polymer. Branching agents such as methylenebisacrylamide or polyethylene glycol diacrylate and other multifunctional crosslinking agents can be added. The resulting polymer can be isolated by precipitation or other well-known techniques. If the polymerization is carried out in aqueous solution, the polymer can be used only in aqueous solution form.

[0077] In various aspects, the weight average molecular weight (Mw) of the charge-balanced copolymer having Formula I can fall within the following ranges: about 1,000 to about 1,000,000; or about 1,000; 2,000; 2,500; 3,000; 3,500; 4,000; 4,500; 5,000; 5,500; 6,000; 6,500; 7,000; 7,500; 8,000; 8,500; 9,000; 9,500; 10,000; 11,000; 12,000; 13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000; 20,000; 21,000; 22,000; 23,000; 24,000; 25,000; 26,000; 27,000; 28,000; 29,000; 30,000; 31,000; 32,000; 33,000; 34,000; 35,000; 36,000; 37,000; 38,000 or about 14,000 to about 16,000, or about 16,000 to about 17,000, or about 16,000 to about 17,000, or any molecular weight falling between any of these values.

[0078] In various aspects, the charge-balancing polymers of the disclosed technology can be used to prevent corrosion on surfaces exposed to aqueous systems and methods for the formation and deposition of fouling species. In various aspects, the method can include adding an effective amount of a charge-balancing polymer to the aqueous system, the charge-balancing polymer comprising an ethylenically unsaturated compound and a monomer comprising a nonionic hydroxyl group. In various aspects, suitable monomers comprising nonionic hydroxyl groups include, but are not limited to, allyloxy monomers, such as 3-allyloxy-1,2-propylene glycol, ethylene glycol vinyl ether, diethylene glycol monoallyl ether, allyl-poly(ethylene glycol), 1,4-butanediol vinyl ether, 2-allyloxyethanol, diethylene glycol vinyl ether, 7-octene-1,2-diol, 3,4-dihydroxy-1-butene, trimethylolpropane allyl ether; allyl PEG-OH monomers with any number of PEG repeating units, including 2-allyloxyethanol, etc.; protected alcohols, such as those used in polyvinyl alcohol synthesis; and alcohol esters with vinyl carboxylic acid monomers, including hydroxyethyl methacrylate, hydroxypropyl acrylate, etc.

[0079] In various aspects, the method can include adding a charge-balancing polymer to the aqueous system, the charge-balancing polymer comprising an ethylenically unsaturated compound and a monomer comprising a nonionic hydroxyl group. In various aspects, the method can include adding a charge-balancing copolymer or terpolymer having a structure of Formula I:

[0080]

[0081] wherein E is the remaining repeating unit after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100 or about 1 to 20; X is selected from SO3 or -O-; Z is H or a water-soluble cationic moiety; and F, when present, is a repeating unit having Formula II:

[0082]

[0083] In Formula II, X and Z are the same as in Formula I. R4 is H or a lower (C1-C4) alkyl group, and R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units.

[0084] About the E of formula I, it can be included in the repeating unit obtained after the polymerization of carboxylic acid, sulfonic acid, phosphonic acid or its amide form or its mixture.Exemplary compounds include but are not limited to the repeating unit remaining after the polymerization of the following: acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, maleic acid or anhydride, fumaric acid, itaconic acid, styrenesulfonic acid, vinylsulfonic acid, isopropenylphosphonic acid, vinylphosphonic acid, vinylidene diphosphonic acid, 2-acrylamido-2-methylpropane sulfonic acid etc. and its mixture.In some respects, the water-soluble salt form of these acids can be used.In some respects, more than one type of monomeric unit E can be present in the polymer of the present disclosure.

[0085] In various aspects, the subscripts c, d, and e in Formula I are the molar ratios of the monomer repeat units. In some aspects, the subscripts c and d are positive integers, while the subscript e is a non-negative integer. In some aspects, c and d are integers of 1 or greater, while e can be 0, 1, 2, etc.

[0086] In some aspects, the methods of the present disclosure may include adding a charge-balancing polymer having the structure of Formula Ia:

[0087]

[0088] Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n ranges from about 1 to 100; X is -O-; and Z is H or a water-soluble cationic moiety; wherein c and d are positive integers.

[0089] In various aspects, the molar ratio c:d ranges from 30:1 to 1:20, or about 15:1 to 1:10, or 5:1 to 1:5, or 3:1 to 1:1.

[0090] In other aspects, the methods of the present disclosure may include adding a charge-balancing polymer having the structure of Formula Ib:

[0091]

[0092] Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO 3 ; and Z is H or a water-soluble cationic moiety; wherein c, d, and e are positive integers.

[0093] In various aspects, the molar ratio of c:d:e can range from about 300:10:1 to 1:1:300.

[0094] In various aspects, the method can further comprise adding a polymer having Formula III:

[0095]

[0096] wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

[0097] In various aspects, the weight average molecular weight (Mw) of the charge-balanced copolymer having Formula I can fall within the following ranges: about 1,000 to about 1,000,000; or about 1,000; 2,000; 2,500; 3,000; 3,500; 4,000; 4,500; 5,000; 5,500; 6,000; 6,500; 7,000; 7,500; 8,000; 8,500; 9,000; 9,500; 10,000; 11,000; 12,000; 13,000; 14,000; 15,000; 16,000; 17,000; 18,000; 19,000; 20,000; 21,000; 22,000; 23,000; 24,000; 25,000; 26,000; 27,000; 28,000; 29,000; 30,000; 31,000; 32,000; 33,000; 34,000; 35,000; 36,000; 37,000; 38,000 or about 14,000 to about 16,000, or about 16,000 to about 17,000, or about 16,000 to about 17,000, or any molecular weight falling between any of these values.

[0098] In various aspects, the charge-balancing polymers of the present disclosure can be used as deposit control agents and / or corrosion inhibitors for water treatment in industrial water systems (such as cooling water systems, boiler systems, closed-loop systems, and steam generation systems). In various aspects, the charge-balancing polymers of the present disclosure can also be used in industrial processes such as mining and / or mineral processing and air scrubbers or cleaners. In various aspects, the charge-balancing polymers of the present disclosure can further be used as deposit control agents in membrane systems to prevent membrane scaling. The appropriate treatment concentration can vary depending on the specific system to be treated and will be affected by factors such as the area subject to corrosion, pH, temperature, water volume, and the corresponding concentrations of potential fouling and deposit-forming species in the water. In various aspects, the charge-balancing polymers of the present disclosure may be effective when used at a level of about 0.1 parts to about 500 parts per million of water contained in the aqueous system to be treated, or about 1 part to about 100 parts per million of water, or about 5 parts to 50 parts per million of water, or about 15 parts to about 30 parts per million of water. The charge-balancing polymer can be added directly to the desired water system in the aqueous solution continuously or intermittently. In various aspects, the water system can include a freshwater source, such as a lake, pond, well, etc.; seawater; treated wastewater; or brackish water.

[0099] The charge-balancing polymers of the present disclosure are not limited to use in any particular class of water systems. For example, in addition to boiler systems and cooling water systems, the charge-balancing polymers can also be effectively used in scrubber systems, etc., where the formation and deposition of corrosion and / or fouling salts is a problem. Other possible environments in which the polymers of the present disclosure can be used include heat distribution type seawater desalination equipment, membrane systems in the steel manufacturing industry, and dust collection systems. In some aspects, the charge-balancing polymers of the present disclosure are also effective as sediment and pitch control agents in paper and pulp manufacturing processes to prevent the deposition of asphalt, calcium oxalate, and barium sulfate. They can also be used as viscosity and rheology modifiers in mining and mineral processing applications to reduce the viscosity of slurries.

[0100] In various aspects, the charge-balancing polymers of the present disclosure can be used as a single agent. In various aspects, the charge-balancing polymers of the present disclosure can be used in combination with a topping agent to supplement and / or enhance its corrosion inhibition and fouling control properties. For example, the charge-balancing polymers of the present disclosure can be used in combination with one or more compounds selected from the group consisting of inorganic phosphoric acid, phosphonates, organic phosphates, and polyvalent metal salts, or mixtures thereof. Such topping agents can be added to the system being treated in an amount of about 0.1 to 500 ppm.

[0101] Examples of inorganic phosphoric acid include condensed phosphoric acid and its water-soluble salts. Examples of phosphoric acid include orthophosphoric acid, primary phosphoric acid and secondary phosphoric acid. Examples of inorganic condensed phosphoric acid include polyphosphoric acid such as pyrophosphoric acid, tripolyphosphoric acid, etc., and metaphosphoric acid such as trimetaphosphoric acid and tetrametaphosphoric acid. In various aspects, the total phosphorus (P) or phosphate (PO4) content of the treated water system can be in the range of 0 ppm to 500 ppm.

[0102] Examples of other phosphoric acid derivatives that can be combined with the charge-balancing polymers of the present disclosure include aminopolyphosphonic acids such as aminotrimethylenephosphonic acid, ethylenediaminetetramethylenephosphonic acid, etc., methylenediphosphonic acid, hydroxyethylenediphosphonic acid, 2-phosphonobutane 1,2,4, tricarboxylic acid, etc.

[0103] Exemplary organic phosphates that can be combined with the charge-balancing polymers of the present disclosure include phosphates of alkyl alcohols, such as methyl phosphate, ethyl phosphate, and the like; phosphates of methyl cellosolve and ethyl cellosolve; and phosphates of polyoxyalkylated polyols obtained by adding ethylene oxide to polyols such as glycerol, mannitol, sorbitol, and the like. Other suitable organic phosphates are phosphates of amino alcohols such as monoethanolamine, diethanolamine, and triethanolamine. The charge-balancing polymers can also be used in combination with molybdates such as sodium molybdate, potassium molybdate, lithium molybdate, ammonium molybdate, and the like.

[0104] The charge-balancing polymers disclosed herein can be used in combination with other topping agents, including corrosion inhibitors for iron, steel, copper and copper alloys or other metals, conventional fouling and pollution inhibitors, metal ion chelating agents and other conventional water treatment agents. Examples of other corrosion inhibitors include tungstates, nitrites, borates, silicates, hydroxycarboxylic acids, amino acids, catechols, aliphatic amino surfactants, N-heterocyclic derivatives, azoles (such as benzotriazole, halogenated triazoles and mercaptobenzothiazole), phosphinosuccinate oligomers (PSO) and phosphonocarboxylic acids (such as phosphonocarboxylic acid (sulfonated) copolymers (POCA)). Other fouling and pollution inhibitors include lignin derivatives, tannic acid, starch, polyacrylic acid and copolymers thereof, including but not limited to acrylic acid / 2-acrylamido-2-methylpropanesulfonic acid copolymers and acrylic acid / allyloxy-2-hydroxypropane-3-sulfonic acid copolymers, stress-resistant polymers (STP), polysulfone copolymers, maleic acid and copolymers thereof, polyepoxysuccinic acid and polyacrylamide, etc.

[0105] Examples of metal ion chelators include polyamines such as ethylenediamine, diethylenetriamine, etc. Other examples of metal ion chelators include polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)ethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, methylglycinediacetic acid (MGDA), N,N-dicarboxymethylglutamic acid tetrasodium salt, (2R,3R,4S,5R,6R)-3,4,6-trihydroxy-5-sulfooxyoxane-2-carboxylic acid or ethylenediamine-N,N'-disuccinic acid or mixtures thereof; polyamino acids or nucleic acids such as polyaspartic acid or peptides comprising more than one amino acid or mixtures thereof; buffers such as N-(2-acetamido)-2-aminoethyl Alkanesulfonic acid, N-(2-acetamido)iminodiacetic acid, adenosine monophosphate, 2-amino-2-methylpropane-1,3-diol, 2-hydroxy-3-[(2-hydroxy-1,1-dimethylethyl)amino]-1-propanesulfonic acid, N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid, hydroxyethylglycine, Bis-Tris, 1,3-bis(tris(hydroxymethyl)methylamino)propane, calcium alkylbenzenesulfonate, N-cyclohexyl-3-aminopropanesulfonic acid, N-cyclohexyl-2-hydroxy-3-aminopropanesulfonic acid, 2-(cyclohexylamino)ethanesulfonic acid, 3-(bis(2-hydroxyethyl)-2-aminoethanesulfonic acid) )amino)-2-hydroxypropane-1-sulfonic acid, 3-[4-(2-hydroxyethyl)-1-piperazinyl]propanesulfonic acid, 4-(2-hydroxyethyl)-1-piperazinepropanesulfonic acid, 4-(4-(2-hydroxyethyl)piperazin-1-yl)butane-1-sulfonic acid, 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid, 2-hydroxy-3-(4-(2-hydroxyethyl)piperazin-1-yl)propane-1-sulfonic acid, 2-(N-morpholino)ethanesulfonic acid, 4-morpholinobutane-1-sulfonic acid, 3-(N-morpholino)propanesulfonic acid, 3-morpholino-2-hydroxypropanesulfonic acid, piperazine-N,N'-bis( 2-ethanesulfonic acid), piperazine-1,4-bis(2-hydroxypropanesulfonic acid), 4-((1,3-dihydroxy-2-(hydroxymethyl)prop-2-yl)amino)butane-1-sulfonic acid, 3-((1,3-dihydroxy-2-(hydroxymethyl)prop-2-yl)amino)propane-1-sulfonic acid, N-[tris(hydroxymethyl)methyl]-3-amino-2-hydroxypropanesulfonic acid, triethanolamine, N-tris(hydroxymethyl)methyl-2-aminoethanesulfonic acid, trimethylglycine, tris(hydroxymethyl)aminomethane or substituted or functionalized compounds thereof, or mixtures thereof; or mixtures of aminoalkylenephosphonic acids represented by the formula

[0106]

[0107] Where R1 is -CH2-R3, -(CH2) y —NR2 or —(CH2) y —NR—(CH2) y-NR2; and wherein R is -(CH2) x —R3; R2 is —(CH2) x R3; and R3 is -PO3 or -OH, wherein R3 is the same or different, and wherein y is between 1 and 4, and x is between 1 and 4; and corresponding hydrolyzates thereof. In various aspects, the charge-balancing polymers of the present disclosure can be used to inhibit the deposition of scale (such as calcium carbonate, calcium phosphate, calcium phosphonate, calcium oxalate, iron oxide, zinc oxide, and metal silicates), and can further be used to enhance clay and iron dispersion. In some aspects, the charge-balancing polymers of the present disclosure can be used to provide corrosion protection for iron and copper metallurgy and alloys.

[0108] Examples

[0109] The present technology will be further described in the following examples, which should be regarded as illustrative and should not be construed to narrow the scope of the disclosed technology or to limit the scope to any particular embodiment.

[0110] Example 1

[0111] Preparation of acrylic acid / allyloxypropylene glycol copolymer

[0112] General copolymers

[0113] Charge-balanced copolymers of acrylic acid and an allyl monomer having at least one hydroxyl group substituted therewith can be prepared by free radical polymerization. The initiator, chain transfer agent, and acrylic acid are all added dropwise simultaneously to a hot solution containing the allyl monomer. The mixture is then maintained at this temperature until polymerization is complete.

[0114] Specific copolymers

[0115] 0.6 mol of 3-allyloxy-1,2-propanediol was added to a 500 mL round-bottom flask equipped with a stirrer, temperature probe, and reflux condenser. It was then diluted to 50% with DI water and heated to 85°C. Simultaneously, 0.6 mol of acrylic acid was added dropwise over 120 minutes, 0.12 mol of sodium hypophosphite diluted to a 30% solution with DI water was added dropwise over 60 minutes, and 0.06 mol of sodium persulfate diluted to a 30% solution with DI water was added dropwise over 130 minutes. The solution was then heated to 95°C and held there for 90 minutes. The solution was then cooled, and 50% caustic soda was added until the desired pH was reached.

[0116] Example 2

[0117] Preparation of acrylic acid / allyl polyethoxy ammonium sulfate / allyloxypropylene glycol terpolymer

[0118] General purpose terpolymers

[0119] A charge-balanced terpolymer of acrylic acid, an allyl monomer having at least one hydroxyl group substituted, and a sulfonic acid-substituted vinyl monomer can be prepared by free radical polymerization. An initiator, a chain transfer agent, and acrylic acid are all added dropwise simultaneously to a hot solution containing the allyl monomer and the sulfonic acid-substituted vinyl monomer. The mixture is then maintained at this temperature until polymerization is complete.

[0120] Specific terpolymer

[0121] 0.06 mol of allylpolyethoxyammonium sulfate, 0.19 mol of 3-allyloxy-1,2-propylene glycol, and 44.79 g of DI water were added to a 500 mL round-bottom flask equipped with a stirrer, temperature probe, and reflux condenser. The flask was then heated to 85°C. Simultaneously, 1.0 mol of acrylic acid was added dropwise over 120 minutes, 0.16 mol of sodium sulfite diluted to 30% with DI water was added over 60 minutes, and 0.06 mol of sodium persulfate diluted to 30% with DI water was added dropwise over 130 minutes. The solution was then heated to 95°C and held for 90 minutes. The solution was then cooled, and 50% caustic soda was added until the desired pH was reached.

[0122] Example 3

[0123] Generation of hydroxyl monomers

[0124] General purpose ring-opening vinyl epoxide

[0125] Hydroxyl monomers can be produced by acid-catalyzed hydrolysis of vinyl epoxides. Vinyl epoxides can be added to acidic water and maintained at elevated temperatures to produce hydroxy vinyl monomers.

[0126] Specific open loop

[0127] 188.3 mL of DI water and 0.5 mL of 96% sulfuric acid were added to a 500 mL round bottom flask equipped with a stirrer and a temperature probe. 125 g of allyl glycidyl ether was then added dropwise over 60 minutes and maintained at 85°C for 5 hours.

[0128] Example 4

[0129] Calcite inhibition

[0130] Maximum calcite saturation test

[0131] Synthetic water is prepared from chloride or sulfate and has the following composition: 600 ppm Ca as CaCO₃ (CaCl₂*2H₂O), 200 ppm Mg as CaCO₃ (MgSO₄*7H₂O), 325 ppm M-alkalinity as CaCO₃ (150 ppm NaHCO₃, 175 ppm Na₂CO₃), 30 ppm SiO₂ as SiO₂ (Na₂SiO₃*5H₂O), and 20 ppm active desired polymer. A recirculating test rig equipped with pH (sulfuric acid) control, stainless steel heat exchanger sedimentation tubes, and continuous feed and chemical treatment is used. The initial pH is set at 7.7-8.0 and maintained at a constant volume and temperature for a 24-hour period. At this point, turbidity is measured as NTU. Maximum saturation is reached when the overall NTU rises by approximately 1.0 or when visible sediment is observed on the heat exchanger tubes. If the measured turbidity does not show a significant change, the test rig's pH is increased by 0.2 units. This process is repeated until maximum saturation is reached. When the NTU is measured to be below or close to a value of 1.0, the holding period is extended by 12 hours and the NTU is measured again. If it exceeds 1.0 NTU, the test is stopped. If it is below 1.0, the pH is increased in increments of less than 0.2. The maximum calcite saturation is calculated using an equilibrium competing ion program that can be developed in-house, downloaded free of charge from online resources, or purchased from software companies.

[0132] The maximum calcite saturation for control monomers and mixtures, and various copolymers and terpolymers of the present disclosure are shown in Table 1 below, where higher values ​​indicate better polymer performance for calcite suppression:

[0133] Table 1

[0134]

[0135]

[0136] a) Monomer containing allyloxy hydroxyl group b) Monomer containing allyl sulfonic acid c) Monomer containing allyloxy hydroxyl group d) Monomer containing allyl sulfonic acid

[0137] Example 5

[0138] Calcite dispersion

[0139] Heat exchanger calcite dispersion test 1

[0140] A recirculating test rig with standard synthetic water was used, with a set treatment of 20 ppm active material fed continuously with make-up. The test was started at pH 8.0 and the acid feed was stopped and the pH allowed to climb naturally to the highest detectable level. Within a few days, the bulk of the water would turn a cloudy white color and the test was continued in this state for several days. During this period, the pH typically cycled between below and just at maximum saturation, and the extent of the pH reduction depended on the rate of precipitation. The heat exchanger / sedimentation tubes were stainless steel. In addition, pre-weighed standard stainless steel coupons and stainless steel sedimentation coupons were added to the system. Evaluation was based on the visual extent of deposition on the heat exchanger tubes and the weight gain on the standard and mesh coupons.

[0141] The results of the evaluations for control monomers and mixtures and various copolymers and terpolymers of the present disclosure are shown in Table 2 below.

[0142] Table 2

[0143]

[0144] a Monomer containing allyloxy hydroxyl group

[0145] b Monomer containing allyl sulfonic acid

[0146] c Monomers containing allyloxy hydroxyl groups

[0147] d Monomers containing allyl sulfonic acid

[0148] Heat Exchanger Calcite Dispersion Test 2

[0149] A recirculating test rig was equipped with clean stainless steel heat exchanger tubes, pre-weighed stainless steel test specimens, and pre-weighed sediment test specimens. The composition of the test water was identical to the maximum calcite test conditions in Example 4. Prior to commencing the test, the pH was adjusted to 7.8 with sulfuric acid. The polymer being evaluated was dosed at 20 ppm. The recirculating rig was allowed to equilibrate for two to four hours at a sump temperature of 120°F and a heat exchanger skin temperature of 133°F before shutting off pH control. Once these temperatures were reached, the acid controller was shut off, and the unit was configured to naturally increase the pH until significant precipitation occurred, turning the sump milky white. The test rig was configured to recirculate for four days. After four days, the unit was shut off, and the heat exchanger tubes and test specimens were removed from the system. Both were gently rinsed with deionized water and isopropyl alcohol and air-dried for two or more hours. The heat exchanger tubes were given a numerical rating: 5 = clean tube, 4 = slight or localized deposits, 3 = visible white dirt with the metal still visible, 2 = no white dirt and no visible metal surface, 1 = very heavily soiled. The test pieces were weighed and their weight gain was determined, with the lowest possible weight gain being desirable. The results are shown in Table 3 below:

[0150] Table 3

[0151]

[0152] a Monomer containing allyloxy hydroxyl group

[0153] b Monomer containing allyl sulfonic acid

[0154] c Monomers containing allyloxy hydroxyl groups

[0155] d Monomers containing allyl sulfonic acid

[0156] Example 6

[0157] Silicate inhibition

[0158] Maximum MgSiO3 saturation

[0159] Synthetic water is prepared from chloride or sulfate and has the following composition: 780 ppm Mg as CaCO₃ (MgSO₄ * 7H₂O), 230 ppm M-alkalinity as CaCO₃ (Na₂CO₃), 130 ppm SiO₂ as SiO₂ (Na₂SiO₃ * 5H₂O), and 20 ppm active polymer. Note that since synthetic water contains no calcium ions, the only potential foulant in this test under these test conditions is MgSiO₃. A recirculating test rig equipped with pH (sulfuric acid) control, stainless steel heat exchanger sedimentation tubes, and continuous make-up feed and chemical treatment is used. The initial pH is set at 7.7-8.0 and maintained at a constant volume and temperature for a 24-hour period. During this period, turbidity is measured as NTU. Maximum saturation is reached when the overall NTU rises by approximately 1.0 or when visible sediment is observed on the heat exchanger tubes. If the measured turbidity does not show a significant change, the test rig's pH is increased by 0.2 units. This process is repeated until maximum saturation is reached. When the NTU is measured to be below or close to a value of 1.0, the hold period is extended by 12 hours and the NTU is measured again. If it exceeds 1.0 NTU, the test is stopped. If it is below 1.0, the pH is increased in increments of less than 0.2. Maximum MgSiO3 saturation is measured using an equilibrium competitive ion program, which can be developed in-house, downloaded free of charge from online resources, or purchased from software companies.

[0160] The maximum MgSiO3 saturation for control monomers and mixtures, and copolymers and terpolymers of the present disclosure are shown in Table 4 below, where higher values ​​indicate better polymer performance for silicate inhibition:

[0161] Table 4

[0162]

[0163]

[0164] a Monomer containing allyloxy hydroxyl group

[0165] b Monomer containing allyl sulfonic acid

[0166] c Monomers containing allyloxy hydroxyl groups

[0167] d Monomers containing allyl sulfonic acid

[0168] Example 7

[0169] Clay dispersion

[0170] A 1.9L beaker was filled with 500ppm of Ca (CaCl2*2H2O) in the form of CaCO3, 200ppm of Mg (MgSO4*7H2O) in the form of CaCO3, and 50ppm of M-alkalinity (NaHCO3) in the form of CaCO3. The water was filled with 10ppm of the desired polymer of active polymer. The beaker, the standard test has 12 beakers, and the test was performed in triplicate, with the pH adjusted to 7.5. If pH 8.6 was used instead, the results did not change. While vortexing, the kaolin solution was added to the beaker to form a 0.1% dispersion. The beaker was stirred for a few minutes, and then stirring was stopped, and the kaolin settled over a 120 minute period. A sample was taken from the top 40%, and the turbidity was measured to obtain an NTU reading. The higher the NTU reading of the first 40%, the better the performance of the polymer in dispersing the clay.

[0171] The results for control monomers and mixtures, and the copolymers and terpolymers of the present disclosure are shown in Table 5 below.

[0172] Table 5

[0173]

[0174]

[0175] a Monomer containing allyloxy hydroxyl group

[0176] b Monomer containing allyl sulfonic acid

[0177] c Monomers containing allyloxy hydroxyl groups

[0178] d Monomers containing allyl sulfonic acid

[0179] Example 8

[0180] Corrosion inhibition

[0181] Recirculating Drilling Rig Corrosion Testing

[0182] The total volume of the recirculation rig was approximately 1.4 L and was equipped with a drain pump, a bypass rack for the corrosion coupons and probes, a Plexiglas encapsulated heat exchanger, and probes for controlling pH and oxidation reduction potential (ORP). Table 6 below provides the water chemistry of Water A and Water B.

[0183] Table 6

[0184]

[0185]

[0186] Heat exchangers are equipped with electric heaters to control heat loads from 0 to 11,000 BTU / ft 2 / hr and flow meter 0-4.7ft / sec. Corrosion rate was monitored using a corrosion meter mounted on a bypass rack. Weight loss corrosion rate was calculated by inserting the test specimens into the bypass rack during the test period (7-8 days). pH was controlled using sulfuric acid additions. The oxidant feed was controlled by an ORP probe and was controlled to a target residual free chlorine value. Residual free chlorine was measured using Hach powder packets and analytical methods. Water flow was maintained at approximately 4ft / sec and the overall water temperature was controlled by a cooling water loop at 50°C.

[0187] The results after adding the terpolymers of the present disclosure to water chemistries A and B at different dosages are shown in Table 7 below:

[0188] Table 7

[0189]

[0190] a Monomer containing allyloxy hydroxyl group

[0191] d Monomers containing allyl sulfonic acid

[0192] As can be seen in Table 7, adding different dosages of the terpolymer to Water A and Water B did not produce corrosion or deposits on the heat exchangers tested. The polymer without a topping agent can handle the water conditions supersaturated with calcite and calcium phosphate, dispersing any corrosive metals and protecting the metal surfaces from galvanic and general corrosion.

[0193] Additional water chemistry (water CG) is provided in Table 8 below:

[0194] Table 8

[0195] Water C Water D Water E Water F Water G pH 8 8 8 8 8.6 <![CDATA[Ca in the form of CaCo3]]> 400 400 600 600 600 <![CDATA[Mg in the form of CaCO3]]> 150 150 200 200 200 <![CDATA[M-alkalinity in the form of CaCO3]]> 250 250 250 250 400 <![CDATA[SiO2]]> 50 50 30 30 30 <![CDATA[o-PO4]]> 0.5 0.5 1 1 1 Cl 283 283 425 425 425 <![CDATA[SO4]]> 96 96 163 163 163 Al 0.25 0.25 0.25 0.5 0.25 Dispersant (ppm) 10 not applicable not applicable not applicable 0 Corrosion inhibitor (ppm) 25 not applicable not applicable not applicable not applicable Calcite inhibitor (non-P) not applicable not applicable not applicable not applicable 10

[0196] The results after adding the copolymers or terpolymers of the present disclosure to the water chemistry DG at different dosages are shown in Table 9 below.

[0197] Table 9

[0198]

[0199] a Monomer containing allyloxy hydroxyl group

[0200] b Monomer containing allyl sulfonic acid

[0201] d Monomers containing allyl sulfonic acid

[0202] Example 9

[0203] Hydroxyapatite inhibition bottle test

[0204] A water chemistry was developed in which CaPO4 was an unstable material and precipitated from the untreated solution (control). In each test, the results were determined by comparing the control sample to the treated sample. The water chemistry was developed so that no pH adjustment was required in the synthetic water. The following are the test parameters:

[0205] 400 ppm Ca in the form of CaCO3

[0206] 100 ppm Mg in the form of CaCO3

[0207] 35ppm M-alkalinity in the form of CaCO3

[0208] 96ppm SO4

[0209] 283ppm Cl-

[0210] 10ppm PO4

[0211] The pH of the water was 8.2 at the test temperature (70°C) and the Langelier Saturation Index (LSI) was 1.34. The treatment stock solution was adjusted to the same pH before addition to the test bottles. The phosphate concentration was adjusted to 4 ppm. The tests were conducted in clean 100 mL glass bottles and the polymer was dosed at 15 ppm to evaluate a range of different polymers.

[0212] At the end of the 18-hour equilibration period, the percent inhibition was determined chemically by filtered phosphate analysis. This was a "static" test, meaning the bottles were heated but not shaken during the equilibration period. The results are shown in Table 10 below.

[0213] Table 10

[0214]

[0215]

[0216] a Monomer containing allyloxy hydroxyl group

[0217] b Monomer containing allyl sulfonic acid

[0218] c Monomers containing allyloxy hydroxyl groups

[0219] d Monomers containing allyl sulfonic acid

[0220] Although embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not limited thereto and that modifications may be made without departing from the disclosed technology. The scope of the disclosed technology is defined by the appended claims, and all devices, processes, and methods within the meaning of the claims, whether literally or by equivalents, are intended to be embraced therein.

Claims

1. A composition comprising a charge-balancing polymer having the formula: wherein E is the remaining repeating unit after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO3 or -O-; Z is H or a water-soluble cationic moiety; and F is a repeating unit having the formula wherein R4 is H or a lower (C1-C4) alkyl group, R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units, etc.; wherein c and d are positive integers; and e is a non-negative integer.

2. The composition of claim 1, wherein the ethylenically unsaturated compound is one or more of: a carboxylic acid, a sulfonic acid, or a mixture thereof.

3. The composition of claim 2, wherein the ethylenically unsaturated compound is one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, maleic acid or anhydride, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof.

4. The composition according to any one of claims 1 to 3, wherein the composition further comprises a polymer having the formula wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

5. The composition according to any one of claims 1 to 4, wherein the water-soluble cationic moiety is selected from the group consisting of: Na, K, Ca and NH4.

6. The composition according to any one of claims 1 to 5, wherein the molar ratio of c:d:e is in the range of 300:10:1 to 1:1:

300.

7. The composition of any one of claims 1 to 6, wherein n is in the range of about 1 to 20.

8. The composition of any one of claims 1 to 7, wherein the charge-balancing polymer has the formula: wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH(OH)-CH2) n , wherein n ranges from about 1 to 100; X is -O-; and Z is H or a water-soluble cationic moiety; wherein c and d are positive integers.

9. The composition of claim 8, wherein the molar ratio of c:d is in the range of 30:1 to 1:

20.

10. The composition of any one of claims 1 to 9, wherein the charge-balancing polymer has the formula: Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO 3 ; and Z is H or a water-soluble cationic moiety; wherein c, d, and e are positive integers.

11. A method of preventing the formation and deposition of corrosion and fouling-generating species on surfaces exposed to an aqueous system, the method comprising adding to the aqueous system an effective amount of a charge-balancing polymer comprising an ethylenically unsaturated compound and a monomer comprising a nonionic hydroxyl group.

12. The method of claim 11, wherein the method comprises adding to the aqueous system an effective amount of a charge-balancing polymer having the formula: wherein E is the remaining repeating unit after polymerization of an ethylenically unsaturated compound; R1 is H or a lower (C1-C4) alkyl group; G is -CH2- or -CHCH3-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO3 or -O-; Z is H or a water-soluble cationic moiety; and F is a repeating unit having the formula wherein R4 is H or a lower (C1-C4) alkyl group, R5 is a hydroxy-substituted alkyl or alkylene group having 1 to 6 carbon atoms, or a monomer containing a nonionic hydroxy group selected from the group consisting of PEG-OH having 1 to 10 repeating units, etc.; wherein c and d are positive integers; and e is a non-negative integer.

13. The method of claim 12, wherein the ethylenically unsaturated compound is one or more of: a carboxylic acid, a sulfonic acid, or a mixture thereof.

14. The method of claim 13, wherein the ethylenically unsaturated compound is one or more of acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, maleic acid or anhydride, styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, or mixtures thereof.

15. The method of any one of claims 12 to 14, wherein the water-soluble cationic moiety is selected from the group consisting of: Na, K, Ca, and NH4.

16. The method of any one of claims 11 to 15, wherein the monomer comprising a nonionic hydroxyl group is an allyloxy monomer.

17. The method according to claim 16, wherein the allyloxy monomer is 3-allyloxy-1,2-propanediol.

18. The method according to any one of claims 12 to 17, wherein the method further comprises adding an effective amount of a polymer having the formula wherein n is in the range of about 1-100; Z is hydrogen or a water-soluble cationic moiety; and c, d, and e are positive integers.

19. The process according to any one of claims 12 to 18, wherein the molar ratio of c:d:e is in the range of 300:10:1 to 1:1:

300.

20. The method of any one of claims 12 to 19, wherein n is in the range of about 1 to 20.

21. The method of any one of claims 12 to 20, wherein the charge-balancing polymer has the formula: Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n ranges from about 1 to 100; X is -O-; and Z is H or a water-soluble cationic moiety; wherein c and d are positive integers.

22. The method of claim 21, wherein the molar ratio of c:d is in the range of 30:1 to 1:

20.

23. The method of any one of claims 12 to 22, wherein the charge-balancing polymer has the formula: Wherein R1 is H or lower (C1-C4) alkyl; G is -CH2-; R2 is -(CH2-CH2-O) n -or–(CH2—CH(OH)—CH2) n , wherein n is in the range of about 1 to 100; X is SO 3 ; and Z is H or a water-soluble cationic moiety; wherein c, d, and e are positive integers.

24. The method of any one of claims 11 to 23, wherein the aqueous system is a steam generating system.

25. The method of any one of claims 11 to 24, wherein the aqueous system is a cooling water system.

26. The method of any one of claims 11 to 25, wherein the aqueous system is a gas scrubber system.

27. The method of any one of claims 11 to 26, wherein the aqueous system is a closed loop system.

28. The method of any one of claims 11 to 27, wherein the charge balancing polymer is added in combination with at least one or more topping agents.

29. A method of preventing membrane fouling, the method comprising adding an effective amount of the charge-balancing polymer according to any one of claims 1 to 10 to a membrane system.

30. A method of preventing corrosion and scale formation and deposition in an industrial water system, the method comprising adding to the industrial water system an effective amount of the charge-balancing polymer according to any one of claims 1 to 10.

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