Compositions of cationic polyacrylamides, cationic polymer surfactant assemblies and glycerol-based surfactants and methods for their use in flocculation

Abstract

A composition is provided comprising a cationic block copolymer and a cationic polyacrylamide having a charge density ranging from 2% to 100%. In some embodiments, the cationic block copolymer is part of a cationic polymer surfactant ensemble. The composition can be used to remove solids from a solid-liquid mixture. The method may include adding the composition to a solid-liquid mixture; b) stirring the solid-liquid mixture with the composition; and c) removing the solids from the stirred mixture. The method may include a) mixing a cationic polyacrylamide polymer with the cationic polymer surfactant ensemble, thereby forming a conditioned flocculant; b) stirring the conditioned flocculant with the solid-liquid mixture, thereby forming a stirred mixture; and c) removing the solids from the stirred mixture.

Description

[Technical Field]

[0001] The present invention relates to the fields of polymers and surface chemistry, and in particular to the use of polymers and surfactants to enhance cohesion. [Background technology]

[0002] Polyacrylamide-based flocculants are commonly used to aggregate suspended solids in water treatment applications. The mechanism of action for these molecules is to "bridge" small particles in solution, promoting their aggregation into larger particles. The formation of larger particles improves solid-liquid separation in traditional sedimentation methods such as separation, flotation, and filtration. The method of attachment of polyacrylamide to particles can be through electrostatic interactions, van der Waals interactions, or hydrogen bonding. Summary of the Invention

[0003] In an exemplary embodiment of the present invention, a composition is provided that includes: a) a cationic block copolymer; and b) a cationic polyacrylamide having a charge density ranging from 2% to 100%.

[0004] In an exemplary embodiment of the present invention, a) an SMA Quat and b) a cationic polyacrylamide having a charge density ranging from 2% to 100%.

[0005] In an exemplary embodiment of the present invention, a composition is provided that includes: a) a cationic polymeric surfactant ensemble that includes a cationic block copolymer and at least one of i) a nonionic surfactant, ii) a cationic surfactant, and iii) a zwitterionic surfactant; and b) a cationic polyacrylamide having a charge density ranging from 2% to 100%.

[0006] In an exemplary embodiment of the present invention, a) an SMA Quatand a cationic polymeric surfactant ensemble comprising at least one of i) a nonionic surfactant, ii) a cationic surfactant, and iii) a zwitterionic surfactant; and b) a cationic polyacrylamide having a charge density ranging from 2% to 100%.

[0007] In an exemplary embodiment of the present invention, there is provided a composition as described herein, wherein the cationic block copolymer is part of a cationic polymeric surfactant ensemble, and the polymeric surfactant ensemble further comprises a stabilizing surfactant and a sizing surfactant.

[0008] In an exemplary embodiment of the present invention, there is provided a composition described herein, wherein the stabilizing surfactant and the sizing surfactant are each independently selected from at least one of: i) a nonionic surfactant, ii) a cationic surfactant, and iii) a zwitterionic surfactant.

[0009] In an exemplary embodiment of the present invention, a composition is provided that includes a cationic polymeric surfactant ensemble and a cationic polyacrylamide having a charge density ranging from 2% to 100%.

[0010] In an exemplary embodiment of the present invention, there is provided a composition as described herein, wherein the cationic polymeric surfactant ensemble comprises a cationic block copolymer, a stabilizing surfactant, and a sizing surfactant.

[0011] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer is selected from the group consisting of styrene carbamate block copolymers, limonene carbamate block copolymers, limonene maleimide block copolymers, and styrene maleimide block copolymers, and combinations thereof.

[0012] In an exemplary embodiment of the invention, the stabilizing surfactant is an ethoxylated amine, a quaternary ammonium salt, Tween™ 20 (polyoxyethylene (20) sorbitan monolaurate), or 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: [ka] C with 14 H 22 O(C2H4O) n

[0013] Provided are compositions described herein comprising at least one of the following: wherein n=4-5, 9, 10, or 30, or a mixture thereof.

[0013] In exemplary embodiments of the invention, the stabilizing surfactant is an ethoxylated amine, a quaternary ammonium salt, Tween™ 20 (polyoxyethylene (20) sorbitan monolaurate), Tween™ 40 (polyoxyethylene (20) sorbitan monopalmitate), Tween™ 60 (polyoxyethylene (20) sorbitan monostearate), Tween™ 80 (polyoxyethylene (20) sorbitan monooleate), Tergitol™ 15-S-20, Tergitol™ 15-S-40, or 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: [ka] C with 14 H 22 O(C2H4O) n

[0013] Provided are compositions described herein comprising at least one of the following: wherein n=4-5, n=9, n=10, n=30, or mixtures thereof.

[0014] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the stabilizing surfactant comprises at least one of Tween™ 40 (polyoxyethylene (20) sorbitan monopalmitate), Tween™ 60 (polyoxyethylene (20) sorbitan monostearate), Tween™ 80 (polyoxyethylene (20) sorbitan monooleate), Tergitol™ 15-S-20, Tergitol™ 15-S-40, or a mixture thereof.

[0015] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the sizing surfactant is at least one selected from the group consisting of alkyl polyglucosides, lipids, oils, polyglycerol 3-caprylate, nonionic surfactants, sugar-derived surfactants, glycidyl-derived surfactants, fatty acid alcohol-derived surfactants, nonionic surfactants, sugar polyethylene oxide combination surfactants, sugar ester surfactants, sulfonated sugar-based surfactants, aldonamide-based surfactants, amide-sugar-based surfactants, amino alcohol surfactants, amino acid-based surfactants, polyol surfactants, 1,2-glycol surfactants, zwitterionic surfactants, and mixtures thereof.

[0016] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer has a charge density of 10% to 100%.

[0017] In exemplary embodiments of the invention, there are provided compositions described herein, wherein the cationic polyacrylamide polymer has a charge density of 2% to 19%, 20 to 40%, 60 to 79%, 80 to 100%, and combinations thereof.

[0018] In an exemplary embodiment of the invention, there is provided a composition described herein having a charge density range of 30%.

[0019] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer has a charge density of 40%.

[0020] In an exemplary embodiment of the invention, there is provided a composition described herein having a charge density range of 50%.

[0021] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer has a charge density of 80%.

[0022] In an exemplary embodiment of the invention, there is provided a composition described herein having a charge density range of 90%.

[0023] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer has a molecular weight of at least 5,000 Da.

[0024] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer has a molecular weight of at least 7,000 Da.

[0025] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer has a molecular weight of at least 27,000 Da.

[0026] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer has a molecular weight of at least 100,000 Da.

[0027] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 3:1.

[0028] In an exemplary embodiment of the invention, there is provided a composition described herein, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 2:1.

[0029] In an exemplary embodiment of the present invention, there is provided a composition described herein, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 1:1.

[0030] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic block copolymer is an amphiphilic polymer.

[0031] In an exemplary embodiment of the present invention, the cationic polyacrylamide is (2) 6 Da to (12) 10 6 Compositions described herein are provided that have molecular weights in the Da range.

[0032] In an exemplary embodiment of the present invention, the cationic polyacrylamide is (5) 6 Da to (12) 10 6 Compositions described herein are provided that have molecular weights in the Da range.

[0033] In an exemplary embodiment of the present invention, the cationic polyacrylamide is (5) 6 Da to (8) 10 6 Compositions described herein are provided that have molecular weights in the Da range.

[0034] In exemplary embodiments of the invention, there is provided a composition described herein, wherein the cationic polyacrylamide polymer has a charge density of 2-19%, 20-40%, 60-79%, 80-100%, and combinations thereof.

[0035] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM611, CPAM911, CPAM911H, and combinations thereof.

[0036] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM611, CPAM911, CPAM911H, CPAM4808SSH, and combinations thereof.

[0037] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM911, CPAM911H, CPAM4808SSH, and combinations thereof.

[0038] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM911, CPAM911H, and combinations thereof.

[0039] In an exemplary embodiment of the invention, there is provided a composition as described herein, wherein the cationic polyacrylamide polymer is CPAM4808SSH.

[0040] In an exemplary embodiment of the present invention, there is provided a method for removing solids from a solid-liquid mixture, the method comprising: a) mixing a cationic polyacrylamide polymer with a cationic polymer surfactant ensemble, thereby forming a conditioned flocculant; b) agitating the conditioned flocculant with the solid-liquid mixture, thereby forming an agitated mixture; and c) removing solids from the agitated mixture.

[0041] In an exemplary embodiment of the present invention, there is provided a method as described herein, further comprising the step of combining a stabilizing surfactant with the cationic polymer surfactant ensemble.

[0042] In an exemplary embodiment of the invention, there is provided a method as described herein, wherein the step of combining a stabilizing surfactant with the cationic polymeric surfactant ensemble precedes the step of combining a cationic polyacrylamide polymer with the cationic polymeric surfactant ensemble.

[0043] In an exemplary embodiment of the present invention, there is provided a method as described herein, wherein the steps of combining a stabilizing surfactant with a cationic polymeric surfactant ensemble and combining a cationic polyacrylamide polymer with a cationic polymeric surfactant ensemble are performed simultaneously.

[0044] In an exemplary embodiment of the present invention, there is provided a method as described herein, further comprising the step of mixing a sizing surfactant with the cationic polymer surfactant assembly.

[0045] In an exemplary embodiment of the present invention, there is provided a method for removing solids from a solid-liquid mixture, the method comprising the steps of: a) adding a composition described herein to the solid-liquid mixture; b) stirring the solid-liquid mixture with the composition, thereby forming an agitated mixture; and c) removing the solids from the agitated mixture.

[0046] In an exemplary embodiment of the invention, there is provided a method as described herein, wherein the step of removing solids comprises at least one selected from the group consisting of filtration, centrifugation, gravity separation, flotation, skimming, and electromagnetic attraction.

[0047] Other aspects and features of the present invention will become apparent to those of ordinary skill in the art upon review of the following description of specific embodiments of the invention in conjunction with the accompanying figures. [Brief explanation of the drawings]

[0048] 1 is a diagram illustrating an embodiment of the present invention.

[0049] [Figure 1]Figure 1 shows the increase in particle aggregate diameter when various polyglycerol caprylate surfactants are used at different concentrations with [SMAQuat725]:[TX305] at [5]:[2.5]%. Figure 1A shows the particle size distribution of a solution with [SMAQuat725]:[TX305]:[PG3-C] at [5]:[2.5]:[0-5]%. Figure 1B shows the particle size distribution of a solution with [SMAQuat725]:[TX305]:[PG6-C] at [5]:[2.5]:[0-5]%. Figure 1C shows the particle size distribution of a solution with [SMAQuat725]:[TX305]:[PG10-C] at [5]:[2.5]:[0-5]%. All solutions were diluted to 0.1 wt.% prior to particle size measurement. [0%PG-C] (very light gray), [1%PG-C] (light gray), [2%PG-C] (gray), [3%PG-C] (dark gray), [5%PG-C] (black). [Figure 2] Turbidity of 0.3% kaolin coagulated with various concentrations of PG3-C surfactant at [5%:2.5% SMAQuat725]:[TX305]: [0% PG3-C] (black), [1% PG3-C] (dark gray), [2% PG3-C] (gray), [3% PG-C] (light gray), and [5% PG3-C] (very light gray). [Figure 3] Figure 1 shows the improvement of flocculation activity of a medium-charge cationic polyacrylamide for a 0.3% kaolin suspension with the addition of NanoNet™. Praestol™ 835BS (CPAM835) was prepared at a 2% wt. stock solution, and the desired amount of NanoNet™ containing [SMAQuat725]:[TX305]:[PG3-C] at [5]:[2.5]:[2]% (NNA) was added to form the final flocculant formulation, CPAM835:NNA. CPAM835 is a medium-charge density, high molecular weight cationic polyacrylamide (solid line, black circles), and the CPAM835:NNA ratio is 1:0.25 (dashed line, light gray triangles). [Figure 4]Figure 1 shows the effect of NanoNet™ addition on the rheological properties of polyacrylamide solutions. CPAM Hyperdrill™ CP911H (CPAM911H) was prepared at a 2% wt. stock solution, and the desired amount of NanoNet™ containing [SMAQuat725]:[TX305]:[PG3-C] in the ratio [5]:[2.5]:[2]% was added to produce a mixed solution of NanoNet™ and polyacrylamide (CPAM911H:NNA). CPAM911H:NNA (1:0.2 mass ratio) (solid line, black circles), CPAM:NNA (1:0.3 ratio) (dashed line, light gray triangles), CPAM:NNA (1:0.4 ratio) (dashed line, gray squares), CPAM911H:NNA (1:0.6 ratio) (dashed line, dark gray triangles), CPAM911H:NNA (1:1 ratio) (dashed line, light gray circles). [Figure 5] Figure 5 shows the floc stability of CPAM:NNA with shear over time at a constant [CPAM] of 18 ppm in diluted mature fine tailings water matrix A. Figure 5A) CPAM835 is a medium charge density, high molecular weight cationic polyacrylamide. Figure 5B) Praestol™ 853BC (CPAM853) is a very high charge density, high molecular weight cationic polyacrylamide. Figure 5C) Praestol™ 859BS (CPAM859) is an extremely high charge density, high molecular weight cationic polyacrylamide. CPAM is prepared as a 2% wt. stock solution and the desired amount of NanoNet™ containing [SMAQuat725]:[TX305]:[PG3-C] at [5]:[2.5]:[2]% is added. Shearing is performed at 200 rpm. CPAM alone (solid line, black circles), CPAM:NN (1:0.25 wt / wt polyacrylamide:SMAQuat725, dashed line, light gray triangles), CPAM:NN (1:0.6 wt / wt polyacrylamide:SMAQuat725, dashed line, gray squares), CPAM:NN (1:1 wt / wt polyacrylamide:SMAQuat725, dashed line, dark gray triangles). [Figure 6]Figure 6A shows the effect of polyacrylamide concentration on the flocculation efficacy of NanoNet™ and polyacrylamide blends in diluted mature fine tailings (water matrix A). CPAM Hyperdrill™ CP911 was formulated at 3% wt / vol, followed by the addition of various amounts of NanoNet™ A (5:2.5:2% [SMAQuat725]:[TX305]:[PG3-C]) to create multiple flocculant formulations (CPAM911H:NNA). The aggregation activity of CPAM alone (solid line, black circles), CPAM911H:NNA (1:0.25 wt / wt CPAM911H:SMAQuat725; dashed line, light gray triangles), CPAM911H:NNA (1:0.4 wt / wt CPAM911H:SMAQuat725; dashed line, gray squares), and CPAM911H:NNA (1:1 wt / wt CPAM911H:SMAQuat725; dashed line, dark gray triangles) was measured in diluted mature fine tailings. Figure 6B) is the same as 6A, but with CPAM Hyperdrill™ CP911 adjusted to 5% followed by the addition of NanoNet™ A. Figure 6C) is the same as 6A, but with CPAM Hyperdrill™ CP911 adjusted to 6% followed by the addition of NanoNet™ A. [Figure 7] Figure 7 shows the efficacy of NanoNet™ on the flocculation effect of highly charged cationic polyacrylamide (CPAM Hyperdrill™ CP911H) in oily sludge water matrix D (diluted 1:1 in distilled water). Figure 7A) shows the CPAM911H dosage required for complete flocculation with or without NNA (CPAM911H alone (black), CPAM911H:NNA (gray)). Figure 7B) shows the turbidity of the filtrate after dewatering the flocculated matrix D. The turbidity of the filtrate was measured at 269 ppm for CPAM911H and 141 ppm for CPAM911H:NNA (1:0.25 wt / wt CPAM911H:SMAQuat725), which were found to provide comparable settling rates in 7A. [Figure 8]Figure 8 shows the effect of NanoNet™ on CPAM911H during flocculation of a high concentration of mature fine tailings water matrix C. CPAM911H was prepared at 3% and the desired amount of NanoNet™ A was added. Figure 8A shows the optimal dosage to achieve complete flocculation: CPAM (black), CPAM911H:NNA (1:0.25 wt / wt CPAM911H:SMAQuat725, dark gray), CPAM911H:NNA (1:0.4 wt / wt CPAM911H:SMAQuat725, gray), CPAM911H:NNA (1:0.6 wt / wt CPAM911H:SMAQuat725, light gray). Figure 8B shows the drainage rate of flocs relative to the total volume during 60 seconds. CPAM (solid line, black circles), CPAM911H:NNA (CPAM911H:SMAQuat725 at 1:0.25 wt / wt, dashed line, light gray triangles), CPAM911H:NNA (CPAM911H:SMAQuat725 at 1:0.4 wt / wt, dashed line, gray squares), CPAM911H:NNA (CPAM911H:SMAQuat725 at 1:0.6 wt / wt, dashed line, dark gray triangles). [Figure 9] Figure 9 shows the stability analysis of CPAM Hyperdrill™ CP911 and CPAM911H:NNA in 0.3% kaolin. CPAM Hyperdrill™ CP911 was adjusted to 5% CPAM and the desired amount of NanoNet™ containing [SMAQuat725]:[TX305]:[PG3-C] at [5]:[2.5]:[2]% was added to reach a final wt / wt ratio of 1:0.25 CPAM911H:SMAQuat725. Figure 9A) shows the effectiveness of the samples over time in agglomerating 0.3% kaolin compared to a fresh sample at day 0. Figure 9B) shows the change in viscosity over time at 30 rpm. CPAM (black), CPAM911H:NNA (gray). [Figure 10]Figure 1 shows particle size increase for a 5:2% SMAQuat725:Tween™ 20 system with various APG ratios: 1% APG (very light grey), 2% APG (light grey), 2% APG (grey), 2.5% APG (dark grey), and 3% PG3-C (black). [Figure 11] Figure 1 shows the relative sedimentation rates of CPAM835 alone or adjusted with NanoNet™ B (5:2:2.5 wt / vol% SMAQuat725:Tween™ 20:APG). Relative sedimentation rates are reported for CPAM835, whether administered alone (solid line, black circles) or after NanoNet™ adjustment (1:0.5 CPAM835:SMAQuat725 wt ratio, dashed line, light gray triangles). [Figure 12] Figure 1 shows the CPAM911H requirement for complete aggregation in water matrix D when dosed alone in dilute water matrix D (50% in distilled water) or adjusted with two different ratios of NanoNet™ B: CPAM (black), CPAM911H:NNB (1:0.25 CPAM911H:SMAQuat725 wt ratio, gray), CPAM911H:NNB (1:0.5 CPAM911H:SMAQuat725 wt ratio, light gray). [Figure 13] FIG. 1 shows FTIR spectra of SMA-I and quaternized SMA-I (SMAQuat725). [Figure 14]

[0023] Figure 1 shows the H NMR spectra of SMA-I and SMAQuat725. Analysis was performed in DMSO-d at 400 MHz. The asterisk indicates residual solvent. [Figure 15] Figure 1 shows the C NMR spectra of SMA-I and SMAQuat725. Analysis was performed in DMSO-d at 400 MHz. The asterisk indicates the solvent. Residual DMF was observed at 35.7 and 30.7 ppm. [Figure 16] FIG. 1 shows the FTIR spectrum of [SMAQuat725]I. [Figure 17]Figure 1 shows the H NMR spectrum of SMAQuat725 I. Analysis was performed in DMSO-d6. [Figure 18] Figure 1 shows the C NMR spectrum of SMAQuat725 I. Analysis was performed in DMSO-d. [Figure 19] FIG. 1 shows the FTIR spectrum of SMAQuat725 Cl. [Figure 20] 1 shows the H NMR spectrum of SMAQuat725 Cl. Analysis was performed in DMSO-d. [Figure 21] Figure 1 shows the C NMR spectrum of SMAQuat725 Cl. Analysis was performed in DMSO-d. [Figure 22] FIG. 1 shows the FTIR spectrum of cumene-terminated SMA-I. [Figure 23] FIG. 1 shows the FTIR spectrum of cumene-terminated SMAQuat. [Figure 24] Figure 1 shows the effectiveness of NNA-containing cationic polymers with two different end groups (non-cumene-terminated SMAQuat725 and cumene-terminated SMAQuat725, respectively) on the flocculation effect of cationic polyacrylamide solutions. CPAM4808SSH was prepared as a 3% wt / vol stock solution, and the desired amount of NanoNet™ containing [cumene-terminated or non-cumene-terminated SMAQuat725]:[TX305]:[PG3-C] at a ratio of [5]:[2.5]:[2]% (NNA) was added in a 1:0.25 ratio of CPAM:NNA to produce a mixed solution of NanoNet™ and cationic polyacrylamide (CPAM:NNA). CPAM (3% wt / vol, control) (solid line, black circles), CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:non-cumene-terminated SMAQuat725) (dashed line, light gray triangles), CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:cumene-terminated SMAQuat725) (dashed line, gray squares). [Figure 25]Figure 1 shows the effect of adding NanoNet™ containing different SMAQuat polymers with different hydrophobic:hydrophilic ratios on the flocculation effect of cationic polyacrylamide solutions. CPAM CP911H was prepared as a 3% wt / vol stock solution, and the desired amount of NanoNet™ containing [SMAQuat]:[TX305]:[PG3-C] in the ratio [5]:[2.5]:[2]% (NNA) was added to produce a mixed solution of NanoNet™ and cationic polyacrylamide (CPAM:NNA). CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:SMAQuat725) (solid line, black circles), CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:NNA containing SMAQuat130, where the NNA has a hydrophobic:hydrophilic ratio of 2:1) (dashed line, light gray triangles), CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:NNA containing SMAQuat150, where the NNA has a hydrophobic:hydrophilic ratio of 1:1) (dashed line, gray squares), CPAM:NNA (1:0.25 wt / wt ratio of polyacrylamide:NNA containing SMAQuat230, where the NNA has a hydrophobic:hydrophilic ratio of 2:1) (dashed line, dark gray triangles). DETAILED DESCRIPTION OF THE INVENTION

[0050] As used herein, unless the context clearly indicates otherwise, the following terms: Bio-soft™ N1-7 (CAS#34398-01-1); BS7; alcohol ethoxylate; ethoxylated undecan-1-ol; and poly(oxy-1,2-ethanediyl), alpha-undecyl-omega-hydroxy, are generally used interchangeably.

[0051] As used herein, unless the context clearly indicates otherwise, the following terms shall apply: Bio-soft™ N1-9 (CAS#34398-01-1); alcohol ethoxylates; and linear alcohols (C 11 ) ethoxylates are commonly used interchangeably.

[0052] As used herein, unless the context clearly indicates otherwise, the following terms shall apply: Bio-soft™ N25-9 (CAS#68131-39-5); and C 12~15 Ethoxylated alcohols are commonly used interchangeably.

[0053] As used herein, unless the context clearly indicates otherwise, the following terms: Bio-soft™ N91-8 (CAS #68439-46-3); BS N91-8; BS8; and C9-11 ethoxylated alcohol are generally used interchangeably.

[0054] As used herein, unless the context clearly indicates otherwise, the following terms: Bio-soft™ surfactants; and linear alcohol ethoxylates are generally used interchangeably.

[0055] As used herein, unless the context clearly indicates otherwise, the following terms are generally used interchangeably: Brij™ 35 (CAS#9002-92-0); 2-(dodecyloxy)ethan-1-ol; polymers of ethylene glycol and 1-dodecyl alcohol having more than 20 moles of ethylene oxide; polyoxyethylene glycol dodecyl ether; and polyoxyethylene (23) lauryl ether.

[0056] As used herein, unless the context clearly indicates otherwise, the following terms: Brij™ O10 (CAS#9004-98-2); polyoxyethylene (10) oleyl ether; Brij™ 97; 2-[(9Z)-9-octadecen-1-yloxy]ethanol are generally used interchangeably.

[0057] As used herein, unless the context clearly indicates otherwise, the following terms: Brij™ surfactants; alcohol ethoxylates; alcohols, ethoxylated fatty alcohols; laureth compounds; and ethoxylated natural fatty alcohols, polyethylene oxide ethers are generally used interchangeably.

[0058] As used herein, unless the context clearly indicates otherwise, the following terms: CPAM Hyperdrill™ 911; and CPAM 911; a cationic polyacrylamide having a medium molecular weight with an 80% charge density, are generally used interchangeably.

[0059] As used herein, unless the context clearly indicates otherwise, the following terms: CPAM Hyperdrill™ 911H; and CPAM 911H; a cationic polyacrylamide having a medium molecular weight with a charge density of 80% are generally used interchangeably.

[0060] As used herein, unless the context clearly indicates otherwise, the following terms: CPAM Praestol™ 835BS (CAS#372543); and CPAM 835; a cationic polyacrylamide with medium charge density and high molecular weight, are generally used interchangeably.

[0061] As used herein, unless the context clearly indicates otherwise, the following terms: CPAM Praestol™ 853BC (CAS#790265); and CPAM 853; a cationic polyacrylamide with a very high charge density and high molecular weight, are generally used interchangeably.

[0062] As used herein, unless the context clearly indicates otherwise, the following terms: CPAM Praestol™ 859BS (CAS#380868); and CPAM 859; a cationic polyacrylamide with an extremely high charge density and high molecular weight, are generally used interchangeably.

[0063] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Brij™ lauryl-olyl-stearyl-cetyl-cetearyl series; and ethoxylated fatty alcohols are generally used interchangeably.

[0064] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ series surfactants; Tween™ series surfactants; and polysorbates are generally used interchangeably.

[0065] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ 20 (CAS#9005-64-5); Tween™ 20; ethoxylated (20) sorbitan ester based on natural fatty acid (lauric acid); polyoxyethylene (20) sorbitan monolaurate; polyethylene glycol sorbitan monolaurate; polyoxyethylene sorbitan monolaurate; polyethylene glycol sorbitan monolaurate; and polysorbate 20 are generally used interchangeably.

[0066] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ 40 (CAS#9005-66-7); Tween™ 40; polyoxyethylene (20) sorbitan monopalmitate; polyoxyethylene sorbitan monopalmitate; and polysorbate 40 are generally used interchangeably.

[0067] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ 60 (CAS#9005-67-8); Tween™ 60; polyoxyethylene (20) sorbitan monostearate; polyethylene glycol sorbitan monostearate; polyoxyethylene sorbitan monostearate; and polysorbate 60 are generally used interchangeably.

[0068] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ 80 (CAS#9005-65-6); Tween™ 80; ethoxylated sorbitan ester based on natural fatty acid (palmitic acid); polyoxyethylene (20) sorbitan monooleate; polyethylene glycol sorbitan monooleate; polyoxyethylene sorbitan monooleate, and polysorbate 80 are generally used interchangeably.

[0069] As used herein, unless the context clearly indicates otherwise, the following terms: Eco Tween™ 85 (CAS#9005-70-3); Tween™ 85; polyoxyethylene sorbitan trioleate; and polysorbate 85 are generally used interchangeably.

[0070] As used herein, unless the context clearly indicates otherwise, the following terms: FLOPAM™ FO4808SSH; and CPAM4808SSH are generally used interchangeably.

[0071] As used herein, unless the context clearly indicates otherwise, the following terms: Genapol™ X80 (CAS#9043-30-5); GP80; polyethylene glycol monoalkyl ether; oligoethylene glycol monoalkyl ether; and iso-tridecyl alcohol polyglycol ether (8EO) are generally used interchangeably.

[0072] As used herein, unless the context clearly indicates otherwise, the following terms: Myrj™ 52 (CAS#9004-99-3); 2-hydroxyethyl octadecenoate; 2-hydroxyethyl stearate; glycol stearate; 2-hydroxyethyl octadecenoate; and polyoxyethylene (40) stearate are generally used interchangeably.

[0073] As used herein, unless the context clearly indicates otherwise, the following terms: Myrj™ surfactant series; nonionic, ethoxylated fatty acids, polyoxyethylene stearates are generally used interchangeably.

[0074] As used herein, unless the context clearly indicates otherwise, the following terms: Praestol™ 611BC; and CPAM611 are generally used interchangeably.

[0075] As used herein, unless the context clearly indicates otherwise, the following terms are generally used interchangeably: sucrose ester S-1670 stearic fatty acid (CAS# 25168-73-4), [(2S,3S,4S,5R)-3,4-dihydroxy-5-(hydroxymethyl)-2-[(2R,3R,4S,5S,6R)-3,4,5-trihydroxy-6-(hydroxymethyl)oxolan-2-yl]methyl octadecanoate; α-D-glucopyranoside β-D-fructofuranosyl monooctadecanoate; sucrose monostearate; and stearic acid monoester with sucrose.

[0076] As used herein, unless the context clearly indicates otherwise, the following terms shall mean the same or similar substances: Tergitol™ 15-S-20 (CAS#84133-50-6); TG15-S-20; secondary alcohol ethoxylate; and C 12~14 The secondary ethoxylated alcohols are generally used interchangeably.

[0077] As used herein, unless the context clearly indicates otherwise, the following terms shall mean the same or similar substances: Tergitol™ 15-S-40 (CAS#84133-50-6); TG15-S-40; secondary alcohol ethoxylate 41EO, and C 12~14 The secondary ethoxylated alcohols are generally used interchangeably.

[0078] As used herein, unless the context clearly indicates otherwise, the following terms are generally used interchangeably: Tergitol™ 15-S-9 (CAS#84133-50-6); secondary alcohol ethoxylate; sec-alkoxypolyethylene glycol (repeating units = 9, molecular weight of 607 g / mol).

[0079] As used herein, unless the context clearly indicates otherwise, the following terms are generally used interchangeably: Tergitol™ NP-10 (CAS# 127087-87-0); 2-{2-[2-(4-nonylphenoxy)ethoxy]ethoxy}ethan-1-ol; nonylphenol ethoxylate; alkylphenol ethoxylate (APE); mono(p-nonylphenyl) ether; and polyethylene glycol mono(branched p-nonylphenyl) ether; (molecular weight of 682 g / mol).

[0080] As used herein, unless the context clearly indicates otherwise, the following terms: Tergitol™ NP-9 (CAS#127087-87-0); mono(p-nonylphenyl) ether; nonoxynol-9; polyethylene glycol mono(branched p-nonylphenyl) ether; (molecular weight of 616 g / mol) are generally used interchangeably.

[0081] As used herein, unless the context clearly indicates otherwise, the following terms: Tergitol™ surfactants; alcohol ethoxylates; nonionic surfactants, and secondary alcohol ethoxylates are generally used interchangeably.

[0082] As used herein, unless the context clearly indicates otherwise, the following terms are used: Triton™ series surfactants; 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (C with n=30, n=9, n=10, and / or n=4-5); 14 H 22 O(C2H4O) nand poly(ethylene glycol) are commonly used interchangeably.

[0083] As used herein, unless the context clearly indicates otherwise, the following terms: Triton™ CG-110 (CAS#68515-73-1); and alkyl polyglucoside (APG) are generally used interchangeably.

[0084] As used herein, unless the context clearly indicates otherwise, the following terms refer to Triton™ X-305 (CAS#9002-93-1); TX305; polyethylene glycol mono(4-tert-octylphenyl) ether; polyethylene glycol p-octylphenol ether; and 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (C with n=30). 14 H 22 O(C2H4O) n ) are commonly used interchangeably.

[0085] As used herein, the term "SMA Quat " refers to a cationic block copolymer formed from styrene maleimide units. Examples of cationic block copolymers include, but are not limited to, styrene carbamate block copolymers, limonene carbamate block copolymers, limonene maleimide block copolymers, and combinations thereof.

[0086] As used herein, the term "polymeric surfactant aggregate" refers to particles formed by the association between a polymer and a surfactant aggregate. The polymeric surfactant aggregate self-assembles in an aqueous environment, is stable in aqueous solution, and comprises i) a polymer and ii) a surfactant aggregate. The polymeric surfactant aggregate remains associated even at low concentrations compared to the surfactant aggregate in the absence of the polymer. The solution stability of the polymeric surfactant aggregate can be inhibited by the addition of a suitable destabilizing material. Often, the polymeric surfactant aggregate is a colloidal particle comprising an amphiphilic block copolymer and a surfactant, and optionally a tailoring surfactant and / or a size-controlling surfactant. The amphiphilic block copolymer often contains hydrophilic and hydrophobic functional groups. Examples of hydrophilic functional groups include, but are not limited to, amide- or imide-linked ethanol groups, amide- or imide-linked primary, secondary, tertiary, or quaternary amines, and amide- or imide-linked thiol groups. The polymer may also contain amide- or imide-linked zwitterionic groups, such as carboxylated quaternary amines. Examples of hydrophobic functional groups include, but are not limited to, linear or branched alkyl chains, saturated, monounsaturated, or polyunsaturated, aliphatic rings, polycyclic rings, aromatic rings having at least one aromatic ring, styrene, diisobutyl, saturated and unsaturated alkyl chains, limonene, and pinene. In some embodiments, the aromatic ring is alkylated. Typically, the hydrophobic monomer unit has only 3 to as many as 12 carbon atoms. Some examples of polymeric surfactant assemblies are described in PCT International Patent Application Publication No. WO2020 / 113330, published June 11, 2020. As used herein, the term "cationic polymeric surfactant assemblies" refers to polymeric surfactant assemblies having an overall positive charge, in which the surfactant and polymer interact through the association of hydrophobic functional groups.Often, the cationic polymeric surfactant assemblies are formed from a cationic block copolymer (such as poly(styrene-co-maleimide) with pendant amine groups and its derivatives), a stabilizing surfactant (such as a Triton™ series surfactant such as Triton™ X-305 or a Tween™ series surfactant such as Tween™ 20), and a sizing surfactant (such as polyglycerol 3-caprylate or decyl glucoside). Often, NanoNet™ compositions are polymeric surfactant assemblies. In some embodiments, the polymeric surfactant assemblies suitable for use in the present invention are nonionic. In other embodiments, the polymeric surfactant assemblies suitable for use in the present invention are ionic, but should not carry an overall anionic charge.

[0087] As used herein, the term "stabilizing surfactant" refers to a surfactant with a hydrophobic lipid balance (HLB) greater than 14, often without a charge in its hydrophilic head group. In some preferred embodiments, the surfactant comprises a repeating ethoxylate hydrophilic head group, sorbate, or other non-ionic water-soluble group. In some other preferred embodiments, the stabilizing surfactant may possess a cationic hydrophilic head group. The hydrophobic portion of the surfactant may comprise a saturated or unsaturated alkyl chain, or an aromatic group. Non-limiting examples of stabilizing surfactants suitable for use in the present invention include ethoxylated amines, ethoxylated sorbitan ester fatty acids, quaternary ammonium salts, Tween™ 20 (polyoxyethylene (20) sorbitan monolaurate), Tween™ 40 (polyoxyethylene (20) sorbitan monopalmitate), Tween™ 60 (polyoxyethylene (20) sorbitan monostearate), Tween™ 80 (polyoxyethylene (20) sorbitan monooleate), or 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: [ka] C with 14 H22 O(C2H4O) n , where n=4-5, n=9, n=10, or n=30, Eco Tween™ series (Eco Tween™ 20 & Eco Tween™ 80) (100% biodegradable), Tergitol™ 15-S-40 (HLB 18), Brij™ 35 (HLB 16.9), Tergitol™ 15-S-20 (HLB 15), sucrose ester S-1670 stearic acid (HLB 16), Myrj™ 52 (polyoxyethylene monostearate) (HLB 16.9), Eco Brij™ lauryl-olyl-stearyl-cetyl-cetearyl based series (HLB 11-18.8, in some cases acting as either or both a sizing and stabilizing surfactant depending on the degree of ethoxylation and HLB), and / or mixtures thereof. In some embodiments, stabilizing surfactants suitable for use in the present invention are non-ionic, hi other embodiments, stabilizing surfactants suitable for use in the present invention are ionic.

[0088] As used herein, the term "sizing surfactant" refers to a surfactant having a hydrophobic lipid balance (HLB) between 10 and 14. Sizing surfactants may be nonionic, zwitterionic, or cationic, but should not carry an overall anionic charge. Examples of sizing surfactants suitable for use in the present invention include, but are not limited to, Tergitol™ surfactants (nonionic surfactants, secondary alcohol ethoxylates), Bio-soft™ (linear alcohol ethoxylates), alginic acid-based surfactants, sucrose ester fatty acids, Brij™ surfactants (ethoxylated natural fatty alcohols, polyethylene oxide ethers), and the Myrj™ surfactant series (nonionic, ethoxylated fatty acids, polyoxyethylene stearate), as well as refatting surfactants. Refatting agents are often polyglycerol-based, and examples include, but are not limited to, glycol distearate, glycerol oleate, glyceryl cocoate, and / or combinations thereof. In some preferred embodiments, the sizing surfactant has a low HLB. Some non-limiting examples of low HLB sizing surfactants include Bio-soft™ N1-9 (HLB=13.9), Bio-soft™ N25-9 (HLB=13.3), Tergitol™ NP-9 (HLB=12.9), Tergitol™ 15-S-9 (HLB=13.3), Tergitol™ NP-10 (HLB=13.3), BS7 (Bio-soft™ N1-7) (HLB=12.9), GP80 (Genapol™ X80) (HLB=12), BS8 (Bio-soft™ N91-8) (HLB=13.9), ethyl lauroyl arginate HCl cationic (HLB=10.5), Brij™ O10 (HLB=12.4), Eco Brij™ Lauryl-Oliyl-Stearyl-Cetyl-Cetearyl Series (HLB 11-18.8, in some cases acting as either or both sizing and stabilizing surfactants depending on the degree of ethoxylation and HLB) and / or combinations thereof.

[0089] As used herein, the term "polyacrylamide" refers to a polymer formed from nonionic acrylamide subunits and an additional monomer suitable for radical polymerization. The additional monomer selection can be cationic in nature, such as [2-(acryloyloxy)ethyl]trimethylammonium chloride (AETAC), dimethyldiallylammonium chloride (DADMAC), methylacrylacyloxyethyltrimethylammonium chloride (DMC), 2-(methacryloyloxy)ethyltrimethylammonium chloride (MAETAC), or methacrylamidopropyltrimethylammonium chloride (MAPTAC). Cationic polyacrylamide (CPAM) is a polyacrylamide having an overall positive charge. CPAMs can be classified according to their charge density. Medium-charge density CPAMs have a charge density ranging from 20% to 40%. High-charge density CPAMs have a charge density ranging from 40% to 60%. Very high-charge density CPAMs have a charge density ranging from 60% to 79%. Ultra-high charge density CPAMs have charge densities ranging from 80% to 100%. Polyacrylamides may have linear or cross-linked structures. Polyacrylamides suitable for use in the present invention include polyacrylamides that are cationic in nature, with the cationic monomer molar percentage incorporated in the final polymer ranging from 2% to 100%. Polyacrylamides not suitable for use in the present invention include polymers that are anionic in charge in aqueous solution. As used herein, the term "acrylamide subunit" refers to a moiety having the chemical formula -CHCHCONH-.

[0090] As used herein, the term "about" means that strict adherence to the exact numerical value following the term "about" is not absolutely required or essential, and that some small deviation from the exact value is acceptable. In many situations, an error of ±10% is acceptable. In preferred situations, an error of ±5% is acceptable. In yet other preferred situations, an error of ±1% is acceptable. In yet other preferred situations, an error of ±0.1% is acceptable.

[0091] As used herein, the term "moiety" refers to the radical of a molecule that is attached to another moiety.

[0092] As used herein, unless otherwise stated, the term "alkyl," by itself or as part of another substituent, means straight-chain, branched-chain, or cyclic hydrocarbon radicals, or combinations thereof, which may be fully saturated, mono- or polyunsaturated, and have the specified number of carbon atoms (e.g., C1 to C6). 10 or 1 to 10 members means 1 to 10 carbons). Examples of saturated hydrocarbon radicals include, but are not limited to, groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, sec-butyl, cyclohexyl, (cyclohexyl)methyl, cyclopropylmethyl, homologs, and isomers such as n-pentyl, n-hexyl, n-heptyl, n-octyl, and the like. Unsaturated alkyl groups are those having one or more double or triple bonds. Examples of unsaturated alkyl groups include, but are not limited to, vinyl, 2-propenyl, crotyl, 2-isopentenyl, 2-(butadienyl), 2,4-pentadienyl, 3-(1,4-pentadienyl), ethynyl, 1- and 3-propynyl, 3-butynyl, and higher homologs and isomers. The term "alkyl," unless otherwise clear from the context, is meant to include both substituted and unsubstituted forms of the indicated radical. Preferred substituents are provided below.

[0093] As used herein, the term "charge density" refers to the mole percent of monomers in a polymer that contain charged functional groups. In some embodiments, charge density can be related to the properties of the moieties, which can be described by the formula: charge density = charge / volume. The charge density of polyacrylamide is described in Smith-Palmer, T; Wentzell, BR, "Definition of the charge density of acrylamide / acrylate copolymers by tensammetry," Can. J. Chem. 68, 26 (1990).

[0094] As used herein, the term "molecular weight" refers to the molecular mass of a given molecule, measured in units of Daltons (Da). Molecular weight is a weighted average, and the mass of a polymer, in particular, is referred to as molecular weight, often expressed in kDa, although the numerical value is often approximate and representative of the average mass per molecule. As is often the case with polymers, bulk polymer compositions contain individual polymers with different molecular weights and are often obtained and / or sold as an average molecular weight, meaning that some of the individual polymers within the bulk polymer may be above or below the average molecular weight, and many of the individual polymers will have the average molecular weight. It is acceptable in embodiments of the present invention for bulk polymers to be used in which the individual polymers have different molecular weights. It is also acceptable in embodiments of the present invention for bulk polymers to be used in which only the individual polymers have the same molecular weight. Those skilled in the art of polymers will be familiar with this approach to determining the average molecular weight of a polymer and will be able to readily identify both polymers, bulk polymers, and single polymers suitable for use in the compositions of the present invention based on the present teachings.

[0095] As used herein, the term "solid-liquid mixture" refers to a mixture having solid particles suspended therein. Often, the solid-liquid mixture is an aqueous mixture.

[0096] As used herein, the term "agitation" refers to mixing, stirring, or otherwise encouraging components in a liquid or solid-liquid mixture to move and come into contact with one another. Those skilled in the art will be familiar with a wide variety of agitation techniques, and such techniques may be used in embodiments of the present invention.

[0097] In an exemplary embodiment, a composition is provided comprising a cationic polymeric surfactant ensemble and a cationic polyacrylamide (CPAM). The CPAM has a charge density ranging from 2% to 100%. In some preferred embodiments, the CPAM has a charge density ranging from 10% to 100%. In some other preferred embodiments, the CPAM has a low charge density (i.e., ranging from 2% to 19%). In some other preferred embodiments, the CPAM has a medium charge density (i.e., ranging from 20% to 40%). In some other preferred embodiments, the CPAM has a high charge density (i.e., ranging from 40% to 60%). In some other preferred embodiments, the CPAM has a very high charge density (i.e., ranging from 60% to 79%). In some other preferred embodiments, the CPAM has an extremely high charge density (i.e., ranging from 80% to 100%). In some preferred embodiments, the polyacrylamide has a charge density of 30%. In some other preferred embodiments, the polyacrylamide has a charge density of 40%. In some other preferred embodiments, the polyacrylamide has a charge density of 50%. In some other preferred embodiments, the polyacrylamide has a charge density of 80%. In some other preferred embodiments, the CPAM has a charge density of 90%.

[0098] In some exemplary embodiments, the cationic polyacrylamide is (2) 6 From (30) 10 6 In some preferred embodiments, the cationic polyacrylamide has a molecular weight in the range of (5)10 6 From (12) 10 6 In some other preferred embodiments, the cationic polyacrylamide has a molecular weight in the range of (5)106 From (8) 10 6 The poly(2-propenamide) or cationic polyacrylamide polymer "CPAM" is selected from the group consisting of CPAM Praestol™ 835BS (CPAM835), Praestol™ 853BC (CPAM853), Praestol™ 611BC (CPAM611), CPAM Hyperdrill™ 911 (CPAM911), CPAM Hyperdrill™ 911H (CPAM911H), and combinations thereof. In some other preferred embodiments, the cationic polyacrylamide polymer is selected from the group consisting of CPAM Praestol™ 835BS (CPAM835), Praestol™ 853BC (CPAM853), CPAM Hyperdrill™ 911 (CPAM911), CPAM Hyperdrill™ 911H (CPAM911H), and combinations thereof.

[0099] In some exemplary embodiments, the cationic polymer surfactant ensemble comprises a cationic block copolymer, a stabilizing surfactant, and a sizing surfactant. In some of these embodiments, the cationic block copolymer is preferably a styrene maleimide block copolymer or a combination thereof.

[0100] In some exemplary embodiments, the cationic block copolymer has a molecular weight of at least 5,000 Da. In some other preferred embodiments, the cationic block copolymer has a molecular weight of at least 7,000 Da. In some other preferred embodiments, the cationic block copolymer has a molecular weight of at least 27,000 Da. In some other preferred embodiments, the cationic block copolymer has a molecular weight of at least 100,000 Da. In some exemplary embodiments, the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 3:1. In some other exemplary embodiments, the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 2:1. In some preferred exemplary embodiments, the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 1:1. In some preferred exemplary embodiments, the cationic block copolymer is an amphiphilic polymer.

[0101] In some exemplary embodiments, the stabilizing surfactant is a Tween™ surfactant, ethoxylated amine, ethoxylated sorbitan ester fatty acid, quaternary ammonium salt, Eco Tween™ series (Eco Tween™ 20 & Eco Tween™ 80), Tergitol™ 15-S-40 (HLB 18), Brij™ 35 (HLB 16.9), Tergitol™ 15-S-20 (HLB 15), sucrose ester S-1670 stearic fatty acid (HLB 16), Myrj™ 52 (polyoxyethylene monostearate) (HLB 16.9), Eco Brij™ lauryl-olyl-stearyl-cetyl-cetearyl series (HLB 11-18.8, in some cases acting as a sizing and / or stabilizing surfactant depending on the degree of ethoxylation and HLB), 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: [ka] C with 14 H 22 O(C2H4O) n, wherein n=4-5, n=9, n=10, and / or n=30 or any combination thereof, and / or ethoxylated amines, quaternary ammonium salts, and / or 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: [ka] C with 14 H 22 O(C2H4O) n , where n=4-5, n=9, n=10, and / or n=30. In some preferred embodiments, the stabilizing surfactant has the following chemical formula: [ka] where w+x+y+z=20.

[0102] In some exemplary embodiments, the sizing surfactant may be an alkyl polyglucoside, a lipid, an oil, a polyglycerol 3-caprylate surfactant, a polyglycerol 6-caprylate surfactant, a polyglycerol 10-caprylate surfactant, a sugar-derived surfactant, a glycidyl-derived surfactant, a fatty acid alcohol-derived surfactant, a nonionic surfactant, a sugar polyethylene oxide combination surfactant, a sugar ester surfactant, a sulfonated sugar-based surfactant, an aldonamide-based surfactant, an amide-based surfactant, an amino alcohol surfactant, an amino acid-based surfactant, a polyol surfactant, a 1,2 glycol surfactant, a zwitterionic surfactant, and / or any mixture and / or combination thereof. In some other preferred embodiments, sizing surfactants suitable for use in the present invention include, but are not limited to, Tergitol™ surfactants (nonionic surfactants, secondary alcohol ethoxylates), Bio-soft™ (linear alcohol ethoxylates), alginic acid-based surfactants, sucrose ester fatty acids, Brij™ surfactants (ethoxylated natural fatty alcohols, polyethylene oxide ethers), and the Myrj™ surfactant series (nonionic, ethoxylated fatty acids, polyoxyethylene stearates), and refatting surfactants. Refatting agents are often polyglycerol-based, and examples include, but are not limited to, glycol distearate, glycerol oleate, glyceryl cocoate, and / or combinations thereof. In some preferred embodiments, the sizing surfactant has a low HLB.Some non-limiting examples of low HLB sizing surfactants include Bio-soft™ N1-9 (HLB=13.9), Bio-soft™ N25-9 (HLB=13.3), Tergitol™ NP-9 (HLB=12.9), Tergitol™ 15-S-9 (HLB=13.3), Tergitol™ NP-10 (HLB=13.3), BS7 (Bio-soft™ N1-7) (HLB=12.9), GP80 (Genapol™ X80) (HLB=12), BS8 (Bio-soft™ N91-8) (HLB=13.9), ethyl lauroyl arginate HCl cationic (HLB=10.5), Brij™ O10 (HLB=12.4), Eco Brij™ Lauryl-Oliyl-Stearyl-Cetyl-Cetearyl Series (HLB 11-18.8, in some cases acting as either or both sizing and stabilizing surfactants depending on the degree of ethoxylation and HLB) and / or combinations thereof.

[0103] The composition of the present invention can be used to remove solids from a solid-liquid mixture. A method for removing solids from a solid-liquid mixture may include adding the composition of the present invention to the solid-liquid mixture, stirring the composition of the present invention with the solid-liquid mixture, and then removing the solid material from the stirred mixture.

[0104] In some embodiments of the present invention, a method for removing solids from a solid-liquid mixture comprises: a) mixing a cationic polyacrylamide polymer with a cationic polymer surfactant ensemble, thereby forming a conditioned flocculant; b) agitating the conditioned flocculant with the solid-liquid mixture, thereby forming an agitated mixture; c) removing solids from the stirred mixture; Includes:

[0105] In some preferred embodiments, the method further comprises the step of mixing a stabilizing surfactant with the cationic polymeric surfactant ensemble.

[0106] In some other preferred embodiments, the method further comprises the step of mixing a sizing surfactant with the cationic polymer surfactant ensemble.

[0107] In some preferred embodiments, the method further comprises the step of mixing a stabilizing surfactant and a sizing surfactant with the cationic polymer surfactant ensemble.

[0108] In some exemplary embodiments of the methods of the present invention, the stabilizing surfactant is mixed with the cationic polymer surfactant ensemble prior to the step of mixing the cationic polyacrylamide polymer with the cationic polymer surfactant ensemble, hi some other preferred embodiments, the stabilizing surfactant and the cationic polyacrylamide polymer are mixed with the cationic polymer surfactant ensemble simultaneously.

[0109] In some exemplary embodiments of the method of the present invention, the sizing surfactant is mixed with the cationic polymer surfactant ensemble prior to the step of mixing the cationic polyacrylamide polymer with the cationic polymer surfactant ensemble, hi some other preferred embodiments, the sizing surfactant and the cationic polyacrylamide polymer are mixed with the cationic polymer surfactant ensemble simultaneously.

[0110] In some exemplary embodiments of the method of the present invention, the stabilizing surfactant and sizing surfactant are mixed with the cationic polymer surfactant ensemble prior to the step of mixing the cationic polyacrylamide polymer with the cationic polymer surfactant ensemble, hi some other preferred embodiments, the stabilizing surfactant and sizing surfactant and cationic polyacrylamide polymer are mixed with the cationic polymer surfactant ensemble simultaneously.

[0111] Polyacrylamides suitable for use in the present invention can be mixed with the cationic polymeric surfactant ensemble using any preparation method known to those skilled in the art, such as inverse emulsion polymerization, brine dispersion, or as dry polyacrylamide.

[0112] In some exemplary embodiments of the methods according to the present invention, the step of removing solids comprises filtration, centrifugation, gravity separation, flotation, skimming, electromagnetic suction and / or any combination thereof. [Example]

[0113] The following examples illustrate some of the embodiments of the invention described herein, but are not intended to limit the spirit or scope of the invention in any way.

[0114] Methods and Materials Triton™ X-305 (CAS#9002-93-1, TX305), Triton™ CG-110 (CAS#68515-73-1), and alkyl polyglucosides (APG) were purchased from Sigma-Aldrich. CPAM Hyperdrill™ CP911 and CPAM Hyperdrill™ CP911H (desalted polymers) with 80% charge density and medium molecular weight were purchased from SNF. CPAM Praestol™ 835BS (CAS#372543), CPAM Praestol™ 853BC CAS (#790265), CPAM Praestol™ 859BS (CAS#380868 ...9BS (CAS#372543), CPAM Praestol™ 859BS (CAS#380868), CPAM Praestol™ 859BS (CAS Polyglycerol surfactants with 3 to 10 repeating glycerol units and carbonyl alkyl chain lengths of 6 to 18 were purchased from Jinan Dowin Chemical Technology Co. Ltd. The mixtures of polyglycerol surfactants have the following hydrophilic-lipophilic balance (HLB) values: PG3-C / PG10-S has an HLB value of 10 / 12, respectively, and PG6-C / PG10-C / PG10-L has an HLB value of 14 / 15 / 16, respectively. Methyl chloride (CAS#74-87-3) was purchased from Linde. Iodomethane (CAS#74-88-4), cyclohexanone (CAS#108-94-1), and 3-(dimethylamino)-1-propylamine (CAS#109-55-7) were purchased from Sigma-Aldrich. Tergitol™ 15-S-20 solution (TG15-S-20, CAS#84133-50-6, TG15-S-20), Tween™ 20 (CAS#9005-64-5), and APG (Triton™ CG-110, CAS#68515-73-1) were purchased from Sigma-Aldrich. Bio-soft™ N91-8 (BS N91-8, CAS#68439-46-3) was obtained from Stepan. Tergitol™ 15-S-40 (TG15-S-40, CAS#84133-50-6) was obtained from DOW.FLOPAM™ FO4808SSH, which has a very high molecular weight with 80% charge density, was purchased from SNF.

[0115] Cationic polymer: [SMA Quat 725]I or [SMA Quat General synthesis of 725]Cl Styrene-maleic anhydride (3:1 copolymer, 420 g, 23.9% maleic anhydride comonomer content), 3-(dimethylamino)-1-propylamine (128 mL, 104.6 g, 1 equiv.), and 1 L of cyclohexanone were combined at ambient temperature. The mixture was heated to approximately 160°C and refluxed for an additional 3–6 h after dissolving all of the polymer. A thick yellow / orange syrup was obtained and allowed to cool to ambient temperature. A 20% SMA-I solution was prepared by combining equal parts of 40% SMA-I and acetone. One aliquot was transferred to a high-viscosity mixer and combined with methyl iodide (1.0 equiv.) or methyl chloride (1.0 equiv.), respectively. Mixing for 10 minutes at 100 rpm produced a white or off-white entangled polymer. Approximately 50% of the solvent could be decanted from the vessel. The polymer could be dried without washing or washed with acetone.

[0116] Cationic polymer: [SMA Quat-クメン末端 725]I or [SMA Quat-クメン末端 General synthesis of 725]Cl Cumene-terminated SMA (3:1 copolymer (SMA-725C), 50.0 g, 23.9% maleic anhydride (MA) comonomer content, 12.0 g, 0.12 mol) was added to cyclohexanone (300 mL, BP = 156 °C) to produce a solution with a concentration of approximately 16%. The mixture was refluxed until a pale yellow solution was obtained. After the reaction was cooled to ambient temperature, 3-(dimethylamino)-1-propylamine (1 equivalent relative to MA, 12.5 g, 15.2 mL) was added dropwise, turning the solution dark yellow or orange. The mixture was refluxed using a water-cooled condenser and heating mantle for a minimum of 3 hours or until complete conversion was observed by FT-IR spectroscopy, and then cooled to ambient temperature. One aliquot (approximately 5 mL) was removed and dried overnight at 60 °C in a vacuum oven to constant weight. Analysis by IR spectroscopy was consistent with the non-cumene-terminated variant, and complete conversion to the ring-closed maleimide product was observed. The product was not isolated prior to conversion to the desired quaternary product, as described below.

[0117] IR (ATR, cm -1 ):3058, 3025, 2917, 2911, 1715, 1687, 1491, 1448, 1396, 1340, 1221, 1215, 1146, 1027, 956, 908, 755, 697 (see Figure 22).

[0118] The synthesis of cumene-terminated SMA-Quat was carried out using the solvated cumene-terminated SMA-I [SMA Quat-クメン末端 725]I. Quat-クメン末端A solution of

[725] I (approximately 21% in cyclohexanone, 100 mL) was diluted with acetone (100 mL) to a concentration of approximately 10%. The mixture was homogenized in a high-viscosity mixer at 100 rpm and heated to 40°C using an external circulating water bath. The vessel was sealed, and methyl chloride was dosed into the mixer. After a short mixing period, the agitator was stopped, and the reaction was allowed to continue for several minutes. The methyl chloride canister was sealed and pressure was applied. The vessel was opened, and the yellow liquid was decanted. The white solid was washed with acetone (3 × 25 mL, with stirring). The solid was vacuum dried in the high-viscosity mixer at 40°C, followed by drying in a vacuum oven at 70°C overnight. The white solid is water-soluble under acidic, neutral, and basic conditions.

[0119] IR (ATR, cm -1 ):3056, 3021, 2922, 2851, 1765, 1687, 1599, 1491, 1448, 1398, 1344, 1310, 1213, 1178, 1141, 1060, 1027, 956, 906, 751, 697 (see Figure 23).

[0120] Particle size measurement The particle size of stabilized NanoNet™ was measured using a Malvern Zetasizer Nano Series instrument. Samples were diluted to 0.1% (SMA Quat The values ​​were diluted to 1000 kJ / ml (based on a concentration of 725) and measured using a polystyrene cuvette. The average values ​​of three replicate measurements are reported herein.

[0121] Viscosity measurement The viscosity of the polymers was measured at ambient temperature using a Brookfield DV-II+Pro viscometer equipped with a Vane spindle S07 at 30 or 60 revolutions per minute (rpm). To report the viscosity, the sample was sheared until the viscosity measurement reached a steady state. After 2 minutes, the viscosity measurement was recorded and reported.

[0122] Preparation of cationic polyacrylamide (CPAM) solution Dry CPAM (835, 853, 859, Hyperdrill™ CP911, Hyperdrill™ CP911H) mixtures were prepared at 2%, 3%, or 5% w / v in distilled (DI) water using a Jiffy mixer and overhead mixer. For example, 2 g of each 2% stock solution was weighed and slowly added to 98 mL of deionized (DI) water with constant high-speed mixing at 800-900 rpm to disperse the cationic polyacrylamide (CPAM) throughout the solution. After 5 minutes of mixing, the speed was reduced to 400 rpm, and the solution was mixed for 2 hours to ensure complete incorporation of the cationic polyacrylamide into the solution. For administration into the jar test, the cationic polyacrylamide solution was diluted to 0.2% CPAM in DI water and vortexed until homogenous.

[0123] Preparation of cationic polymer surfactant aggregate solutions To prepare the cationic polymer surfactant assemblies referred to as "NanoNet™" solutions, SMA Quat 725 and different SMA Quat Polymers (cumene-terminated, non-cumene-terminated, 130, 150, 230, 725, etc.) were dissolved in DI water and refluxed at 90°C for 3 hours to obtain 2 wt% or 5 wt% solutions, respectively. Surfactants TC CAB35 (30% stock solution in water) or Triton™ X-305 (70% concentration in water) were added to the SMA. Quat 725 solution to obtain the desired final concentration of 1 wt% or 2.5 wt%, respectively, and mixed for 2 minutes. Polyglyceryl surfactants (caprylate, laurate, stearate) were added, vortexed, heated to 60°C for 10 minutes, and cooled to ambient temperature.

[0124] Preparation of CPAM:NanoNet™ Solution Samples were prepared by thoroughly mixing the appropriate amount of NanoNet™ (NN) into cationic CPAM solutions (prepared at concentrations of 2%, 3%, and 5%) at final CPAM:NN ratios of 1:0.25, 1:0.4, 1:0.6, and 1:1%. The mixtures were then vortexed, degassed, and allowed to equilibrate overnight. All samples were homogenous prior to testing. These samples were used for viscosity measurements.

[0125] For the flocculation jar test, samples were diluted to a certain CPAM concentration. 2% CPAM stock samples were diluted to a final CPAM concentration of 0.2%, for CPAM:NN made with 3% CPAM stock samples were diluted to a final CPAM concentration of 0.3%, and for CPAM:NN made with 5% CPAM stock samples were diluted to a final CPAM concentration of 0.5%. Unless otherwise stated, NanoNet™ A is [SMA Quat 725]:[TX305]:[PG3-C] is [5]:[2.5]:[2]%wt / vol(NN A ), and NanoNet™ B consists of [SMA Quat 725]:[Tween™ 20]:[APG]:[5]:[2]:[2.5]wt / vol%, (NN B ) consists of

[0126] Preparation of kaolin-water matrix A kaolin mixture consisting of 0.3% kaolin (Ward's Science, CAS#1332-58-7, 42 g) was added to 14 L of tap water at 20° C. and mixed at 200-300 rpm until dispersed.

[0127] Coagulation test in 0.3% kaolin water A coagulation test was performed to determine the flocculation ability of NN. In a jar test configuration, various doses of NN were administered to six beakers, each containing 400 mL of 0.3% kaolin. The mixture was stirred at 200 rpm for 2 minutes, followed by an additional minute at 30 rpm. During the coagulation process, longer mixing times achieved better coagulation of the suspended kaolin particles. After 5 minutes of sedimentation, the turbidity of the supernatant was measured using an EXTECH TB400 turbidity meter.

[0128] Jar testing and efficacy testing Jar tests were performed using a VELP Scientifica JLT6 Flocculation Tester in a 600 mL beaker using 400 mL of 0.3% kaolin or diluted water matrices A, B, and C (diluted 1 / 60 with tap water). The diluted CPAM or CPAM:NN solution was added to water matrices A, B, and C, respectively, via a Hamilton glass syringe or a 1 mL plastic syringe. The jars were then mixed at 200 rpm for 1 minute. Mixing was then stopped, and the mixtures inside the jars were allowed to settle for 45 seconds. The final minute of this process was recorded and analyzed using video analysis to determine the relative settling rate of each individual jar, which was then plotted against the CPAM dose.

[0129] Flocculation of concentrated water matrices A, B, or C (5 mL of water matrix was mixed in 45 mL tap water to a total volume of 50 mL) was tested by adding the desired amount of diluted CPAM or CPAM:NN and inverting the sample vial after each addition until floc formation appeared. The optimal floc dose at which visible flocs and phase separation of the water matrix were observed was reported.

[0130] For the oily sludge system (water matrix D), the matrix water was diluted with water at a 1:1 ratio and continuously stirred. Then, 10 mL of diluted matrix water was transferred to a 15 mL centrifuge tube, and diluted CPAM or CPAM:NN was added to determine the optimal dosage for complete flocculation of the sludge. To facilitate agitation and flocculation, the falcon tube was gently inverted 20 times after flocculation addition. The sludge drainage rate was recorded over time using a 100-micron pore size sieve. The volume of water discharged into a graduated cylinder was recorded at different time intervals, from 10 seconds to 60 minutes. The turbidity of the discharged water was measured using an EXTECH TB400 turbidity meter.

[0131] Rheological properties of NanoNet™ solutions For the rheometry measurements, a Thermo HAAKE Rheoscope 1 rheometer was applied using a 20 mm diameter spindle geometry and a 1° cone angle (C20 / 1). Experiments were carried out at ambient temperature with strain amplitudes of 0.001–10 and a frequency of 1 Hz.

[0132] water composition The solids content of the different water matrices was determined by constructing a mass balance as follows: (net mass of dried specimen / original mass of specimen) × 100 (Hamilton, D., & Zhang, H. (2011). Solids content of wastewater and manure. Oklahoma Cooperative Extension Service).

[0133] Water Matrix A. Water Matrix A was mature fine tailings water purchased from the Canada Oil Sands Innovation Alliance with a net solids content of 34.7%. [Table 1]

[0134] Water matrix B. Water Matrix B was mature fine tailings water purchased from the Canada Oil Sands Innovation Alliance with a net solids content of 38.2%. [Table 2]

[0135] Water matrix C. Water Matrix C was mature fine tailings water purchased from the Canada Oil Sands Innovation Alliance with a net solids content of 34.4%. [Table 3]

[0136] Water matrix D. Water Matrix D is an oily sludge composed of drilling waste from Alberta, Canada, with a net solids content of 17.9%. [Table 4]

[0137] synthetic water In a jar test setup, synthetic kaolin water is used to evaluate flocculation performance. A kaolin mixture consisting of 0.3% kaolin (Ward's Science, CAS#1332-58-7) was prepared in tap water.

[0138] ICP analysis Inductively coupled plasma optical emission spectroscopy (ICP-OES) analysis of water samples was performed on an Agilent 5110 spectrometer. Samples were prepared by digesting 0.5 mL of water matrix in 1 mL of 70% nitric acid and heating in a water bath at 60 °C for 45 minutes. After digestion, the sample was diluted in 3.5 mL of 1 M nitric acid and processed on the instrument. The ICP was set to an 8 mm radial view mode and a standard IntelliQuant readout. The chemical composition of the sample was detected and reported in mg / L. Samples A through D were diluted to a final solids concentration of 0.04%.

[0139] Image analysis explanation Image analysis software was used to quantify the apparent relative settling velocity of flocculated solids in a standard jar test apparatus. Jar test experiments are often used during bench-scale testing to qualitatively compare the solids separation efficacy of two or more flocculants. This image analysis routine provides a robust and easy method for quantitatively comparing the effectiveness of different flocculants via measured relative settling velocity across the entire dose curve. A camera (Angetube 920U) was used to capture settling videos after flocculant addition and sample mixing, with all camera settings (e.g., exposure) manually configured. Camera parameters were configured to maximize contrast between the opaque, untreated water sample and the beaker background. To measure relative settling velocity, a region of interest (ROI) spanning the width of the beaker and positioned between the top of the fluid and the top of the impeller blades was tracked over time. This ROI measured the average grayscale pixel intensity at each time point. The average grayscale pixel intensity is a measure of brightness and provides an indication of water clarity. The average grayscale pixel intensity values ​​over time (effective water clarity versus time) are then fitted to a sigmoidal function to determine the coefficient of the slope parameter, which is a measure of relative settling velocity. Although the software was not calibrated to estimate floc size, it can be generally inferred that for the systems tested, larger flocs will produce faster relative settling velocities.

[0140] Stability Analysis and Shelf Life In accelerated shelf life, climatic conditions are increased to more extreme levels in order to compress the required test time. This is done by applying the Arrhenius equation to determine the rate of time acceleration based on the increase in temperature. The accelerated aging process is based on the relationship between temperature and reaction rate, where an increase in temperature increases the reaction rate. According to ASTM-F1980, Q 10 Using a pH of 2.0 and 5.3 weeks of storage, this is equivalent to one year of product storage at 22°C. (Bandara, PC et al., (2019), Impact of water chemistry, shelf-life, and regeneration in the removal of different chemical and biological contaminants in water by a model Polymeric Graphene Oxide Nanocomposite Membrane Coating, Journal of Water Process Engineering, 32, 100967.) Samples are tightly sealed in glass vials and stored at 55°C to mimic storage for up to six months, and the viscosity / effectiveness of the samples in 0.3% kaolin compared to fresh samples is measured.

[0141] (Example 1) The increase in cationic polymer surfactant aggregate diameter by the addition of polyglycerol surfactant to the cationic amphiphilic copolymer favors the coagulation effect. [Table 5]

[0142] The results from Example 1 are shown in Figures 1 and 2 and Table 5, and show the effectiveness of the cationic NanoNet™ [SMA Quat725]: [Stabilizing Surfactant] (using TX305 as the stabilizing surfactant) on the cationic polymer surfactant aggregate diameter. Table 5 shows that in the Triton™ X305 (TX305) system, sizing surfactants with HLB values ​​less than 14 result in significant particle expansion, as the addition of PG3-C and PG10-S results in larger polymer surfactant aggregate diameters. As the polymer surfactant aggregates begin to expand, coagulation performance is maximized, as indicated by the best performance in kaolin turbidity removal. Larger cationic polymer surfactant aggregate diameters appear to lead to better particle settling.

[0143] SMA Quat The particle aggregate diameter of cationic NanoNet™, consisting of 725 and TX305 in a ratio of [5]:[2.5]%, respectively, was measured upon the addition of various size-adjusting polyglycerol surfactants at different concentrations. The addition of PG3-C surfactant resulted in the most significant increase in particle aggregate diameter. PG3-C surfactant concentrations greater than 5% may potentially lead to aggregate formation. Based on this example, the optimal PG3-C surfactant concentration determined is 2%. The addition of PG6-C and PG10-C surfactants up to a surfactant concentration of 3% showed little increase in particle aggregate diameter.

[0144] [SMA Quat The coagulation effect of [SMA 725]:[TX305]:[PG3-C] was tested at various PG3-C surfactant concentrations. Figure 2 shows the effect of [SMA 725]:[TX305]:[PG3-C] in 0.3% kaolin in a jar test configuration at various cationic NanoNet™ doses. Quat The turbidity removal rate of

[725] :[TX305]:[PG3-C] at [5]:[2.5]:[0-5]% is shown. The composition with 2% PG3-C achieves the highest coagulation effect and shows the lowest turbidity value. When a coagulant at a concentration of 7.5 ppm is administered into kaolin water, the lowest turbidity value is shown, ranging from 4.8 to 5 NTU. [SMA], which first demonstrated an increase in particle size, QuatIt was found that a blend of

[725] :[TX305]:[PG3-C] at [5]:[2.5]:[2]% resulted in improved clotting effects.

[0145] (Example 2) Enhanced performance of cationic polyacrylamides with different charge densities upon addition of cationic polymer surfactant assemblies. The results of Example 2 are shown in Tables 6A through 6D and Figure 3. Tables 6A-6D show the improvement of CPAM with different charge densities to diluted water matrix A (1 in 60 dilution) upon the addition of NanoNet™. CPAM835 is a medium charge density, high molecular weight cationic polyacrylamide. CPAM853 is a very high charge density, high molecular weight cationic polyacrylamide. CPAM859 is an extremely high charge density, high molecular weight cationic polyacrylamide. CPAM Hyperdrill™ CP911 and CPAM Hyperdrill™ CP911H (desalting polymer) are both cationic polyacrylamide polymers with a medium molecular weight and 80% charge density. All CPAMs were prepared as 2% wt. stock solutions, and NanoNet™ was added to obtain the desired ratio of CPAM:NN. NanoNet™ was used to improve the [SMA Quat 725]:[TX305]:[PG3-C] in the ratio of [5]:[2.5]:[2]%. [Table 6A] [Table 6B] [Table 6C] [Table 6D]

[0146] Tables 6A to 6D show the effectiveness of different NanoNet™ ratios on the flocculation effect of CPAM with respect to the charge density of CPAM. The % improvement is based on the difference in the relative sedimentation velocity of CPAM alone versus CPAM:NN after flocculation in dilute aqueous Matrix A. The results show that NN A until the system becomes saturated, at which point further addition of N N does not increase the flocculation performance. A It shows that flocculant performance increases with increasing concentration. Furthermore, the addition of NanoNet™ A to the lower charge density CPAM835 appears to show the greatest improvement (43-61%, Table 6A).

[0147] Figure 3 shows the relative sedimentation rate of medium-charge CPAM835 and its improvement with the addition of NanoNet™ at a 1:0.25 ratio dosed to kaolin. The results suggest a 50% improvement in the performance of CPAM:NN compared to CPAM alone to achieve the same relative sedimentation rate (calculated based on ppm relative sedimentation rate at different CPAM doses).

[0148] (Example 3) Rheological changes of cationic polyacrylamide combined with cationic polymer surfactant assemblies. The results of Example 3 are shown in Figure 4, which shows the rheological properties of CPAM Hyperdrill™ CP911H with different NanoNet™ ratios, as determined by Young's modulus and loss modulus. The slope of the Han plot G' / G" indicates changes in the apparent microstructure, with materials where G' is greater than G" indicating a highly structured matrix (Li, C. et al., 2017, SiC-fixed organophilic montmorillonite hybrids for poly(phenylene sulfide) composites with enhanced oxidation resistance, RSC Advances, 7(74), pp. 46678-46689). The results show that increasing the concentration of NanoNet™ solution in the CPAM gel reduces the solid-like behavior in the network. Viscosity also evidences this by a decrease in viscosity value, with the viscosity of 2% CPAM (3100 cP) dropping to 2500 cP with the addition of 1:0.3% CPAM:NN. Viscosity is measured at 60 rpm. The decrease in viscosity is beneficial for dosing and material handleability when applying the flocculant formulation through a dosing pump.

[0149] (Example 4) Floc stability of cationic polyacrylamide combined with cationic polymer surfactant aggregates with shear over time. The results of Example 4 are set forth in Figures 5 and 6 and Table 7. Overall, it can be seen that the systems containing the cationic polymer surfactant aggregate "NanoNet™ A" show improved floc strength. [Table 7]

[0150] Table 7 and Figure 5 show the floc strength against shear over time in dilution water matrix A. CPAM or CPAM:NN AAfter the addition of CPAM:NN, flocs are initially formed and allowed to settle, then sheared and settled for 5 minutes, and then sheared and settled for another 5 minutes. Turbidity and relative settling velocity results are reported at these three stages. After 10 minutes of shear, CPAM:NN A Minimal change in sample turbidity is observed. However, the flocs formed by CPAM alone break down over time, increasing turbidity. The addition of NanoNet™ to CPAM also helps maintain a high relative settling velocity in contrast to the CPAM system (see Figure 5). All three different CPAM:NN A Flocs formed with a ratio of 0.05 to 0.15 appear to be less prone to break down under shear over time.

[0151] (Example 5) The addition of the cationic polymer surfactant ensemble "NanoNet™" similarly provides improved performance for cationic polyacrylamide with different concentrations. The results of Example 5 are shown in Figure 6. Figure 6 shows the effect of NanoNet™ on the relative sedimentation rate of dilution water matrix A at different ratios of CPAM concentration. The addition of NanoNet™ consistently increases the relative sedimentation rate at lower CPAM concentrations, regardless of the CPAM concentration (3-6%).

[0152] (Example 6) Improved required dosing of cationic polyacrylamide in combination with cationic polymer surfactant ensembles in the flocculation of high concentrations of mature fine tailings and oily sludge. The results of Example 6 are shown in Figures 7 and 8. Figure 7 shows the aggregation of water matrix D at the optimum dosage. NN A The addition of NN reduced the consumption of CPAM911H by 47.5% and the turbidity of the filtrate after draining / dewatering the sludge also decreased. AFigure 8 shows the optimum dosage required to completely flocculate a high concentration of water matrix C (diluted 1:1). The results show that the higher the concentration of NanoNet™ A in the system, the lower the consumption of CPAM911H (optimal dosage shifts from 297 ppm to 162 ppm). The drainage or dewatering experiments (Figure 8B) also reveal that the addition of NanoNet™ A improves water drainage, a key parameter in sludge dewatering applications. The best performing mixture is CPAM911H:NN A The ratio seems to be (1:0.25).

[0153] (Example 7) Stability and shelf life of cationic polyacrylamide combined with cationic polymer surfactant assemblies "NanoNet™" The results of Example 7 are shown in Figure 9. Figure 9 shows the CPAM911H:NN in an accelerated aging environment (1 day at 55°C = 10 days at room temperature). A The shelf life and stability of the formulation is evaluated. Sample stability is tested against 0.3% kaolin. The addition of NanoNet™ A to CPAM911H forms a stable product with minimal change in potency and viscosity for up to 5 months, while the addition of CPAM alone begins to show substantial signs of degradation after 50 days.

[0154] (Example 8) Formulation of cationic polymer surfactant ensembles with sustainable surfactants. The results of Example 8 are shown in Figure 10 and Table 8. Table 8 describes the screening of sustainable surfactants for the formation of green NanoNet™. [SMA Quat 725]: Particle aggregate diameter and turbidity removal rate of 0.3% kaolin after 5 minutes of settling at 5 ppm surfactant. Particle aggregate diameter determined by ZetaSizer and turbidity removal rate determined by jar test for kaolin alone (1100-1200 NTU). [Table 8-1] [Table 8-2]

[0155] Table 8 shows the SMA QuatThis study provides evidence that the interaction of different green surfactants with 5% 725 kaolin forms a green NanoNet™. Turbidity removal in 0.3% kaolin was tested, and the reduction in turbidity after settling was reported. HLB values ​​were 8.6 for SPAN 20, 17 for Tween™ 20, 15-16 for Tween™ 40, 14.9 for Tween™ 60, 15 for Tween™ 80, 11 for Tween™ 85, and 12-13 for APG (Iglauer, S., Wu, Y., Shuler, P.J., Blanco, M., Tang, Y., & Goddard, W.A. (April 2004). Alkyl polyglycoside surfactants for improved oil recovery. SPE / DOE Symposium on Improved Oil Recovery. OnePetro). As expected, the high HLB surfactant, Tween™ 20, provided the most stable and smallest particle aggregate diameter (approximately 20 nm, Table 8). Particle size increased with effective HLB value (SPAN 20 > Tween™ 85 > APG > Tween™ 60 > Tween™ 80 > Tween™ 40 > Tween™ 20). Surfactants with HLB values ​​below 12 ultimately aggregated, while surfactants with HLB values ​​between 12 and 15 were found to begin to gel at higher concentrations (nearly 3%), confirming that these surfactants were not effective stabilizing surfactants. To form a balanced NanoNet™, APG (Triton™ CG-110) was selected as the sizing surfactant due to its low HLB value, high turbidity removal, and large particle aggregate diameter in the experiments presented in Table 8. Tween™ 20 was chosen as the stabilizing surfactant due to its robust stabilizing efficacy and small particle size. QuatSystems containing 725, Tween™ 20, and APG (as stabilizing and sizing surfactants, respectively) were formulated and optimized in the following sections. Overall, the results presented above indicate that surfactants with an HLB greater than 14-15 are applicable as stabilizing surfactants. Surfactants with an HLB less than 14-15 are used as sizing surfactants.

[0156] Figure 10 shows the SMA Quat This shows that adding more APG to a 5:2%

[725] :[Tween™ 20] system leads to larger particle sizes of NanoNet™. However, samples solidified above 2.5% APG, indicating that the balance of surfactants in NanoNet™ is important for stability and activity.

[0157] (Example 9) Improving the performance of cationic polyacrylamide blended with a green cationic polymer surfactant ensemble (NanoNet™ B). The results of Example 9 are shown in Figures 11-20 and Table 9. Table 9 shows CPAM Hyperdrill™ CP911H:NN (1:0.25% ratio) at 18 ppm in dilution water matrix A (diluted 1 in 60), where NN is [SMA Quat 725]:[Tween™ 20] 5:2% and various ratios of [APG] 1-3%. [Table 9]

[0158] Table 9 shows the SMA Quat This shows that the addition of APG up to 2.5% improves the relative sedimentation rate at a given concentration of CPAM853 in a 725:Tween™ 20:5:2% system. The improvement decreases at 3% APG due to sample aggregation, highlighting the importance of NanoNet™ stability during the formulation process.

[0159] Figure 11 shows the benefit of adding NanoNet™ to CPAM853 in matrix water B. The results show a 50% improvement in the ability to achieve a constant relative settling velocity. Figure 12 shows the dosage required to completely flocculate water matrix D (750 ppm for CPAM853, CPAM853:NN B The results show that the consumption of CPAM was reduced by 46.7% with increasing ratio of NanoNet™ B in the formulation. Figure 13 shows the results of the comparison of SMA-I and quaternized SMA-I (SMA Quat Figure 14 shows the Fourier transform infrared spectroscopy (FTIR) spectra of SMA-I and SMA-II. Quat 725 products 1 1H NMR spectra of SMA-I and SMA-I. Analysis was performed in DMSO-d6 at 400 MHz. The asterisk indicates residual solvent. Quat 725 products 13 16 is a C NMR spectrum. Analysis was performed in DMSO-d6 at 400 MHz. The asterisk indicates the solvent. Residual dimethylformamide was observed at 35.7 and 30.7 ppm. Figure 16 shows the [SMA Quat FTIR of 725I is -1 ): 3381, 3027, 2937, 2857, 1769, 1690, 1490, 1452, 1400, 1349, 1180, 1141, 1027, 962, 919, 759, 699. Figure 17 shows the SMA Quat 725 I 1 1 H NMR spectrum. Analysis was performed in DMSO-d6. 1 H NMR (400 MHz, DMSO-d6): 7.11, 7.09, 6.63, 5.36, 5.35, 5.34, 3.91, 3.35, 3.10, 3.07, 3.07, 3.06, 2.99, 2.96, 2.73, 2.27, 2.25, 2.23, 1.97, 1.96, 1.86, 1.85, 1.80, 1.77, 1.77, 1.75, 1.74, 1.74, 1.64, 1.54. Figure 18 shows the SMA Quat725 I 13 C NMR spectrum. Analysis was performed in DMSO-d. 13 C NMR (100 MHz, DMSO-d6): 210.8, 210.3, 136.1, 128.1, 122.4, 70.6, 62.7, 57.6, 52.2, 43.0, 41.6, 41.3, 34.5, 31.4, 27.8, 27.1, 26.6, 26.4, 24.7, 24.3, 24.3, 22.4, 22.0, 21.3. Figure 19 shows the SMA Quat FT-IR spectrum of 725 Cl. FTIR (cm -1 ):3440, 3362, 3324, 3302, 3273, 3025, 2926, 2855, 1769, 1694, 1493, 1452, 1402, 1351, 1180, 1141, 1027, 964, 919, 755, 699. Figure 20 shows the SMA Quat 725 Cl 1 1 H NMR spectrum. Analysis was performed in DMSO-d6. 1 H NMR (400 MHz, DMSO-d6): 7.10, 6.62, 5.34, 3.91, 3.34, 3.13, 3.09, 3.06, 3.00, 2.27, 2.25, 2.23, 1.96, 1.86, 1.85, 1.77, 1.77, 1.75, 1.74, 1.72, 1.65, 1.64, 1.54, 1.53. Figure 21 shows the SMA Quat 725 Cl 13 C NMR spectrum. Analysis was performed in DMSO-d. 13 C NMR (100 MHz, DMSO-d6): 210.8, 210.3, 136.1, 122.5, 57.7, 52.1, 41.6, 41.3, 31.4, 27.1, 26.7, 26.4, 24.7, 24.3, 24.3, 22.4, 22.0, 20.9.

[0160] (Example 10) The addition of cationic polymeric surfactant ensembles with polymers having different end groups provides improved performance of cationic polyacrylamides. The results of Example 10 are shown in Figure 24. Figure 24 shows that NanoNet™ administered in dilution water matrix A was compared with highly charged CPAM4808SSH and NN at a ratio of 1:0.25. A In this example, the relative settling velocity of NN A [SMA Quat The same blend of

[725] :[TX305]:[PG3-C] in a ratio of 5:2.5:2 was used, with different cationic polymer end groups (i.e., non-cumene terminated SMA, respectively). Quat 725 and cumene-terminated SMA Quat 725). The result is a cumene-terminated SMA. Quat CPAM:NN prepared at 725 A 37.5% improvement in performance of non-cumene terminated SMA Quat CPAM:NN prepared at 725 A This suggests a 32.8% improvement in performance compared to CPAM alone to achieve the same relative sedimentation rate (calculated based on ppm relative sedimentation rate at different CPAM doses).

[0161] (Example 11) Enhancement of the flocculation performance of cationic polyacrylamide with high charge density when NanoNet™ containing cationic polymers with different hydrophobic:hydrophilic ratios is added to the same surfactant ensemble. Figure 25 shows the results of the highly charged CPAM CP911H and NanoNet™ at a ratio of 1:0.25 CPAM:NanoNet™ dosed in dilution water matrix A. A The relative settling velocity of NN is shown. A SMA blended in Quat The effectiveness of different hydrophobic:hydrophilic ratios in the polymer was studied herein, and SMA Quat 725 has a molecular weight of at least 100,000 Da in a 3:1 ratio, and SMA Quat 130 has a molecular weight of at least 7,500 Da in a 2:1 ratio, and SMA Quat 150 has a molecular weight of at least 5,500 Da in a 1:1 ratio, and SMA Quat 230 has a molecular weight of at least 27,000 Da in a 2:1 ratio. A[SMA Quat X]:[TX305]:[PG3-C](SMA Quat X contains the same blend of CPAM:NN (5:2.5:2, where X is 725, 230, 130, 150). The sedimentation rate versus dose of CPAM is A Compared to the blend, SMA Quat NN containing 725 A 44% improvement in performance when added, SMA Quat NN containing 230 A 41.6% performance improvement when SMA is added Quat NN containing 130 A The addition of SMA resulted in a 39.2% improvement in performance. Quat NN containing 150 A The addition of 27.2% of the cellulose acetate showed a performance improvement of 27.2%.

[0162] (Example 12) Formulating cationic polymer surfactant ensembles with sustainable surfactants. [Table 10]

[0163] Table 10 shows the SMA QuatThis study provides evidence that the interaction of 725 5% with different biodegradable surfactants forms the green NanoNet™. Turbidity removal in 0.3% kaolin was tested, and the reduction in turbidity after sedimentation was reported. TG15-S-20 has an HLB value of 15.6, and TG15-S-40 has an HLB value of 18 (Gala Marti, V., Coenen, A., & Schorken, U. (2021). Synthesis of linoleic acid 13-hydroperoxides from safflower oil utilizing lipoxygenase in a coupled enzyme system with in-situ oxygen generation. Catalysts, 11(9), 1119). BS N91-8 has an HLB value of 13.9. The high HLB surfactants TG15-S-40 and TG15-S-20 provided stable small particle diameters (approximately 25 nm and 28 nm, respectively, Table 10). In the NanoNet™ system containing surfactant BS N91-8, signs of gelation were observed in the [SMA Quat 725]:[BS N91-8] was found to exhibit a higher ratio of over 5:2.

[0164] Overall, the results shown in Table 10 confirm that surfactants with an HLB greater than 15 are applicable as stabilizing surfactants. Surfactants with an HLB less than 15 are not effective stabilizing surfactants.

[0165] (Example 13) Formulation of sustainable cationic NanoNet™ with stabilizing and sizing surfactants. [Table 11]

[0166] To form a balanced, sustainable NanoNet™, APG (Triton™ CG-110) and PG3-C were selected as sizing surfactants at 2.5% each due to their sustainability and biodegradability, low HLB value, high turbidity removal rate, and large particle aggregate diameter in the experiments presented in Table 8. Surfactant TG15-S-40 was selected as the stabilizing surfactant due to its green nature and biodegradability, high HLB value, robust stabilization efficacy, and small particle size. TG15-S-40 has an HLB value of 18. The very high HLB value of this surfactant is expected to facilitate the production of a stable NanoNet™. Therefore, SMA Quat 725, TG15-S-40 and APG (as stabilizing surfactant and sizing surfactant, respectively) and SMA Quat A system containing 725, TG15-S-40, and PG3-C (as the stabilizing surfactant and sizing surfactant, respectively) was formed, Table 11. Turbidity removal in 0.3% kaolin was tested and the reduction in turbidity after settling was reported.

[0167] Overall, the results shown in Table 11 indicate that green NanoNet™ can be formed using a variety of sustainable surfactants when the stabilizing surfactant has an HLB value greater than 15 and the sizing surfactant has an HLB value less than 14.

[0168] While various embodiments of the present invention have been disclosed herein, many adaptations and modifications may be made within the scope of the present invention in accordance with the common general knowledge of those skilled in the art. Such modifications include the substitution of known equivalents for any aspect of the invention to achieve the same result in substantially the same way. Numerical ranges include the numerical values ​​defining the range. Moreover, when no range exists, numerical ranges are provided to recite a range of values, as well as any individual value within the recited range that is specifically recited. The term "comprising" is used herein as an open-ended term and is substantially equivalent to the phrase "including, but not limited to," and the term "comprises" has a corresponding meaning. As used herein, the singular forms "a," "an," and "the" include plurals unless the context clearly dictates otherwise. Thus, for example, reference to "an item" includes more than one such item. Citation of a reference herein is not an admission that such reference is prior art to the present invention. Moreover, the appearance of material in the Background section of this specification is not an admission that such material is prior art to the present invention. Any priority document(s) are incorporated herein by reference to the same extent as if each individual priority document were specifically and individually indicated to be incorporated by reference. The present invention includes all embodiments and variations substantially as hereinbefore described and with reference to the examples and drawings.

Claims

1. a) a cationic block copolymer; and b) a cationic polyacrylamide having a charge density ranging from 2% to 100%; A composition comprising:

2. 2. The composition of claim 1, wherein the cationic block copolymer is selected from the group consisting of styrene carbamate block copolymers, limonene carbamate block copolymers, limonene maleimide block copolymers, and styrene maleimide block copolymers, and combinations thereof.

3. The composition of claim 1 or 2, wherein the cationic block copolymer is an amphiphilic polymer.

4. 4. The composition of claim 1, wherein the cationic block copolymer has a molecular weight of at least 5,000 Da.

5. 4. The composition of claim 1, wherein the cationic block copolymer has a molecular weight of at least 7,000 Da.

6. 4. The composition of claim 1, wherein the cationic block copolymer has a molecular weight of at least 27,000 Da.

7. 4. The composition of claim 1, wherein the cationic block copolymer has a molecular weight of at least 100,000 Da.

8. 8. The composition of claim 1, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 3:

1.

9. 8. The composition of claim 1, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 2:

1.

10. 8. The composition of claim 1, wherein the cationic block copolymer comprises a ratio of hydrophobic groups to hydrophilic groups of about 1:

1.

11. Cationic block copolymer is SMA Ｑｕａｔ 2. The composition of claim 1, wherein:

12. Cationic block copolymer is SMA Ｑｕａｔ 725, SMA Ｑｕａｔ 230, SMA Ｑｕａｔ 130, or SMA Ｑｕａｔ 150. The composition of claim 1 .

13. 13. The composition of claim 1, wherein the cationic block copolymer is part of a cationic polymeric surfactant ensemble, the polymeric surfactant ensemble further comprising a stabilizing surfactant and a sizing surfactant.

14. the stabilizing surfactant and the sizing surfactant each independently comprise: i) a nonionic surfactant, ii) a cationic surfactant, and iii) Zwitterionic surfactants The composition of claim 13, wherein the compound is selected from at least one of:

15. The stabilizing surfactant may be an ethoxylated amine, a quaternary ammonium salt, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, (polyoxyethylene (20) sorbitan monooleate, Tergitol™ 15-S-20, Tergitol™ 15-S-40, or 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethanol (chemical formula: 【Chemical 1】 C having １４ H ２２ O (C ２ H ４ O) ｎ 15. The composition of claim 13 or 14, comprising at least one of the following formulas: wherein n=4-5, 9, 10, or 30, or mixtures thereof.

16. 16. The composition of any one of claims 13 to 15, wherein the sizing surfactant is at least one selected from the group consisting of alkyl polyglucosides, lipids, oils, polyglycerol 3-caprylate, nonionic surfactants, sugar-derived surfactants, glycidyl-derived surfactants, fatty acid alcohol-derived surfactants, nonionic surfactants, sugar polyethylene oxide combination surfactants, sugar ester surfactants, sulfonated sugar-based surfactants, aldonamide-based surfactants, amide-sugar-based surfactants, amino alcohol surfactants, amino acid-based surfactants, polyol surfactants, 1,2 glycol surfactants, zwitterionic surfactants, and mixtures thereof.

17. 17. The composition of any one of claims 1 to 16, wherein the cationic polyacrylamide polymer has a charge density of from 10% to 100%.

18. 17. The composition of any one of claims 1 to 16, wherein the cationic polyacrylamide polymer has a charge density of 2% to 19%, 20 to 40%, 60 to 79%, 80 to 100%, and combinations thereof.

19. 17. The composition of claim 1, wherein the cationic polyacrylamide polymer has a charge density of 30%.

20. 17. The composition of claim 1, wherein the cationic polyacrylamide polymer has a charge density of 40%.

21. 17. The composition of claim 1, wherein the cationic polyacrylamide polymer has a charge density of 50%.

22. 17. The composition of claim 1, wherein the cationic polyacrylamide polymer has a charge density of 80%.

23. 17. The composition of claim 1, wherein the cationic polyacrylamide polymer has a charge density of 90%.

24. Cationic polyacrylamide (2) 10 ６ Da to (12) 10 ６ 24. The composition of any one of claims 1 to 23, having a molecular weight in the range of Da.

25. Cationic polyacrylamide (5) 10 ６ Da to (12) 10 ６ 24. The composition of any one of claims 1 to 23, having a molecular weight in the range of Da.

26. Cationic polyacrylamide (5) 10 ６ Da to (8) 10 ６ 24. The composition of any one of claims 1 to 23, having a molecular weight in the range of Da.

27. 27. The composition of any one of claims 1 to 26, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM611, CPAM911, CPAM911H, CPAM4808SSH, and combinations thereof.

28. 27. The composition of any one of claims 1 to 26, wherein the cationic polyacrylamide polymer is selected from the group consisting of CPAM835, CPAM853, CPAM911, CPAM911H, CPAM4808SSH, and combinations thereof.

29. 1. A method for removing solids from a solid-liquid mixture, comprising: a) mixing a cationic polyacrylamide polymer with a cationic polymer surfactant ensemble, thereby forming a conditioned flocculant; b) agitating the conditioned flocculant with the solid-liquid mixture, thereby forming an agitated mixture; c) removing solids from the stirred mixture; A method comprising:

30. 30. The method of claim 29, further comprising mixing a stabilizing surfactant with the cationic polymer surfactant ensemble.

31. 31. The method of claim 30, wherein the step of combining the stabilizing surfactant with the cationic polymeric surfactant ensemble precedes the step of combining the cationic polyacrylamide polymer with the cationic polymeric surfactant ensemble.

32. 31. The method of claim 30, wherein the steps of combining the stabilizing surfactant with the cationic polymeric surfactant ensemble and combining the cationic polyacrylamide polymer with the cationic polymeric surfactant ensemble are performed simultaneously.

33. 33. The method of any one of claims 29 to 32, further comprising the step of mixing a sizing surfactant with the cationic polymer surfactant ensemble.

34. 1. A method for removing solids from a solid-liquid mixture, comprising: a) adding a composition according to any one of claims 1 to 28 to a solid-liquid mixture; b) stirring the solid-liquid mixture with the composition, thereby forming an stirred mixture; c) removing solids from the stirred mixture; A method comprising:

35. 35. The method of any one of claims 29 to 34, wherein the step of removing solids comprises at least one selected from the group consisting of filtration, centrifugation, gravity separation, flotation, skimming, and electromagnetic attraction.

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