Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
  • B01D61/025—Reverse osmosis; Hyperfiltration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/04—Tubular membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/12—Composite membranes; Ultra-thin membranes
  • B01D69/1213—Laminated layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/22—Esters containing halogen
  • C08F220/24—Esters containing halogen containing perhaloalkyl radicals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/38—Esters containing sulfur
  • C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
  • C09D133/16—Homopolymers or copolymers of esters containing halogen atoms
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/04—Characteristic thickness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/18—Membrane materials having mixed charged functional groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/38—Hydrophobic membranes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/42—Ion-exchange membranes

Definitions

• Membranes are excellent candidates for achieving efficient separations: they are scalable, energy efficient, and already widely used in gas and liquid separation processes. Nonetheless, their broader use is limited by the separation capabilities, fouling, and stability of membranes prepared by conventional methods.
• the separation of similarly sized molecules is achieved by using highly energy-intensive methods, such as, chromatography, distillation, and extraction.
• highly energy-intensive methods such as, chromatography, distillation, and extraction.
• the purification of propane and ethene alone accounts for 0.3% of the global energy consumption.
• Utilizing membranes instead of current methods for these challenging separations would significantly reduce energy consumption while increasing the sustainability of these processes.
• Other separations such as benzene derivatives from each other and the isolation of bioactive compounds with added value, are potential processes where membranes could be used.
• Fouling is one of the most relevant fields of study in membrane filtration and is a major obstacle to improving the performance of membrane separation processes. 6 Fouling has detrimental effects on the performance and integrity of membranes. Given the limitations of commercial membranes against foulants,
• SUBSTITUTE SHEET ( RULE 26 ) being able to tune membrane properties like permeance, pore size, and selectivity, while maintaining easy manufacturability and high fouling resistance could transform the water filtration field.
• membranes with higher selectivity can improve the economic feasibility of membrane processes for many applications.
• membranes with tunable pore size and charge at the nanometer scale could be useful in bioseparations, treating complex wastewaters, selective removal of organics (e.g., dyes) and other contaminants from solutions for reuse, water softening, pretreatment of seawater for desalination by reverse osmosis (RO), and final treatment of secondary and tertiary wastewater effluents.
• RO reverse osmosis
• r-ZAC random zwitterionic amphiphilic copolymer
• LBL layer-by-layer
• a multilayer approach that allows the development of membranes based on the formation of polyelectrolyte complexes between multiple oppositely charged water soluble homopolymers. Although these membranes have shown good membrane performance, especially in the removal of micropollutants, there is no significant research on their uncrossed-linked long term stability. Additionally, their fabrication method requires multiple steps and would be complex to scale up. These coatings are typically fabricated several rounds of dip- or spray-coating of alternating anionic and cationic, water-soluble poly electrolytes, separated by rinses. Typically, at least 3-5 bilayers are needed (so 12-20 dip or spray steps).
• the present disclosure provides composite membranes, comprising a porous support; and a selective layer comprising a first copolymer and a second copolymer; wherein: the first copolymer comprises a first plurality of hydrophobic repeat units and a plurality of cationic repeat units; the second copolymer comprises a second plurality of hydrophobic repeat units and a plurality of anionic repeat units; and the first copolymer and the second copolymer are essentially insoluble in water (e.g., under operating conditions).
• the present disclosed provides methods of separating a solute from a solution comprising contacting the solution with a composite membrane disclosed herein.
• the present disclosure provides methods of fabricating a composite membrane disclosed herein comprising applying a first copolymer, as disclosed herein, and a second copolymer, as disclosed herein, to a porous support, thereby fabricating a composite membrane disclosed herein.
• FIG. 1 shows an NMR spectrum of A+ chemical structure indicating copolymerization of two monomer units.
• FIG. 2 shows an NMR spectrum of S- chemical structure indicating copolymerization of the two monomer units.
• FIG. 3 shows a SEM image of SA coated on top of PS35.
• FIG. 4 shows the rejection of neutral dyes by all membranes.
• FIG. 5 shows the S-curves using neutral solutes.
• FIG. 6 shows NaiSOa rejections at different concentrations.
• FIG. 7 shows NaiSOa rejections at different concentrations.
• FIG. 8 shows NaiSCU rejections at different concentrations.
• FIG. 9 shows MgCh rejections at different concentrations.
• FIG. 10 shows MgCh rejections at different concentrations.
• FIG. 11 shows MgCh rejections at different concentrations.
• FIG. 12 shows NaCl rejections at different concentrations.
• FIG. 13 shows NaCl rejections at different concentrations.
• FIG. 14 shows NaCl rejections at different concentrations.
• FIG. 15 shows an oil-in-water 5 h fouling test of S- and SA. The initial flux of these membranes was set at 10 L/m 2 .h.
• FIG. 16 shows an NMR spectrum of M- chemical structure depicting the copolymerization of the two monomer units.
• FIG. 17 shows a SEM image of AM coated on top of PS35.
• FIG. 18 shows a SEM image of 70/30 coated on top of PS35.
• FIG. 19 shows the water permeance of different APEC blend layers.
• FIG. 20 show vitamin B 12 rejection using different APEC blend layers.
• FIG. 21 shows NaiSCU rejections at different concentrations.
• FIG. 22 shows MgCh rejections at different concentrations.
• FIG. 23 shows NaCl rejections at different concentrations.
• FIG. 24 shows an NMR spectrum of A2+ chemical structure indicating copolymerization of the two monomer units.
• FIG. 25 shows an NMR spectrum of S- chemical structure indicating copolymerization of the two monomer units.
• FIG. 26 shows an SEM image of A2S coated on top of PS35.
• FIG. 27 shows the rejection of neutral dyes by A2S, AS, and control membranes.
• FIG. 28 shows S-curves using neutral solutes.
• FIG. 29 shows NaiSCE rejections at different concentrations.
• FIG. 30 shows MgCh rejections at different concentrations.
• FIG. 31 shows NaCl rejections at different concentrations.
• FIG. 32 shows an NMR spectrum of A+ chemical structure indicating copolymerization of the two monomer units.
• FIG. 33 shows an NMR spectrum of S2- chemical structure indicating copolymerization of the two monomer units.
• FIG. 34 shows an SEM image of AS2 coated on top of PS35.
• FIG. 35 shows the Rejection of neutral dyes by AS2, AS, and control membranes.
• FIG. 36 shows NaiSCh rejections at different concentrations.
• FIG. 37 shows MgCh rejections at different concentrations.
• FIG. 38 shows NaCl rejections at different concentrations.
• TFC thin film composite
• a “cationic copolymer” comprising at least two types of repeat units: a hydrophobic repeat unit whose homopolymer would be insoluble in water, and a cationic repeat unit which becomes at least partially positively charged when in water,
• An “anionic copolymer” comprising at least two types of repeat units: a hydrophobic repeat unit as above, and an anionic repeat unit which becomes at least partially negatively charged when in water.
• both of the copolymers are essentially insoluble in water under use conditions.
• each copolymer contains -5-80 wt% of the charged (anionic or cationic) repeat units, more preferably 15-75% of the charged repeat units, and more preferably 30-60% of the charged repeat units.
• This feature differentiates the technology from polyelectrolyte multilayer coatings, which involve water-soluble polyelectrolytes without hydrophobic repeat units deposited from aqueous solutions.
• both of the copolymers may be of average molar mass of at least 30,000 g/mol, more preferably over 50,000 g/mol, and even more preferably of over 100,000 g/mol.
• the two copolymers may be deposited onto the porous support to form a selective layer, for example, by one of the two following methods: i) Sequential coating of each copolymer onto the support, creating at least one layer of anionic copolymer and one layer of cationic copolymer on the support.
• This family of membranes will be termed “bilayer membranes” below, though in principle a higher number of layers is also possible.
• ii) Creating a mixture, or blend, of the two copolymers by dissolving both in the same solvent, then coating this blend onto the support, creating the selective layer. This family of membranes will be termed “blend membranes”.
• the support membrane s effective pore size is significantly higher than that of the TFC membrane; the selective layer significantly changes the rejection properties of the support.
• hydrophobic repeat units include repeat units derived from 2,2- trifluoroethyl methacrylate (TFEMA); other fluorinated acrylates, methacrylates, and acrylamides e.g., pentafluoropropyl methacrylate, heptafluorobutyl methacrylate,
• TFEMA 2,2- trifluoroethyl methacrylate
• acrylamides e.g., pentafluoropropyl methacrylate, heptafluorobutyl methacrylate
• SUBSTITUTE SHEET ( RULE 26 ) pentafluorophenyl methacrylate); styrene; methyl methacrylate; acrylonitrile; 2-chloroethyl methacrylate; 2-bromoethyl methacrylate; allyl methacrylate; other monomers that fit the above criteria. Additionally, hydrophobic monomeric peptides or blocked amino acids with no ionizable/charged groups under use conditions can be used as the hydrophobic monomer unit.
• Exemplary anionic repeat units include repeat units derived from methacrylic acid (MAA); 2-sulfoethyl methacrylate (SEMA); L-tryptophan-methacrylamide; D-tryptophan- methacrylamide; L or D-tryptophan-acrylamide; L or D-alanine-methacrylamide; L or D- alanine-acrylamide; L or D-valine-methacrylamide; L or D-valine-acrylamide; L or D- isoleucine-methacrylamide; L or D-isoleucine-acrylamide; L or D-allo-isoleucine- methacrylamide; L or D-allo-isoleucine-acrylamide; L or D-methionine-methacrylamide; L or D-methionine-acrylamide; L or D-phenylalanine-methacrylamide; L or D-phenylalanine- acrylamide; L or D-tyrosine-methacrylamide; L or D-t
• Exemplary cationic repeat units include repeat units derived from [2- (methacryloyloxy)ethyl] trimethylammonium chloride (MAETA); [3 (methacryloylamino )propyl] trimethylammonium chloride; [2-(acryloyloxy)ethyl] trimethylammonium chloride; (3-acrylamidopropyl)trimethylammonium chloride; 4- vinylbenzyl(triphenyl)phosphonium chloride; (vinylbenzyl)trimethylammonium chloridemethacrylate; 3-vinylaniline; 4-vinylaniline; 2-isopropenylaniline; N-(3- aminopropyl)methacrylamide hydrochloride; N-vinylimidazolium salts; l-allyl-3- vinylimidazolium salts; l-allyl-2methyl-5-vinyl-pyridinium salt; l-allyl-5-vinyl-pyridinium
• SUBSTITUTE SHEET ( RULE 26 ) salt; 1 -Methyl- l-(l-vinylcyclohexyl)pyrrolidinium iodide; methacrylate, acrylate, methacrylamide, acrylamide, styrene, or vinyl derivatives containing amine, pyridinium, imidazolium, phosphonium, pyrrolidinium, or other ionizable/charged groups that carry a positive charge under use conditions. Repeat units that have strong cationic charges (e.g., quaternary amine groups) are preferred. Additionally, monomeric peptides with ionizable/charged groups that carry a positive charge under use conditions can be used as the cationic monomer unit.
• the membranes described herein comprise the following features: i) Lower effective pore size than the support ii) Scalable manufacturing
• the membranes disclosed herein such as the bilayer membranes, comprise the following features:
• Copolymers featuring essentially any pair of ionizable or charged groups i.e., anionic and cationic
• the selectivity/effective pore size of these membranes can be controlled by the hydrophobic/charged monomer ratio of each copolymer. Furthermore, the degree of interlayer mixing, which is affected by factors such as solvent choice, temperature, casting speed, external air flow, and post-processing may influence effective pore size, as well as the chemical nature of the pair of charged groups.
• SUBSTITUTE SHEET ( RULE 26 ) close to neutrally charged to be particularly fouling resistant, mimicking the polyampholyte membranes that have been reported before.
• the bilayer membranes can be designed to be crosslinkable, including at the interface (e.g., via a reaction between the anionic copolymer and the cationic copolymer), further offering stability and tunability.
• These reactions could include reactions between, for example, epoxide with primary amine or alcohol; alkyl halide with tertiary amine; azide with alkyne. This would require either the presence of a third monomer unit in the polymers; and/or a reactive group either in the charged monomer units and/or hydrophobic monomer units.
• the membranes disclosed herein, such as the blend membranes comprise the following features:
• Blend membranes also have a lower effective pore size than the support, and usually than each separate copolymer, quantified through measuring the rejection of a neutral solute. Their effective pore sizes, however, are typically higher than membranes prepared using the bilayer approach with the same copolymers.
• Fouling-resistant as compared with other membranes in the market, and those that are neutrally charged or close to neutrally charged will be particularly highly fouling resistant.
• the membranes disclosed herein such as the bilayer and blend membranes, comprise the following features
• a material system and a method of manufacturing membranes are described that have improved capabilities.
• Past multilayer membranes incorporating charged groups have exclusively focused on water-soluble polyelectrolyte multi-layers, deposited by
• SUBSTITUTE SHEET ( RULE 26 ) adsorption from water; this invention describes rod-coating water-insoluble copolymers from organic solutions. The performance of the membranes is highly tunable and adaptable.
• the membranes disclosed herein act differently than polyelectrolyte multi-layer membranes.
• the formation of a tightly interwoven/complexed layer at the interface of two separately deposited layers has not been reported in any other systems.
• the disclosed invention can be used in many filtration processes where size- and charge-selective separations are needed, including water and wastewater treatment, and nutrient separation and recovery.
• the present disclosure provides a composite membrane, comprising a porous support; and a selective layer comprising a first copolymer and a second copolymer; wherein: the first copolymer comprises a first plurality of hydrophobic repeat units and a plurality of cationic repeat units; the second copolymer comprises a second plurality of hydrophobic repeat units and a plurality of anionic repeat units; and the first copolymer and the second copolymer are essentially insoluble in water (e.g., under operating conditions).
• the first copolymer and the second copolymer are insoluble in water (e.g., under operating conditions).
• the composite membrane is a thin film composite membrane.
• the composite membrane has a thickness of about 20 pm to about 1,000 pm. In certain embodiments, the composite membrane has a thickness of about 50 pm to about 200 pm.
• the selective layer has a thickness of about 30 nm to about 5 pm. In certain embodiments, the selective layer has a thickness of about 30 nm to about 1,000 nm. In certain embodiments, the selective layer has a thickness of about 10 nm, about 25 nm, about 50 nm, about 75 nm, about 100 nm, about 125 nm, about 150 nm, about 175 nm, about 200 nm, about 225 nm, about 250 nm, about 275 nm, about 300 nm, about 325 nm, about 350 nm, about 375 nm, about 400 nm, about 425 nm, about 450 nm, about 475 nm, about 500 nm, about 525 nm, about 550 nm, about 575 nm, or about 600 nm.
• the selective layer has a thickness of about 400 nm, about 425 nm, about 450 nm, about 475 nm, about 500 nm, about 525 nm, about 550 nm, about 575 nm, or about 600 nm.
• the plurality of cationic repeat units is partially positively charged in water (e.g., in water at a neutral pH or in water under operating conditions).
• the plurality of cationic repeat units is positively charged in water (e.g., in water at a neutral pH or in water under operating conditions).
• the plurality of anionic repeat units is partially negatively charged in water (e.g., in water at a neutral pH or in water under operating conditions). In certain embodiments, the plurality of anionic repeat units is negatively charged in water (e.g., in water at a neutral pH or in water under operating conditions).
• the selective layer consists essentially of the first copolymer and a second copolymer.
• the first copolymer comprises about 5 - 80 wt% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 wt% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 30 - 60 wt% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 80 wt% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 5 - 80 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 mol% of the plurality of cationic repeat units.
• the first copolymer comprises about 5 - 80 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 30 - 60 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 10 mol%, about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 5 - 80 mol% of the plurality of cationic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 mol% of the plurality of cationic repeat units.
• the first copolymer comprises about 5 - 80 wt% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 wt% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 30 - 60 wt% of the plurality of the first plurality of hydrophobic repeat units.
• the first copolymer comprises about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 80 wt% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 5 - 80 wt% of the
• the first copolymer comprises about 15 - 75 wt% of the plurality of the first plurality of hydrophobic repeat units.
• the first copolymer comprises about 5 - 80 mol% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 mol% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 30 - 60 mol% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 10 mol%, about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol% of the plurality of the first plurality of hydrophobic repeat units.
• the first copolymer comprises about 5 - 80 mol% of the plurality of the first plurality of hydrophobic repeat units. In certain embodiments, the first copolymer comprises about 15 - 75 mol% of the plurality of the first plurality of hydrophobic repeat units.
• the second copolymer comprises about 5 - 80 wt% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 wt% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 30 - 60 wt% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 80 wt% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 5 - 80 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 mol% of the plurality of anionic repeat units.
• the second copolymer comprises about 5 - 80 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 30 - 60 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 10 mol%, about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 5 - 80 mol% of the plurality of anionic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 mol% of the plurality of anionic repeat units.
• the second copolymer comprises about 5 - 80 wt% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the
• SUBSTITUTE SHEET ( RULE 26 ) second copolymer comprises about 15 - 75 wt% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 30
• the second copolymer comprises about 10 wt%, about 20 wt%, about 30 wt%, about 40 wt%, about 50 wt%, about 60 wt%, about 70 wt%, or about 80 wt% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 5 - 80 wt% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 wt% of the plurality of the second plurality of hydrophobic repeat units.
• the second copolymer comprises about 5 - 80 mol% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 mol% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 30
• the second copolymer comprises about 10 mol%, about 20 mol%, about 30 mol%, about 40 mol%, about 50 mol%, about 60 mol%, about 70 mol%, or about 80 mol% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 5 - 80 mol% of the plurality of the second plurality of hydrophobic repeat units. In certain embodiments, the second copolymer comprises about 15 - 75 mol% of the plurality of the second plurality of hydrophobic repeat units.
• the first copolymer has an average molar mass of at least 50,000 g/mol. In certain embodiments, the first copolymer has an average molar mass of at least 100,000 g/mol. In certain embodiments, the first copolymer has an average molar mass of 20,000 g/mol to about 500,000 g/mol. In certain embodiments, the first copolymer has an average molar mass of 30,000 g/mol to about 500,000 g/mol. In certain embodiments, the first copolymer has an average molar mass of 50,000 g/mol to about 500,000 g/mol. In certain embodiments, the first copolymer has an average molar mass of 100,000 g/mol to about 500,000 g/mol.
• the second copolymer has an average molar mass of at least 50,000 g/mol. In certain embodiments, the second copolymer has an average molar mass of at least 100,000 g/mol. In certain embodiments, the second copolymer has an average molar mass of 20,000 g/mol to about 500,000 g/mol. In certain embodiments, the second copolymer has an average molar mass of 30,000 g/mol to about 500,000 g/mol. In certain embodiments, the second copolymer has an average molar mass of 50,000 g/mol to about 500,000 g/mol. In
• the second copolymer has an average molar mass of 100,000 g/mol to about 500,000 g/mol.
• the first copolymer and the second copolymer are sequentially layered on the porous support (e.g., the first copolymer and the second copolymer have been applied to the porous support layer sequentially).
• the first copolymer is the first layer (e.g., the outermost layer) and the second copolymer is the second layer (e.g., the first copolymer layer is on the second copolymer layer and the second copolymer layer is in contact with the porous support).
• the second copolymer is the first layer (e.g., the outmost layer) and the first copolymer is the second layer (e.g., the second copolymer layer is on the first copolymer layer and the first copolymer layer is in contact with the porous support).
• the first copolymer and the second copolymer are intermingled on the porous support (e.g., the first copolymer and the second copolymer form a homogenous layer on the porous support).
• the first plurality of hydrophobic repeat units comprises repeat units derived from acrylates (e.g., alkyl acrylates, fluorinated acrylates or methacrylates), acrylamides (e.g., fluorinated acrylamides), styrene, or hydrophobic amino acids.
• the first plurality of hydrophobic repeat units comprises repeat units derived from methacrylate.
• the first plurality of hydrophobic repeat units comprises repeat units derived from 2, 2 -trifluoroethyl methacrylate (TFEMA), pentafluoropropyl methacrylate, heptafluorobutyl, pentafluorophenyl methacrylate, styrene, methyl methacrylate, acrylonitrile, 2-chloroethyl methacrylate, 2-bromoethyl methacrylate, and allyl methacrylate.
• the first plurality of hydrophobic repeat units comprises repeat units derived from 2,2-trifluoroethyl methacrylate (TFEMA).
• the second plurality of hydrophobic repeat units comprises repeat units derived from acrylates (e.g., alkyl acrylates, fluorinated acrylates or methacrylates), acrylamides (e.g., fluorinated acrylamides), styrene, or hydrophobic amino acids.
• the second plurality of hydrophobic repeat units comprises repeat units derived from methacrylate.
• the second plurality of hydrophobic repeat units comprises repeat units derived from 2,2-trifluoroethyl methacrylate (TFEMA), pentafluoropropyl methacrylate, heptafluorobutyl, pentafluorophenyl methacrylate, styrene, methyl methacrylate, acrylonitrile, 2-chloroethyl methacrylate, 2-bromoethyl methacrylate, and allyl methacrylate.
• the second plurality of hydrophobic repeat units comprises repeat units derived from 2,2-trifluoroethyl methacrylate (TFEMA).
• the plurality of cationic repeat units comprises repeat units derived from acrylate, acrylamide, styrene, or vinyl monomers substituted with amine, pyridinium, imidazolium, phosphonium, or pyrrolidinium.
• the plurality of cationic repeat units comprises repeat units derived from [2- (methacryloyloxy)ethyl] trimethylammonium chloride (MAETA), [3 (methacryloylamino )propyl] trimethylammonium chloride, [2-(acryloyloxy)ethyl] trimethylammonium chloride, (3-acrylamidopropyl)trimethylammonium chloride; 4- vinylbenzyl(triphenyl)phosphonium chloride, (vinylbenzyl)trimethylammonium chloridemethacrylate, 3-vinylaniline, 4-vinylaniline, 2-isopropenylaniline, N-(3- aminopropyl)methacrylamide hydrochloride, N-vinylimidazolium, l-allyl-3- vinylimidazoliums, l-allyl-2methyl-5-vinyl-pyridinium, l-allyl-5-vinyl-pyridinium, or 1- Me
• the plurality of anionic repeat units comprises repeat units derived from acrylate, acrylamide, styrene, or vinyl monomers substituted with carboxylic acid, sulfonate, or phosphate. In certain embodiments, the plurality of anionic repeat units comprises repeat units derived from methacrylate.
• the plurality of anionic repeat units comprises repeat units derived from methacrylic acid (MAA), 2- sulfoethyl methacrylate (SEMA), L-tryptophan-methacrylamide, D-tryptophan-methacrylamide, L or D-tryptophan- acrylamide, L or D-alanine-methacrylamide, L or D-alanine-acrylamide, L or D-valine- methacrylamide, L or D-valine-acrylamide, L or D-isoleucine -methacrylamide, L or D- isoleucine-acrylamide, L or D-allo-isoleucine-methacrylamide, L or D-allo-isoleucine- acrylamide, L or D-methionine-methacrylamide, L or D-methionine-acrylamide, L or D- phenylalanine-methacrylamide, L or D-phenylalanine-acrylamide, L or D-tyrosine- me
• MAA
• the plurality of anionic repeat units comprises repeat units derived from 2-sulfoethyl methacrylate. In other preferred embodiments, the plurality of anionic repeat units comprises repeat units derived from methacrylic acid.
• the first copolymer is a block copolymer. In certain embodiments, the first copolymer is a statistical (e.g., approximately random) copolymer. In certain preferred embodiments, the first copolymer is a random copolymer. In certain embodiments, the second copolymer is a graft copolymer or a comb- shaped copolymer.
• the second copolymer is a block copolymer.
• the first copolymer is a statistical (e.g., approximately random) copolymer.
• the second copolymer is a random copolymer.
• the second copolymer is a graft copolymer or a comb-shaped copolymer.
• the effective pore size of the composite membrane is less than the effective pore size of a membrane prepared by coating only the first copolymer or only the second copolymer on the same porous support.
• the effective pore size is quantified by measuring the rejection of a neutral (e.g., uncharged) solute.
• the first copolymer is crosslinked.
• the second copolymer is crosslinked.
• the present disclosure provides methods of separating a solute from a solution, comprising contacting the solution with a composite membrane.
• the solution is passed e.g., filtered) through the composite membrane.
• the solute is a salt (e.g., sodium chloride).
• the solution is seawater.
• the present disclosure provides methods of fabricating a composite membrane disclosed herein comprising applying a first copolymer, as disclosed herein, and a second copolymer, as disclosed herein, to a porous support, thereby fabricating a composite membrane disclosed herein.
• the first copolymer and the second copolymer are applied to the porous support layer sequentially, thereby forming a bilayer membrane. In certain embodiments, the first copolymer is applied first, and the second copolymer is applied second. In certain embodiments, the first copolymer is applied second, and the second copolymer is applied first. In other embodiments, the first copolymer and the second copolymer are applied
• the first copolymer is dissolved in a protic solvent (e.g., methanol) prior to application.
• the second copolymer is dissolved in a protic solvent (e.g., methanol) prior to application.
• the first copolymer and the second copolymer are each dissolved in a protic solvent (e.g., methanol) prior to application.
• the terms “optional” or “optionally” mean that the subsequently described event or circumstance may occur or may not occur, and that the description includes instances where the event or circumstance occurs as well as instances in which it does not.
• “optionally substituted alkyl” refers to the alkyl may be substituted as well as where the alkyl is not substituted.
• substituents and substitution patterns on the compounds of the present invention can be selected by one of ordinary skilled person in the art to result chemically stable compounds which can be readily synthesized by techniques known in the art, as well as those methods set forth below, from readily available starting materials. If a substituent is itself substituted with more than one group, it is understood that these multiple groups may be on the same carbon or on different carbons, so long as a stable structure results.
• the term “optionally substituted” refers to the replacement of one to six hydrogen radicals in a given structure with the radical of a specified substituent including, but
• SUBSTITUTE SHEET not limited to: hydroxyl, hydroxyalkyl, alkoxy, halogen, alkyl, nitro, silyl, acyl, acyloxy, aryl, cycloalkyl, heterocyclyl, amino, aminoalkyl, cyano, haloalkyl, haloalkoxy, -OCO-CH2-O- alkyl, -OP(O)(O-alkyl)2 or -CH2-OP(O)(O-alkyl)2.
• “optionally substituted” refers to the replacement of one to four hydrogen radicals in a given structure with the substituents mentioned above. More preferably, one to three hydrogen radicals are replaced by the substituents as mentioned above. It is understood that the substituent can be further substituted.
• alkyl refers to saturated aliphatic groups, including but not limited to C1-C10 straight-chain alkyl groups or C1-C10 branched-chain alkyl groups.
• the “alkyl” group refers to Ci-Ce straight-chain alkyl groups or Ci-Ce branched- chain alkyl groups.
• the “alkyl” group refers to C1-C4 straight-chain alkyl groups or C1-C4 branched-chain alkyl groups.
• alkyl examples include, but are not limited to, methyl, ethyl, 1 -propyl, 2-propyl, n-butyl, sec -butyl, tert-butyl, 1 -pentyl, 2-pentyl, 3 -pentyl, neo-pentyl, 1 -hexyl, 2-hexyl, 3 -hexyl, 1 -heptyl, 2-heptyl, 3 -heptyl, 4-heptyl, 1 -octyl, 2-octyl, 3-octyl or 4-octyl and the like.
• the “alkyl” group may be optionally substituted.
• acyl is art-recognized and refers to a group represented by the general formula hydrocarbylC(O)-, preferably alkylC(O)-.
• acylamino is art-recognized and refers to an amino group substituted with an acyl group and may be represented, for example, by the formula hydrocarbylC(O)NH-.
• acyloxy is art-recognized and refers to a group represented by the general formula hydrocarb ylC(O)O-, preferably alkylC(O)O-.
• alkoxy refers to an alkyl group having an oxygen attached thereto.
• Representative alkoxy groups include methoxy, ethoxy, propoxy, tert-butoxy and the like.
• alkoxyalkyl refers to an alkyl group substituted with an alkoxy group and may be represented by the general formula alkyl-O-alkyl.
• alkyl refers to saturated aliphatic groups, including straight-chain alkyl groups, branched-chain alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups.
• a straight chain or branched chain alkyl has 30 or fewer carbon atoms in its backbone (e.g., Ci- 30 for straight chains, C3-30 for branched chains), and more preferably 20 or fewer.
• alkyl as used throughout the specification, examples, and claims is intended to include both unsubstituted and substituted alkyl groups, the latter of which refers to alkyl moieties having substituents replacing a hydrogen on one or more carbons of the hydrocarbon backbone, including haloalkyl groups such as trifluoromethyl and 2,2,2- trifluoroethyl, etc.
• C x.y or “C x -C y ”, when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups that contain from x to y carbons in the chain.
• Coalkyl indicates a hydrogen where the group is in a terminal position, a bond if internal.
• a Ci-6alkyl group for example, contains from one to six carbon atoms in the chain.
• alkylamino refers to an amino group substituted with at least one alkyl group.
• alkylthio refers to a thiol group substituted with an alkyl group and may be represented by the general formula alkylS-.
• amido refers to a group wherein R 9 and R 10 each independently represent a hydrogen or hydrocarbyl group, or R 9 and R 10 taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.
• amine and “amino” are art-recognized and refer to both unsubstituted and substituted amines and salts thereof, e.g., a moiety that can be represented by wherein R 9 , R 10 , and R 10 ’ each independently represent a hydrogen or a hydrocarbyl group, or R 9 and R 10 taken together with the N atom to which they are attached complete a heterocycle having from 4 to 8 atoms in the ring structure.
• aminoalkyl refers to an alkyl group substituted with an amino group.
• aralkyl refers to an alkyl group substituted with an aryl group.
• aryl as used herein include substituted or unsubstituted single-ring aromatic groups in which each atom of the ring is carbon.
• the ring is a 5- to 7-membered ring, more preferably a 6-membered ring.
• aryl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is aromatic, e.g., the other cyclic rings can be cycloalkyls,
• SUBSTITUTE SHEET ( RULE 26 ) cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
• Aryl groups include benzene, naphthalene, phenanthrene, phenol, aniline, and the like.
• carboxylate is art-recognized and refers to a group wherein R 9 and R 10 independently represent hydrogen or a hydrocarbyl group.
• Carbocyclylalkyl refers to an alkyl group substituted with a carbocycle group.
• Carbocycle includes 5-7 membered monocyclic and 8-12 membered bicyclic rings. Each ring of a bicyclic carbocycle may be selected from saturated, unsaturated and aromatic rings. Carbocycle includes bicyclic molecules in which one, two or three or more atoms are shared between the two rings.
• fused carbocycle refers to a bicyclic carbocycle in which each of the rings shares two adjacent atoms with the other ring. Each ring of a fused carbocycle may be selected from saturated, unsaturated and aromatic rings.
• an aromatic ring e.g., phenyl
• a saturated or unsaturated ring e.g., cyclohexane, cyclopentane, or cyclohexene.
• Exemplary “carbocycles” include cyclopentane, cyclohexane, bicyclo[2.2.1]heptane, 1,5-cyclooctadiene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]oct- 3-ene, naphthalene and adamantane.
• Exemplary fused carbocycles include decalin, naphthalene, 1,2,3,4-tetrahydronaphthalene, bicyclo[4.2.0]octane, 4, 5, 6, 7 -tetrahydro -1H- indene and bicyclo [4.1.0]hept-3-ene.
• “Carbocycles” may be substituted at any one or more positions capable of bearing a hydrogen atom.
• Carbocyclylalkyl refers to an alkyl group substituted with a carbocycle group.
• carbonate is art-recognized and refers to a group -OCO2-.
• cycloalkyl includes substituted or unsubstituted non-aromatic single ring structures, preferably 4- to 8-membered rings, more preferably 4- to 6-membered rings.
• cycloalkyl also includes polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is cycloalkyl and the substituent (e.g., R 100 ) is attached to the cycloalkyl ring, e.g., the other
• SUBSTITUTE SHEET (RULE 26 ) cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
• Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, pyrimidine, denzodioxane, tetrahydroquinoline, and the like.
• esters refers to a group -C(O)OR 9 wherein R 9 represents a hydrocarb yl group.
• ether refers to a hydrocarbyl group linked through an oxygen to another hydrocarbyl group. Accordingly, an ether substituent of a hydrocarbyl group may be hydrocarb yl-O-. Ethers may be either symmetrical or unsymmetrical. Examples of ethers include, but are not limited to, heterocycle-O-heterocycle and aryl-O-heterocycle. Ethers include “alkoxyalkyl” groups, which may be represented by the general formula alkyl-O-alkyl.
• halo and “halogen” as used herein means halogen and includes chloro, fluoro, bromo, and iodo.
• heteroalkyl and “heteroaralkyl”, as used herein, refers to an alkyl group substituted with a hetaryl group.
• heteroaryl and “hetaryl” include substituted or unsubstituted aromatic single ring structures, preferably 5- to 7-membered rings, more preferably 5- to 6-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms.
• heteroaryl and “hetaryl” also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least one of the rings is heteroaromatic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
• Heteroaryl groups include, for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrazine, pyridazine, and pyrimidine, and the like.
• heteroatom as used herein means an atom of any element other than carbon or hydrogen. Preferred heteroatoms are nitrogen, oxygen, and sulfur.
• heterocyclylalkyl refers to an alkyl group substituted with a heterocycle group.
• heterocyclyl refers to substituted or unsubstituted non-aromatic ring structures, preferably 3- to 10-membered rings, more preferably 3- to 7-membered rings, whose ring structures include at least one heteroatom, preferably one to four heteroatoms, more preferably one or two heteroatoms.
• heterocyclyl and heterocyclic also include polycyclic ring systems having two or more cyclic rings in which two or more carbons are common to two adjoining rings wherein at least
• one of the rings is heterocyclic, e.g., the other cyclic rings can be cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls.
• Heterocyclyl groups include, for example, piperidine, piperazine, pyrrolidine, morpholine, lactones, lactams, and the like.
• Hydrocarbyl groups include, but are not limited to aryl, heteroaryl, carbocycle, heterocycle, alkyl, alkenyl, alkynyl, and combinations thereof.
• hydroxyalkyl refers to an alkyl group substituted with a hydroxy group.
• lower when used in conjunction with a chemical moiety, such as, acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy is meant to include groups where there are ten or fewer atoms in the substituent, preferably six or fewer.
• acyl, acyloxy, alkyl, alkenyl, alkynyl, or alkoxy substituents defined herein are respectively lower acyl, lower acyloxy, lower alkyl, lower alkenyl, lower alkynyl, or lower alkoxy, whether they appear alone or in combination with other substituents, such as in the recitations hydroxyalkyl and aralkyl (in which case, for example, the atoms within the aryl group are not counted when counting the carbon atoms in the alkyl substituent).
• polycyclyl refers to two or more rings (e.g., cycloalkyls, cycloalkenyls, cycloalkynyls, aryls, heteroaryls, and/or heterocyclyls) in which two or more atoms are common to two adjoining rings, e.g., the rings are “fused rings”.
• Each of the rings of the polycycle can be substituted or unsubstituted.
• each ring of the polycycle contains from 3 to 10 atoms in the ring, preferably from 5 to 7.
• sulfate is art-recognized and refers to the group -OSO3H, or a pharmaceutically acceptable salt thereof.
• sulfoxide is art-recognized and refers to the group -S(O)-.
• sulfonate is art-recognized and refers to the group SO3H, or a pharmaceutically acceptable salt thereof.
• substituted refers to moieties having substituents replacing a hydrogen on one or more carbons of the backbone. It will be understood that “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with permitted valence of the substituted atom and the substituent, and that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. As used herein, the term “substituted” is contemplated to include all permissible substituents of organic compounds.
• the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents of organic compounds.
• the permissible substituents can be one or more and the same or different for appropriate organic compounds.
• the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatoms.
• Substituents can include any substituents described herein, for example, a halogen, a hydroxyl, a carbonyl (such as a carboxyl, an alkoxycarbonyl, a formyl, or an acyl), a thiocarbonyl (such as a thioester, a thioacetate, or a thioformate), an alkoxyl, a phosphoryl, a phosphate, a phosphonate, a phosphinate, an amino, an amido, an amidine, an imine, a cyano, a nitro, an azido, a sulfhydryl, an alkylthio, a sulfate, a sulfonate, a sulfamoyl, a sulfonamide, a sulfonyl, a heterocyclyl, an aralkyl, or an aromatic or heteroaromatic moiety.
• thioalkyl refers to an alkyl group substituted with a thiol group.
• thioester refers to a group -C(O)SR 9 or -SC(O)R 9 wherein R 9 represents a hydrocarbyl.
• thioether is equivalent to an ether, wherein the oxygen is replaced with a sulfur.
• urea is art-recognized and may be represented by the general formula
• stereogenic center in their structure.
• This stereogenic center may be present in a R or a S configuration, said R and S notation is used in correspondence with the rules described in Pure Appl. Chem. (1976), 45, 11-30.
• the disclosure contemplates all stereoisomeric forms such as enantiomeric and diastereoisomeric forms of the compounds, salts, prodrugs or mixtures thereof (including all possible mixtures of stereoisomers). See, e.g., WO 01/062726.
• a filtration membrane may be designed to treat produced water ⁇ e.g., water that is produced as a byproduct during the extraction of oil and natural gas), grey water ⁇ e.g., water that already has been used domestically, commercially and industrially), a hot stream ⁇ e.g., frack water), a saline stream, water from mine drainage, or industrial cleaning.
• the term “operating conditions” may refer to conditions associated with the treatment of acidic water, optionally containing suspended solids ⁇ e.g., inorganic salts).
• the operating conditions may refer to conditions associated with the treatment of basic water, optionally containing suspended solids ⁇ e.g., inorganic salts).
• SUBSTITUTE SHEET ( RULE 26 ) methacrylate)-random- poly (2-sulfoethyl methacrylate) (S-) used as an Amphiphilic Polyelectrolyte Complex (APEC) multilayer
• the reaction mixture was then precipitated in acetone and purified by stirring two fresh portions of 1:3 ethanol to hexane volume ratio for at least 3 hours. Finally, the copolymer was dried in the vacuum oven for 72h at 60 °C.
• the composition of the copolymer was calculated from the 1 H-NMR spectrum (FIG. 1), using the ratio of protons from the two different monomer units. The calculated composition was: 41 mol% MAETA, and 59 mol% TFEMA. The final conversion of this reaction was 45%.
• the reaction mixture was then precipitated in 1:3 ethanol to hexane volume ratio and purified by stirring two fresh portions of 2:3 ethanol to hexane volume ratio for at least 3 hours. Finally, the copolymer was dried in the vacuum oven for 72h at 60 °C.
• the composition of the copolymer was calculated from the ’H-NMR spectrum (FIG. 2), using the ratio of protons from the two different monomer units. The calculated composition was: 37 mol% SEMA, and 63 mol% TFEMA. The final conversion of this reaction was 55%.
• PS35 (PSf) ultrafiltration membrane purchased from Solecta (Oceanside, Calif.), was used as the base membrane. After coating, the membrane was immersed in a water bath.
• Film thickness and morphology was determined by the examination of freeze-fractured cross-sections of the membranes using a scanning electron microscope. The coating layer can be observed with a thickness of about 0.6 micrometers.
• the pure water fluxes through the membranes described in example 1 were measured using an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi. After a stabilization period of at least one hour, a sample of the permeate was collected over 120 minutes and weighed. The value obtained was divided by filtration area and experiment time to obtain flux. The flux value was normalized by pressure to obtain pure water permeance (Table 1, 2, and 3). These membranes have permeances comparable to nanofiltration and ultrafiltration commercial membranes.
• Water uptake measurements were performed by utilizing approximately 40 micrometers thick polymer films.
• the films were prepared by mixing equal amounts (by weight) of S- and A+ copolymer solutions (both 5 wt%) on a Teflon dish, the mixture was left overnight to dry on a nutating mixer.
• the films were equilibrated in deionized water at room temperature overnight, excess water was removed by placing the films onto a Kimwipe for 5 s, after that the samples were weighted. The dry weight was obtained from drying the same samples overnight in a vacuum oven set at 60 °C.
• the membranes prepared as described in example 1 were used in experiments aimed at identifying their effective pore size, or size cut-off. Dye molecules and sugars were used to probe this property.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects.
• the cell After running pure water through the membrane for at least an hour, the cell was emptied, and a 0.1 mM solution of the probe dye (vitamin B12 (B12), or riboflavin (Rib)); or 4000 ppm solution of sugar molecule (sucrose, or glucose) or glycerol in water was placed in the cell. After rejecting the first 1 mL, to avoid pure water contamination, enough volume was collected for analysis by COD kits (K-7365, CHEMetrics), or UV-vis spectrometer (GenesyslO, ThermoScientific) and the solute rejection (%) was calculated (FIG.s 4, and 5). The cell was
• SUBSTITUTE SHEET ( RULE 26 ) rinsed several times with water. Pure water was filtered through the membrane until the permeate was completely clear before switching to a new solute.
• the membranes prepared as described in example 1 were used in experiments to determine their salt retention properties. Different salts at different concentrations were used to probe this property, their concentrations were easily measured by a standard conductivity probe.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects. After running pure water through the membrane for at least an hour, the cell was emptied, and a solution of the probe salt in water was placed in the cell.
• SUBSTITUTE SHEET ( RULE 26 ) methacryiate)-raadom- poly (methacrylic acid) (M-) used as an Amphiphilic Polyelectrelyte Complex (APEC) multilayer
• A+ was synthesized using the same protocol of example 1 and same copolymer (FIG. 1) was used.
• the reaction mixture was then precipitated in 1:3 ethanol to hexane volume ratio and purified by stirring two fresh portions of 1:3 ethanol to hexane volume ratio for at least 8 hours. Finally, the copolymer was dried in the vacuum oven for 120h at 50 °C.
• the composition of the copolymer was calculated from the 1 H-NMR spectrum (FIG. 16), using the ratio of protons from the two different monomer units. The calculated composition was: 59 mol% MAA, and 41 mol% TFEMA. The final conversion of this reaction was 35%.
• Film thickness and morphology was determined by the examination of freeze-fractured cross-sections of the membranes using a scanning electron microscope. The coating layer can be observed with a thickness of about 0.4 micrometers. FIG. 17.
• the pure water flux through the membrane described in example 6, AM was measured using an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi. After a stabilization period of at least one hour, a sample of the permeate was collected over 120 minutes and weighed. The value obtained was divided by filtration area and experiment time to obtain flux. The flux value was normalized by pressure to obtain a pure water permeance of 1.5 L/m 2 .h.bar.
• the membrane prepared as described in example 6 was used in experiments aimed at identifying their effective pore size, or size cut-off. Vitamin B12 was used to probe this property.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi.
• the cell was stirred at 500 rpm to minimize concentration polarization effects.
• A+ and M- were synthesized using the same protocols of Examples 1 and 6, and the same copolymers (FIG.s 1 and 16 respectively) were used.
• SUBSTITUTE SHEET (RULE 26 ) at approximately 25° C. Both solutions were combined into solutions with different molar ratios of the ionizable/charged monomeric units and passed all solutions through a 0.45 micrometer syringe filter (Whatman) and degassed them in a vacuum oven for at least 1 hour.
• the membranes were prepared by coating a thin layer of the combined solutions on top of a commercial ultrafiltration (UF) membrane using a film applicator rod.
• UF commercial ultrafiltration
• PS35 (PSf) ultrafiltration membrane purchased from Solecta (Oceanside, Calif.), was used as the base membrane. After coating, the membranes were immersed in a water bath.
• Film thickness and morphology was determined by the examination of freeze-fractured cross-sections of the membranes using a scanning electron microscope. The coating layer can be observed with a thickness of about 3 micrometers. FIG. 18.
• the pure water fluxes through the membranes described in example 9 were measured using an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi. After a stabilization period of at least one hour, a sample of the permeate was collected over 120 minutes and weighed. The value obtained was divided by filtration area and experiment time to obtain flux. The flux value was normalized by pressure to obtain pure water permeance (FIG. 19).
• These membranes have permeances comparable to nanofiltration and ultrafiltration commercial membranes.
• the membrane prepared as described in example 9 were used in experiments aimed at identifying their effective pore size, or size cut-off. Vitamin B12 was used to probe this property.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi.
• the cell was stirred at 500 rpm to minimize concentration polarization effects. After running pure water through the membrane for at least an hour, the cell was emptied, and a 0.1 mM
• SUBSTITUTE SHEET ( RULE 26 ) solution of the probe dye (vitamin B12 (B12)) in water was placed in the cell. After rejecting the first 1 mL, to avoid pure water contamination, enough volume was collected for analysis by UV-vis spectrometer (GenesyslO, ThermoScientific) and the solute rejection was calculated (FIG. 20).
• the membranes prepared as described in example 9 were used in experiments to determine their salt retention properties. Different salts at different concentrations were used to probe this property, their concentrations were easily measured by a standard conductivity probe.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects. After running pure water through the membrane for at least an hour, the cell was emptied, and a solution of the probe salt in water was placed in the cell.
• poly (2,2,2-trifluoroethyI methacrylate) -random- poly (2- (methacryloyloxy)ethyl]trimethylammonium chloride) is synthesized using a higher content of TFEMA (A2+). While the anionic copolymer is the same S- copolymer described in example 1.
• the reaction mixture was then precipitated in 1:3 ethanol to hexane volume ratio and purified by stirring two fresh portions of 2:3 ethanol to hexane volume ratio for at least 3 hours. Finally, the copolymer was dried in the vacuum oven for 72h at 60 °C.
• the composition of the copolymer was calculated from the X H-NMR spectrum (FIG. 25), using the ratio of protons from the two different monomer units. The calculated composition was: 37 mol% SEMA, and 63 mol% TFEMA. The final conversion of this reaction was 55%.
• Film thickness and morphology was determined by the examination of freeze-fractured cross-sections of the membranes using a scanning electron microscope. The coating layer can be observed with a thickness of about 0.5 micrometers. FIG. 26.
• the pure water fluxes through the membranes described in example 13 were measured using an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi. After a stabilization period of at least one hour, a sample of the permeate was collected over 120 minutes and weighed. The value obtained was divided by filtration area and experiment time to obtain flux. The flux value was normalized by pressure to obtain pure water permeance.
• the permeance of A2S was 8.5 ⁇ 0.9 L/m 2 .h.bar. While the permeance of A2+ (only A2+ is coated) was 59 + 11 L/m 2 .h.bar.
• the membranes prepared as described in example 13 were used in experiments aimed at identifying their effective pore size, or size cut-off. Dye molecules and sugars were used to probe this property.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects.
• the cell After running pure water through the membrane for at least an hour, the cell was emptied, and a 0.1 mM solution of the probe dye (vitamin B12 (B12), or riboflavin (Rib)); or 4000 ppm solution of sugar molecule (sucrose, or glucose) or glycerol in water was placed in the cell. After rejecting the first 1 mL, to avoid pure water contamination, enough volume was collected for analysis by COD kits (K-7365, CHEMetrics), or UV-vis spectrometer (GenesyslO, ThermoScientific) and the solute rejection (%) was calculated (FIG.s 27-28). The cell was rinsed several times with water. Pure water was filtered through the membrane until the permeate was completely clear before switching to a new solute.
• the probe dye vitamin B12 (B12), or riboflavin (Rib)
• 4000 ppm solution of sugar molecule sucrose, or glucose
• sugar molecule sucrose,
• the membranes prepared as described in example 13 were used in experiments to determine their salt retention properties. Different salts at different concentrations were used to probe this property, their concentrations were easily measured by a standard conductivity probe.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects. After running pure water through the membrane for at least an hour, the cell was emptied, and a solution of the probe salt in water was placed in the cell.
• poly (2,2,2-trifluoroethyl methacrylate) -random- poly (2-sulfoethyl methacrylate) is synthesized using a higher content of TFEMA (S2-). While the cationic copolymer is the same A+ copolymer described in example 1.
• the reaction mixture was then precipitated in acetone and purified by stirring two fresh portions of 1:3 ethanol to hexane volume ratio for at least 3 hours. Finally, the copolymer was dried in the vacuum oven for 72h at 60 °C. The composition of the copolymer was calculated from the 1 H-NMR spectrum (FIG. 32), using the ratio of protons from the two different monomer units. The calculated
• SUBSTITUTE SHEET ( RULE 26 ) composition was: 41 mol% MAETA, and 59 mol% TFEMA. The final conversion of this reaction was 45%.
• the copolymer was dried in the vacuum oven for 48h at 60 °C. After that the copolymer was purified by stirring two fresh portions of hexane for at least 3 hours. Finally, the copolymer was dried in the vacuum oven for 72h at 60 °C.
• the composition of the copolymer was calculated from the 1 H- NMR spectrum (FIG. 33), using the ratio of protons from the two different monomer units. The calculated composition was: 30 mol% SEMA, and 70 mol% TFEMA. The final conversion of this reaction was 21%.
• Film thickness and morphology was determined by the examination of freeze-fractured cross-sections of the membranes using a scanning electron microscope. The coating layer can be observed with a thickness of about 0.4 micrometers. FIG. 34.
• the pure water fluxes through the membranes described in example 17 were measured using an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 .
• the cell was stirred at 500 rpm, and the test was performed at 40 psi. After a stabilization period of at least one hour, a sample of the permeate was collected over 120 minutes and weighed. The value obtained was divided by filtration area and experiment time to obtain flux. The flux value was normalized by pressure to obtain pure water permeance.
• the permeance of AS2 was 4.7 ⁇ 0.8 L/m 2 .h.bar. While the permeance of S2- (only S2- is coated) was 98 ⁇ 17 L/m 2 .h.bar.
• the membranes prepared as described in example 17 were used in experiments aimed at identifying their effective pore size, or size cut-off. Dye molecules were used to probe this property.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects.
• the cell After running pure water through the membrane for at least an hour, the cell was emptied, and a 0.1 mM water solution of the probe dye (vitamin B 12 (B12), or riboflavin (Rib)) was placed in the cell. After rejecting the first 1 mL, to avoid pure water contamination, enough volume was collected for analysis by UV-vis spectrometer (GenesyslO, ThermoScientific) and the solute rejection (%) was calculated (FIG. 35). The cell was rinsed several times with water. Pure water was filtered through the membrane until the permeate was completely clear before switching to a new solute.
• the probe dye vitamin B 12 (B12), or riboflavin (Rib)
• the membranes prepared as described in example 17 were used in experiments to determine their salt retention properties. Different salts at different concentrations were used to probe this property, their concentrations were easily measured by a standard conductivity probe.
• the retention experiments were performed on an Amicon 8010 stirred, dead-end filtration cell (Millipore) with a cell volume of 10 mL and an effective filtration area of 4.1 cm 2 . The cell was stirred at 500 rpm, and the test was performed at 40 psi. The cell was stirred at 500 rpm to minimize concentration polarization effects. After running pure water through the membrane for at least an hour, the cell was emptied, and a solution of the probe salt in water was placed in the cell.

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