WO2020092018A1 - Substrat de cellulose à fonction amine pour membranes composites à film mince et procédés de préparation associés - Google Patents

Substrat de cellulose à fonction amine pour membranes composites à film mince et procédés de préparation associés Download PDF

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WO2020092018A1
WO2020092018A1 PCT/US2019/056906 US2019056906W WO2020092018A1 WO 2020092018 A1 WO2020092018 A1 WO 2020092018A1 US 2019056906 W US2019056906 W US 2019056906W WO 2020092018 A1 WO2020092018 A1 WO 2020092018A1
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amine
support
cellulose ester
substrate
cellulose
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Jason T. ARENA
John R. Herron
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Fluid Technology Solutions Inc
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Fluid Technology Solutions Inc
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    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • 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
    • B01D69/1214—Chemically bonded layers, e.g. cross-linking
    • 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
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/10—Cellulose; Modified cellulose
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • 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
    • B01D71/08—Polysaccharides
    • B01D71/12—Cellulose derivatives
    • B01D71/14—Esters of organic acids
    • B01D71/16—Cellulose acetate
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B01D2323/345—UV-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/36—Introduction of specific chemical groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/38—Graft polymerization
    • B01D2323/385—Graft polymerization involving radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes
    • B01D2325/0233—Asymmetric membranes with clearly distinguishable layers
    • 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

Definitions

  • a commercial standard for reverse osmosis membranes is the thin film composite (TFC) membrane developed by John Cadotte at FILMTEC in the late l970s.
  • the membranes are prepared from an interfacially polymerized polyamide formed on a polysulfone substrate.
  • Interfacial polymerization or interfacial synthesis refers to the preparation of a polymer film at the interface between immiscible solvents.
  • this polymer is often a polyamide but can also be a polyurea or polypiperamide.
  • the immiscible solvents are often water and an alkane, or a mixture thereof.
  • the polyamide is prepared from a solution of 2% m-phenylenediamine (MPD) dissolved in water reacted with a solution of 0.1% 1,3, 5-benzene tricarbonyl chloride (also known as trimesoyl chloride or TMC) dissolved in C5-C14 alkanes.
  • MPD m-phenylenediamine
  • TMC trimesoyl chloride
  • Figure 2 illustrates a method of preparing a polysulfone-supported thin film composite membrane.
  • Interfacial polymerization of a polyamide may be performed on polysulfone or other porous polymer substrates prepared by the non solvent induced phase separation (NIPS) technique, whereby a polymer in solution with a water miscible solvent is drawn into a thin film over a substrate and immersed in a water bath.
  • This substrate can be non-woven fabric, a woven fabric, or a nonporous surface, such as a glass plate.
  • the solvent of the polymer solution mixes with water.
  • the water- insoluble polymer precipitates to form a porous film.
  • the polyamide active layer can be formed by bringing the porous polymer film into contact with an aqueous solution of MPD and kept in contact for a desired period of time.
  • the MPD solution is removed and any remaining droplets of the MPD solution are removed from the polymer substrate’s surface by a rubber roller or an air knife.
  • the polymer film is brought in contact with a TMC solution. While TMC has minimal solubility in water, MPD is soluble in alkanes. The defined phase separation between the water within the polymer and the alkane on the polymer’s surface prevents MPD and TMC from mixing, but diffusive transport of the MPD into the alkane does occur.
  • Asymmetric membranes having selectivity to water over dissolved salts typically include three distinct regions, as shown in Figure 3.
  • the densest and topmost region, during formation, of these membranes is the active (selective) layer, which imparts permselectivity of water to dissolved chemical species to osmotic membranes.
  • the active layer of an asymmetric membrane is also typically the thinnest, which helps minimize mass transfer resistance to water flow and allows for more permeable membranes.
  • Beneath and adjacent to the active layer is a support layer.
  • the support layer typically includes two layers: a porous polymer layer and a fabric layer.
  • the porous polymer support layer is often prepared by an induced phase separation either with a non solvent (i.e., non-solvent induced phase separation, NIPS) or thermally (i.e., thermally induced phase separation, TIPS).
  • NIPS non-solvent induced phase separation
  • TIPS thermally induced phase separation
  • the porous polymer is often formed on a non-woven fabric, which provides most of the mechanical strength for the asymmetric membrane structure.
  • the fabric layer can be thick and in some seawater membranes represents -70% of the entire thickness (see Figure 3, for which the dimensions are based on a seawater reverse osmosis membrane). In addition to their large relative thickness, some denser non-woven fabrics have low porosity.
  • Membranes for osmotically driven membrane processes may instead employ a woven support layer, which has a more open, thinner, and ordered structure as compared to the random fiber orientations in non-woven fabric. These characteristics of a woven support allow for the preparation of membranes that have improved water flux in osmotically driven membrane separations. Transport in osmotically driven membrane processes
  • Water flow through a semipermeable membrane in osmotically driven membrane processes occurs primarily through an osmotic pressure difference between a feed solution and a draw solution.
  • the draw solution is selected to have a higher osmotic pressure than the feed solution so that it draws water through the membrane separating the draw solution from the feed solution.
  • the osmotic pressures of the draw and feed solutions are generally related to the concentration of dissolved solutes within them.
  • Hydrostatic pressure difference across a membrane also influences rate of water flow. For example, a hydrostatic pressure can be applied to the draw solution to retard the flow of water (pressure retarded osmosis) or to the feed solution to increase the flow of water through the membrane (pressure assisted forward osmosis).
  • the flow of water through a membrane in an osmotically driven membrane process occurs due to both the osmotic pressure difference across the membrane and in the same direction as the osmotic pressure gradient.
  • water flow occurs against as osmotic pressure difference.
  • the osmotic pressure difference across the membrane is not exclusively impacted by membrane selectivity and is instead mediated by a solution with less salinity than the feed solution on the permeate side of the membrane.
  • an osmotically driven membrane process is characterized by the concentration dependence of the feed and draw solutions on osmotic pressure. Because of this dependence, a competition between solution convection and salt diffusion arises within the support layer of an asymmetric membrane, thereby reducing the osmotic pressure difference across the membrane. The reduced pressure difference limits water flux though the membrane, which results in internal concentration polarization (ICP). The detrimental effect of internal concentration polarization on water flux can be mitigated by increasing support layer porosity and reducing support layer thickness.
  • ICP internal concentration polarization
  • a membrane’s support layer is not spontaneously and completely wetted by aqueous solutions. Incomplete wetting reduces the diffusive mass transfer coefficient through the support layer, which significantly reduces the driving force for water flow across the membrane in osmotically driven membrane processes.
  • the hydrophobicity of the polysulfone can be mitigated by pre- wetting a TFC membrane with an alcohol or by adding a surfactant to the draw solution. In large commercial applications, these approaches may not be feasible. Therefore, membranes that are intrinsically hydrophilic and would be unaffected by reduced mass transfer due to poor pore wetting are needed.
  • Some commercially available membranes for osmotically driven membrane processes are constructed of cellulose acetates with varying degrees of acetate functionality up to and including cellulose triacetate. Developed in the l950s and’60s, cellulose acetate membranes were amongst the first practical membranes for the desalination of seawater. Their continued usability for osmotically driven membrane processes is in part due to the innate hydrophilicity of a cellulose acetate when used in the preparation of semi-permeable membranes. This innate hydrophilicity ensures the membrane is more easily wetted when used for an osmotically driven membrane process, which produces a membrane with less severe internal concentration polarization than comparable thin film composite membranes.
  • the active layer and porous mid-layer of a cellulose acetate membrane are chemically homogenous, and the two layers are formed simultaneously. As a result, active layer and support layer characteristics of these membranes must be carefully tailored in tandem, complicating fine tuning of the membrane design. Also, cellulose acetate membranes, compared to TFC reverse osmosis membranes, have relatively thick selective layers resulting in reduced water permeance at comparable selectivity.
  • TFC membrane on a cellulose substrate has faced challenges, including in developing techniques for synthesizing a polyamide active layer on cellulose supports. While polysulfone (and the similar polyethersulfone) is aromatic (like both MPD and TMC), cellulose is not. As a result, one of the common routes of intermolecular attraction that may promote adhesion between layers, namely p-p stacking, is unavailable to TFCs prepared upon support layers of cellulosic materials such as cellulose esters.
  • One publication proposed the covalent linking of a polyamide to a cellulosic support (U.S. Patent Application Publication No. 2013/0089727).
  • the publication applied a polyamide film to cellulose acetate supports that had been hydrolyzed by caustic (i.e., potassium hydroxide or sodium hydroxide) and had subsequently been treated with TMC in a non- aqueous solvent (i.e., diethylene glycol diethyl ether).
  • caustic i.e., potassium hydroxide or sodium hydroxide
  • TMC a non- aqueous solvent
  • This technique sought to functionalize the surface of the cellulosic substrate with acyl chloride functional groups onto which a synthesized polyamide would grow by the subsequent introduction of an aqueous MPD solution followed by TMC in hexane.
  • amine attack on the ester linkage formed between the TMC and hydroxyl groups on the cellulose substrate can break the ester linkage, instead forming an amide bond.
  • the synthesized polyamide is not covalently bonded to the cellulose substrate.
  • Embodiments disclosed herein are directed to membranes for filtration and methods of making the same.
  • a method of preparing an amine- functionalized cellulosic substrate is disclosed.
  • a cellulose ester solution is cast onto a material.
  • the material is immersed in a water bath to produce a porous cellulose ester substrate.
  • the substrate is immersed in an aqueous solution including an amine and a photo-initiator.
  • the substrate is exposed to ultraviolet light to produce an amine- functionalized cellulose ester substrate.
  • a method of preparing a cellulose-supported thin film composite membrane is disclosed.
  • a cellulose ester solution is cast onto a material to produce a cellulosic support.
  • the support is immersed in a water bath.
  • the support is immersed in an aqueous solution including an amine and a photo-initiator.
  • the support is exposed to ultraviolet light to produce an amine-functionalized cellulosic support.
  • the support is immersed in an aqueous solution including a di- or higher- functional amine.
  • the support is immersed in a non-polar solution including a di- or higher- functional acyl chloride or an isocyanate to produce an active layer on the support.
  • the layer and support are cured to produce a thin film composite membrane.
  • FIG. 1 is an illustration of a polyamide for use in thin film composite membranes.
  • FIG. 2 is a flow chart of a method of preparing a poly sulf one-supported thin film composite membrane.
  • FIG. 3 is a schematic of an asymmetric osmotic membrane
  • FIG. 4 is a flow chart of a method of preparing a cellulose-supported thin film composite membrane according to embodiments.
  • FIG. 5 is a flow chart of a method of preparing a cellulose-supported thin film composite membrane according to embodiments.
  • FIG. 6 is a flow chart of a method of preparing a cellulose-supported thin film composite membrane according to embodiments.
  • FIG. 7 is an illustration of a polyamide covalently bound to an amide functionalized cellulose, prepared according to the method of FIG. 4, FIG. 5, or FIG. 6.
  • Embodiments disclosed herein are directed to methods of preparing an amine- functionalized cellulosic substrate.
  • the amine functionalization may help produce a substrate capable of covalently bonding with other compounds that have amines as monomers, such as polyamides, polypiperamides, and polyureas.
  • the ability to covalently bond with additional compounds may produce a substrate that can adhere well to another layer, such as an active layer in a thin film composite membrane.
  • Embodiments disclosed herein are also directed to methods of preparing thin film composite membranes on cellulosic supports.
  • the cellulosic supports are amine functionalized, which may improve adhesion of synthesized polyamides. Improved adhesion may help layers of the membranes remain bound together. Improved adhesion may also prevent membranes from failing by separation of component layers.
  • Embodiments disclosed herein are also directed to methods of preparing amine- functionalized cellulose ester supports. Methods of constructing a thin film composite membrane having an active layer that is covalently bound to an amine functionality on a cellulose ester support layer are also disclosed.
  • an active layer is covalently bound to an amine functional group attached to a cellulose ester support by a method that employs a photo-initiator.
  • the method 100 includes a step 102 of casting a cellulose solution onto a material, a step 104 of immersing the material in a water bath, a step 106 of immersing the material in a solution comprising an amine and a photo-initiator, a step 108 of exposing the material to ultraviolet light, a step 110 of immersing the material in an aqueous solution comprising a di- or higher- functional amine, a step 112 of immersing the material in a non-polar solution comprising a di- or higher-functional acyl chloride or an isocyanate, and a step 114 of curing the material.
  • the material may be, for example, woven fabric, non-woven fabric, or a material having a non-porous surface, such as a glass plate.
  • the cellulose solution may include a cellulose ester, such as cellulose acetate.
  • Step 104 may include the non-solvent induced phase separation (NIPS) technique, whereby a polymer in solution with a water miscible solvent is drawn into a thin film over a substrate and immersed in a water bath. Step 104 may help form the porous structure that helps to minimize the membrane’s resistance. In some embodiments, step 104 is excluded from the method 100.
  • NIPS non-solvent induced phase separation
  • the photo-initiator may be 2, 2-dimethyl- l,2-diphenylethan-l -one.
  • the di- or higher-functional amine may be m-phenylenediamine (MPD) or may be piperazine.
  • MPD m-phenylenediamine
  • the selection of a given amine may help produce a membrane with targeted permselectivity.
  • the acyl chloride may be trimesoyl chloride (TMC) and/or the isocyanate may be toluene di-isocyante.
  • TMC trimesoyl chloride
  • the isocyanate may be toluene di-isocyante.
  • the selection of a given acyl chloride or isocyanate may help produce a membrane with targeted permselectivity.
  • the use of an isocyanate instead of an acyl chloride helps produce a polyurea membrane.
  • step 114 curing the material may help tailor the thin film composite membrane selectivity.
  • steps 110, 112, and 114 may include the interfacial polymerization of a polyamide, polypiperamide, or polyurea according to known methods in the art of constructing thin film composite membranes.
  • 2% MPD is dissolved in water and is reacted with 0.1% TMC dissolved in C5-C14 alkanes.
  • Figure 7 illustrates an example of a polyamide covalently bound to an amide functionalized cellulosic substrate, produced by the method 100.
  • a partially cross-linked aromatic polyamide is covalently bound to the polymer chains of an amine-functionalized cellulosic substrate.
  • the method 100 included an (acrylamidomethyl)cellulose acetate solution, allylamine, MPD, and TMC.
  • the di- or higher-functional amine is MPD and the acyl chloride is TMC.
  • the TMC reacts with the amines on the functionalized cellulose ester substrate and with the MPD. Amide bonds are formed in both reactions.
  • the competition between amine functional groups on the functionalized cellulosic substrate and MPD can be modified by altering the concentration of each of TMC and MPD.
  • an active layer is covalently bound to an amine functional group attached to a cellulose ester support by a method that employs a chemical initiator following non-solvent induced phase separation (NIPS).
  • the method 200 includes a step 202 of casting a cellulose solution onto a material, a step 204 of immersing the material in a water bath, a step 206 of immersing the material in a solution comprising an amine, a step 208 of immersing the material in a solution comprising a chemical initiator, a step 210 of immersing the material in an aqueous solution comprising a di- or higher-functional amine, a step 212 of immersing the material in a non-polar solution comprising a di- or higher- functional acyl chloride or an isocyanate, and a step 214 of curing the material.
  • the material may be, for example, woven fabric, non-woven fabric, or a material having a non-porous surface, such as a glass plate.
  • the cellulose solution may include a cellulose ester, such as cellulose acetate.
  • Step 204 may include the non-solvent induced phase separation (NIPS) technique, whereby a polymer in solution with a water miscible solvent is drawn into a thin film over a substrate and immersed in a water bath. Step 204 may help form the porous structure that helps to minimize the membrane’s resistance. In some embodiments, step 204 is excluded from the method 200.
  • NIPS non-solvent induced phase separation
  • the di- or higher-functional amine may be m-phenylenediamine (MPD) or may be piperazine.
  • MPD m-phenylenediamine
  • the selection of a given amine may help produce a membrane with targeted permselectivity.
  • the acyl chloride may be trimesoyl chloride (TMC) and/or the isocyanate may be toluene di-isocyante.
  • TMC trimesoyl chloride
  • the isocyanate may be toluene di-isocyante.
  • the selection of a given acyl chloride or isocyanate may help produce a membrane with targeted permselectivity.
  • the use of an isocyanate instead of an acyl chloride helps produce a polyurea membrane.
  • steps 210, 212, and 214 may include the interfacial polymerization of a polyamide, polypiperamide, or polyurea according to known methods in the art of constructing thin film composite membranes.
  • 2% MPD is dissolved in water and is reacted with 0.1% TMC dissolved in C5-C14 alkanes.
  • step 214 curing the material may help tailor the thin film composite membrane selectivity.
  • Figure 7 illustrates an example of a polyamide covalently bound to an amide functionalized cellulosic substrate, produced by the method 200.
  • a partially cross-linked aromatic polyamide is covalently bound to the polymer chains of an amine-functionalized cellulosic substrate.
  • the di- or higher-functional amine is MPD and the acyl chloride is TMC.
  • the TMC reacts with the amines on the functionalized cellulose ester substrate and with the MPD. Amide bonds are formed in both reactions.
  • the competition between amine functional groups on the functionalized cellulosic substrate and MPD can be modified by altering the concentration of each of TMC and MPD.
  • an active layer is covalently bound to an amine functional group attached to a cellulose ester in a method that employs a chemical initiator during a step of non-solvent induced phase separation.
  • the method 300 includes a step 302 of casting a cellulose solution containing an amine onto a material, a step 304 of immersing the material in an aqueous solution of a chemical initiator, a step 306 of immersing the material in an aqueous solution comprising a di- or higher-functional amine, a step 308 of immersing the material in a non-polar solution comprising a di- or higher-functional acyl chloride or an isocyanate, and a step 310 of curing the material to produce a membrane.
  • the material may be, for example, woven fabric, non-woven fabric, or a material having a non-porous surface, such as a glass plate.
  • the cellulose solution may include a cellulose ester, such as cellulose acetate.
  • the chemical initiator may be a free radical initiator.
  • the chemical initiator is hydrogen peroxide.
  • the di- or higher-functional amine may be m-phenylenediamine (MPD) or may be piperazine.
  • MPD m-phenylenediamine
  • the selection of a given amine may help produce a membrane with targeted permselectivity.
  • the acyl chloride may be trimesoyl chloride (TMC) and/or the isocyanate may be toluene di-isocyante.
  • TMC trimesoyl chloride
  • the isocyanate may be toluene di-isocyante.
  • the selection of a given acyl chloride or isocyanate may help produce a membrane with targeted permselectivity.
  • the use of an isocyanate instead of an acyl chloride helps produce a polyurea membrane.
  • steps 306, 308, and 310 may include the interfacial polymerization of a polyamide, polypiperamide, or polyurea according to known methods in the art of constructing thin film composite membranes.
  • 2% MPD is dissolved in water and is reacted with 0.1% TMC dissolved in C5-C14 alkanes.
  • Figure 7 illustrates an example of a polyamide covalently bound to an amide functionalized cellulosic substrate, produced by the method 300.
  • a partially cross-linked aromatic polyamide is covalently bound to the polymer chains of an amine-functionalized cellulosic substrate.
  • the di- or higher-functional amine is MPD and the acyl chloride is TMC.
  • the TMC reacts with the amines on the functionalized cellulose ester substrate and with the MPD. Amide bonds are formed in both reactions.
  • the competition between amine functional groups on the functionalized cellulosic substrate and MPD can be modified by altering the concentration of each of TMC and MPD.
  • the methods 100, 200, and 300 may produce a cellulose substrate with greater water and amine tolerance than the method disclosed in U.S. Patent Application Publication No. 2013/0089727.
  • the following working examples set forth methods of preparing thin film composite membranes having a polyamide covalently bound to an amine functionalized cellulose ester support.
  • the method 100 is performed by casting an (acrylamidomethyl)cellulose acetate solution onto a fabric support, immersing the support in a water bath, immersing the support in an aqueous solution comprising allylamine and 2, 2-dimethyl- l,2-diphenylethan-l -one as a photo-initiator, exposing the support to ultraviolet light, immersing the support in an aqueous solution of MPD, immersing the material in a solution of TMC in C5-C14 alkanes, and curing the substrate to produce a membrane.
  • the method 200 is performed by casting an (acrylamidomethyl)cellulose acetate solution onto a fabric support, immersing the support in a water bath, immersing the support in an aqueous solution comprising allylamine, immersing the support in a solution of hydrogen peroxide, immersing the support in an aqueous solution of MPD, immersing the material in a solution of TMC in C5-C14 alkanes, and curing the substrate to produce a membrane.
  • the method 300 is performed by casting an (acrylamidomethyl)cellulose acetate solution comprising allylamine onto a fabric support, immersing the support in an aqueous solution of hydrogen peroxide, immersing the support in an aqueous solution of MPD, immersing the material in a solution of TMC in C5-C14 alkanes, and curing the substrate to produce a membrane. While various aspects and embodiments have been disclosed herein, other aspects and embodiments are contemplated. The various aspects and embodiments disclosed herein are for purposes of illustration and are not intended to be limiting.

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  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne des membranes pour filtration et des procédés de fabrication de celles-ci. Dans des modes de réalisation, les procédés comprennent le coulage d'une solution d'ester de cellulose sur un matériau, qui est immergé dans un bain d'eau et dans une solution aqueuse comprenant une amine et un photoamorceur. Le matériau est exposé à une lumière ultraviolette pour produire un substrat d'ester de cellulose à fonction amine. Dans des modes de réalisation, le substrat est immergé dans une solution aqueuse comprenant une amine difonctionnelle ou supérieure et dans une solution non polaire comprenant un chlorure d'acyle difonctionnel ou supérieur ou un isocyanate pour produire une couche active sur le substrat. La couche et le substrat sont durcis pour produire une membrane composite à film mince.
PCT/US2019/056906 2018-10-31 2019-10-18 Substrat de cellulose à fonction amine pour membranes composites à film mince et procédés de préparation associés Ceased WO2020092018A1 (fr)

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CN120459811A (zh) * 2025-07-14 2025-08-12 德州学院 一种超亲水-水下超疏油聚丙烯腈纳米纤维膜及其制备方法与应用

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CN101239284A (zh) * 2008-03-19 2008-08-13 天津大学 分离酸性气体的含聚烯丙基胺促进传递膜的制备方法
US9022227B2 (en) * 2011-03-21 2015-05-05 International Business Machines Corporation Composite membranes and methods of preparation thereof
CN105327623A (zh) * 2015-12-03 2016-02-17 中国科学院化学研究所 一种醋酸纤维素纳滤膜及其制备方法
WO2016113518A1 (fr) * 2015-01-16 2016-07-21 Fujifilm Manufacturing Europe Bv Compositions durcissables et membranes

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EP0312943B1 (fr) * 1987-10-19 1994-03-23 W.R. Grace & Co.-Conn. Membranes de séparation de gaz en acéto-butyrate de cellulose
CN101239284A (zh) * 2008-03-19 2008-08-13 天津大学 分离酸性气体的含聚烯丙基胺促进传递膜的制备方法
US9022227B2 (en) * 2011-03-21 2015-05-05 International Business Machines Corporation Composite membranes and methods of preparation thereof
WO2016113518A1 (fr) * 2015-01-16 2016-07-21 Fujifilm Manufacturing Europe Bv Compositions durcissables et membranes
CN105327623A (zh) * 2015-12-03 2016-02-17 中国科学院化学研究所 一种醋酸纤维素纳滤膜及其制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN120459811A (zh) * 2025-07-14 2025-08-12 德州学院 一种超亲水-水下超疏油聚丙烯腈纳米纤维膜及其制备方法与应用

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