• 专利附录
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    • 专利摘要:
    composite membrane for nanofiltration, use of a membrane, and interfacial polymerization process to form a composite membrane for solvent nanofiltration. the present invention relates to a composite membrane for nanofiltration of a feed stream solution comprising a solvent and dissolved solutes and causing preferential rejection of the solutes. the composite membrane comprises a thin polymeric film formed by interfacial polymerization on a support membrane. the support membrane is further impregnated with a conditioning agent and is stable in polar aprotic solvents. the composite membrane is optionally treated in a deactivation medium, in which the interfacial polymerization reaction can be deactivated and, in some embodiments, the membrane chemistry can be modified. finally, the composite membrane is treated with an activating solvent before nanofiltration.
    公开号:BR112013001377B1
    申请号:R112013001377
    申请日:2011-07-19
    公开日:2020-06-09
    发明作者:Guy Livingston Andrew；Fernanda Jimenez Solomon Maria；Suresh Bhole Yogesh
    申请人:Imperial Innovations Ltd；
    IPC主号:
    专利说明:

    “INTERFACIAL POLYMERIZATION PROCESS TO FORM A COMPOSITE MEMBRANE FOR NANOFILTRATION OPERATIONS IN POLAR APROTIC SOLVENTS.”
    [0001] The work that led to this invention received funding from the European Union Seventh Framework Program (FP7 / 20072013) under concession contract No. 214226.
    Field of the Invention
    [0002] The present invention relates to thin film composite membranes formed by interfacial polymerization. Membranes and membrane systems described here can be used in a variety of applications, including, but not limited to, nanofiltration, desalination, and water treatment, and, in particular, the nanofiltration of solutes dissolved in organic solvents.
    Background of the Invention
    [0003] Membrane processes have been widely applied in separation science, and can be applied to a range of separations of species of different molecular weights in liquid phase and gas (see for example, "Membrane Technology and Applications" 2nd edition , RW Baker, John Wiley and Sons Ltd, ISBN 0-470-85445-6).
    [0004] With particular reference to nanofiltration, such applications have received attention based on the relatively low operating pressures, high flows and low operating and maintenance costs associated with them. Nanofiltration is a membrane process using membranes with a cut molecular weight in the range of 200-2,000 Daltons. Cutting the molecular weight of a membrane is generally defined as the molecular weight of a molecule that must exhibit a 90% rejection when subjected to membrane nanofiltration. Nanofiltration has been widely applied for the filtration of aqueous fluids, but due to the lack of stable membranes in appropriate solvent it has not been widely applied for separation
    Petition 870200038220, of 03/23/2020, p. 10/46 / 33 of solutes in organic solvents. This is despite the fact that organic solvent nanofiltration (OSN) has many potential applications in the manufacturing industry, including solvent exchange, catalyst recovery and recycling, purifications and concentrations. US Patents. No. 5,174,899 5,215,667; 5,288,818; 5,298,669 and 5,395,979 describe the separation of organometallic compounds and / or carbonyls from metals from their solutions in organic media. UK Patent No. GB 2373743 describes the application of OSN to solvent exchange; UK Patent No. GB 2369311 describes the application of OSN to recycle phase transfer agents, and European Patent Application EP1590361 describes the application of OSN to the separation of tunons during oligonucleotide synthesis.
    [0005] Nanofiltration membranes for aqueous applications are generally manufactured by making composite membranes. Thin-film composite membranes can be manufactured by interfacial polymerization (here also referred to as IP) or by dip coating [Lu, X .; Bian, X .; Shi, L., “Preparation and characterization of NF composite membrane. ”J. Membr. Sci., 210, 3-11, 2002].
    [0006] In the IP technique, an aqueous solution of a reactive monomer (often a polyamine) is first deposited in the pores of a supporting microporous membrane, often of a polysulfone ultrafiltration membrane. Then, the supporting polysulfone membrane loaded with the monomer is immersed in a water-immiscible solvent solution that contains a reactive monomer, such as diacid chloride in hexane. The two monomers react at the interface of the two non-miscible solutions, until a thin film presents a diffusion barrier and the reaction is complete, to form a layer of highly cross-linked thin film that remains attached to the support membrane. The thin film layer can be several tens of nanometers to several micrometers thick. The IP technique is well known to those skilled in the art [Petersen, R. J.
    Petition 870200038220, of 03/23/2020, p. 11/46 / 33 “Composite reverse osmosis and nanofiltration membranes”. J. Membr. Sci, 83, 81-150, 1993]. The thin film is selective between the molecules, and this selective layer can be optimized for the rejection of solutes and solvent flow by controlling the coating conditions and the characteristics of the reactive monomers. The microporous support membrane can be selectively selected for porosity, strength and solvent resistance. A particularly preferred class of thin film materials for nanofiltration are polyamides formed by interfacial polymerization. Examples of such thin polyamide films are found in US Patents. Nos. 5,582,725, 4,876,009, 4,853,122, 4,259,183, 4,529,646, 4,277,344 and 4,039,440, the pertinent descriptions of which are incorporated herein by reference. [0007] US patent. No. 4,277,344 describes an aromatic polyamide membrane produced by interfacial polymerization of an aromatic polyamine with at least two primary amine substituents and an acyl halide with at least three acyl halide substituents. Wherein, the aqueous solution contains a monomeric aromatic polyamine reagent and the organic solution contains an amino-reactive polyfunctional acyl halide. The TFC membrane polyamide layer is typically obtained by interfacial polymerization between a piperazine or an amine or cyclohexane-substituted piperidine, and a polyfunctional acyl halide, as described in the US Patents. Nos. 4,769,148 and 4,859,384. One way of modifying TFC membranes by reverse osmosis (here also referred to as RO) for nanofiltration is described in US Patents. No. 4,765,897; 4,812,270 and 4,824,574. Interfacial postpolymerization treatments have also been used to increase the pore size of TFC membranes by RO.
    [0008] US patent. No. 5,246,587 describes an aromatic polyamide RO membrane that is made first by coating a porous support material with an aqueous solution containing a polyamine reagent and a salt
    Petition 870200038220, of 03/23/2020, p. 12/46 / 33 amine. Examples of suitable polyamine reagents provided include aromatic primary diamines (such as, m-phenylenediamine or p-phenylenediamine or substituted derivatives thereof, where the substituent is an alkyl group, an alkoxy group, a hydroxy alkyl group, a hydroxy group or an atom halogen; secondary aromatic diamines (such as, N, N diphenylethylene-diamine), primary cycloaliphatic diamines (such as cyclohexane-diamine), secondary cycloaliphatic diamines (such as piperazine or trimethylene dipiperidine), and diamines such as xylene ( m-xylene diamine).
    [0009] In another process described in the US Patent. No. 6245234, a TFC polyamide membrane is made first by coating a porous polysulfone support with an aqueous solution containing: 1) a primary or secondary polyfunctional amine, 2) a tertiary polyfunctional amine, and, 3) a polar solvent. The excess aqueous solution is removed and the coated support is then immersed in an organic solvent solution of trimesoyl chloride (TMC) and a mixture of alkanes having 8 to 12 carbon atoms. [00010] Many different types of polymers can be synthesized interfacially using interfacial polymerization. Polymers typically used in interfacial polymerization applications include, but are not limited to, polyamides, polyurea, polypyrrolidines, polyesters, polyurethanes, polysiloxanes, poly (amide-imide), poly (ether-amide), poly (urea amide) (PUA) [Petersen, RJ “Composite reverse osmosis and nanofiltration membranes”. J. Membr. Sci, 83, 81-150, 1993]. For example, the US Patent. No. 5,290,452 describes the formation of a TFC crosslinked membrane of amide polyester produced by interfacial polymerization. The membrane is made by reacting a dianhydride (or its corresponding diacid - diester) with a polyester diol to produce an end-ended prepolymer. The resulting finished prepolymer is then reacted with excess thionyl chloride to convert all unreacted anhydride and
    Petition 870200038220, of 03/23/2020, p. 13/46 / 33 all groups of carboxylic acid, in groups of acid chloride. The resulting acid-chloride derivative is dissolved in an organic solvent and interfacially reacted with a diamine dissolved in an aqueous phase.
    [00011] The support membranes generally used for commercial TFC membranes are often polysulfone or polyethersulfone ultrafiltration membranes. These supports have limited stability for organic solvents and, therefore, thin film composite membranes of the prior art, which are manufactured with supports of this type cannot be used effectively for all organic solvent nanofiltration applications.
    [00012] Although interfacially polymerized TFC membranes of the prior art have been specially designed to separate aqueous feed streams at a molecular level, they can be applied in certain organic solvents, too [Koseoglu, SS, Lawhon, JT & Lusas, EW “Membrane processing of crude vegetable oils pilot plant scale removal of solvent from oil miscellas ”, J. Am. Oil Chem. Soc. 67, 315-322, 1990., US Patent No. 5,274,047]. Its effectiveness depends on the specific molecular structure of the thin film layer and the stability of the support membrane. US patent. No. 5,173,191 suggests cellulose, nylon, polyester, teflon and polypropylene as substrates resistant to organic solvents. US 6,986,844 proposes the use of cross-linked polybenzimidazole to make supporting membranes suitable for TFC. TFC membranes comprising a thin film synthesized from piperazine / mphenylenediamine and trimesol chloride on a PAN support membrane performed well in ethanol, methanol and acetone, much less in ipropanol and MEK, and did not flow in hexane [Kim , I.-C, Jegal, J. & Lee, K.-H. “Effect of aqueous and organic solutions on the performance of polyamide thin-film-composite nanofiltration membranes. ”Journal of Polymer Science Part B: Polimer Physics 40, 2151-2163, 2002].
    Petition 870200038220, of 03/23/2020, p. 14/46 / 33
    [00013] US 2008/0197070 describes the formation of thin-film composite membranes on polyolefin supports (for example, polypropylene) prepared by interfacial polymerization. These membranes performed well in water, ethanol and methanol.
    [00014] Non-reactive polydimethylsiloxane (PDMS), was added during the interfacial polymerization reaction using polyacrylonitrile (PAN) as the support membrane [Kim, IC & Lee, KH “Preparation of interfacially synthesized and silicone-coated composite polyamide nanofiltration membranes with high performance. ” Ind. Eng. Chem. Res. 41, 5523-5528, 2002, US Patent No. 6,887,380, US Patent Application No. 0098274 2003]. The PA membrane mixed with the resulting silicone showed high hexane permeabilities.
    [00015] TFC membranes were also applied by filtration in nonpolar solvents. A method for separating lubricating oil from organic solvents (eg furfural, MEK / toluene, etc.), with a TFC membrane using poly (ethylene imine) and a diisocyanate on a nylon 6,6 support resistant solvent resistant has been described in US Patent No. 5,173 91.
    [00016] In interfacially polymerized composite membranes, both the chemical surface and the morphology of the supporting membrane play a crucial role in determining the overall performance of the composite membrane. Membrane performance can be increased by modifying the membrane surface [D.S. Wavhal, E.R. Fisher, “Membrane surface modification by plasma-induced polymerization of acrylamide for improved surface properties and reduced protein fouling”, Langmuir 19, 79, 2003]. Thus, several procedures have been carried out to chemically modify the membrane surface and modify its properties. These procedures can increase hydrophilicity, improve selectivity and flow, adjust transport properties, and
    Petition 870200038220, of 03/23/2020, p. 15/46 / 33 increase resistance to the formation of scale and chlorine. Many methods have been reported for membrane surface modification, such as grafts, coating [US Patent 5,234,598, US Patent 5,358,745, US Patent 6,837,381] and mixing hydrophilic / hydrophobic surface modifying macromolecules (SMMs) [ BJ Abu Tarboush, D. Rana, T. Matsuura, H.A. Arafat, R.M.Narbaitz, “Preparation of thin-film-composite polyamide membranes for Desalination using novel hydrophilic surface modifying macromolecules”, J. Membr. Sci. 325, 166, 2008].
    [00017] In order to improve the performance of TFC membranes, different constituents have been added to the amine and / or acyl halide solutions. For example, the US Patent. No. 4,950,404, describes a process for increasing the flow of a TFC membrane by the addition of a polar aprotic solvent and an optional acid acceptor to the aqueous amine solution prior to the interfacial polymerization reaction. Similarly, US Patents. Nos. 5,989,426; 6,024,873; 5,843,351; 5,614,099; 5,733,602 and 5,576,057 describe the addition of alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds selected for the aqueous amine solution and / or the organic acid halide solution before the reaction of interfacial polymerization.
    [00018] It has been claimed that the immersion of freshly prepared TFC membranes in solutions containing various organic species, including glycerol, sodium lauryl sulfate, and the triethylamine salt with camphor sulfonic acid can increase the flow of water in RO applications by 3070% [3]. As described in US Patents. Nos. 5,234,598 and 5,358,745, the physical properties of TFC membranes (abrasion resistance), and flow stability can also be improved by applying an aqueous solution composed of poly (vinyl alcohol) (PVA) and a buffer solution, as a post-formation step during membrane preparation. Adding alcohols, ethers, sulfur-containing compounds,
    Petition 870200038220, of 03/23/2020, p. 16/46 / 33 aromatic monohydric compounds and more specifically dimethyl sulfoxide (DMSO), in the aqueous phase, can produce TFC membranes with excellent performance [S.-Y. Kwak, S.G. Jung, S.H. Kim, “Structure-motionperformance relationship of flux-enhanced reverse osmosis (RO) membranes composed of aromatic polyamide thin films”, Environ. Sci. Technol. 35, 4334, 2001; US patent 5,576,057; US patent 5,614,099]. After adding DMSO to the interfacial polymerization system, TFC membranes with a water flow five times greater than the normal flow of TFC water with a small loss in rejection were obtained [S.H. Kim, S.-Y. Kwak, T. Suzuki, “Positron annihilation spectroscopic evidence to demonstrate the flux-enhancement mechanism in morphology-controlled thin-film-composite (TFC) membrane”, Environ. Sci. Technol. 39, 1764, 2005].
    [00019] However, in these prior art TFC membranes the use of a polysulfone support membrane limits the potential for additives to either an aqueous amine solution or an organic acid halide solution. [00020] Various methods for improving the performance of the membrane after forming are also known. For example, the US Patent. No. 5,876,602 describes the treatment of the TFC membrane with an aqueous chlorinating agent to improve flow, lower salt passage, and / or increase the stability of the membrane to bases. US patent. No. 5,755,965 discloses a process in which the surface of the TFC membrane is treated with selected ammonia or amines, for example, 1.6, hexane diamine, cyclohexylamine and butylamine. US patent. No. 4,765,879 describes the post-treatment of a membrane with a strong mineral acid followed by treatment with a rejection-improving agent.
    [00021] A chemical treatment method is claimed to be capable of causing simultaneous improvement in water flow and rejection of thin-film composite membrane (TFC) salts for reverse osmosis [Debabrata Mukherjee, Ashish Kulkarni, William N. Gill , “Chemical
    Petition 870200038220, of 03/23/2020, p. 17/46 / 33 treatment for improved performance of reverse osmosis membranes ”, Desalination 104, 239-249, 1996]. Hydrophilization by treating the membrane surface with water-soluble solvent (acids, alcohols, and mixtures of acids, alcohols and water) is a known surface modification technique. This process increases the flow without changing the chemical structure [Kulkarni, D. Mukherjee, W.N. Gill, “Flux enhancement by hydrophilization of thin film composite reverse osmosis membranes”, J. Membr. Sci. 114, 39, 1996]. Using a mixture of acid and alcohol in water for surface treatment can improve surface properties, since acid and alcohol in water cause partial hydrolysis and skin modification, which produces a membrane with a higher flow and greater rejection . It has been suggested that the presence of hydrogen bonds on the membrane surface stimulates acid and water to react with these sites producing more charges [D. Mukherjee, A. Kulkarni, W.N. Gill, “Flux enhancement of reverse osmosis membranes by chemical surface modification”, J. Membr. Sci. 97, 231, 1994]. Kulkarni et al. a TFC-RO membrane was hydrophilized using ethanol, 2propanol, hydrofluoric acid and hydrochloric acid. They found that there was an increase in hydrophobicity, which led to a noticeable increase in water flow, without loss of rejection.
    [00022] A hydrophilic loaded TFC can be achieved using a two monomer radical graft, methacrylic acid and poly (ethylene glycol) methacrylate on a commercial PA-TFC-RO membrane [S. Belfer, Y. Purinson, R. Fainshtein, Y. Radchenko, O. Kedem, “Surface modification of commercial composite polyamide reverse osmosis membranes”, J. Membr. Sci. 139, 175, 1998]. It was found that the use of amines containing ethylene glycol blocks improved the performance of the membrane, and highly improved the water permeability of the membrane by increasing hydrophilicity [M. Sforca, S.P. Nunes, K.-V. Peinemann, “Composite nanofiltration membranes prepared by in-situ polycondensation of amines in a poly (ethylene oxide -b
    Petition 870200038220, of 03/23/2020, p. 18/46 / 33 amide) layer ”, J. Membr. Sci. 135, 179, 1997]. Poly (ethylene glycol) (PEG) and derivatives thereof have been used for surface modification. The resistance of the TFC membrane to fouling can be improved by grafting PEG chains onto the TFC-RO membranes [1, 2].
    [00023] PEG has also been used to improve the formation of TFC membranes [Shih-Hsiung Chen, Dong-Jang Chang, Rey-May Liou, Ching-Shan Hsu, Shiow-Shyung Lin, “Preparation and Separation Properties of Polyamide Nanofiltration Membrane ”, J Appl Polym Sci, 83, 1112-1118, 2002]. Due to the poor hydrophilicity of the polysulfone support membrane, poly (ethylene glycol) (PEG) was added to the aqueous solution as a wetting agent. The effect of PEG concentration on the performance of the resulting membrane was also studied.
    [00024] It has been reported that PEG is often used as an additive in the polymer solution to influence the membrane structure during phase inversion [Y. Liu, G. H. Koops, H. Strathmann, “Characterization of morphology controlled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution”, J. Membr. Sci. 223, 187, 2003]. The role of these additives is to create a spongy membrane structure by preventing the formation of macro-voids and to improve the formation of pores during phase inversion. Other frequently used additives are: glycerol, alcohols, dialcools, water, polyethylene oxide (PEO), LiCl and ZnCE. US Patent Nos. 2008/0312349 A and 2008/207822 A also describe the use of PEG in the polymeric doping solution during the preparation of microporous support membranes.
    [00025] Membranes of the prior art TFC are not claimed to be suitable for filtration in aggressive solvents (eg, THF, DMF). Thus, current and emerging applications, using non-aqueous media, in pressure driven membrane processes, present a need for the production of membranes that demonstrate greater stability. The membrane products and membrane-related methods of this
    Petition 870200038220, of 03/23/2020, p. 19/46 / 33 invention, advantageously, without addressing and / or overcoming the obstacles, limitations and problems associated with current membrane technologies and address effectively the membrane-related needs that are mentioned here.
    Summary of the Invention
    [00026] The present invention provides composite membranes formed by interfacial polymerization, which are particularly suitable for nanofiltration in organic solvents.
    [00027] More particularly, the present invention relates to the production and use of membranes for nanofiltration operations in polar aprotic solvents.
    [00028] In a first aspect, the invention provides a membrane for nanofiltration of a feed stream solution comprising a solvent and dissolved solutes and showing preferential rejection of the solutes, in which the membrane is a composite membrane formed from the interfacial polymerization of a thin polymeric film on a support membrane, in which the support membrane is impregnated with a conditioning agent and is stable in polar aprotic solvents, and in which the composite membrane is treated with an activating solvent before use in nanofiltration.
    [00029] Appropriately, the composite membrane is treated with an activating solvent, during or after interfacial polymerization. Without wishing to be bound by any particular theory, the use of an activating solvent to treat the membrane is believed to wash away any debris and unreacted materials from the membrane pores following the interfacial polymerization reaction. Treatment of the composite membrane with an activating solvent provides a membrane with improved properties, including, but not limited to, the membrane flow.
    [00030] In another aspect, the invention provides a process of
    Petition 870200038220, of 03/23/2020, p. 20/46 / 33 interfacial polymerization to form a composite membrane for solvent nanofiltration as defined herein, comprising the steps of:
    (a) impregnating a porous support membrane comprising a first conditioning agent, with a first reactive monomer solution comprising:
    (i) a first solvent for said first reactive monomer, (ii) a first reactive monomer, and (iii) optionally, an activating solvent, (iv) optionally, additives, including alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds, aromatic monohydric compounds;
    wherein said support membrane is stable in polar aprotic solvents;
    (b) contacting the support membrane impregnated with a second reactive monomer solution comprising:
    (i) a second solvent for the second reactive monomer, (ii) a second reactive monomer, (iii) optionally, additives, including alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds, monohydric aromatic compounds ;
    wherein the first solvent and the second solvent form a two-phase system (c) after a reaction period, immerse the resulting composite membrane in a deactivation medium;
    (d) treating the resulting asymmetric membrane with an activating solvent, and:
    (e) optionally, impregnating the resulting composite membrane with a second conditioning agent.
    [00031] In another aspect the present invention provides a membrane obtained by any of the methods defined herein.
    Petition 870200038220, of 03/23/2020, p. 21/46 / 33
    [00032] In another aspect the present invention provides a membrane obtained by any of the methods defined herein.
    [00033] In another aspect the present invention provides a membrane directly obtained by any of the methods defined herein.
    [00034] The membranes of the present invention can be used for nanofiltration operations in organic solvents. In particular, they can be used for nanofiltration operations in polar aprotic solvents. This is advantageous over many of the prior art thin-film nanofiltration composite membranes, which lose structure and dissolve in polar aprotic solvents, such as dimethylacetimide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran ( THF), N-methyl-2-pyrrolidone (NMP), and dichloromethane (DCM). Yet another advantage of the membranes of the present invention is that the activating solvents can include polar aprotic solvents, and the additives can include a wide variety of species in which the supporting membrane is stable. Yet another advantage of the membranes of the present invention is that they can exhibit greater flows than the known membranes when mixtures of water and organic solvent are being processed.
    Brief Description of Drawings
    [00035] Figure 1 shows molecular weight cut curves (MWCO) and TFC membrane flows after treatment with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00036] Figure 2 shows the MWCO curves and TFC membrane flows after treatment with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00037] Figure 3 shows the MWCO curves and membrane flows
    Petition 870200038220, of 03/23/2020, p. 22/46 / 33
    TFC after contacting DMF as the activating solvent. Nanofiltration of a feed solution comprising alkanes dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00038] Figure 4 shows the MWCO curve and flow of a TFC membrane that has not been treated with an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 30 bar (3 MPa) and 30 ° C.
    [00039] Figure 5 shows the MWCO curve and flow of a TFC membrane that has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 30 bar (3 MPa) and 30 ° C.
    [00040] Figure 6 shows the MWCO curve and flow of a TFC membrane that has not been treated with an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol was carried out at 30 bar (3 MPa) and 30 ° C.
    [00041] Figure 7 shows the MWCO curve and flow of a TFC membrane that has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol was carried out at 30 bar (3 MPa) and 30 ° C.
    [00042] Figure 8 shows the curve of MWCO and flow of a TFC membrane that has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in toluene was carried out at 30 bar (3 MPa) and 30 ° C.
    [00043] Figure 9 shows the MWCO curve and flow of a TFC membrane that has been treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in ethyl acetate was carried out at 30 bar (3 MPa) and 30 ° C.
    [00044] Figure 10 shows the MWCO curves and flows of TFC membranes prepared on a support membrane with cross-linked polyimide.
    Petition 870200038220, of 03/23/2020, p. 23/46 / 33 that was not impregnated with a conditioning agent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00045] Figure 11 shows the MWCO and flow curve of a TFC membrane prepared on a cross-linked polyimide support membrane that has been impregnated with PEG as a conditioning agent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00046] Figure 12 shows the MWCO curves and TFC membrane flows prepared on a PEEK support membrane. The TFC membrane was not treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00047] Figure 13 shows the MWCO curves and TFC membrane flows prepared on a PEEK support membrane. The TFC membrane was treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00048] Figure 14 shows the MWCO curves and TFC membrane flows containing hydrophobic groups added after the interfacial polymerization reaction. The resulting composite membranes are treated with DMF as an activating solvent. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    [00049] Figure 15 shows the MWCO curves and TFC membrane flows containing hydrophobic groups added during the interfacial polymerization reaction. The resulting composite membranes are treated with DMF as an activating solvent. Nanofiltration of a solution of
    Petition 870200038220, of 03/23/2020, p. 24/46 / 33 feeding comprising polystyrene oligomers dissolved in THF was carried out at 30 bar (3 MPa) and 30 ° C.
    Description of the Various Forms of Realization
    [00050] Thin-film composite membranes (also referred to as TFC membranes) formed by interfacial polymerization are known to those skilled in the art and include an entity composed of a layer of ultra-thin dense film on a support membrane, where the support membrane is previously formed from a different material.
    [00051] Appropriate support membranes can be produced from polymeric materials including cross-linked polyimide, cross-linked polybenzimidazole, cross-linked polyacrylonitrile, Teflon, polypropylene, and polyether ether ketone (PEEK), or polyether ether sulfonated ketone (S-PEEK).
    [00052] The polymer used to form the support membrane includes, but is not limited to, sources of polyimide polymers. The identities of such polymers are disclosed in the prior art, US Patent. N ° 0038306, the complete content of which is incorporated by reference. More preferably, the support membrane of the invention is prepared from a polyimide polymer described in the US Patent. No. 3,708,458, assigned to Upjohn, the complete content of which is incorporated herein by reference. The polymer, available from HP Polymers GmbH, Austria, as P84, is a copolymer derived from the condensation of benzophenone 3.3 ', 4-4'-tetracarboxylic acid dianhydride (BTDA) and a mixture of di (4aminophenyl) ) methane and toluene-diamine or the corresponding diisocyanates, 4,4'-methylenebis (phenyl isocyanate) and toluene diisocyanate.
    [00053] The copolyimide obtained has imide bonds, which can be represented by the structural formulas:
    Petition 870200038220, of 03/23/2020, p. 25/46 / 33

    wherein the copolymer comprises about 80% I and 20% II. [00054] Supporting membranes can be prepared following the methods described in GB 2437519, the total content of which is incorporated herein by reference, and comprising both nanofiltration and ultrafiltration membranes. Most preferably, the membranes of the present invention used as supports are within the ultrafiltration range. The membrane supports of the invention can be cross-linked using appropriate amine cross-linking agents and the method of cross-linking and timing can be that described in GB 2437519.
    [00055] It is an important feature of the present invention that the support membrane is impregnated with a conditioning agent. The "conditioning agent" is used here to refer to any agent that, when impregnated in the support membrane before the interfacial polymerization reaction, provides a resulting membrane, with a higher flow rate after drying. Any suitable conditioning agent can be used. Fittingly, the conditioning agent is a low volatility organic liquid. The conditioning agent can be chosen from synthetic oils (for example, polyolefin oils, silicone oils, polyalphaolefin oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils and aromatic alkyl oils),
    Petition 870200038220, of 03/23/2020, p. 26/46 / 33 mineral oils (including oils refined in hydroprocessed solvents and mineral oils and petroleum wax isomerate oils), vegetable fats and oils, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols, and glycols (for example example, polypropylene glycols, polyethylene glycols, polyalkylene glycols). Suitable solvents for dissolving the conditioning agent include water, alcohols, ketones, aromatics, hydrocarbons, or mixtures thereof. The first and second conditioning agents referred to herein can be the same or different.
    [00056] In the present invention, before the interfacial polymerization reaction, the support membrane is treated with a first conditioning agent dissolved in a solvent to impregnate the support membrane. Appropriately, the first conditioning agent is a low volatility organic liquid, as defined above.
    [00057] After treatment with the conditioning agent, the support membrane is typically air dried under ambient conditions to remove residual solvent.
    [00058] The interfacial polymerization reaction is generally maintained to occur at the interface between the solution of the first reactive monomer, and the solution of the second reactive monomer, which form two phases. Each phase can include a solution of a dissolved monomer, or a combination thereof. Concentrations of dissolved monomers may vary. Variables in the system can include, but are not limited to, the nature of the solvents, the nature of the monomers, the concentration of monomer, the use of additives in any of the phases, reaction temperature and reaction time. These variables can be controlled to define the properties of the membrane, for example, membrane selectivity, flow, top layer thickness. Monomers used in reactive monomer solutions can include, but are not limited to, diamines and diacyl halides. The resulting reaction can form a selective polyamide layer on top of the
    Petition 870200038220, of 03/23/2020, p. 27/46 / 33 support membrane.
    [00059] In this invention, the polymer matrix of the top layer can comprise any three-dimensional polymeric network known to those skilled in the art. In one aspect, the thin film comprises at least one of an aliphatic or aromatic polyamide, aromatic polyhydrazide, polybenzimidazolone, polyepiamine / amide, polyepiamine / urea, polyethyleneimine / urea, sulfonated polyurethane, polybenzimidazole, polyphenylamine, a polyphenylamine, an polyether-urea, a polyester, or a polyimide or a copolymer thereof or a mixture thereof. Typically, the polymer selected to form the thin film can be formed by an interfacial polymerization reaction.
    [00060] In another embodiment of this invention, the film comprises a polyamide. The polyamide can be an aromatic polyamide or a non-aromatic polyamide. For example, the polyamide may comprise residues of phthaloyl halide (e.g., terephthaloyl or isophthaloyl), of a trimesyl halide, or a mixture thereof. In another example, the polyamide may comprise residues of diaminobenzene, triaminobenzene, piperazine, polypiperazine, polyetherimine or a mixture thereof. In another embodiment, the film comprises residues of trimesol halide and residues of a diaminobenzene. In another embodiment, the film comprises residues of trimesol chloride and phenylenediamine. In a further aspect, the film comprises the reaction product of trimesol chloride and m-phenylenediamine.
    [00061] The first reactive monomer solution can comprise an aqueous solution of a polyamine. This aqueous amine solution can also contain other components, such as the polyhydric compounds as described in the US Patent. No. 4,830,885. Examples of such compounds include ethylene glycol, propylene glycol, glycerin, polyethylene glycol, polypropylene glycol, and copolymers of ethylene glycol and propylene glycol. THE
    Petition 870200038220, of 03/23/2020, p. 28/46 / 33 aqueous amine solution may also contain polar aprotic solvents.
    [00062] Aqueous monomer solutions may include, but are not limited to, an aqueous solution containing 1.6 hexenediamine, poly (ethyleneimine), an alternative aqueous monomer solution, and / or combinations thereof. The concentrations of the solutions used in the interfacial polymerization can be in a range of about 0.01% by weight to about 30% by weight. Preferably, the concentrations of the interfacial polymerization solutions can be in the range of about 0.1% by weight% and about 5% by weight.
    [00063] The solution of the second reactive monomer may contain di- or triacyl chlorides such as trimesoyl chloride or other monomers, dissolved in a non-polar solvent, such as hexane, heptane, toluene or xylene. In addition, the second reactive monomer solution may include, but is not limited to, a solution of iso-phthaloyl dichloride xylene, sebacoyl chloride, an alternative organic monomer solution, and / or combinations thereof.
    [00064] The interfacial polymerization reaction time described in step (b) may vary. For example, an interfacial polymerization reaction time can be in the range of about 5 seconds to about 2 hours. [00065] The deactivation step (c) includes contacting or treating the membrane after the interfacial polymerization reaction with a deactivation medium. The deactivation medium deactivates any unreacted functional groups present after the interfacial polymerization reaction.
    [00066] In one embodiment, the means of deactivation is water.
    [00067] The means of deactivation can also include an alcohol. The presence of an alcohol will terminate any unreacted acyl chloride groups present after the interfacial polymerization reaction. Suitable alcohols include, but are not limited to, R-OH, Ar-OH, alcohols, optionally with one or more siloxane substituents, alcohols with one or more
    Petition 870200038220, of 03/23/2020, p. 29/46 / 33 plus halo substituents (including fluorinated alcohols R F OH, where R F is an alkyl group with one or more hydrogen atoms replaced by fluorine atoms), where R includes, but is not limited to, alkyl groups, alkene, haloalkyl (for example, R F ), or Si-O-Si, and Ar is aryl (for example phenyl). [00068] The deactivation medium can also comprise one or more monomers as deactivation agents. Such terminating monomers can include amines. Suitable amines include, but are not limited to R-NH2, Ar-NH2, amines with siloxane substituents, alkylamines with halo substituents, including fluorine RFNH2 (where RF is an alkyl group in which one or more hydrogen atoms are replaced by atoms of fluorine), where R includes, but is not limited to, alkyl, alkene, RF, Si-O-Si groups.
    [00069] The deactivation medium may also comprise a solution containing R-acyl halides or Ar-acyl halides, where R includes, but is not limited to, alkyl, alkene, RF, Si-O-Si groups.
    [00070] In the above definitions, the appropriate alkyl groups or moieties comprise 1-20 carbon atoms and the appropriate alkene groups or fractions comprise 2-20 carbon atoms.
    [00071] A post-treatment step (d) includes contacting the composite membranes prior to use for nanofiltration with an activating solvent, including, but not limited to, polar aprotic solvents. In particular, the activating solvents include DMAc, NMP, DMF and DMSO. The activating solvent in this technique is defined as a liquid that improves the flow of the composite membrane after treatment. The choice of activating solvent depends on the top layer and the stability of the membrane support. Contact can be made by any means, including passing the composite membrane through an activating solvent bath, or filtering the activating solvent through the composite membrane.
    [00072] The second conditioning agent optionally applied in step (e) can be impregnated in the membrane by immersing the membrane
    Petition 870200038220, of 03/23/2020, p. 30/46 / 33
    TFC in a water or organic solvent bath or baths comprising the second conditioning agent.
    [00073] The high flow semipermeable TFC membranes resulting from the invention can be used for nanofiltration operations, particularly in organic solvents, and, more particularly, nanofiltration operations in polar aprotic solvents.
    [00074] The term "nanofiltration" means a membrane process that will allow the passage of solvents while delaying the passage of larger solute molecules, when a pressure gradient is applied across the membrane. This can be defined in terms of rejection of the Ri membrane, a common measure known to those skilled in the art and defined as:
    C c Ί
    R = 1 - - x 100% (1) k C Ri)
    [00075] where C pi = concentration of species i in the permeate, permeate being the liquid that has passed through the membrane, and Crí = concentration of species i in the retentate, retained being the liquid, which has not passed through the membrane. It will be appreciated that the membrane is selectively permeable for species i if Ri> 0. It is well understood by those skilled in the art that nanofiltration is a process in which at least one molecule of solute i with a molecular weight in the range of 100-2,000 g mol -1 is retained on the membrane surface over at least one solvent, so that Ri> 0. Typical nanofiltration pressures are in the range of 5 bar (0.5 MPa) to 50 bar (5 MPa).
    [00076] The term "solvent" will be well understood by the skilled reader and includes an organic or aqueous liquid with a molecular weight of less than 300 Daltons. It is understood that the term solvent also includes a mixture of solvents.
    [00077] As a non-limiting example, solvents include aromatics, alkanes, ketones, glycols, chlorinated solvents, esters, ethers,
    Petition 870200038220, of 03/23/2020, p. 31/46 / 33 amines, nitriles, aldehydes, phenols, amides, carboxylic acids, alcohols, furans and polar and aprotic polar protic, water, and mixtures thereof.
    [00078] As a non-limiting example, specific examples of solvents include toluene, benzene, xylene, styrene, anisol, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, methyl acetate, ethyl acetate, butyl acetate, methyl ether ketone (MEK), methyl iso butyl ketone (MIBK), acetone, ethylene glycols, ethanol, methanol, propanol, butanol, hexane, cyclohexane, dimethoxyethane, methyl tert-butyl ether (MTBE), diethyl ether, adiponitrile, N, N-dimethylformamide, dimethyl sulfoxide, N, N dimethylacetamide, dioxane, nitromethane, nitrobenzene, pyridine, carbon disulfide, tetrahydrofuran, methyltetrahydrofuran, N-methyl-pyrrolidone, acetonitrile, water, and mixtures thereof.
    [00079] The term "solute" will be well understood by the skilled reader and includes an organic molecule present in a liquid solution comprising a solvent and at least one solute molecule such that the weight fraction of the solute in the liquid is less than the weight fraction of the solvent, and where the molecular weight of the solute is at least 20 g mol 1 higher than that of the solvent.
    [00080] The membrane of the present invention can be configured according to any of the models known to those skilled in the art, such as in plate and frame, hull and tube, spiral-wound, and configurations derived therefrom.
    [00081] The following examples illustrate the invention.
    examples
    [00082] In the following examples, the performance of the membrane was evaluated according to the flow profiles and molecular weight cut curves (MWCO) of. All nanofiltration experiments were carried out at 30 bar (3 MPa) using a cross-flow filtration system. The membrane discs, with an active area of 14 cm, were cut from flat sheets and
    Petition 870200038220, of 03/23/2020, p. 32/46 / 33 placed in four cross-flow cells in series. Permeate samples for flow measurements were collected at 1 h intervals, and samples for rejection assessments were taken after stationary permeate flow was reached. MWCO was determined by interpolation from the rejection graph against a molecular weight of marker compounds. The solute rejection test was performed using two standard solutions. The first was a standard feed solution composed of a homologous series of styrene oligomers (PS), dissolved in the selected solvent. The styrene oligomer mixture contained 1-2 g L -1 each of PS 580 and PS 1090 (Polymer Labs, UK), and 0.01 g L -1 of an α-methylstyrene dimer (Sigma-Aldrich, UK). The analysis of the styrene oligomers was done using an Angilent HPLC system with UV / Vis detector configured at a wavelength of 264nm. The separation was achieved using a reverse phase column (C18-300, 250x 4.6 mm). The mobile phase consisted of 35% by volume of analytical water and 65% by volume of tetrahydrofuran with 0.1% by volume of trifluoroacetic acid. The second standard marker solution consisted of an alkanes solution containing 0.1% (weight / volume) of each alkane. The alkanes used were: decane, n-hexadecane, n-tetradecane, eicosane, tetracosane, hexacosane. Their MWs are 142.3 Dalton, Dalton 198.4, 226.4 Dalton, Dalton 280.5, 338.7 Dalton, and 366.7 Dalton, respectively. Analysis of the alkanes was by gas chromatography.
    [00083] Solvent flow (J) was determined by measuring the volume of permeate (V) per unit area (A) per unit time (t) according to the following equation:
    J = AL (1)A · t [00084] The rejection (Ri) of the markers was calculated from the equation
    2, where Cp, i and Cf, í, í, correspond to styrene concentrations in the permeate and in the feed, respectively.
    Petition 870200038220, of 03/23/2020, p. 33/46 / 33 c
    Ri = (1 -) · 100% (2) C F, i
    EXAMPLE 1
    [00085] In the following example, the membranes of the present invention are formed through interfacial polymerization to form a polyamide on a cross-linked polyimide support membrane, as follows: Formation of cross-linked polyimide support membrane
    [00086] The polymer doping solution was prepared by dissolving 24% (weight / weight) of polyimide (P84 from Evonik AG) in DMSO and stirring overnight, until complete dissolution. The viscous solution was formed, and left for 10 hours to remove air bubbles. The doping solution was then molded on a polyester or polypropylene non-woven lining material (Viledon, Germany), glued to a glass plate using a molding knife (Elcometer 3700) configured with a thickness of 250 μηι. Immediately after molding, the membrane was immersed in a water bath where the phase inversion occurred. After 15 minutes, she was changed to a new water bath and left for an hour. The wet membrane was then immersed in a solvent exchange bath (isopropanol) to remove any residual water and preparation solvents.
    [00087] The support membrane was then cross-linked using a solution of hexanediamine in isopropanol, by immersing the support membrane in the solution for 16 hours at room temperature. The support membrane was then removed from the cross-linking bath and washed with isopropanol for 1 h to remove any residual hexanediamine (HDA).
    [00088] The final step for preparing the crosslinked polyimide support membrane involved immersing the membrane overnight in a conditioning agent bath that consists of a 3: 2 volume ratio of polyethylene glycol 400 / isopropanol. The membrane was then cleaned with tissue paper and air dried.
    Formation of thin-film composite membranes by polymerization
    Petition 870200038220, of 03/23/2020, p. 34/46
    26/33 interfacial:
    [00089] TFC membranes were molded by hand on the cross-linked polyimide support membrane through interfacial polymerization. The support membrane was placed on a glass plate and in a 2% (weight / volume) aqueous solution of m-phenylenediamine (MPD,> 99%, Sigma-Aldrich) for about 2 min. The support membrane loaded with MPD was then laminated with a roller to remove excess solution. The support membrane saturated with MPD was then immersed in a solution of 0.1% (weight / volume) of trimesoyl chloride (TMC, 98%, SigmaAldrich) in hexane. After 1 min of reaction, the resulting membranes were removed from the hexane solution and rinsed with water (which corresponds to step (c) of the process defined here, that is, immersing the membrane in a deactivation medium). The chemical structures of the monomers used for the interfacial polymerization reaction are shown in Scheme 1.
    polyamide mesh
    Scheme 1. Interfacial polymerization reaction
    [00090] Membrane identification codes for membranes
    TFCs prepared in this Example are as follows:
    Entry No. Membrane Membrane code 1 TFC membrane prepared in reticulated PI as a support impregnated with polyethylene glycol (PEG) MPD-n
    wherein it does not identify membranes made in an independent batch.
    Treatment of TFC membranes with activating solvent (step d). [00091] A post-training treatment step was carried out in the
    Petition 870200038220, of 03/23/2020, p. 35/46 / 33 composite membranes, where the membranes were contacted with an activating solvent. In this example, the activating solvent was DMF. The contact time was 10 minutes through filtration or immersion.
    Performance of the composite membrane.
    [00092] The performances of TFC membranes in DMF and THF were evaluated before and after treatment with DMF as an activating solvent. The rejection curves and flows for TFC membranes in DMF / PS solution and in THF / PS solution after a post-treatment with DMF are shown in Figures 1 and 2. Figure 3 shows the rejection and flow curves for TFC membranes in THF / alkanes solution. The TFC membranes did not flow with THF before post-treatment with an activating solvent. It is clear that the contact of the membrane with the activating solvent improves the flow.
    EXAMPLE 2
    [00093] TFC membranes were manufactured according to EXAMPLE
    1. The post-formation step (d) (contacting DMF as the activating solvent) was only performed for some of the membranes. The performance of TFC membranes with and without the activation step (d) contacting DMF was evaluated in different solvents, including acetone, methanol, ethyl acetate and toluene.
    [00094] For the MWCO curves and flow test in MeOH, acetone, toluene and ethyl acetate, with and without contact with DMF, eight new MPD membranes were tested at each time and the results for both rejection and flow were reproducible .
    [00095] Figure 4 shows the rejection and flow curves for TFC membranes in acetone / PS without treating the membrane with an activating solvent. Figure 5 shows the rejection and flow curves for TFC membranes during nanofiltration of acetone / PS solution after treating the membranes with DMF.
    Petition 870200038220, of 03/23/2020, p. 36/46 / 33
    [00096] Figure 6 shows the rejection and flow curves for TFC membranes during MeOH / PS nanofiltration without treating the membrane with an activating solvent. Figure 7 shows the rejection and flow curves for TFC membranes during nanofiltration of MeOH / PS solution after treating the membranes with DMF.
    [00097] TFC membranes that have not been treated with DMF have shown no flow in toluene and ethyl acetate. Figure 8 shows rejection and flow curves for TFC membranes in toluene / PS solution after treating the membranes with DMF.
    [00098] Figure 9 shows rejection and flow curves for TFC membranes during nanofiltration of ethyl acetate / PS solution. Without DMF treatment, the TFC membranes did not flow in toluene or ethyl acetate.
    EXAMPLE 3
    [00099] Membrane supports were manufactured according to Example 1, but were not conditioned with PEG. TFC membranes were fabricated on these unconditioned support membranes as in Example 1. The performance of TFC membranes prepared on membrane supports with and without PEG was then evaluated and compared.
    [000100] The membrane identification codes for the TFC membranes prepared in this Example are as follows:
    Entry No. Membrane Membrane code 2 TFC membrane prepared in reticulated PI as a support impregnated with PEG MPD-n 3 TFC membrane prepared as a support not impregnated with PEG MPD-NP-n
    wherein it does not identify membranes made in an independent batch.
    [000101] Figure 10 shows the rejection and flow curves for TFC membranes prepared on membrane supports without PEG in DMF / PS solution. Figure 11 shows the rejection and flow curves for TFC membranes prepared on support membrane with PEG in DMF / PS solution. An increase in flow can be seen when the TFC membranes are
    Petition 870200038220, of 03/23/2020, p. 37/46 / 33 prepared on membrane supports containing PEG.
    [000102] In this example, the salt rejection of TFC membranes prepared with support membranes impregnated with PEG was compared with those prepared with non-impregnated supports. For the flow and rejection test, 150 mL of 0.2% NaCl (2000 ppm) aqueous solution was used in a dead cell filtration configuration at 30 bar (3 MPa) pressure. It is clear that impregnating the substrate with PEG before the interfacial polymerization reaction improves the water flow, without altering the salt rejection. The choice of material for the support membrane depends on the application. For water applications, it is not necessary to have a solvent-stable support membrane, so support membranes impregnated with PEG made from polysulfone and polyethersulfone are appropriate and lead to an improved water flow without changing the rejection.
    Membrane NaCl rejection (%) aqueous NaCl solution flow (L m -2 h -1 ) at 30 bar (3 MPa) MPD-NP 97.5 6.0 MPD 97.5 22.4
    EXAMPLE 4
    [000103] In this particular example, TFC membranes were prepared on PEEK support membranes, as follows:
    Manufacture of polyetheretherketone (PEEK) membrane supports:
    [000104] The polymer doping solution was prepared by dissolving 12.3% (weight / weight) in PEEK 79.4% methanesulfonic acid (MSA) and 8.3% sulfuric acid (H2SO4). The solution was stirred overnight until complete dissolution. The viscous solution was formed, and left to stand for 10 hours to remove air bubbles. The solution was then placed on a non-woven polyester backing material glued to a glass plate using a molding knife (Elcometer 3700) configured with a thickness of 250 μηι. Immediately after molding, the membrane was immersed in a water bath where the phase inversion occurred. After 15 minutes, it was changed to a new water bath and left for an hour. The wet membrane was then immersed in a water bath, to remove
    Petition 870200038220, of 03/23/2020, p. 38/46 / 33 any residual preparation solvents.
    [000105] The final step for the preparation of the PEEK support membrane involved immersing the membrane overnight in a conditioning agent bath that consists of a 3: 2 volume ratio of polyethylene glycol 400 / isopropanol. The membrane was then cleaned with tissue paper and air dried.
    [000106] TFC membranes were manufactured according to Example 1, section 1.2, on top of the PEEK support membrane. The TFC membranes were treated with DMF as an activating solvent such as 1. Some of the TFC membranes were not treated with an activating solvent for comparison.
    [000107] Figure 12 shows the rejection and flow curves for TFC membranes during nanofiltration of THF / PS solution without treating the membrane with an activating solvent. Figure 13 shows the rejection and flow curves for TFC membranes during nanofiltration of THF / PS solution after treating the membranes with DMF as an activating solvent.
    EXAMPLE 5
    [000108] TFC membranes were manufactured according to EXAMPLE
    1. After the interfacial polymerization reaction, the membranes were treated in a deactivation medium comprising a reactive monomer dissolved in a solvent (step c)
    Treatment of TFC membranes in deactivation medium
    [000109] A post-formation treatment step was carried out on the composite membranes, in which the membranes were contacted with a means of deactivation. In this example, the deactivation medium was a solution of a fluoroamine or aminosiloxane in hexane. The contact time was 1 minute by immersion. The reactive monomer ends the ends of the chloride-free acyl groups left in the polyamide film. In this example, the deactivation step modifies the chemistry of the membrane, making it
    Petition 870200038220, of 03/23/2020, p. 39/46
    31/33 more hydrophobic by termination of the acyl chloride groups not reacted with amines comprising halo, silyl or siloxane substituents. The chemical structures of the monomers used for the interfacial polymerization reaction are shown in Scheme 2.

    Polyamide
    Scheme 2. Polyamide with fluorinated dorsal structure (incorporating fluoroamine through termination).
    çh 3
    Si-OH-Si-O
    ÇH 3 f ÇH 3
    HjC-Si-oj-s::
    CH 3 1 CH 3 çh 3 -Sí-CH 3 CHj
    [000110] Membrane identification codes for membranes
    TFCs prepared in this Example are as follows:
    Entry No. Membrane Membrane code 4 TFC membrane prepared in reticulated PI as a support impregnated with PEG. MPD-n 5 TFC membrane prepared in reticulated PI as a support impregnated with PEG. The TFC membrane is post-treated with a solution of 2,2,3,3,3 pentafluoro propylamine in hexane. Fluoroamine-MPD-n 6 TFC membrane prepared in reticulated PI as a support impregnated with PEG. The TFC membrane is post-treated with a solution of poly [dimethylsiloxane-co- (3aminopropyl) methylsiloxanol in hexane. Aminosiloxane-MPD-n
    wherein it does not identify membranes made in an independent batch.
    [000111] The performance of chemically modified TFC membranes was evaluated in toluene. For the MWCO curves and flow test in toluene, eight new TFC membranes were tested at each time and the results for both rejection and flow were reproducible. Figure 14 shows the rejection and flow curves for these TFC hydrophobic membranes
    Petition 870200038220, of 03/23/2020, p. 40/46 in toluene / PS solution.
    EXAMPLE 6
    [000112] Cross-linked polyimide supports were manufactured as in Example 1 and impregnated with PEG. During the interfacial polymerization reaction, trimesol chloride was mixed with a fluoromonoacil chloride to make the membrane more hydrophobic and more open.
    Formation of thin-film composite membranes by interfacial polymerization:
    [000113] TFC membranes were hand molded on the cross-linked polyimide support membrane containing PEG by means of interfacial polymerization. The support membrane was placed on a glass plate and placed in a 2% (weight / volume) aqueous solution of m-phenylenediamine (MPD,> 99%, Sigma-Aldrich) for about 2 min. The support membrane loaded with kMPD was then laminated with a roller to remove excess solution. The support membrane saturated with MPD was then immersed in a 0.1% (weight / volume) solution of trimesoyl chloride (TMC, 98%, Sigma-Aldrich) mixed with perfluorooctanoyl chloride (7: 1) in hexane. After 1 min of reaction, the resulting membranes were removed from the hexane solution and rinsed with water step (c) (immersing the membrane in the deactivation medium). The chemical structures of the monomers used for the interfacial polymerization reaction are shown in the Scheme
    3.
    mpd + TMC + Fluoroacylchloride
    O F F F F F F
    Scheme 3. Polyamide with fluorinated dorsal structure (incorporating chloride
    Petition 870200038220, of 03/23/2020, p. 41/46 / 33 fluoride in the organic phase).
    [000114] Membrane identification codes for membranes
    TFCs prepared in this Example are as follows:
    Entry No. Membrane Membrane code 7 TEC membrane prepared in reticulated PI as a support impregnated with PEG. MPD-n 8 TEC membrane prepared in reticulated PI as a support impregnated with PEG. During interfacial polymerization, TMC is mixed with perfluorooctanoyl chloride to make the membrane more hydrophobic and with greater MWCO Fluoroacylchloride-MPD-n
    wherein it does not identify membranes made in an independent batch.
    [000115] The performance of chemically modified TFC membranes was evaluated in ethyl acetate. For the MWCO curves and ethyl acetate flow test, eight new TFC membranes were tested at each time and the results for both rejection and flow were reproducible. Figure 15 shows rejection and flow curves for these hydrophobic TFC membranes in ethyl acetate / PS solution.
    权利要求:
    Claims (14)
    [1]
    1. Interfacial polymerization process to form a composite membrane for nanofiltration operations in polar aprotic solvents, characterized by the fact that it comprises the steps of:
    (a) impregnating a porous support membrane comprising a first conditioning agent selected from glycols, with a first reactive monomer solution comprising:
    (i) a first solvent for said first reactive monomer; (ii) a first reactive monomer;
    wherein said support membrane is stable in polar aprotic solvents;
    (b) contacting the support membrane impregnated with a second reactive monomer solution comprising:
    (i) a second solvent for the second reactive monomer; (ii) a second reactive monomer;
    wherein the first solvent and the second solvent form a two-phase system (c) after a reaction period, immerse the resulting composite membrane in a deactivation medium; and (d) treating the resulting asymmetric membrane with an activating solvent being a polar aprotic solvent.
    [2]
    Process according to claim 1, characterized in that the support membrane is formed from cross-linked polyimide, cross-linked polybenzimidazole, cross-linked polyacrylonitrile, Teflon, polypropylene, or polyether ether ketone (PEEK), or polyether ether sulfonated ketone (S-PEEK).
    [3]
    Process according to claim 1 or 2, characterized in that it comprises an additional step (e) of impregnating the composite membrane with a second
    Petition 870200038220, of 03/23/2020, p. 43/46
    2/3 conditioning selected from one or more synthetic oils, mineral oils, vegetable fats and oils, higher alcohols, glycerols, and glycols.
    [4]
    Process according to any one of claims 1 to 3, characterized in that the first reactive monomer solution comprises an aqueous solution of a polyamine.
    [5]
    Process according to any one of claims 1 to 4, characterized in that the first reactive monomer solution comprises an aqueous solution of a 1,6 hexenediamine or poly (ethyleneimine).
    [6]
    Process according to any one of claims 1 to 5, characterized in that the first reactive monomer solution contains ethylene glycol, propylene glycol, glycerin, polyethylene glycol, polypropylene glycol, and copolymers of ethylene glycol and propylene glycol, or polar aprotic solvents.
    [7]
    Process according to any one of claims 1 to 6, characterized in that the second reactive monomer solution may contain monoacyl chlorides, polyacyl chlorides or a mixture thereof, or other monomers.
    [8]
    Process according to any one of claims 1 to 7, characterized in that the second reactive monomer solution can contain trimesoyl chloride, iso-phthaloyl dichloride, or sebacoyl chloride or a mixture thereof.
    [9]
    Process according to any one of claims 1 to 8, characterized in that the composite membrane is treated in step (d) with an activating solvent by immersion or washing in the activating solvent.
    [10]
    Process according to any one of claims 1 to 9, characterized in that the composite membrane is treated in step (d) with an activating solvent by filtration through the membrane using the activating solvent.
    Petition 870200038220, of 03/23/2020, p. 44/46
    3/3
    [11]
    Process according to any one of claims 1 to 10, characterized in that the composite membrane is treated in step (d) with an activating solvent comprising dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide, dimethylacetamide or a mixture thereof.
    [12]
    Process according to any one of claims 1 to 11, characterized in that the contact time in step (b) is chosen between 5 seconds and 5 hours.
    [13]
    Process according to any one of claims 1 to 12, characterized in that the temperature of the contact step (b) of the solution is maintained between 10 and 100 ° C.
    [14]
    Process according to any one of claims 1 to 13, characterized in that the resulting membrane is configured as a plate and frame, hull and tube, spiral-wound, or configurations derived therefrom.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-04-24| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-07-09| B06G| Technical and formal requirements: other requirements [chapter 6.7 patent gazette]|Free format text: CONFORME A IN INPI/DIRPA NO 03 DE 30/09/2016, O DEPOSITANTE DEVERA COMPLEMENTAR A RETRIBUICAO RELATIVA AO PEDIDO DE EXAME DO PRESENTE PEDIDO, DE ACORDO COM TABELA VIGENTE, REFERENTE A(S) GUIA(S) DE RECOLHIMENTO 0000921405161719 (PETICAO800140152100, DE 10/07/2014). |
    2019-12-24| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-04-14| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-06-09| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2011, OBSERVADAS AS CONDICOES LEGAIS. |
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    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1012083.0A|GB201012083D0|2010-07-19|2010-07-19|Thin film composite membranes for separation|
    PCT/GB2011/051364|WO2012010889A1|2010-07-19|2011-07-19|Solvent resistant polyamide nanofiltration membranes|
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