process of interfacial polymerization to form a thin-film composite membrane

专利摘要:
THIN FILM COMPOSITE MEMBRANE FOR GAS SEPARATION OR LIQUID FILTRATION, AND INTERFACIAL POLYMERIZATION PROCESS TO FORM A THIN FILM COMPOSITE MEMBRANE. The present invention relates to a composite membrane for gas separation and / or nanofiltration of a solution from a feed stream solution comprising a solvent and dissolved solutes and showing preferential rejection of the solutes. The composite membrane comprises a separation layer with intrinsic microporosity. The separation layer is suitably formed by interfacial polymerization on a support membrane. Appropriately, at least one of the monomers used in the interfacial polymerization reaction must have a concavity, resulting in a network polymer with interconnected nanopores and a membrane with increased permeability. The support membrane can optionally be impregnated with a conditioning agent, and can be optionally stable in organic solvents, particularly in polar aprotic solvents. The top layer of the composite membrane is optionally finished with functional groups to change the surface chemistry. The composite membrane can be cured in the oven to improve rejection. Finally, the composite membrane can be treated with an activating solvent before nanofiltration.
公开号:BR112014009214B1
申请号:R112014009214-1
申请日:2012-10-18
公开日:2020-12-01
发明作者:Andrew Guy Livingston；Maria Fernanda Jimenez Solomon
申请人:Imperial Innovations Limited；
IPC主号:

专利说明:

[0001] The work that led to this invention received funds from the European Union Seventh Framework Program (FP7 / 2007-2013) under Grant Agreement No. 241226. Field of invention
[0002] The present invention relates to separation membranes. More specifically, the present invention relates to composite thin-film membranes comprising the support membrane coated with a separating layer, wherein the separating layer comprises a network polymer having intrinsic microporosity. The present invention also relates to processes for the preparation of these membranes and their use in a variety of applications, including, but not limited to, gas separation, pervaporation, nanofiltration, desalination and water treatment, and particularly the nanofiltration of dissolved solutes. 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 species separations of varying molecular weights in liquid and gas phases (see, for example, "Membrane Technology and Applications" 2a. Ed. , RW Baker, John Wiley and Sons Ltd, ISBN 0-470-85445-6).
[0004] With particular reference to nanofiltration, such applications have gained 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 molecular weight fraction in the range of 200-2,000 Daltons. A molecular weight fraction of a membrane is generally defined as the molecular weight of a molecule that would exhibit 90% rejection when subjected to membrane nanofiltration.
[0005] Membranes for nanofiltration, pervaporation and gas separation are generally manufactured by producing composite membranes. Thin-film composite membranes can be manufactured via interfacial polymerization (here also referred to as IP) or by coating [Lu, X .; Bian, X .; Shi, L., "Preparation and characterization of NF composite membrane." J. Membr. Sci., 210, 3-11, 2002].
[0006] In glassy polymers, gas permeability depends strongly on the amount and distribution of free volume in the polymer (ie the space not occupied by polymer molecules) and on chain mobility. In liquid applications when using defect-free thin-film composite membranes, high free volume leads to high permeability. Polymers with the highest permeability have rigid twisted macromolecular backbones that give rise to microvazios. When the free volume is very high, these microvazios are interconnected resulting in intrinsic microporosity. Here, microporous materials are solids having interconnected pores of less than 2 nm in size [Handbook of Porous Solids, Schuth F, Sing K, Weitkamp J Eds. Wiley-VCH; Berlin 2002, Vols 1-5]. This porosity size is also commonly referred to as nanoporosity, and materials with this microporosity are referred to as nanoporous.
[0007] In order to achieve very high permeabilities, high free volume and microporosity are sought. Polymers showing these properties are so-called high free volume polymers. These highly permeable polymers were applied mainly for gas separations. Some examples include certain substituted polyacetylenes (for example, PTMSP), some perfluoropolymers (for example, Teflon AF), some poly (norbornene) s, intrinsic microporosity polymers, and some polyimides. Its microporosity was demonstrated by molecular modeling and positron annihilation spectroscopy (PALS). Highly permeable polyacetylenes have bulky side groups that inhibit conformational change and force the backbone into a twisted shape. These hard polymer macromolecules cannot properly wrap in the solid state, resulting in high free volume. The free volume distribution comprises disconnected elements such as vitreous polymers and continuous micro-voids. In Teflon perfluoropolymers its high free volume is due to a high barrier for rotation between contiguous dioxolane rings, coupled with weak inter-chain interactions, which are well known for fluoropolymers, leading to a low packing density and, therefore, high permeability. In the case of poly (norborene) s and PTMSP, the presence of bulky trimethylsilyl groups in the ring greatly restricts the freedom of the polymer to undergo conformational change. In intrinsic microporosity polymers (PIMs), molecular connectors containing contortion points are kept in a non-coplanar orientation by rigid molecules, which does not allow the resulting polymers to pack closely and ensure a high microporosity. The concept of PIMs has been reported for polimides [P M Budd and N B McKewon, “High permeable polymers for gas separation membranes, Polymer Chemistry, 1, 63-68, 2010].
[0008] There are two different types of PIMs, i) non-mesh polymers (linear) that can be soluble in organic solvents, and ii) mesh polymer that are generally insoluble, depending on the choice of monomer. PIMs have an internal molecular free volume (IMFV), which is a measure of concavity and is defined by Swager as the difference in volume of the concave unit as compared to the non-concave format [TM Long and TM Swager, “Minimization of free volume: Alignment of Triptycenes in Liquid Crystals and Stretched Polymers ”, Adv. Mater, 13, 8, 601-604, 2001]. While intrinsic microporosity in linear PIMs is claimed to derive from the impenetrable concavities given by their contorted structures, in network PIMs, microporosity is also claimed to derive from the concavities associated with macrocycles. In PIMs without a network, the rotation of simple connections should be avoided, considering that branching and cross-linking in network PIMs are difficult to avoid and a structural reorganization can result in the loss of microporosity (McKeown, 2010), so that simple connections can be present without loss of microporosity. In general, it was observed that network PIMs have greater microporosity than non-network PIMs due to their macrocyclization [NB McKewon, PM Budd, “Explotation of intrinsic microporosity in polymer-based materials in Polymer-Based materials”, Macromolecules, 43, 51635176, 2010]. However, since prior art network PIMs are not soluble, they can only be incorporated into a membrane if mixed as fillers with soluble microporous materials, which include soluble PIMs or other soluble polymers.
[0009] There is a strict requirement in PIMs without a network that there are no simple connections on the polymer backbone, to avoid rotational freedom and thus provide intrinsic microporosity. Highly rigid and contorted molecular structures are required, providing inappropriate macromolecular shapes that cannot efficiently pack in space. Molecules with inappropriate shapes are those that attribute conditioning problems due to their concavities. However, in order to have microporosity in non-meshed PIMs, concave-shaped molecules are not sufficient as voids must be sufficiently interconnected for transport to occur with minimal energy (ie intrinsic microporosity) [NB McKewon, PM Budd, “Explotation of intrinsic microporosity in polymer-based materials ”, Macromolecules, 43, 5163-5176, 2010]. Non-meshed PIMs can be soluble and thus suitable for molding a membrane by phase inversion, or for coating in use a support membrane to produce a thin film composite. However, its solubility in a solvent range restricts its applications in organic solvent nanofiltration [Ulbricht M, Advanced functional polymer membranes. Single Chain Polymers, 47, 2217-2262, 2006].
[00010] US patent 7,690,514 B2 describes intrinsic microporosity materials comprising organic macromolecules consisting of a first generally planar species connected by linkers having a contortion point such that two first adjacent planar species connected by a linker are maintained in non-coplanar orientation. Preferred points of contortion are spiro groups, bridged and stereochemically congested ring portions around which limited rotation occurs. These non-mesh PIMs can be soluble in common organic solvents, allowing them to be molded into membranes, or coated over other support membranes to produce a thin film composite.
[00011] PIM-1 membranes (soluble PIM) exhibit gas permeabilities that are exceeded only by many high free volume polymers such as Teflon AF2400 and PTMSP, presenting selectivities above Robenson's 1991 upper bond for gas pairs such as CO2 / CH4 and O2 / N2. Studies show that the permeability is improved by methanol treatment, helping to wash the residual molding solvent and allowing the chains to relax [PM Budd and NB McKewon, D Fritsch, “Polymers of Intrinsic Microporosity (PIMs): High free volume polymers for membrane applications ”, Macromol Symp, 245-246, 403-405, 2006].
[00012] A range of polyimides with characteristics similar to an intrinsic microporosity polymer (PIM) were prepared by Ghanem et al. and membrane gas permeation experiments have shown these PIM polyimides to be among the most permeable of all polyimides and having selectivities close to the upper bond for several important gas pairs [BG Ghanem, NB McKeown, PM Budd, NM Al-Harbi , D Fritsch, K Heinrich, L Starannikova, A Tokarev and Y Yampolskii, “Synthesis, characterization, and gas permeation properties of a novel group of polymers with intrinsec microporosity: PIM-polimides”, Macromolecules, 42, 7781-7888, 2009] .
[00013] US patent 7,410,525 B1, describes mixed polymer / polymer matrix membranes incorporating soluble polymers of intrinsic microporosity as microporous fillers for use in gas separation applications.
[00014] International Patent Publication WO 2005/113121 (PCT / GB2005 / 002028) describes the formation of thin-film composite membranes of PIMs by coating a solution of PIMs in organic solvent on a backing membrane, and then optionally cross-linking that film. PIM to increase its stability in organic solvents.
[00015] In order to improve the stability of soluble PIM membranes, US patent 7,758,751 B1, describes high-performance UV-crosslinked membranes from intrinsic microporosity polymers (PIMs) and their use in both gas separations and separations of liquid involving organic solvents such as olefin / paraffin, deep desulfurization of gasoline and diesel fuel, and ethanol / water separations.
[00016] Organic solvent nanofiltration (OSN) has many potential applications in manufacturing industries including solvent exchange, catalyst recovery and recycling, purifications, and concentrations. US patents 5,174,899 5,215,667; 5,288,818; 5,298,669 and 5,395,979 describe the separation of organometallic compounds and / or metal carbonyls from their solutions in organic media. UK Patent 2,373,743 describes the application of OSN for solvent exchange; UKGB patent 2,369. 311 describes the application of OSN for recycling phase transfer agents, and; European Patent Application EP1590361 describes the application of OSN for the separation of syntons during oligonucleotide synthesis.
[00017] Membranes for reverse osmosis and nanofiltration can be produced by the technique of interfacial polymerization (IP). In the IP technique, an aqueous solution of a first reactive monomer (often a polyamine) is first deposited within the porous structure of a support membrane, often a polysulfone ultrafiltration membrane. Then, the polysulfone support membrane loaded with the reactive monomer solution is immersed in a water-immiscible solvent solution containing a second reactive monomer, such as tracid chloride in hexane. The first and second reactive monomers react at the interface of the two immiscible solutions, until a thin film presents a diffusion barrier and the reaction is completed to form a highly cross-linked thin film layer that remains attached to the support membrane. The thin film layer can have a thickness of several tens of nanometers to several micrometers. The IP technique is well known to those skilled in the art [Petersen, R. J. “Composite reverse osmosis and nanofiltration membranes” .J. Membr. Sci, 83, 81-150, 1993]. The thin film is selective between molecules, and this selective layer can be optimized for solute rejection and solvent flow by controlling the reaction conditions, characteristics of the reactive monomers, chosen solvents and post-reaction treatments. The porous support membrane can be selectively chosen for porosity, strength and solvent stability. 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 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.
[00018] US patent 4,277,344 describes an aromatic polyamide membrane produced by the interfacial polymerization of an aromatic polyamine with at least two primary amine substituents and an acyl halide having at least three acyl halide substituents. Whereupon, the aqueous solution contains a monomeric aromatic polyamine reagent and the organic solution contains an amine reactive polyfunctional acyl halide. The TFC membrane polyamide layer is typically obtained by interfacial polymerization between an amine or cyclohexane-substituted piperazine or piperidine, and a polyfunctional acyl halide as described in US patents 4,769,148 and 4,859,384. One way to modify TFC membranes from reverse osmosis (also referred to here as RO) for nanofiltration is described in US patents 4,765,897; 4,812,270; and 4,824,574. Postpolymerization interfacial treatments were also used to increase the pore size of TFC RO membranes.
[00019] US patent 5,246,587 describes an aromatic polyamide RO membrane which is produced by first coating a porous support material with an aqueous solution containing a polyamine reagent and an amine salt. 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 a halogen atom; aromatic secondary diamines (such as N, N-diphenylethylene diamine), cycloaliphatic primary diamines (such as cyclohexane diamine), cycloaliphatic secondary diamines (such as trimethylene piperazine or dipiperidine); and xylene diamines ( such as m-xylene diamine).
[00020] In another method described in US Patent 6,245,234, a TFC polyamide membrane is made first by coating a porous polysulfone support with an aqueous solution containing: 1) a polyfunctional primary or secondary amine; 2) a polyfunctional tertiary amine; and; 3) a polar solvent. The excess aqueous solution is removed and the coated support is then immersed in a solution of organic trimesoyl chloride (TMC) solvent and a mixture of alkanes having eight to twelve carbon atoms.
[00021] Many different types of polymers can be interfacially synthesized using interfacial polymerization. Polymers typically used in interfacial polymerization applications include, but are not limited to, polyamides, polyurea, polypyrrolidines, polyesters, poly (ester amides), polyurethanes, polysiloxanes, poly (amide imides), polyimides, poly (ether amides), polyethers, poly (urea amides) (PUA) [Petersen, RJ “Composite reverse osmosis and nanofiltration membranes”. J. Membr. Sci, 83, 81-150, 1993]. For example, US patent 5,290,452 describes the formation of a cross-linked polyesteramide TFC membrane produced by interfacial polymerization. The membrane is made by reacting a dianhydride (or its corresponding diacid-diester) with a polyester diol to produce a finished prepolymer. The resulting finished prepolymer is then reacted with excess thionyl chloride to convert all unreacted anhydride and all groups of carboxylic acid to 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.
[00022] In order to improve the stability of TFC prepared by interfacial polymerization, TFC membranes based on poly (stearide) have been developed showing improved oxidative (chlorine) resistance compared to polyamide membranes [M.M. Jayaraniand S.S.Kulkarni, "Thin-film composite poly (steroid) -based membranes", Desalination, 130, 17-30, 2000]. It has been reported that the rejection of polyesteramide TFC membranes can be adapted by varying the ester / amide ratio; more open TFC membranes were prepared using bisphenols with bulky substituents for diafiltration to separate organic molecules (MW> 400 Da) from salts [Uday Razadan and SS Kulkarni, “Nanofiltration thin-film composite polyesteramide membranes based on bulky diols”, Desalination, 161 , 25-32, 2004].
[00023] US patent 5,593,588 describes a thin film composite reverse osmosis membrane having an active layer of aromatic polyester or aromatic polyester and aromatic polyamide copolymer, which has improved chlorine resistance and oxidation stability. The active layer is prepared by interfacial polymerization of an aqueous solution of polyhydric phenol and a solution of aromatic acyl halide dissolved in organic solvent.
[00024] Spiral-wrapped thin poly (ether / amide) composite membranes designated PA-300, have previously been reported for water desalination applications. PA-300 was formed by an in situ interfacial polymerization of an aqueous solution of epichlorohydrin-ethylene diamine and an organic solution of isophthalyl dichloride [RL Riley, RL Fox, CR Lyons, CE Milstead, MW Seroy, and M Tagami, “ Spiralwound poly (ether / amide) Thin-Film composite membrane systems ”, Desalination, 19, 113-126, 1976].
[00025] The support membranes generally used for commercial TFC membranes produced by interfacial polymerization 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 that were manufactured with such supports cannot be effectively used for all organic solvent nanofiltration applications.
[00026] Although interfacially polymerized TFC membranes of the prior art have been specifically designed to separate aqueous feed streams down to a molecular level, they can be applied to certain organic solvents as well [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 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 5,173,191, suggests nylon, cellulose, polyester, Teflon and polypropylene as resistant supports of organic solvent. 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 / m-phenylenediamine and trimesoyl chloride on a PAN support membrane made well in methanol, ethanol and acetone, less well in i-propanol and MEK, and did not provide any 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 Science Part B: Polymer Physics40, 2151-2163, 2002].
[00027] US 2008/0197070 describes the formation of thin-film composite membranes on polyolefin supports (e.g., polypropylene) prepared by interfacial polymerization. These membranes carried out well in water, ethanol and methanol.
[00028] Non-reactive polydimethylsiloxane (PDMS) was added during the interfacial polymerization reaction using polyacrylonitrile (PAN) as the supporting 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 6,887 380, US Patent Application 0098274 2003]. The resulting PA membrane mixed with silicone showed high hexane permeabilities.
[00029] TFC membranes have also been applied for 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 solvent-resistant nylon 6.6 support described in US patent 5,173 91.
[00030] In interfacially polymerized composite membranes, both surface chemistry and support membrane morphology 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]. In this way, different procedures were 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 improve resistance to scale and chlorine. Many methods have been reported for membrane surface modification such as grafting, coating [US Patent 5,234,598, US Patent 5,358,745, US Patent 6,837,381] and mixing macromolecules modifying the hydrophilic / hydrophobic surface (SMMs) [B.J. 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].
[00031] In order to improve the performance of TFC membranes, different constituents were added to the amine and / or acyl halide solutions. For example, US patent 4,950,404, describes a method for increasing the flow of a TFC membrane by adding a polar aprotic solvent and an optional acid receptor to the aqueous amine solution prior to the interfacial polymerization reaction. In a similar manner, US patents 5,989,426; 6,024,873; 5,843,351; 5,614,099; 5,733,602 and 5,576,057 describe the addition of selected alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds to the aqueous amine solution and / or organic acid halide solution prior to the polymerization reaction interfacial.
[00032] It has been claimed that soaking freshly prepared TFC membranes in solutions containing various organic species, including glycerol, sodium lauryl sulfate, and the triethylamine salt with camphorsulfonic acid can increase water flow in RO applications by 3070% [M.A. Kuehne, R.Q. Song, N.N. Li, R.J. Petersen, "Flux enhancement in TFC RO membranes", Environ. Prog. 20 (1), 23, 2001]. As described in US patents 5,234,598 and 5,358,745, the physical properties of TFC (abrasion resistance) membrane, 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, 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-motion- performance 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 water flow five times greater than the normal TFC water flow with a small loss in rejection were obtained [S.H. Kim, S.-Y. Kwak, T. Suzuki, “Positron annihilation spectroscopic evidence to demonstrate the fluxenhancement mechanism in morphology-controlled thin-film-composite (TFC) membrane”, Environ. Sci. Technol. 39, 1764, 2005].
[00033] However, in these prior art TFC membranes, the use of a polysulfone support membrane limits the potential for additives to any aqueous amine solution or organic acid halide solution.
[00034] Various methods for improving TFC membrane post-formation performance are also known. For example, US Patent 5,876,602 describes treating the TFC membrane with an aqueous chlorinating agent to improve flow, less salt flow, and / or increase membrane stability to bases. US patent 5,755,965 describes a process in which the surface of the TFC membrane is treated with ammonia or selected amines, for example, 1.6, hexane diamine, cyclohexylamine and butylamine. US patent 4,765,879 describes the post-treatment of a membrane with a strong mineral acid followed by treatment with a rejection-improving agent.
[00035] A chemical treatment method is claimed to be capable of causing simultaneous improvement of water flow and salt rejection of thin-film composite (TFC) membranes for reverse osmosis [Debabrata Mukherjee, Ashish Kulkarni, William N. Gill , “Chemical treatment for improved performance of reverse osmosis membranes”, Desalination 104, 239-249, 1996]. Hydrophilization treating the membrane surface with water-soluble solvent (acids, alcohols, and mixtures of acids, alcohols and water) is a well-known technique of surface modification. This method 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, as 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 bonding on the membrane surface encourages acid and water to react at 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. hydrophilized an RO-TFC membrane using ethanol, 2-propanol, hydrofluoric acid and hydrochloric acid. They found that there was an increase in hydrophilicity, which leads to a noticeable increase in water flow without loss in rejection.
[00036] A hydrophilic loaded TFC can be achieved using two monomer radical grafting, 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 ethylene glycol blocks containing amine increased the membrane performance, and highly improved membrane water permeability increased the hydrophilicity [M. Sforça, S.P. Nunes, K.-V. Peinemann, “Composite nanofiltration membranes prepared by in-situ polycondensation of amines in a poly (ethtylene oxide-b-amide) layer”, J. Membr. Sci. 135, 179, 1997]. Poly (ethylene glycol) (PEG) and its derivatives were used for surface modification. TFC membrane resistance to fouling could be improved by grafting PEG chains onto RO-TFC membranes [G. Kang, M. Liu, B. Lin, Y. Cao, Q. Yuan, “A novel method of surface modification on thin-film composite reverse osmosis membrane by grafting poly (ethylene glycol)”, Polymer 48, 1165, 2007, V Freger, J. Gilron, S. Belfer, “TFCpolyamide membranes modified by grafting of hydrophilic polymers: an FT-IR / AFM / TEM study”, J. Membr. Sci. 209, 283, 2002].
[00037] PEG was also used to improve TFC membrane formation [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 polim 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 resulting membrane performance was also studied.
[00038] 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 formation of macrovazios and to increase the formation of pores during phase inversion. Other frequently used additives are: glycerol, alcohols, dialkols, water, polyethylene oxide (PEO), LiCl and ZnCl2. US patents 2008/0312349 A and 2008/207822 A also describe the use of PEG in the polymeric doping solution during the preparation of porous support micronembranes.
[00039] It is generally known that heating, also known as curing, of thin-film composite membranes may be required to facilitate the removal of organic solvent from nascent polyamide thin films, and to promote additional cross-linking by dehydration of unreacted amine and groups of carboxyl. [Asim K. Ghosh, Byeong-Heon Jeong, Xiaofei Huang, Eric M.V. Hoek, Impacts of reaction and curing conditions on polyamide composite reverse osmosis membrane properties, Journal de Membrana Science 311 (2008) 34-45]. This heating or curing is usually suffered after the reaction of interfacial polymerization, and can be in the range of 45oC to 90oC or higher.
[00040] The membrane products and membrane-related methods of the present invention advantageously address and / or overcome the obstacles, limitations and problems associated with current membrane technologies and effectively address the membrane-related needs that are noted here. Summary of the invention
[00041] The present invention provides, in a first aspect, a thin film composite membrane comprising a support membrane coated with a separation layer, wherein the separation layer comprises a network polymer having intrinsic microporosity. The membranes of the invention are particularly suitable for gas separation, pervaporation, nanofiltration, desalination and water treatment.
[00042] Suitably, at least a proportion of the monomeric components of the network polymer have a concavity.
[00043] More particularly, the present invention relates to the production and use of membranes for nanofiltration operations in organic solvents.
[00044] Furthermore, the present invention also provides thin-film composite membranes formed by interfacial polymerization. Thus, in another aspect, the present invention provides a thin film composite membrane comprising a support membrane coated with a separation layer, where the subsequent separation is formed in the support layer by interfacial polymerization, and in which the layer of The separation comprises a network polymer having intrinsic microporosity.
[00045] In a particular embodiment, thin-film composite membranes are formed by interfacial polymerization, in which at least one of the monomers used in the interfacial polymerization reaction has a concavity.
[00046] In another aspect, the invention provides a thin-film composite membrane, wherein the membrane is a composite membrane comprising a separation layer formed by interfacial polymerization of at least one first reactive monomer and at least one second reactive monomer in one support membrane, wherein the resulting separation layer comprises a polymer network with intrinsic microporosity. The support membrane can be impregnated with a conditioning agent and can be stable in organic solvents; and wherein the composite membrane can be temperature cured and / or treated with an activating solvent before use.
[00047] Appropriately, at least one of the reactive monomers used in the interfacial polymerization reaction is a molecule with a concave shape (ie impractical or contorted) preferably rigid, restricting the freedom of the resulting network polymer undergoing structural reorganization, granting an increase to interconnected microvazios and associated intrinsic microporosity.
[00048] In one embodiment, the composite membrane can be temperature cured for a given time to improve some properties, including, but not limited to, membrane selectivity.
[00049] In another embodiment, the composite membrane can be treated with an activating solvent during or after interfacial polymerization. Without being bound by any particular theory, the use of an activating solvent to treat the membrane is believed to expel any debris, unreacted material and small oligomers 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, membrane flow.
[00050] In another aspect, the invention provides an interfacial polymerization process to form a thin film composite membrane as defined here, comprising the steps of: (a) impregnating a porous support membrane, which can comprise 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 / or a reactive monomer having a concavity; (iii) optionally, an activating solvent, (iv) optionally, additives, including alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds, monohydric aromatic compounds; (b) contacting a support membrane impregnated with a second reactive monomer solution, comprising: (i) a second solvent for the second reactive monomer; (ii) a second reactive monomer and / or a reactive monomer having a concavity; (iii) optionally, additives, including alcohols, ketones, ethers, esters, halogenated hydrocarbons, nitrogen-containing compounds and sulfur-containing compounds, aromatic monohydric compounds; wherein: the first solvent and the second solvent form a two-phase system; at least one of the reactive monomers has a concavity; and a reaction of the monomers results in a separating layer forming on a support membrane to give a composite membrane; (c) optionally, after a reaction period, terminating the unreacted groups of the separation layer with functional groups to modify the composition and surface chemistry; (d) after a reaction period, immerse a resulting composite membrane in an abrupt cooling medium; (e) optionally, curing a temperature or microwave membrane for a specified time; (f) optionally, treating a resulting composite membrane with an activating solvent; and (g) optionally, impregnating a resulting composite membrane with a second conditioning agent.
[00051] In another aspect the present invention provides a thin film composite membrane that can be obtained by any of the methods defined here.
[00052] In another aspect the present invention provides a thin-film composite membrane obtained by any of the methods defined herein.
[00053] In another aspect the present invention provides a thin film composite membrane directly obtained by any of the methods defined here.
[00054] TFC membranes of the invention are suitably produced by interfacial polymerization, comprising a separating layer formed from a polymer lattice having intrinsic microporosity. The TFC membranes of the invention can be used for gas separation and / or nanofiltration operations in aqueous and / or organic solvents. In particular, they can be used for nanofiltration operations in organic solvents. An advantage of the membranes of the present invention is that a crosslinked network of polymer having intrinsic microporosity is formed in situ during the interfacial polymerization reaction as the separating layer, whereas prior art thin film composite membranes with intrinsic microporosity polymers are prepared by coating and are restricted to soluble polymers of intrinsic microporosity that are not polymers without mesh. The use of the composite membranes of the invention in nanofiltration with polar aprotic solvents is advantageous when using a stable solvent support with respect to many prior art thin-film composite nanofiltration membranes, which are not stable in solvents such as dimethylacetimide (DMAc), dimethylformamide (DMF), dimethylsulfoxide (DMSO), tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), and dichloromethane (DCM) or requires another crosslinking for solvent stability. Another advantage of the membranes of the present invention is their thin separation layer (thickness in the order of nanometers), in relation to many prior art thin-film composite membranes and TFCs with intrinsic microporosity, which are prepared by immersion coating or solvent molding and have a separating layer thickness in the order of microns. Thinner separation layers lead to greater permeability and require less material in the separation layer. Yet another advantage of the membranes of the present invention is that the activating solvents can include polar aprotic solvents, and additives can include a wide range of species in which the supporting membrane is stable. TFC membranes of the present invention may exhibit greater permeability and selectivity than known membranes for gas separation and so mixtures of water and organic solvent are being processed. Brief description of the drawings
[00055] Figure 1 shows the curve of the molecular weight fraction (MWCO) and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 3 MPa and 30oC.
[00056] Figure 2 shows a MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was not cured in the oven. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 3 MPa and 30oC.
[00057] Figure 3 shows the MWCO curve and membrane flow of TFC-IP-PIMs prepared on a crosslinked P84 support. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol was carried out at 3 MPa and 30oC.
[00058] Figure 4 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was not cured in the oven. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in methanol was carried out at 3 MPa and 30oC.
[00059] Figure 5 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF was carried out at 3 MPa and 30oC.
[00060] Figure 6 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was not cured in the oven. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in DMF was carried out at 3 MPa and 30oC.
[00061] Figure 7 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 3 MPa and 30oC.
[00062] Figure 8 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was not cured in the oven. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 3 MPa and 30oC.
[00063] Figure 9 shows the MWCO curve and flow of a TFC-IP-PIMs membrane prepared on a crosslinked P84 support. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in toluene was carried out at 3 MPa and 30oC.
[00064] Figure 10 shows the MWCO curve and membrane flow of TFC-IP-PIMs prepared on a crosslinked P84 support. The TFC membrane was not cured in the oven. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in toluene was carried out at 3 MPa and 30oC.
[00065] Figure 11 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PEEK support membrane. The TFC membrane was cured in an oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 3 MPa and 30oC.
[00066] Figure 12 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PEEK support membrane. The TFC membrane was cured in an oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 3 MPa and 30oC.
[00067] Figure 13 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PEEK support membrane. The TFC membrane was cured in the oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in toluene was carried out at 3 MPa and 30oC.
[00068] Figure 14 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PEEK support membrane. The TFC membrane was cured in an oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in heptane was carried out at 3 MPa and 30oC.
[00069] Figure 15 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PBI support membrane. The TFC membrane was cured in an oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in THF was carried out at 3 MPa and 30oC.
[00070] Figure 16 shows the MWCO and flow curve for a TFC-IP-PIMs membrane prepared on a PBI support membrane. The TFC membrane was cured in an oven at 85 ° C for 10 minutes. Nanofiltration of a feed solution comprising polystyrene oligomers dissolved in acetone was carried out at 3 MPa and 30oC.
[00071] Figure 17 shows the gas separation performance for a TFC-IP-PIMs membrane prepared on a PEEK support membrane. The membrane was cured in an oven at 85 ° C for 10 minutes. The gas permeation experiments were carried out 275.79; 344.73; 413.69 KPa. Figure 17 (a) shows CO2 / N2 selectivity against CO2 permeability; (b) shows CO2 / CH4 selectivity versus CO2 permeability, and (c) shows O2 / N2 selectivity against O2 permeability. Description of the various embodiments Definitions
[00072] As used here, the terms "optionally" or "optional" mean that the later described event or action may or may not occur, and that the description includes examples, where that event or action occurs and examples where it does not.
[00073] The term "network polymer" is used here to refer to a covalently cross-linked three-dimensional polymeric network. This is in contrast to a "netless polymer" (or a "linear" polymer) in which the polymers do not have a covalently cross-linked three-dimensional structure.
[00074] The term "microporosity" is used here to refer to the membrane separation layer comprising pores less than or equal to 2 nm in size.
[00075] The term "intrinsic microporosity" is used here to mean the network polymer provides a continuous network of interconnected intermolecular voids (appropriately less than or equal to 2 nM in size), which forms as a direct consequence of shape and stiffness (or concavity) of at least the proportion of the network polymer component monomers. As will be appreciated by a person skilled in the art, intrinsic microporosity arises due to the structure of the monomers used to form the network polymer and, as the term suggests, it is an intrinsic property of a network polymer formed from such monomers. The shape and stiffness of the monomer used to form the network polymer means that the polymer has an internal molecular free volume (IMFV), which is a measure of the monomer concavity and is the difference between the volume of the concave monomer unit compared to that corresponding flat format.
[00076] It is understood that the network polymers described here have a certain property (that is, intrinsic microporosity). Here some structural requirements are described in the monomers used to grant a polymer performing the described function, and it is understood that there are a variety of structures that can perform the same function, which are related to the same described monomer structures, and that these structures will typically achieve the same result.
[00077] The monomers to be used to prepare the network polymers of the invention are described as well as the polymers alone, to be used within the methods described herein. It is understood that when combinations, subsets, etc. of these monomers are described, which while specific reference to each of the various individual and collective combinations and permutation of these monomers may not be explicitly described, each is specifically contemplated and described here. If a particular polymer is described and discussed and a number of modifications that can be made to a number of monomers are discussed, specifically contemplated is each and every combination and permutation of the monomers and the modifications that are possible unless specifically stated otherwise. Thus, if a class of monomers A, B, and C is described, as well as a class of monomers D, E and F and an example of a combination AD polymer is described, then even if each is not individually recited it is individually and collectively contemplated meaning that combinations of AE, AF, BD, BE, BF, CD, CE and CF are considered described. Similarly, any subset or combination of these is also described. Thus, for example, the subgroup of A-E, B-F, and C-E would be considered described. This concept applies to all aspects of that application including, but not limited to, steps in methods of making and using compositions of the invention.
[00078] By the term "nanofiltration" is meant 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 Ri membrane rejection, a common measurement known to those skilled in the art and being defined as:
where CP, i = concentration of species i in the permeate, permeated being the liquid that passed through the membrane, and CR, i = concentration of species i in the retained, the retained being the liquid that did not pass through the membrane. It will be appreciated that a membrane is selectively permeable for a species i if Ri> 0. It is well understood for those skilled in the art that nanofiltration is a process in which at least one molecule i of solute with a molecular weight in the range 100-2,000 g mol -1 is retained on the membrane surface for at least one solvent, so that Ri> 0. Typical applied pressures in the nanofiltration range from 500 KPa to 5 MPa (5 bar to 50 bar).
[00079] The term "solvent" will be well understood by the skilled person and includes an organic or aqueous liquid with a molecular weight less than 300 Daltons. It is understood that the term solvent also includes a mixture of solvents.
[00080] As a non-limiting example, solvents include aromatics, alkanes, ketones, glycols, chlorinated solvents, esters, ethers, amines, nitriles, aldehydes, phenols, amides, carboxylic acids, alcohols, furans, and polar protic and aprotic solvents polar, water, and mixtures of these.
[00081] As a non-limiting example, specific examples of solvents include toluene, xylene, benzene, 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, dimethylsulfoxide , N, N dimethylacetamide, dioxane, nitromethane, nitrobenzene, pyridine, carbon disulfide, tetrahydrofuran, methyltetrahydrofuran, N-methyl pyrrolidone, acetonitrile, water, and mixtures thereof.
[00082] The term "solute" will be well understood by the average versed reader and includes an organic molecule present in a liquid solution comprising a solvent and at least one solute molecule that has the weight fraction of the solute in the liquid is less than the fraction weight of the solvent, and where the molecular weight of the solute is at least 20 g mol-1 greater than that of the solvent. Thin-film composite membranes
[00083] Thin film composite membranes (also referred to as TFC) will be familiar to one skilled in the art and include an entity composed of a thin film separating layer on a support membrane, where the support membrane is previously formed of a material different. TFC membranes are appropriately formed by interfacial polymerization.
[00084] Suitable support membranes can be produced from polymer materials including polysulfone, polyethersulfone, poly (ether-sulfone-ketone), polyacrylonitrile, polypropylene, polyamide, cellulose acetate, cellulose diacetate, cellulose triacetate, poly (ethyl ether ketone), poly (phthalazinone ether-sulfone-ketone), a perfluoropolymer, polyimide, polybenzimidazole, perfluropolymers, polyether ether ketone (PEEK), sulfonated polyether ketone ether (S-PEEK), or other polymeric materials known to those versed in those known to those versed in those technical. Wherein, the polymer support membrane can be further cross-linked.
[00085] Preferably, suitable support membranes can be prepared from an inorganic material such as by way of non-limiting example: silicon carbide, silicon oxide, zirconium oxide, titanium oxide, aluminum oxides or zeolites, using any technique known to those skilled in the art such as sintering, leaching or sol-gel processes.
[00086] The polymer used to form the support membrane includes, but is not limited to, sources of polyimide polymer. The identities of such polymers are disclosed in the prior art, US Patent 0038306, the entire contents of which are incorporated herein by reference. More preferably, the support membrane of the invention is prepared from a polyimide polymer described in US Patent 3,708,458, assigned to Upjohn, the complete contents of which are 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 (BTDA) and a mixture of di (4-aminophenyl) methane and toluene diamine or the corresponding diisocyanates, 4,4'-methylenebis (phenyl isocyanate) and toluene diisocyanate.
[00087] Supporting membranes can be prepared following the methods described in GB 2,437,519, the complete contents of which are incorporated herein by reference, and comprise both nanofiltration and ultrafiltration membranes. More preferably, the membranes of the 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 and time of cross-linking can be that described in GB 2,437,519.
[00088] The support membrane is optionally impregnated with a conditioning agent. The term "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. Any suitable conditioning agent can be used. Appropriately, 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), mineral oils (including refined solvent oils and hydroprocessed mineral oils and oils from petroleum wax isomerates), vegetable fats and oils, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols, and glycols (such as polypropylene glycols, polyethylene glycols, polyalkylene glycols) . Suitable solvents to dissolve the conditioning agent include water, alcohols, ketones, aromatics, hydrocarbons, or mixtures thereof. The first and second conditioning agents referred to here can be the same or different.
[00089] In this invention, before the interfacial polymerization reaction, the support membrane is optionally 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.
[00090] Following treatment with the conditioning agent, the support membrane is typically air-dried under ambient conditions to remove residual solvent.
[00091] The interfacial polymerization reaction is generally maintained to occur at the interface between the first reactive monomer solution, and the second reactive monomer solution, which forms two phases. Each phase can include a solution of a dissolved monomer or a combination of these. 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, monomer concentrations, the use of additives in any of the phases, reaction temperature and reaction time. Such variables can be controlled to define membrane properties, for example, membrane selectivity, flow, separation layer thickness. At least one of the monomers used in reactive monomer solutions must have a well-defined concavity (ie, concave shape). Monomers in the first reactive solution may include, but are not limited to, polyphenols, polyamines, or mixtures thereof. The monomers in the second reactive solution include, but are not limited to, polyfunctional acyl halides, polyfunctional haloalkylbenzenes, polyfunctional halogenated aromatic species, or mixtures thereof. The resulting reaction can form a layer of polymer separation mesh on top of the backing membrane, including, but not limited to, a layer of polyester mesh, a layer of polyether mesh, a layer of polyamide mesh, or a layer of polyester mesh. network that includes mixtures of these.
[00092] Although water is a preferred solvent for the first reactive monomer solution, non-aqueous solvents can be used, such as acetyl nitrile and dimethylformamide (DMF). Although no specific order of addition is necessarily required, the first reactive monomer solution is typically coated or impregnated on the support membrane first, followed by the second reactive monomer solution being contacted with the support membrane. Although one or both of the first monomer and the second monomer can be applied to the porous support of a solution, they can alternatively be applied by other means such as vapor deposition, or simple
[00093] A residue of a chemical species refers to the portion that is the product resulting from the chemical species in a particular reaction or subsequent chemical product, regardless of whether the portion is actually obtained from the chemical species. Thus, an ethylene glycol residue in a polyester refers to one or more OCH2CH2O units in the polyester, regardless of whether the residue is obtained by reacting ethylene glycol to obtain the polyester.
[00094] In this invention, the polymer matrix of the separation layer can comprise any three-dimensional polymer network having intrinsic microporosity. In one aspect, the separation layer comprises at least one of an aliphatic or aromatic polyamide, aromatic polyhydrazide, poly-benzimidazolone, poly-amine / amide, poly-polyamine / urea, poly-ethyleneimine / urea, sulfonated polyurethane, polyether, a polyether-amide, a polyether-urea, a polyester, a polyester-amide, polybenzimidazole, polypiperazine isophthalamide, or a polyimide or a copolymer thereof or a mixture thereof. The polymer selected to form the separation layer can be formed by an interfacial polymerization reaction.
[00095] It is an important aspect of the present invention that at least one of the monomers participating in the interfacial polymerization reaction is a molecule with a concave shape (i.e. concavity), preferably rigid and bonded to another monomer or monomers to form a polymer network inside, whose molecular rotation is preferably impaired. Monomers containing concavity include, but are not limited to molecules containing a spiro-contoured center, bridged ring portions and unique stereochemically congested covalent bonds around which rotation is restricted. These molecules are also known as molecules with inappropriate shapes (that is, those that have conditioning problems due to their concavities). Structural units with well-defined cavities include, but are not limited to, 1,1-spirobisindans (for example, 1, 3, 4-7, 19 in Scheme 1), 9,9-spirobisfluorenes (for example, 16, 20 in Scheme 1), bisnaphthalenes (for example, 2, 17 in Scheme 1) 1,1-spirobis, 2,3,4-tetrahydro-naphthalenes (for example, 11-14 in Scheme 1), and 9,10-ethananthracene ( for example 8.9 in Scheme 1). Generally, the polymer network of the invention is prepared by reacting two or more monomers, in which at least one of the monomers has a concavity. In one aspect, the first monomer is a dinucleophilic or polynucleophilic monomer and the second monomer is a dielectrophilic or a polyelectrophilic monomer. Wherein, each monomer can have two or more reactive groups. Both electrophiles and nucleophiles are well known in the art, and one skilled in the art can choose appropriate monomers for the interfacial polymerization reaction. The first and second monomers can be chosen so as to be able to undergo an interfacial polymerization reaction to form a three-dimensional polymer network when placed in contact.
[00096] In Scheme 1, the reactive groups are shown as Z. Here Z can be any suitable nucleophilic group such as hydroxyl or amine groups, and specifically Z = -OH, -NH2. Alternatively, Z can be any electrophilic group such as an acyl halide, specifically an acyl chloride, or an electron withdrawing group that confers the electrophilic monomer. Suitable electron withdrawal groups include halogenated species F, Cl, Br, or I. 3, 4, 9 and 13 in Scheme 1 show monomers where Z could be a halogen. Scheme 2 shows examples of rigid monomers, which are optional monomers for the interfacial polymerization reaction. Such monomers can be used individually or mixtures with other monomers. Reactive groups in Scheme 2 are designated as Y. Here Y can be any suitable nucleophilic group, such as hydroxyl or amine groups, and specifically Z = -OH, -NH2. Alternatively, Z can be any electrophilic group such as an acyl halide, specifically an acyl chloride, or an electron withdrawing group that confers the electrophilic monomer. Appropriate electron withdrawal groups include halogenated species F, Cl, Br, or I. Species 2,5,8,9,11-22 in Scheme 2 show monomers where Y could be a halogen. For the purposes of the current invention, when Z is an electrophile or an assignment group that makes the monomer an electrophile, then Y is a nucleophile, and, when Z is a nucleophile, then Y is an electrophile or an assignment group that makes the monomer is an electrophile. When Y is an electrophile, or an electron withdrawing group that makes the electrophilic monomer, including F, Cl, Br, or I, then it may be particularly advantageous to combine a Scheme 2 rigid monomer present in the second reactive monomer solution with any of the monomers described above in Scheme 1 that are suitable for use in the first reactive monomer solution, such as polyamines, or polyphenols, to form the separation layer. Layout 1


[00097] In another embodiment of this invention, the separation layer comprises a network composed of, but not limited to, a polyester, a polyether, a polyamide, a polyimide or a mixture thereof. Polyester, polyamide, polyether or polyimide can be aromatic or non-aromatic. For example, polyester can comprise residues of a phthaloyl halide (e.g., terephthaloyl or isophthaloyl), a trimesoyl halide, or a mixture thereof. In another example, the polyester may comprise residues of a polyphenol containing a spiro-contoured center, or ring portions bridged by stereochemically congested single covalent bonds around which rotation is restricted, or a mixture thereof. Wherein, a concave monomer may include, but is not limited to, small oligomers (n = 0-10) of a polymer with intrinsic microporosity (PIM) containing nucleophilic or reactive electrophilic groups. One skilled in the art can choose appropriate PIM oligomers with reactive groups capable of undergoing an interfacial polymerization reaction, which include, but are not limited to polyphenols or polyamines (for example, 25 and 26 in Scheme 1). In another embodiment, the separation layer comprises residues of a trimesoyl halide and residues of tetrafenol with a spiro-contoured center. In another embodiment, the film comprises residues of trimesoyl chloride and 5.5 ', 6.6'-tetrahydroxy -3,3,3', 3'-tetramethyl-1,1'-spirobisindane (TTSBI, monomer 1 in Scheme 1). In another aspect, the film comprises the reaction product of trimesoyl chloride and the sodium salt of 5.5 ', 6.6'-tetrahydroxy -3,3,3', 3'-tetramethyl-1,1'- spirobisindan (TTSBI).
[00098] The first reactive monomer solution may comprise an aqueous monomer solution, and or either a rigid monomer (see Scheme 2, for examples), and or a concave monomer (see Scheme 1 for examples), including, but not limited to a polyphenol with a concave shape. Such an aqueous polyphenol solution may also contain other components, such as polyhydric compounds as described in U. S. Pat. 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 aqueous polyphenol solution can also contain polar aprotic solvents.
[00099] Aqueous monomer solutions may include, but are not limited to, an aqueous solution containing a 5.5 ', 6,6'-tetrahydroxy - 3,3,3', 3'-tetramethyl-1,1 salt '-spirobisindane (TTSBI), an aqueous solution of alternative monomer, and / or combinations thereof. Concentrations of solutions used in interfacial polymerization can be in the range of about 0.01% by weight to about 30% by weight. Preferably, concentrations of the interfacial polymerization solutions can be in the range of about 0.1% by weight to about 5% by weight. In addition, aqueous monomer solutions can be made acidic or basic by adding appropriate reagents, so that the monomers are made soluble as acidic or basic salts.
[000100] The second reactive monomer solution may contain monomers with or without a concavity (see Scheme 1 for examples), or / and PIMs oligomers, and or a rigid monomer (see Scheme 2 for examples). Monomers in the second solution include, but are not limited to polyfunctional acyl halides such as trimesoyl chloride, or / and other monomers including, but not limited to polyfunctional haloalkylbenzenes, such as 1,3,5-tris (bromomethyl) benzene, or / and rigid monomers with electrophilic or nucleophilic reactive groups (designated as Y) that can undergo interfacial polymerization (see Scheme 2 for examples of rigid monomers) including but not limited to polyfunctional halobenzenes, such as 2,3,5,6-tetrafluorotereftalonitrile , or a mixture thereof dissolved in a nonpolar 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 isophthaloyl dichloride xylene, sebacoyl chloride, an alternative organic monomer solution, and / or combinations thereof.
[000101] The reaction time for interfacial polymerization described in step (b) may vary. For example, an interfacial polymerization reaction time can be in the range of about 5 seconds to about 48 hours.
[000102] Optionally, a leveling step (c) can be performed, in which groups without unreacted polymer mesh are leveled to modify the surface chemistry of the composite membrane. It comprises contacting the membrane with a solution containing leveling monomers, which may include alcohols including, but not limited to R-OH, Ar-OH, alcohols with siloxane substituents, alcohols with halosubstitutants including fluorine RFOH, where R includes, but is not limited to alkyl, alkene, RF, H, Si-O-Si. Amines may also be used, as leveling monomers and may include, but are not limited to R-NH2, Ar-NH2, amines with siloxane substituents, amines with halo substituents including fluorine RFNH2, where R includes but is not limited to alkyl , alkene, RF, H, Si-O-Si. The leveling medium may comprise a solution containing R-acyl halides or Ar-acyl halides, where R includes, but is not limited to, alkyl, alkene, RF, H, Si-O-Si. Layout 2

[000103] A blast cooling step (d) includes contacting or trapping the membrane after the interfacial polymerization reaction with a blast cooling medium which may include, but is not limited to, water.
[000104] Optionally, a post-treatment step (e) comprises curing the membrane with temperature or with a microwave.
[000105] Optionally, a post-treatment step (f) comprises contacting the composite membranes prior to use for nanofiltration with an activating solvent, including, but not limited to, aprotic polar solvents. In particular, activating solvents include DMAc, NMP, DMF and DMSO. The activating solvent in this technique is defined as a liquid that increases the flow of the composite membrane after treatment. The choice of activating solvent depends on the separation layer and stability of the membrane support. Contact can be made through any practical means, including passing the composite membrane through a bath of the activating solvent, or filtering the activating solvent through the composite membrane.
[000106] The second conditioning agent applied in step (g) is optionally impregnated in the membrane by immersing the TFC membrane in a bath or bath of water or organic solvent comprising the second conditioning agent.
[000107] The resulting high flow semipermeable mesh TFC membranes with intrinsic microporosity of the invention can be used for gas separation or nanofiltration operations, particularly in nanofiltration in organic solvents, and more particularly nanofiltration operations in polar aprotic solvents.
[000108] Gas separations include the separation of torque, ternary and multicomponent mixtures including oxygen, nitrogen, hydrogen, carbon dioxide, methane.
[000109] A variety of membrane formats are useful and can be provided using the present invention. These include, but are not limited to, spiral winding, concave, tubular fiber, or flat sheet type membranes. The membrane of the present invention can be configured according to any of the drawings known to those skilled in the art, such as spiral winding, plate and structure, shell and tube, and drawings derived therefrom.
[000110] The following examples illustrate the invention. EXAMPLES
[000111] In the following examples 1-3, nanofiltration performance of the inventive membranes was evaluated according to flow profiles and molecular weight fraction (MWCO) curves. All nanofiltration experiments were carried out at 3 MPa using a cross-flow filtration system. Membrane discs, with an active area of 14 cm2, were cut from flat sheets and placed in 4 cross-flow cells in series. Permeate samples for flow measurements were collected at 1 h intervals, and samples for rejection assessments were taken after constant permeate flow was achieved. MWCO was determined by interpolating the rejection graph against molecular weight of marker compounds. The solute rejection test was performed using a standard feed solution comprised of a homologous series of styrene (PS) oligomers 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 α-methylstyrene dimer (Sigma-Aldrich, UK). Analysis of the styrene oligomers was done using an Agilent HPLC system with UV / Vis detector configured at a wavelength of 264nm. 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 tetrahydrofuran with 0.1% by volume trifluoroacetic acid.
[000112] Solvent flow (J) was determined by measuring volume of permeate (V) per unit area (A) per unit time (t) according to the following equation:

[000113] The rejection (Ri) of markers was calculated from equation 2, where CP, ie CF, i correspond to styrene concentrations in the permeate and the feed respectively.

[000114] In example 4, gas separation performance of inventive membranes was assessed according to pure gas permeation measurements with CH4, N2, O2 and CO2. Gas selectivities were measured for CO2 / N2, CO2 / CH4 and O2 / N2. Gas permeabilities were measured with a soap bubble meter at feed pressure of 2.8, 3.5 and 4.5 kg / cm2 (40, 50 and 60 psig). The gas selectivity of inventive membranes was calculated by:
where a is selectivity and Pg is gas permeability. EXAMPLE 1
[000115] In the following example, membranes of the present invention are formed through interfacial polymerization to form a polyester on a cross-linked polyimide support membrane, as follows:
[000116] Formation of cross-linked polyimide support membrane
[000117] A polymer doping solution was prepared by dissolving 24% (by weight) polyimide (P84 from HP polymer AG) in DMSO and stirring overnight until complete dissolution. A viscous solution was formed, and allowed to remain for 10 hours to remove air bubbles. The doping solution was then molded in a polyester or polypropylene non-woven lining material (Viledon, Germany) taped to a glass plate using a molding knife (Elcometer 3700) set to a thickness of 250 gm. Immediately after molding, the membrane was immersed in a water bath where 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.
[000118] The support membrane was then cross-linked using a solution of hexanediamine in isopropanol, 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).
[000119] The final step to prepare the crosslinked polyimide support membrane involved by dipping the membrane overnight in a conditioning agent bath consisting of a 3: 2 polyethylene glycol 400 / isopropanol volume ratio. The membrane was then dried with tissue paper and air dried. Formation of thin-film composite membranes by interfacial polymerization:
[000120] TFC membranes were hand molded on the crosslinked polyimide support membrane through interfacial polymerization. The support membrane was taped to a glass plate and placed in a 2% aqueous solution (pH = 13) 2% (weight by volume) NaOH 5.5 ', 6.6'-tetrahydroxy -3.3 , 3 ', 3'-tetramethyl-1,1'-spirobisindane (98%, ABCR GmbH) for approximately 2 min. The support membrane loaded with phenoxide was then laminated with a roller to remove excess solution. The saturated membrane support was then immersed in a 0.1% (weight by volume) solution of trimesoyl chloride (TMC, 98%, Sigma-Aldrich) in hexane. After 2 min of reaction, the resulting membranes were removed from the hexane solution and rinsed with water (which corresponds to step (d) of the process defined here, that is, to immerse the membrane in a sudden cooling medium). The chemical structures of the monomers used for the interfacial polymerization reaction are shown in Scheme 1.
Scheme 1. Monomers involved in interfacial polymerization.
[000121] Membrane identification codes for the TFC membranes prepared in this Example are as follows:
where it does not identify membranes made in independent batch n. Curing of TFC membranes in the oven (step e)
[000122] A post-formation treatment step was carried out on the composite membranes in which the membranes were cured in the oven at 85 ° C for 10 minutes. Performance of composite membrane
[000123] The performances of TFC membranes in DMF, THF, acetone, methanol and toluene were evaluated with and without temperature cure. The rejection curves and flows for TFC membranes in DMF / PS solution, THF / PS solution, acetone / PS solution, methanol / PS solution and toluene / PS solution with and without oven curing are shown in Figures 1 to 10. Of course, curing the membranes at 85 ° C increases rejection. EXAMPLE 2
[000124] TFC membranes have been pre-bonded to PEEK support membranes, as follows: Manufacture of polyetheretherketone (PEEK) membrane supports:
[000125] A polymer doping solution was prepared by dissolving 12.3% (by weight) PEEK (Vicote 704 from Victrex) in 79.4% methane sulfonic acid (MSA) and 8.3% sulfuric acid (H2SO4). The solution was stirred overnight until complete dissolution. A viscous solution was formed, and allowed to remain for 10 hours to remove air bubbles. The solution was then molded in a non-woven polyester lining material taped to a glass plate using a molding knife (Elcometer 3700) set to a thickness of 250 gm. Immediately after molding, the membrane was immersed in a water bath where 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 any residual preparation solvents.
[000126] The final step in preparing the PEEK support membrane involved immersing the membrane overnight in a conditioning agent bath consisting of a 3: 2 polyethylene glycol 400 / isopropanol volume ratio. The membrane was then dried with tissue paper and air dried.
[000127] TFC membranes were manufactured as in EXAMPLE 1, on top of the PEEK support membrane. The TFC membranes were cured in the oven at 85 ° C for 10 minutes as in EXAMPLE 1.
[000128] Membrane identification codes for the TFC membranes prepared in this Example are as follows:

[000129] When n identifies membranes made in independent batch n. Performance of composite membrane
[000130] The performance of temperature-cured TFC membranes was evaluated in acetone, THF, toluene and heptane. The rejection and flow curves for TFC membranes cured in acetone / PS, THF / PS, toluene / PS, and heptane / PS solutions are shown in Figures 11, 12, 13 and 14 respectively. EXAMPLE 3
[000131] In this particular example, TFC membranes were pre-bonded to PBI support membranes, as follows: Manufacture of polybenzimidazole (PBI) membrane supports:
[000132] A polymer doping solution was prepared by diluting a commercial doping solution of 26% by weight of PBI dissolved in DMAc (trade name: Celazole®) to 15% by weight with DMAc. The solution was stirred for 4 hours until complete dissolution. The viscous solution was formed, and allowed to remain for 10 hours to remove air bubbles. The solution was then molded in a polypropylene material of non-woven lining taped to a glass plate using a molding knife (Elcometer 3700) configured in a thickness of 250 gm. Immediately after molding, the membrane was immersed in a water bath where phase inversion occurred. After 15 minutes, it was changed to a new water bath and left for an hour. The wet membrane was then dipped in a water bath to remove any residual preparation solvents.
[000133] The final step to prepare the PBI support membrane involved by immersing the membrane overnight in a conditioning agent bath consisting of a 3: 2 polyethylene glycol 400 / isopropanol volume ratio. The membrane was then dried with tissue paper and air dried.
[000134] TFC membranes were manufactured as in EXAMPLE 1, on top of the PBI support membranes. The TFC membranes were cured in the oven at 85 ° C for 10 minutes as in EXAMPLE 1.
[000135] Membrane identification codes for the TFC membranes prepared in this Example are as follows:

[000136] Where n identifies membranes made in independent batch n. Performance of composite membrane
[000137] The performance of temperature-cured TFC membranes was evaluated in acetone and THF. The rejection and flow curves for TFC membranes cured in acetone / PS and THF / PS solutions are shown in Figures 15 and 16 respectively. EXAMPLE 4
[000138] TFC membranes were manufactured as in EXAMPLE 2 (ie with PEEK as support membrane without conditioning with PEG). The TFC membranes were cured in the oven at 85 ° C for 10 minutes. Before the gas permeation membranes were dipped in MeOH, followed by hexane and allowed to dry overnight. Performance of composite membrane
[000139] The gas separation performance of temperature-cured TFC membranes was evaluated for N2, CO2, CH4 and O2. The permeabilities against selectivities at different pressures are shown in Figure 17.

权利要求:
Claims (15)
[0001]
1. Interfacial polymerization process to form a thin film composite membrane for gas separation or liquid filtration, the process characterized by the fact that it comprises the steps of: (a) impregnating a porous support membrane with a first solution of reactive monomers, comprising: (i) a first solvent for said first reactive monomer; (ii) a first reactive monomer; (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; at least one of the first and second reactive monomers comprises at least one spiro-contoured center, at least one bridged ring portion and / or stereochemically congested single covalent bonds around which rotation is restricted; the reaction of the first and second reactive monomers results in the IN-SITU formation of a covalently cross-linked three-dimensional polymeric network having intrinsic microporosity, said intrinsic microporosity being defined as a continuous network of interconnected intermolecular voids, said voids arising from the structure of the first and second monomers; and the reaction of the first and second reactive monomers resulting in a separation layer that forms on the support membrane to form a composite membrane (c) optionally, after a reaction period, terminate the unreacted groups of the separation layer with functional groups to modify the surface chemical composition; (d) after a reaction period, immerse the resulting composite membrane in an abrupt cooling medium; and (e) optionally, curing the membrane with temperature or microwave for a specified time.
[0002]
2. Process according to claim 1, characterized in that the support membrane is formed from an inorganic material including silicon carbide, silicon oxide, zirconium oxide, titanium oxide, aluminum oxides or zeolites
[0003]
Process according to claim 1, characterized in that the support membrane is formed from polysulfone, polyethersulfone, poly (ether-sulfone-ketone), polyacrylonitrile, polypropylene, polyamide, cellulose acetate, cellulose diacetate , cellulose triacetate, poly (ethyl ketone ether), poly (phthalazinone ether-sulfone-ketone), a perfluoropolymer, polyimide, polybenzimidazole, polyether ether ketone, or polyether ether ketone.
[0004]
4. Process according to claim 1, 2 or 3, characterized by the fact that step (a) comprises the impregnation of the porous support membrane, which comprises a first conditioning agent, with the first reactive monomer solution, wherein the first conditioning agent is selected from one or more synthetic oils (including polyolefin oils, silicone oils, polyalphaolefin oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils and aromatic oils from alkyl), mineral oils (including solvent-refined oils and hydro-processed mineral oils and petroleum wax isomerate oils), vegetable oils and fats, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols and glycols (such as polypropylene glycols, polyethylene glycols, polyalkylene glycols).
[0005]
Process according to any one of claims 1 to 4, characterized in that the process additionally comprises a step of impregnating the thin film composite membrane with a second conditioning agent, in which the second conditioning agent is selected from from one or more of the synthetic oils (including polyolefin oils, silicone oils, polyalphaolefin oils, polyisobutylene oils, synthetic wax isomerate oils, ester oils and aromatic alkyl oils), mineral oils (including oils refined by solvent and hydro-processed mineral oils and oils of petroleum wax isomerates), vegetable fats and oils, higher alcohols (such as decanol, dodecanol, heptadecanol), glycerols, and glycols (such as polypropylene glycols, polyethylene glycols, polyalkylene glycols).
[0006]
Process according to any one of claims 1 to 5, characterized in that the first reactive monomer solution comprises an aqueous solution of a polyphenol or polyamine salt that has a concavity.
[0007]
Process according to any one of claims 1 to 6, characterized by the fact that the first reactive monomer is selected from the group consisting of 1,1-spirobisindanes, 9,9-spirobisfluorenes, bisnafthalenes, 1,1-spirobis , 2,3,4-tetrahydro-naphthalenes, and 9,10-ethane anthracene.
[0008]
Process according to any one of claims 1 to 7, characterized in that the first reactive monomer solution comprises an aqueous solution of a 5.5 ', 6.6'-tetrahydroxy -3,3,3' salt , 3'-tetramethyl-1,1'-spirobisindane.
[0009]
Process according to any one of claims 1 to 8, characterized in that the second reactive monomer solution contains mono-acyl chlorides, polyacyl chlorides, or a mixture thereof, or other monomers.
[0010]
Process according to any one of claims 1 to 9, characterized in that the second reactive monomer solution contains trimesoyl chloride, iso-phthaloyl dichloride, or sebacoyl chloride, or a mixture thereof.
[0011]
Process according to any one of claims 1 to 10, characterized in that the composite membrane is treated with an activating solvent, being a polar aprotic solvent.
[0012]
Process according to claim 11, characterized in that the composite membrane is treated with an activating solvent by filtration through the membrane using the activating solvent.
[0013]
13. Process according to any one of the preceding claims, characterized in that the composite membrane is treated with an activating solvent comprising DMF, NMP, DMSO, DMAc, or a mixture thereof.
[0014]
14. Process according to any of the preceding claims, characterized by the fact that the contact time in step (b) is chosen between 1 second and 5 hours.
[0015]
15. Process according to any one of the preceding claims, characterized by the fact that the temperature of the solution of the contact step (b) is maintained between 10 and 100oC.

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公开号 | 公开日

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ES2833108T3|2021-06-14|

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CN104010718B|2018-01-30|

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BR112014009214A2|2017-04-18|

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CN108176258A|2018-06-19|

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KR101988491B1|2019-06-12|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-08-13| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-08-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/10/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-04-06| B16C| Correction of notification of the grant [chapter 16.3 patent gazette]|Free format text: REF. RPI 2604 DE 01/12/2020 QUANTO AO ENDERECO. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1117950.4|2011-10-18|

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GBGB1117950.4A|GB201117950D0|2011-10-18|2011-10-18|Membranes for separation|

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PCT/GB2012/052576|WO2013057492A1|2011-10-18|2012-10-18|Membranes for separation|

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