WO2024105106A1 - Membranes composites à film mince de polyamine aliphatique fabriquées par polymérisation interfaciale - Google Patents

Membranes composites à film mince de polyamine aliphatique fabriquées par polymérisation interfaciale Download PDF

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Publication number
WO2024105106A1
WO2024105106A1 PCT/EP2023/081911 EP2023081911W WO2024105106A1 WO 2024105106 A1 WO2024105106 A1 WO 2024105106A1 EP 2023081911 W EP2023081911 W EP 2023081911W WO 2024105106 A1 WO2024105106 A1 WO 2024105106A1
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halide
membrane
polymerization
functional groups
membranes
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PCT/EP2023/081911
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English (en)
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Robin DHONDT
Guy Koeckelberghs
Marie LENAERTS
Marloes THIJS
Ivo Vankelecom
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Katholieke Universiteit Leuven
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0006—Organic membrane manufacture by chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
    • B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/60—Polyamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/22—Thermal or heat-resistance properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/30—Chemical resistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration

Definitions

  • the present invention relates to thin-film composite (TFC) membranes produced by interfacial polymerization (IP). More particularly, TFC membranes with an aliphatic polyamine top layer.
  • TFC membranes are stable in various challenging conditions of extreme pH and chlorine exposure.
  • the polyamine membrane can be tuned in different ways. It is possible to functionalize and cross-link the membrane. Additionally, a positive or negative charge can be introduced.
  • a method of preparing a polyamine-based membranes comprising the steps of polymerizing An with Bm, wherein A is a molecule or a part of a molecule with n amine functional groups, and, wherein Bm is a molecule or a part of a molecule with m aliphatic halide functional groups or pseudohalide, ammonium, phosphonium, sulfonium functional groups wherein n ⁇ 1 ⁇ ⁇ 5, ⁇ 10, or ⁇ 20 and wherein m ⁇ 2, ⁇ 5, ⁇ 10, or ⁇ 20.
  • An can be a polymer itself with a plurality of amine functional groups. Hence the possibility of A having n ⁇ 1, ⁇ 5, ⁇ 10 n amine functional groups.
  • a subunit typically comprises 2 or 4 amine functional groups. In specific embodiments all subunits have the same amount of functional groups. In other embodiments only a fraction (eg 1/2, 1/4 1/8) of the subunits have amine functional groups.
  • Bn can be a polymer itself with a plurality of aliphatic halide functional groups. Hence the possibility of Bm having m ⁇ 2, ⁇ 5, ⁇ 10, or ⁇ 20.
  • a subunit typically comprises 2 or 4 aliphatic halide functional groups. In specific embodiments all subunits have the same amount of functional groups. In other embodiments only a fraction (eg 1/2, 1/4 1/8) of the subunits have aliphatic halide functional groups.
  • An aliphatic polyamine membrane is chosen because of its amine bond which is more robust than amide bonds.
  • the amine bonds are resistant to hydrolysis and are more pH resistant.
  • the polymer is made by a reaction of an aliphatic (oligo) amine, e.g. trans-cyclohexane diamine, and an aliphatic oligohalide via a nucleophilic substitution, e.g.
  • One aspect of the invention relates to methods of preparing a polyamine-based membranes comprising the steps of polymerizing compound An with compound Bm.
  • An is a molecule with n amine functional groups
  • Bm is a molecule with m aliphatic functional groups selected from a halide, pseudohalide, ammonium, phosphonium, and sulfonium functional group.
  • n 1, ⁇ 5, ⁇ 10, or ⁇ 20 and m ⁇ 2, ⁇ 5, ⁇ 10, or ⁇ 20.
  • the m functional group is a halide.
  • Examples of the amine functional group of An are substituents such as -NH 2 , -CH 2 - NH 2 , -(CH 2 ) 2 -NH 2 , -(CH 2 ) 3 -NH 2 , or -(CH 2 ) 4 -NH Z .
  • Examples of the aliphatic functional group are substituents such -CH 2 -halide, - (CH 2 ) 2 -halide, -(CH 2 ) 3 -halide, or -(CH z ) 4 -halide.
  • Equally such C1-C4 alkyl chains can have a pseudohalide, ammonium, phosphonium, or sulfonium functional group instead of the halide group.
  • n is between 2 and 5 and m is between 2 and 5, more specifically is 2 or 4, and m is 2 or 4.
  • n and m values are typical for An and Bm molecules with a molecular weight below 500, below 1000 or below 2000
  • Typical molecules as use in the examples contain one six-membered aliphatic or six- membered aromatic ring.
  • Examples are 1,2-cyclohexane diamine (CHDA), l,2,4,5-tetra(bromomethyl)benzene and l,4-di(bromomethyl)benzene (TBMB).
  • CHDA 1,2-cyclohexane diamine
  • TBMB l,2,4,5-tetra(bromomethyl)benzene
  • An and/or Bm themselves can be polymers of repeating subunits with n and m functional group. These polymers are used in the formation of membranes in the currently claimed methods
  • An and Bm as a whole m and n have higher values, e.g ⁇ 10, ⁇ 20, ⁇ 50.
  • n and m values are independently between 10 and 50, 10 and 100, 10 and 150, 10 and 200, 25 and 50, 25 and 100, 25 and 150, 25 and 200, 50 and 100, 50 and 150, 50 and 200, 100 and 150, 100 and 200, 150 and 200.
  • each repeating subunit typically has n or m values of 2 or 4.
  • the polymerization of An with Bm can be performed by interfacial polymerization, phase inversion or solvent evaporation, typically by interfacial polymerization. After or during polymerization residual functional groups can be treated to alter the membrane structure and performance, for example by quaternization or crosslinking. Quaternization can be performed with methyliodide or benzylbromide.
  • Crosslinking can be performed with 1,6-dibromohexane.
  • Membranes obtained by the methods of the present invention can be used in harsh physicochemical conditions such as
  • filtration in these conditions can occur at room temperature or at a temperature above 100 °C, above 150 °C or above 200 °C.
  • Reproducibility via interfacial polymerization is obtained by increasing the degree of polymerization and reaction rate. Slower reactions result in looser and thicker films characterized by a lower rejection (Zhu et al. (2020) Sep. Purif. Technol. 239, 116528; Wang eta/. (2019) RscAdv. 9, 2042-2054).
  • the reason is that the monomer in the aqueous phase has more time to diffuse deeper into the organic phase, which results in a thicker reaction zone.
  • the precise membrane formation must be considered, and is achieved by the formation of a cross-linked polymer network. This is typically obtained by a polycondensation of An and Bm monomers.
  • the formation of the network polymer depends on the Pn, the degree of polymerization, which is most affected by f, the mean number of functional groups, and p, the conversion.
  • a network is formed if Pn reaches infinity, this implies that f and p must be high.
  • unreacted functional groups can still react with each other, which further tightens the network.
  • the reaction is performed fast, to avoid that the monomer in one phase can diffuse in the other phase further away from the interface. Two different circumstances occur, one close to the interface, where the monomer concentration reaches its maximum, and one further away from the interface, where the monomer concentration is lower. Because of the lower concentration, a fully cross-linked network polymer can never be formed. As a result, a very tick film, which is very loose on top and denser at the support layer is obtained.
  • the solution to make a reproducible, thin and dense top layer is achieved by increasing the mean number of functional groups f.
  • Membrane separation technology has gained an important place in the chemical industry. It can be applied in the separation of a range of components of varying molecular weights in gas or liquid phases, including but not limited to nanofiltration, desalination, and water treatment. It has several advantages to offer compared to the traditional separation processes, such as distillation, adsorption, absorption or solvent extraction. The benefits include continuous operation, lower energy consumption, the possibility of integration with other separation processes, mild conditions and thus more environment friendly, easy but linear up-scaling, the feasibility of making tailor-made membranes and less requirement of additives (Basic Principles of Membrane Technology, Second Edition, M. Mulder, Kluwer Academic Press, Dordrecht. 564p).
  • Membranes are used in many applications, for example as inorganic semiconductors, biosensors, heparinized surfaces, facilitated transport membranes utilizing crown ethers and other carriers, targeted drug delivery systems including membrane-bound antigens, catalyst containing membranes, treated surfaces, sharpened resolution chromatographic packing materials, narrow-band optical absorbers, and in various water treatments which involve removal of a solute or contaminant for example dialysis, electrolysis, microfiltration, ultrafiltration and reverse osmosis (Membrane technology and applications, R. Baker, John Wiley & Sons, 2004, 538p).
  • membrane separation processes are widely applied in the filtration of mild aqueous fluids, they have not been (widely) used under highly challenging pH or oxidizing conditions. Their relatively poor performance and/or stability in these conditions decreases their applicability in more aggressive feeds, despite an enormous potential economical market.
  • chemical and pharmaceutical syntheses or textile dyeing are frequently performed in organic solvents containing products with high added value, like acids and bases or catalysts, which would be recoverable via membrane technology.
  • the recovery of metal salts from acid mine leachates, treatment of harsh waste streams from chemical and pharmaceutical industries and purification of chlorinated water streams in desalination are other examples in which ultra-stable membranes could serve a purpose.
  • TFC thin film composite
  • IFP interfacial polymerization
  • an aqueous solution of a reactive monomer (often an amine (e.g. a diamine)) is first deposited in the pores of a porous support membrane (e.g. a polysulfone ultrafiltration membrane)- this step is also referred to as support membrane impregnation.
  • a porous support membrane e.g. a polysulfone ultrafiltration membrane
  • the porous support membrane, loaded with the first monomer is immersed in a water-immiscible (organic) solvent solution containing a second reactive monomer (e.g. a tri- or diacid chloride).
  • a second reactive monomer e.g. a tri- or diacid chloride
  • the thin film layer can be from several tens of nanometers to a few micrometers thick.
  • the thin film is selective between molecules, and this selective layer can be optimized for solute rejection and solvent flux by controlling the coating conditions, the characteristics and concentrations of the reactive monomers, the choice of the support membrane or the use of additives (e.g. acid-acceptors, surfactants ... ).
  • the (micro-)porous support can be selectively chosen for porosity, strength and solvent resistance.
  • supports or substrates for membranes There is a myriad of supports or substrates for membranes. Specific physical and chemical characteristics to be considered when selecting a suitable substrate include porosity, surface porosity, pore size distribution of surface and bulk, permeability, solvent resistance, hydrophilicity, flexibility, mechanical integrity and charges. Pore size distribution and overall surface porosity of the surface pores are of great importance when preparing a support for IFP.
  • polyamides which belong to a class of polymers referred to as polyamides.
  • One such polyamide is made, for example, by reacting a triacyl chloride, such as trimesoylchloride, with a diamine, such as m- phenylenediamine. The reaction can be carried out at an interface by dissolving the diamine in water and bringing a hexane solution of the triacyl chloride on top of the water phase. The diamine reacts with the triacyl chloride at the interface between these two immiscible solvents, forming a polyamide film at or near the interface which is less permeable to the reactants. Thus, once the film forms, the reaction slows down drastically, leaving a very thin film. In fact, if the film is removed from the interface by mechanical means, fresh film forms almost instantly at the interface, because the reactants are so highly reactive.
  • interfacial polymerization examples include polyamides, polyureas, polyurethanes, polysulfonamides, polyesters (US 4,917,800), polyacrylates, or 13- alkanolamines (US20170065937).
  • Factors affecting the making of continuous, thin interfacial films include temperature, the nature of the solvents and co-solvents (including ionic liquids: Marien et al. (2016) ChemSusChem 9, 1101-111), and the concentration and the reactivity of monomers and additives.
  • Example 1 Membranes from 1,2-cyclohexanediamine (CHDA) with 1, 2,4,5- tetra(bromomethyl)benzene (TBMB)
  • 1,2-cyclohexanediamine (CHDA) and potassiumphosphate (K3PO4) were dissolved in water, (the aqueous phase), and l,2,4,5-tetra(bromomethyl)benzene (TBMB) was dissolved in methylisobutylketon (MIBK) (the organic phase) ( Figure 1 top part).
  • MIBK methylisobutylketon
  • a polyimide support was immersed in the aqueous amine solution for 5 minutes. Afterwards, the support was removed from the solution, residual amine solution was removed with a wiper and the top of the support was contacted with the organic phase. The two phases were kept in contact for 30 minutes, whereafter the organic solution was removed. The membrane was rinsed with clean MIBK, left to dry in the air for 1 min and placed in a beaker with distilled water.
  • the performance of the membranes was determined using a dead-end high- throughput filtration set-up. A feed solution of 35pM Rose Bengal (RB 1017 g/mol) or Methyl Orange (MO, 327 g/mol) in water is used and stirred at 340 ppm to minimize concentration polarization. Three coupons were cut from the membrane and tested to check the reproducibility and determine the standard deviation. The pressure applied on the membranes were kept at 10 bar. The permeance (P, L/m z hbar) was calculated using the following equation
  • Membranes as prepared in Example 1 were treated with methyl iodide (Mel) for quaternation or with 1,6-dibromohexane (BrC 6 Hi Z Br) for crosslinking (figure 2 top panel). This was done by pouring a solution of these compounds on top of the membrane. The treatment was performed for both reagents of 10 minutes and 1 hour.
  • Mel methyl iodide
  • BrC 6 Hi Z Br 1,6-dibromohexane
  • Example 3 stability of membranes from 1,2-cyclohexane diamine with l,2,4,5-tetra(bromomethyl)benzene.
  • Membranes prepared from via interfacial polymerization 1,2-cyclohexane diamine with 1,2,4, 5 tetra (bromomethyl) benzene, and were treated with IM HCI, IM NaOH, NaOCI room temperature and at 40 °C for 1 h and 24 h, respectively.
  • FTIR of the membranes does not change significantly after treatment with acid, alkali or oxidizing reagents (figure).
  • Example 4 Membranes from 1,2-cyclohexane diamine (CHDA) with 1,4- di(bromomethyl)benzene (TBMB)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne des procédés de préparation de membranes à base de polyamine comprenant les étapes consistant à polymériser un composé A avec un composé Bm, A étant une molécule avec n groupes fonctionnels amine, et Bm étant une molécule avec m groupes fonctionnels aliphatiques choisis parmi un groupe fonctionnel halogénure, pseudohalogénure, ammonium, phosphonium et sulfonium, n > 1, >5, >10, ou >20 et m > 2, >5, >10, ou >20.
PCT/EP2023/081911 2022-11-15 2023-11-15 Membranes composites à film mince de polyamine aliphatique fabriquées par polymérisation interfaciale WO2024105106A1 (fr)

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Citations (10)

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US4277244A (en) 1976-08-20 1981-07-07 Societe Anonyme Dite: L'oreal Dye compositions for keratinic fibers containing paraphenylenediamines
US4277344A (en) 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
US4917800A (en) 1986-07-07 1990-04-17 Bend Research, Inc. Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers
US4950404A (en) 1989-08-30 1990-08-21 Allied-Signal Inc. High flux semipermeable membranes
CN103657610A (zh) * 2013-12-09 2014-03-26 南京工业大学 选择性吸附二氧化碳的多孔聚合物吸附剂及其制备方法
KR101599864B1 (ko) * 2012-03-05 2016-03-04 도레이케미칼 주식회사 산업폐수에서의 디메틸포름아미드 분리회수방법
US20170065937A1 (en) 2014-02-27 2017-03-09 Katholieke Universiteit Leuven Solvent resistant thin film composite membrane and its preparation
CN115007003A (zh) * 2022-05-13 2022-09-06 天津工业大学 一种高通量荷正电复合纳滤膜、制备方法及应用

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3133132A (en) 1960-11-29 1964-05-12 Univ California High flow porous membranes for separating water from saline solutions
US3744642A (en) 1970-12-30 1973-07-10 Westinghouse Electric Corp Interface condensation desalination membranes
US4277244A (en) 1976-08-20 1981-07-07 Societe Anonyme Dite: L'oreal Dye compositions for keratinic fibers containing paraphenylenediamines
US4277344A (en) 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
US4917800A (en) 1986-07-07 1990-04-17 Bend Research, Inc. Functional, photochemically active, and chemically asymmetric membranes by interfacial polymerization of derivatized multifunctional prepolymers
US4950404A (en) 1989-08-30 1990-08-21 Allied-Signal Inc. High flux semipermeable membranes
US4950404B1 (fr) 1989-08-30 1991-10-01 Allied Signal Inc
KR101599864B1 (ko) * 2012-03-05 2016-03-04 도레이케미칼 주식회사 산업폐수에서의 디메틸포름아미드 분리회수방법
CN103657610A (zh) * 2013-12-09 2014-03-26 南京工业大学 选择性吸附二氧化碳的多孔聚合物吸附剂及其制备方法
US20170065937A1 (en) 2014-02-27 2017-03-09 Katholieke Universiteit Leuven Solvent resistant thin film composite membrane and its preparation
CN115007003A (zh) * 2022-05-13 2022-09-06 天津工业大学 一种高通量荷正电复合纳滤膜、制备方法及应用

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