WO2021110468A1 - Membranes d'affinité, composés, compositions et procédés pour leur préparation et leur utilisation - Google Patents

Membranes d'affinité, composés, compositions et procédés pour leur préparation et leur utilisation Download PDF

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Publication number
WO2021110468A1
WO2021110468A1 PCT/EP2020/083128 EP2020083128W WO2021110468A1 WO 2021110468 A1 WO2021110468 A1 WO 2021110468A1 EP 2020083128 W EP2020083128 W EP 2020083128W WO 2021110468 A1 WO2021110468 A1 WO 2021110468A1
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component
membrane
composition
membrane according
group
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PCT/EP2020/083128
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English (en)
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Berry BOGELS
Yujiro Itami
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Fujifilm Manufacturing Europe Bv
Fujifilm Corporation
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Publication of WO2021110468A1 publication Critical patent/WO2021110468A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/34—Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • B01D69/1071—Woven, non-woven or net mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/34—Use of radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/40—Details relating to membrane preparation in-situ membrane formation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/14—Membrane materials having negatively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/16—Membrane materials having positively charged functional groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/42—Ion-exchange membranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07K—PEPTIDES
    • C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
    • C07K1/14—Extraction; Separation; Purification
    • C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis

Definitions

  • the present invention relates to porous membranes, to compounds and to their preparation and use, e.g. for purifying biomolecules and compositions comprising metal ions.
  • AMF affinity membrane filtration
  • AMF may also be used for the purification of mixtures comprising metals, e.g. by using membranes having a higher affinity for some metals compared to others.
  • AMF may be used, for example, to remove heavy metals from waste streams, water or organic solvents.
  • affinity membranes have a high affinity for a target chemicals
  • affinity membranes are prepared from polyethylene, polypropylene, nylon, polysulfone, and glass.
  • these membranes are usually hydrophobic and relatively inert, and hence require difficult (chemical) modifications.
  • some of the membranes have low numbers of ligand groups due to the harsh chemical post-treatments required to introduce the ligands.
  • a second approach has been employed wherein membranes are prepared that have pre-incorporated ligand groups. Flowever, the problems with this type of membrane include high hydrophobicity and brittleness.
  • Another drawback with both of the above methods is that the pore size of the membrane cannot be easily controlled and the membranes typically have low water flux, low porosity, low capacity for removing target materials and often suffer from excessive swelling in aqueous media.
  • a porous membrane obtainable by a process comprising curing a composition comprising:
  • component (i) present in the composition is greater than the wt% of component (ii) present in the composition.
  • component (ii) (and optionally component (i)) is completely dissolved in component (iii) and the membrane is insoluble in component (iii).
  • the cross-linking agent preferably comprises at least two polymerisable groups, e.g. at least two groups selected from epoxy, thiol (-SH), oxetane and especially ethylenically unsaturated groups.
  • the polymerisable groups will typically be selected such they are reactive with each other and/or with at least one polymerisable group present in another, chemically different component (i) (when present).
  • component (v) is present (see below), the polymerisable groups of the cross-linking agent are preferably reactive with component (v).
  • Curing causes the cross-linking agent to cross-link, e.g. to form the membrane as a cross-linked, three dimensional polymer matrix.
  • the at least two polymerisable groups present in component (i) may all be chemically identical or they may be different.
  • Preferred polymerisable groups are ethylenically unsaturated groups, especially (meth)acrylic groups and/or vinyl groups (e.g. vinyl ether groups, aromatic vinyl compounds, N-vinyl compounds and allyl groups).
  • vinyl groups e.g. vinyl ether groups, aromatic vinyl compounds, N-vinyl compounds and allyl groups.
  • Acrylic groups are preferred over methacrylic groups because acrylic groups are more reactive.
  • ethylenically unsaturated groups are free from ester groups because this can improve the stability and the pH tolerance of the resultant membrane.
  • Ethylenically unsaturated groups which are free from ester groups include (meth)acrylamide groups and vinyl ether groups ((meth)acrylamide groups are especially preferred).
  • Suitable cross-linking agents which may be used as component (i) include di-, tri- and polyfunctional aliphatic and aromatic acrylate oligomers including urethane, polyester and epoxy type oligomers, such as oligomers from Sartomer and Soltech Ltd, in each case having the above mentioned MWT.
  • Suitable commercially available cross-linking agent(s) which may be used as component (i) include CN2003EU (epoxy diacrylate of MWT 3,000), CNUVE150/80 (diacrylate of MWT 4,000), CNUVE151 M (diacrylate of MWT 4,000), CN790 (acrylated polyester of MWT 5,000), CN9143 (aromatic urethane diacrylate of MWT 3,800), CN9761 (diacrylate of MWT 2,700), CN9170 (diacrylate of MWT 5,000), CN970 (triacrylate of MWT 2,600), CN9761 (diacrylate of MWT 2,700), CN9001 (aliphatic urethane diacrylate of MWT 3,250), CN9002 (diacrylate of MWT 7,650), CN9012 (diacrylate of MWT 3,000), CN910 (diacrylate of MWT 3,600), CN936 (diacrylate
  • cross-linking agent(s) which may be used as component (i) are commercially available from Soltech Ltd., e.g. SU500, SU514, SU5225, SU530, SU704, SU710 and SU7206. Especially preferred are the diacrylamide and triacrylamide versions of the compounds mentioned above.
  • component (i) has an anionic group.
  • component (i) is free from ionic groups, e.g. free from anionic (e.g. sulpho, carboxy or phosphato) and cationic (e.g. quaternary ammonium) groups.
  • component (i) is free from sulpho groups.
  • component (i) is free from heterocyclic groups.
  • component (ii) contains a ligand group, in one embodiment component (i) is free from ligand groups.
  • the amount of component (i) present in the composition, relative to the total weight of the composition is preferably 21 to 75wt%, more preferably 21 to 60wt%, and especially 21 to 44wt%. As stated above, the wt% of component (i) present in the composition is greater than the wt% of component (ii) present in the composition.
  • component (ii) is free from ionic groups or comprises one or more ionic groups selected from the group consisting of phosphato groups and carboxy groups (which may be in the free acid or salt form).
  • Component (ii) has one and only one polymerisable group.
  • Component (ii) preferably is or comprises a compound of the Formula (1 ) (such compounds and their use for preparing membranes (especially affinity membranes) forming further features of the present invention):
  • each L independently is a ligand group
  • A is an organic linking group
  • R is a polymerisable group; q has a value of at least 1 ; m has a value of 0 or 1 ; and n has a value of 1 .
  • each L independently is a ligand group comprising a heterocyclic ring, and/or one or more sulphonic acid groups, and/or one or more carboxylic acid groups.
  • the organic linking group(s) represented by A each independently comprise from 2 to 12 carbon atoms (e.g. from two to twelve -Chh- groups) and optionally one or more (e.g. 1 to 10) hetero atoms (e.g. nitrogen (e.g. - NH-) and/or oxygen (e.g. -0-) and/or sulfur (e.g. -S-)).
  • the organic linking group A (when present) is preferably a backbone to which the ligand group(s) L and the polymerisable group R is attached.
  • m has a value of zero the organic linking group A is absent from the compound of Formula (1 ) and the polymerisable group is attached directly to the ligand group(s) L, e.g. through a single covalent bond.
  • q has a value of 1 , 2, 3 or 4, especially 1 , 2 or 3.
  • the polymerisable group represented by R is an ethylenically unsaturated group.
  • the compounds of Formula (1) may be obtained by attaching ligand group(s) L and polymerisable group R to an organic linking group, e.g. by a process comprising amide formation.
  • ligand groups carrying an acid chloride group and a polymerisable group carrying an acid chloride group may be reacted with an organic linking group having amine substituents, typically under mildly alkaline conditions, to form an amide bond between the ligand groups and the organic linking group and between the polymerisable group and the organic linking group.
  • the ligand group can bind to target biomolecules or metal atoms covalently or, more typically, non-covalently.
  • the ligand group can form a coordination complex with metal ions, in particular alkali metals, alkaline earth metals, lanthanide, actinide, transition metals, post-transition metals and metalloids.
  • the bonding typically involves donation of 1 or more of the ligand group’s free electron pairs to the metal ion.
  • the ligand group is non-ionic or non-charged and has a binding constant for a metal with a valency of 1 or more or for a biomolecule (especially a biomolecule comprising amino acids) of at least 10 4 M 1 (especially 10 4 M 1 to 10 30 M 1 ).
  • ligand groups having a variety of different degrees of bulkiness (size), a variety of different coordination atoms and a variety of different electrons which may be donated to a metal (denticity and hapticity).
  • the ligand group can bind biomolecules by forming a ligand-biomolecule complex, e.g. a ligand-protein or ligand-DNA complex.
  • Binding of the ligand group with biomolecules typically occurs by a non- covalent interaction, for example hydrogen-bonding, a pi-pi interaction, van derWaals forces, a hydrophobic effect, a host-guest interaction, halogen bonding, a dipole-dipole interaction, a dipole-induced dipole interaction or by two or more of the foregoing binding mechanisms.
  • the affinity of the ligand group for particular biomolecule(s) or metal(s) enables the membrane to be used in AMF.
  • the ligand groups are neutral and non-ionic in nature.
  • Flerein acidic and basic groups in the neutral form are considered to be non-ionic in nature.
  • Preferred heterocyclic rings are cyclic ethers and 5- or 6-membered rings comprising 1 , 2 or 3 atoms selected from oxygen, sulphur and nitrogen.
  • heterocyclic rings include pyridyl (e.g. 2,2’-bipyridyl and picolinic acid groups); crown ethers; cryptands; cyclams; cyclens; siderophores (e.g. heterocyclic groups comprising catechol and/or hydroxamate groups); bipyrimidines; terpyridines; sarcophagines (e.g. calix[4]arene, carcerand, cavitand and phytochelatin groups); porphine clathrochelates; corroles; phtalocyanines; corrins; salens; and cyclic biomolecule-binding groups (e.g. peptide, (strepta)avidin, biotin, curcurbituril and cyclodextrin groups).
  • pyridyl e.g. 2,2’-bipyridyl and picolinic acid groups
  • crown ethers cryptands
  • cryptands e.g. hetero
  • the heterocyclic ring has one or more metal-chelating substituents, for example, hydroxy (e.g. vicinal diol); thiol (e.g. vicinal dithiol); 1 ,3-diketone groups; amidoxime groups; amine (e.g. vicinal diamine); carboxylic acid groups; phosphoric acid groups and/or sulphonic acid groups.
  • metal-chelating substituents for example, hydroxy (e.g. vicinal diol); thiol (e.g. vicinal dithiol); 1 ,3-diketone groups; amidoxime groups; amine (e.g. vicinal diamine); carboxylic acid groups; phosphoric acid groups and/or sulphonic acid groups.
  • Crown ethers have a particularly high affinity for alkali metals
  • pyridyl groups have a particularly high affinity for transition metals
  • carboxylic acid groups have a high affinity for all metals.
  • heterocyclic rings include pyridyl groups, pyranyl groups, cyclic ether groups (e.g. crown ether groups, pyranyl groups and tetrahydropyranyl groups) and biotin groups, e.g. groups having at least one of the following formulae (wherein n has a value of from 1 to 3):
  • component (ii) comprises a backbone, one polymerisable group and at least one (more preferably at least two, e.g. two, three or four) ligand group(s) attached to the backbone.
  • the backbone preferably comprises an alkylene group, especially an alkylene group comprising from 2 to 10, especially 2 to 8 carbon atoms.
  • deferred examples of component (ii) include the compounds L1 to L44 below:
  • each L independently comprises a pyridyl group (especially two pyridyl groups), a crown ether group, a 3,4-dihydroxybenzyl group, a pyranyl group having two or three hydroxy substituents or a biotin group.
  • a pyridyl group especially two pyridyl groups
  • a crown ether group especially two pyridyl groups
  • 3,4-dihydroxybenzyl group a pyranyl group having two or three hydroxy substituents or a biotin group.
  • Examples of compounds of Formula (1) in which each L comprises a pyridyl group (in fact two pyridyl groups) include L1 to L16 shown above.
  • Examples of compounds of Formula (1) in which each L comprises a cyclic ether group include L17 to L30 shown above.
  • Examples of compounds of Formula (1 ) in which each L comprises a carboxy group include L31 to L44 shown above. These compounds are free from heterocyclic rings.
  • the amount of component (ii) present in the composition is preferably below 21wt%, more preferably 1 to 20.99wt% and especially 1 to 20wt%.
  • components (i) and (ii) are completely dissolved in the composition (e.g. in component (iii)).
  • component (ii) has a molecular weight below 2,000 g/mol, more preferably 1 ,500 g/mol or below and especially 100 g/mol to 1 ,500 g/mol.
  • each L independently is as defined above.
  • int means non-polymerisable. Thus component (iii) is incapable of polymerising with component (i).
  • Component (iii) preferably consists of isopropanol and one or more miscible solvents (e.g. organic solvents).
  • miscible solvents e.g. organic solvents.
  • component (iii) is a non-solvent for the membrane (i.e. preferably the membrane is insoluble in component (iii)).
  • Component (iii) performs the function of dissolving component (i) and (ii), and preferably also components (iv) and (v) (when present).
  • Component (iii) can also help to ensure that the membrane precipitates from the composition as it is formed, e.g. by a phase separation process.
  • the amount of component (iii) present in the composition, relative to the total weight of the composition, is preferably 3.49 to 78.98wt%, more preferably 18.49 to 77.99wt% and especially 35.5 to 77.99wt%.
  • Curing causes component (i) to cross-link, e.g. to form the membrane as a crosslinked, three dimensional polymer matrix.
  • component (iii) comprises isopropanol and an alcohol-miscible solvent having an alcohol-solubility of at least 5wt%.
  • alcohol-miscible solvents which may be used in component (iii) include other alcohol-based solvents, water, ether-based solvents, amide-based solvents, ketone-based solvents, sulfoxide-based solvents, sulfone-based solvents, nitrile-based solvents and organic phosphorus-based solvents, of which inert, polar solvents are preferred.
  • examples of alcohol-based solvents which may be used as or in component (iii) (especially in combination with water) include methanol, ethanol, isopropanol, n- butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and mixtures comprising two or more thereof. Isopropanol is particularly preferred.
  • organic solvents which may be used as or in component (iii) include dimethyl sulfoxide, dimethyl imidazolidinone, sulfolane, N- methyl pyrrolidone, dimethyl formamide, acetonitrile, acetone, 1 ,4-dioxane, 1 ,3- dioxolane, tetramethyl urea, hexamethyl phosphoramide, hexamethyl phosphorotriamide, pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, ethylene glycol diacetate, cyclopentylmethylether, methylethylketone, ethyl acetate, y-butyrolactone and mixtures comprising two or more thereof.
  • Dimethyl sulfoxide, N-methyl pyrrolidone, dimethyl formamide, dimethyl imidazolidinone, sulfolane, acetone, cyclopentylmethylether, methylethylketone, acetonitrile, tetrahydrofuran, 2- methyltetrahydrofuran and mixtures comprising two or more thereof are preferable.
  • component (iii) comprises isopropanol, one or more solvents selected from list (iiia) and optionally one or more solvents selected from list (iiib): list (iiia): water, methanol, ethanol, acetone, tetramethyl urea, hexamethyl phosphoramide, hexamethyl phosphorotriamide, butanone, cyclohexanone, methylethylketone, tetrahydrofuran, tetrahydropyran, 2-methyltetrahydrofuran, cyclopentylmethylether, propionitrile, acetonitrile, 1 ,4-dioxane, 1 ,3-dioxolane, ethyl acetate, y-butyrolactone and ethanolamine; and list (iiib): glycerol, ethylene glycol, dimethyl sulfoxide, sulpholane, dimethyl
  • composition comprises isopropanol and one or more other solvents from list (iiia) and/or list (iiib).
  • a preferred composition comprises 21 to 75.0wt% of component (i), below 21 wt% (e.g. 0.1 to 20.99wt%) of component (ii), 3.49 to 78.98wt% of component (iii) and 0.01 to 0.5wt% of component (iv), more preferably 21 to 60.0wt% of component (i), 1.0 to 20.99wt% of component (ii), 18.49 to 77.99wt% of component (iii) and 0.01 to 0.5wt% of component (iv), especially 21.0 to 44.0wt% of component (i), 1 .0 to 20.0wt% of component (ii), 35.5 to 77.99wt% of component (iii) and 0.01 to 0.5wt% of component (iv).
  • the polymerisation initiator comprises a thermal initiator and/or a photoinitiator.
  • thermal initiators examples include 2,2’-azobis(2-methylpropionitrile) (AIBN), 4,4’-azobis(4- cyanovaleric acid), 2, 2’-azobis(2, 4-dimethyl valeronitrile), 2,2’-azobis(2- methylbutyronitrile), 1 ,1’-azobis(cyclohexane-1-carbonitrile), 2,2’-azobis(4-methoxy- 2, 4-dimethyl valeronitrile), dimethyl 2,2’-azobis(2-methylpropionate), 2,2’-azobis[N-(2- propenyl)-2-methylpropionamide, 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'- Azobis(N-butyl-2-methylpropionamide), 2,2'-Azobis(N-cyclohexyl-2- methylpropionamide), 2,2'-Azobis(2-methylpropionamidine) dihydrochloride, 2,2'
  • Suitable photoinitiators which may be included in the composition include aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon halogen bond, and an alkyl amine compounds.
  • Preferred examples of the aromatic ketones, the acylphosphine oxide compound, and the thio compound include compounds having a benzophenone skeleton or a thioxanthone skeleton described in "RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY", pp.77-117 (1993).
  • More preferred examples thereof include an alpha-thiobenzophenone compound described in JP1972-6416B (JP-S47-6416B), a benzoin ether compound described in JP1972- 3981 B (JP-S47-3981 B), an alpha-substituted benzoin compound described in JP1972-22326B (JP-S47-22326B), a benzoin derivative described in JP1972-23664B (JP-S47-23664B), an aroylphosphonic acid ester described in JP1982-30704A (JP- S57-30704A), dialkoxybenzophenone described in JP1985-26483B (JP-S60- 26483B), benzoin ethers described in JP1985-26403B (JP-S60-26403B) and JP1987- 81345A (JP-S62-81345A), alpha-amino benzophenones described in JP1989- 34242B (JP
  • JP1990-211452A JP-H02-211452A
  • JP-S61-194062A a thio substituted aromatic ketone described in JP1986-194062A
  • an acylphosphine sulfide described in JP1990-9597B JP-H02-9597B
  • an acylphosphine described in JP1990-9596B JP-H02-9596B
  • thioxanthones described in JP1988-61950B JP-S63-61950B
  • coumarins described in JP1984-42864B JP-S59-42864B
  • photoinitiators described in JP2008-105379A and JP2009-114290A are also preferable.
  • photoinitiators described in pp. 65 to 148 of "Ultraviolet Curing System” written by Kato Kiyomi may be used.
  • the polymerisation initiator is preferably water-soluble.
  • the polymerisation initiator (iv) preferably has a water-solubility of at least 1wt%, more preferably at least 3wt%, when measured at 25 °C.
  • the composition preferably comprises 0.01 to 2wt%, more preferably 0.01 to 0.5wt%, of the component (iv), based on the total weight of the composition.
  • composition further comprises (v) a monomer other than component (i) and component (ii) which is reactive with component (i), for example a monomer which comprises one (and only one) polymerisable group (e.g. an ethylenically unsaturated group) which is free from ligand groups.
  • a monomer which comprises one (and only one) polymerisable group e.g. an ethylenically unsaturated group
  • Preferred polymerisable groups are ethylenically unsaturated groups and especially (meth)acrylic groups, as described above in relation to component (i).
  • the number of moles of component (i) exceeds the number of moles of component (v), when present.
  • the number of moles of component (ii) exceeds the number of moles of component (iv), when present.
  • the composition preferably comprises 0 to 20wt% of component (v), based on the total weight of the composition.
  • component (v) when component (v) is present, the amount (wt%) of component (i) present in the composition is greater than the amount of (component (ii) + component (v)).
  • component (v) is soluble in component (iii).
  • the composition includes one or more further components, e.g. a surfactant, a polymer dispersant, a polymerization reaction controlling agent, a thickening agent, an anti-crater agent, or the like, in addition to the above-described components.
  • a surfactant e.g. a surfactant, a polymer dispersant, a polymerization reaction controlling agent, a thickening agent, an anti-crater agent, or the like, in addition to the above-described components.
  • the composition may be cured by any suitable process, including thermal curing, photocuring and combinations of the foregoing.
  • the composition is preferably cured by photocuring, e.g. by irradiating the composition and thereby causing component (i) and any other polymerisable components present in the composition to polymerise.
  • Component (iii) is inert and does not polymerise, instead leaving pores in the resultant membrane.
  • the curing comprises photo-polymerization induced phase separation ("PIPS") of the membrane from the composition.
  • PIPS photo-polymerization induced phase separation
  • the curing comprises photo-polymerization induced phase separation ("PIPS") of the membrane from the composition.
  • PIPS photo-polymerization induced phase separation
  • a suitable amount of component (i), component (ii), component (iii), component (iv) and optionally component (v) allows one to obtain particularly good membranes having good waterflux, porosity and low swelling in water.
  • Using too much of component (i) and too little of component (iii) can result in a dense membrane with low waterflux, low porosity, and low swelling.
  • too little of component (i) and too much of component (iii) can result in a dense membrane material having low waterflux, but high porosity and high swelling. The latter appears dense; however the pore structure tends to collapse and therefore forms a more dense material.
  • the composition comprises 21 .0 to 55.0wt% of component (i), below 21.0wt% (e.g. 1 to 20.99wt%) of component (ii), 3.49 to 78.98wt% of component (iii), 0.01 to 0.5wt% of component (iv) and 0.0 to 20.0wt% of component (v) and the curing comprises photo-polymerization induced phase separation of the membrane from the composition.
  • a process for preparing a membrane according to the first aspect of the present invention comprising curing the composition defined in the first aspect of the present invention.
  • the membrane according to the first aspect of the present invention is obtained by a process comprising the steps of:
  • component (a) mixing component (i), (ii), (iii), (iv) and optionally (v) to form a composition comprising components (i), (ii), (iii), (iv) and optionally (v), wherein the wt% of component (i) present in the composition is greater than the wt% of component (ii) present in the composition;
  • step (b) curing (e.g. irradiating) the composition arising from step (a) and thereby polymerising components (i) and (ii) (and component (v) when present) to form a membrane;
  • step (c) optionally washing the membrane arising from step (b).
  • compositions used in the process of the second aspect of the present invention are as described in relation to the first aspect of the present invention.
  • component (ii) is free from ionic groups during step (a).
  • the process preferably further comprises the step of providing the ligand derived from component (ii) with an ionic charge after performing step (i).
  • the process used to prepare the membranes of the present invention comprise polymerisation-induced phase separation, more preferably photo polymerization induced phase separation, e.g. of the membrane from the composition.
  • the polymer is formed due to a photo-polymerization reaction.
  • step (b) may be performed by one or more further irradiation and/or heating steps in order to fully cure the membrane.
  • Including component (iii) in the composition has the advantage of helping the polymerisation in step (b) proceed uniformly and smoothly.
  • component (iii) acts as a solvent for components (i) and (ii) assists the formation of the pores in the resultant membrane.
  • component (iii) acts as a non-solvent for the resultant membrane.
  • the process according to the second aspect of the present invention provides substantially uniform membranes, often with a substantially uniform bicontinuous structure.
  • the curing causes components (i) and (ii) (and component (v) when present) to form substantially uniform polymer particles which then merge to form the membranes of the present invention.
  • the polymer particles, or agglomerates thereof preferably have an average diameter in the range of 0.1 nm to 5,000nm.
  • the polymer particles have an average particle or agglomerate size of 1nm to 2,000nm, most preferably, 5nm to 1 ,000nm.
  • the average particle or agglomerate size may be determined by cross-sectional analysis using Scanning Electron Microscopy (SEM).
  • the membrane of the present invention further comprises a support, especially a porous support.
  • a support can provide the membrane with increased mechanical strength.
  • the composition may be applied to the support between steps (a) and (b) of the process for preparing the membranes according to the second aspect of the present invention. In this way the porous support may be impregnated with the composition and the composition may then be polymerised on and/or within the support.
  • suitable supports include synthetic woven fabrics and synthetic non-woven fabrics, sponge-like films, and films having fine through holes.
  • the material for forming the optional porous support can be a porous membrane based on, for example, polyolefin (polyethylene, polypropylene, or the like), polyacrylonitrile, polyvinyl chloride, polyester, polyamide, or copolymers thereof, or, for example, polysulfone, polyether sulfone, polyphenylene sulfone, polyphenylene sulfide, polyimide, polyethermide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, cellulose, polypropylene, poly(4- methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, polychlorotrifluoroethylene, or copolymers thereof.
  • polyolefin polyethylene, polypropylene,
  • the membrane comprises a support and the curing comprises photocuring then preferably the support does not shield the wavelength of light used to cure the composition.
  • the support is preferably a low-leaching support, with organic or inorganic leachables below 1 .0 ppb or not continuous leaching but to be lowered up to 1 .0 ppb by extracting with water or organic solvent and/or hot water or hot organic solvent.
  • the membrane according to the present invention may optionally include more than one support and the more than one support may be identical to each other or different.
  • the membrane comprises 33.0 to 99.0wt% of component (i), 0.01 to 49.99wt% of component (ii), and 0 to 48.77wt% of component (v).
  • the membrane comprises a support the aforementioned % relate to the part of the membrane other than the support.
  • the membrane preferably has a mean flow pore size of 5 to 5,000nm, more preferably 100 to 2,000nm.
  • the mean flow pore size of the membrane according to the present invention may be measured using a porometer, e.g. a PoroluxTM porometer.
  • a porometer e.g. a PoroluxTM porometer.
  • a wetting fluid e.g. PorefilTM wetting Fluid, an inert, non-toxic, fluorocarbon wetting fluid with zero contact angle
  • the porometer can then provide the bubble point, maximum pore size, mean flow pore size, minimum pore size, average pore size distribution (of uniform materials) and air permeability of the membrane under test.
  • the membrane When the membrane does not comprise a support, the membrane preferably has a porosity of 15 to 99%, preferably 20 to 99% and especially 20 to 85%.
  • the membrane when the membrane further comprises a support, the membrane preferably has a porosity of 21 to 70%.
  • the porosity of the membrane may be determined by gas displacement pycnometry, e.g. using a pycnometer (especially the AccuPycTM II 1340 gas displacement pycnometry system available from Micromeritics Instrument Corporation).
  • the porosity of the membrane is the amount of volume that can be accessed by external fluid or gas. This may be determined as described below. Preferably, the porosity of the membrane of the present invention is more than 20%.
  • the thickness of the membrane including the support, in the dry state is preferably 20pm to 2,000pm, more preferably 40pm to 1 ,000 pm, and particularly preferably 70pm to 800pm.
  • the thickness of the membrane in a dry state is preferably 20pm to 2,000 pm, more preferably 100pm to 2,000pm, and particularly preferably 150pm to 2,000pm.
  • the thickness of the membrane including the support when measured after storing for 12 hours in a 0.1 M NaCI solution, is preferably 10pm to 4,000pm, more preferably 20pm to 2,000pm and particularly preferably 20pm to 1 ,500pm.
  • the thickness of the membrane when measured after storing for 12 hours in a 0.1 M NaCI solution, is preferably 10pm to 4,000pm, more preferably 50pm to 4,000pm and especially 70pm to 4,000pm.
  • the composition may be applied to a support (especially a porous support) between steps (a) and (b) of the process according to the second aspect of the present invention.
  • Step (b) may be performed on the composition which is present on and/or in the support.
  • the membrane When the membrane is not required to comprise a support, the membrane may be peeled-off the support. Alternatively if the membrane is required to comprise a support then the membrane may be left on and/or in the support.
  • the composition may be applied to the support or the support may be immersed in the composition by various methods, for example, curtain coating, extrusion coating, air knife coating, slide coating, nip roll coating, forward roll coating, reverse roll coating, dip coating, kiss coating, rod bar coating, and spray coating. Coating of a plurality of layers can be performed simultaneously or sequentially. In simultaneous multilayer coating, curtain coating, slide coating, slot die coating, or extrusion coating is preferable.
  • the composition may be applied to a support at a temperature which assists the desired phase separation of the membrane from the composition.
  • the temperature at which the composition is applied to the support (when present) is preferably below 80°C, more preferably between 10 and 60°C and especially between 15 and 50°C.
  • the membrane comprises a support
  • the composition before the composition is applied to the surface of the support one may treat the surface of the support e.g. using a corona discharge treatment, a glow discharge treatment, a flame treatment, or an ultraviolet rays irradiation treatment. In this way one may improve the wettability and the adhesion of the support.
  • Step (b) optionally further comprises heating the composition.
  • the composition is applied continuously to a moving support, more preferably by means of a manufacturing unit comprising one or more composition application station(s), one or more irradiation source(s) for curing the composition, a membrane collecting station and a means for moving the support from the composition application station(s) to the irradiation source(s) and to the membrane collecting station.
  • the composition application station can be placed at the upstream position with respect to the irradiation source, and the irradiation source can be placed at the upstream position with respect to the composite membrane collecting station.
  • the curing of the composition is initiated within 60 seconds, more preferably within 15 seconds, particularly preferably within 5 seconds and most preferably within 3 seconds from when the composition is applied to the support or from when the support has been impregnated with the composition (when a support is used).
  • Light irradiation for photocuring is preferably performed for less than 10 seconds, more preferably for less than 5 seconds, particularly preferably for less than 3 seconds and most preferably for less than 2 seconds.
  • the membrane may be irradiated continuously. The speed at which the composition is moved through the irradiation beam created by the irradiation source then determines the cure time and radiation dose.
  • the composition is cured by a process comprising irradiating the composition with ultraviolet (UV) light.
  • UV ultraviolet
  • the wavelength of the UV light used depends on the photoinitiator present in the composition and, for example, the UV light is UV- A (400nm to 320nm), UV-B (320nm to 280nm) and/or UV-C (280nm to 200nm).
  • UV light When high intensity UV light is used to cure the composition a significant amount of heat may be generated. In order to prevent overheating, it is preferable to cool the lamp of the light source and/or the support/membrane with cooling air.
  • irradiation with UV light is preferably performed by using an IR reflecting quartz plate as a filter.
  • UV light sources include a mercury arc lamp, a carbon arc lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a swirling flow plasma arc lamp, a metal halide lamp, a xenon lamp, a tungsten lamp, a halogen lamp, laser, and an ultraviolet ray emitting diode.
  • a medium pressure or high pressure mercury vapor type ultraviolet ray emitting lamp is particularly preferable.
  • an additive such as metal halide may be present.
  • a lamp having an emission maximum at a wavelength of 200nm to 450nm is particularly suitable.
  • the energy output of the radiation source is preferably 20W/cm to 1000W/cm and more preferably 40W/cm to 500W/cm, but if a desired exposure dose can be achieved, the energy output may be higher or lower than the aforementioned exposure dose.
  • the exposure intensity curing of the film is adjusted.
  • the exposure dose is measured in a wavelength range of UV-A by using a High Energy UV Radiometer (UV Power Puck (Registered Trademark) manufactured by EIT-lnstrument Markets), and the exposure dose is preferably 40mJ/cm 2 or greater, more preferably 100mJ/cm 2 to 3,000mJ/cm 2 , and most preferably 150mJ/cm 2 to 1 ,500mJ/cm 2 .
  • the exposure time can be freely selected, and is preferably short, and most preferably less than 2 seconds.
  • the membrane of the present invention is particularly useful for purifying biomolecules and compositions comprising metal ions.
  • the biomolecules include, for example, proteins, peptides, amino acids, anti-bodies and nucleic acids in biomedical applications.
  • the waterflux of the membrane of the present invention is preferably more than 1 l/(m 2 /bar/h), more preferably more than 5 l/(hr.m 2 .bar), especially more than 10 l/(m 2 /bar/hr) and especially preferably more than 100 l/(m 2 /bar/hr).
  • the membrane has a water flux above of 10 to 1500 l/(hr.m 2 .bar).
  • the water flux of the membranes according to the present invention may be determined as described below.
  • the swelling of the membranes of the present invention may be determined by measuring the volume of the membrane when dry and when wet with water (e.g. after being left in distilled water for 16 hours) and performing the following calculation:
  • the swelling (i.e. % increase in volume) of the membranes in water is preferably less than 10%, more preferable less than 5%, especially less than 3.5% and most preferably less than 1 .0%.
  • the membranes of the present invention are preferably affinity membranes.
  • the membranes are particularly useful for affinity membrane filtration.
  • the membrane has a water permeability of at least 1 .0 L/(h.m 2 .bar), more preferably at least 5 L/(h.m 2 .bar), especially at least 10 L/(h.m 2 .bar) and more especially at least 100 L/(h.m 2 .bar).
  • the membrane has the following properties (a), (b), optionally (c) and optionally (d):
  • a membrane according to the first aspect of the present invention for purifying biomolecules and/or compositions comprising metal ions.
  • the membranes according to the first aspect of the present invention may be used for detecting, filtering and/or purifying compositions comprising metal-ions (e.g. one or more metal-ions and optionally contaminants) from metal ions by, for example, contacting the membranes with a fed solution comprising one or more species of metal-ions, allowing the ligand present in the membrane to bind to one or more of the metal ions present in the composition and then collecting the remainder of the feed solution which has a lower content of the metal ions due to the metal ions being bound to the ligand present in the membrane.
  • the metal-ions from the feed solution are attracted to the ligand group from component (i).
  • the affinity of the ligand groups for the metal-ions depends on the binding capacity or stability constant of the ligand group for the particular metal-ions concerned.
  • the membranes of the present invention may be used to purify feed solutions by a number of processes, including use of the membranes in AMF, in size-exclusion chromatography (e.g. where the pores of the membrane are used to remove metal ions or colloids containing metals or agglomerates of metal particles based on their size (i.e. , physical exclusion)) and in affinity chromatography (e.g. where liquids are purified according to the binding capacity (stability constant) of the metal-ions with the ligand groups in the membrane (i.e. covalent or non-covalent interactions).
  • the membrane has a metal removal capacity for Cu of 150 to 1000 pmol/g of the membrane, more preferably of 197 to 661 pmol/g of the membrane.
  • the membranes according to the first aspect of the present invention may be used for filtering, and/or purifying biomolecules by eluting solutions containing biomolecules, especially biomolecules which carry a molecular unit which has an affinity for the ligand group.
  • the biomolecules are attracted to and bind to the ligand group of the membrane derived from component (i).
  • the membranes of the present invention may be used to purify biomolecules by a number of processes, including use of the membranes in size-exclusion chromatography (e.g. where the pores of the membrane are used to separate or purify biomolecules based on their size (i.e., physical exclusion)) and in affinity chromatography (e.g. where biomolecules are purified or separated according to the binding capacity (stability constant) of the biomolecules with the ligand groups in the membrane (i.e. covalent or non-covalent interactions)).
  • size-exclusion chromatography e.g. where the pores of the membrane are used to separate or purify biomolecules based on their size (i.e., physical exclusion)
  • affinity chromatography e.g. where biomolecules are purified or separated according to the binding capacity (stability constant) of the biomolecules with the ligand groups in the membrane (i.e. covalent or non-covalent interactions)
  • the membranes according to the first aspect of the present invention may be used for filtering, and/or purifying biomolecules by analogous techniques to those described above for biomolecules, especially by affinity membrane filtration.
  • the membranes according to the first aspect of the present invention may be used for detecting biomolecules by techniques involving the detection of colour, especially when the biomolecules comprise a fluorescent or coloured marker.
  • a further aspect of the present invention comprises a process for purifying an impure composition comprising a desired biomolecule comprising the steps:
  • step (ii) washing membrane product of step (i) to remove impurities from the composition such that the desired biomolecule remains bound to the ligand group;
  • step (ii) comprises washing the membrane product of step (i) with an aqueous buffer which ensures that most or all of the desired biomolecule remains bound to the ligand group and impurities (e.g. biomolecules which are not desired) are washed away.
  • Step (iii) may be performed by washing the membrane with an aqueous solution comprising a buffer having a different pH to the buffer used in step (i) or an aqueous solution comprising a chemical which has a higher affinity for the ligand than the desired biomolecule.
  • a process for purifying a feed composition comprising metal ions comprising the steps of contacting the feed composition with a membrane according to the present invention and allowing the metal ions to bond to the ligand group such that a composition is obtained which has a lower metal content than the feed composition.
  • the process for purifying a biomolecule and/or separating a biomolecule from other biomolecules comprises membrane size-exclusion chromatography or affinity chromatography.
  • the membranes may of course be used for other purposes too.
  • FO-2223-10 is a non-woven, polypropylene-based, porous cloth of thickness 100pm obtained from Freudenberg Group. This acts as a porous support
  • L1 is a monomer comprising one polymerisable group and a ligand group comprising two pyridine rings. L1 may be prepared by the method described for compound (11) in Sterk, M. and Bannwarth, W. (2015), Modulation of Reactivities of Dienophiles for Diels-Alder Reactions via Complexation of a,b-Unsaturated Chelating Amides. HCA, 98: 287-307.
  • L15 is a monomer comprising one polymerisable group and a ligand group comprising two pyridine rings.
  • L15 may be prepared by the method described for compound (1b) in Kunz, P.C., Bruckmann, N.E., Spingler, B. (2007), Towards Polymer Diagnostic Agents Copolymers of N-(2-Hydroxypropyl)- methacrylamide and Bis(2-pyridylmethyl)-4-vinylbenzylamine: Synthesis, Characterisation and Re(CO)3-Labelling, Eur. J. Inorg. Chem., 394-399
  • L5 L10 and L21 were prepared as described below.
  • L17 is a monomer comprising one polymerisable group and a ligand group comprising a cyclic ether ring.
  • L17 may be prepared by the method described for compound (1) in Drake, P. L, & Price, G. J. (2000). Crown-ether containing copolymers as selective membranes for quartz crystal microbalance chemical sensors. Polymer International, 49(9), 926-930.
  • L29 is a monomer comprising one polymerisable group and a ligand group comprising a cyclic ether ring. L29 may be prepared by the method described below.
  • L31 is a monomer comprising one polymerisable group and a ligand group comprising two carboxylic acid groups.
  • L31 may be prepared by the method described for N-Acryloylaspartic acid in Heilmann, S. M., & Smith, H. K. (1979). Acrylic-functional aminocarboxylic acids and derivatives as components of pressure-sensitive adhesives. Journal of Applied Polymer Science, 24(6), 1551-1564.
  • L35 is a monomer comprising one polymerisable group and a ligand group comprising two carboxylic acid groups.
  • L35 may be prepared by the method described for (VI) in Morris, L. R., Mock, R. A., Marshall, C. A., & Howe, J. H. (1959). Synthesis of Some Amino Acid Derivatives of Styrenel . Journal of the American Chemical Society, 81 (2), 377-382.
  • M282 is a cross-linking agent obtained from Sigma-Aldrich and has the structure shown below.
  • EBA is N,N'-ethylenebis(acrylamide) obtained from Sigma-Aldrich.
  • IrgacureTM 1173 is a photoinitiator obtained from BASF.
  • DVB is divinylbenzene obtained from Sigma-Aldrich.
  • MBA is a cross-linking agent having no ligand groups and having the structure shown below (from Sigma-Aldrich).
  • Water flux of the membranes was measured using a device where the weight of water passing through the membrane was measured over time.
  • a column of feed solution pure water
  • the feed solution was forced through the membrane by a constant applied air pressure on top of the water column.
  • the membrane under evaluation was stored for 12 hours in pure water prior to use.
  • the feed solution 250ml of pure water
  • the water column was closed and pressurized with air pressure and the membrane was flushed with one water column (250ml).
  • the feed solution was refreshed and a constant air pressure of lOOmbar was applied.
  • the measurements were performed by monitoring the weight by balance at a constant flow.
  • the membrane Prior to measuring a membrane's metal removal capacity, the membrane was weighed in the dry state. The membrane was then flushed 3x with demineralized water and 3x with iso-propanol. Subsequently, the membrane was placed in a filter holder and 50ml of a 2.0mM solution of CuSC in MeOH was passed through the membrane. The membrane was digested in acid solution and analysed by ICP-OES to determine the amount of Cu per unit weight of membrane in pmol/g (i.e micromoles of copper per gram of dry membrane).
  • the mean flow pore size of the membrane was measured using a porometer, e.g. a PoroluxTM porometer.
  • the membrane to be tested was fully wetted with a wetting fluid (e.g. PorefilTM wetting Fluid, an inert, non-toxic, fluorocarbon wetting fluid with zero contact angle).
  • a wetting fluid e.g. PorefilTM wetting Fluid, an inert, non-toxic, fluorocarbon wetting fluid with zero contact angle.
  • the porometer can then measure the flow of gas through the sample, as the liquid is displaced out of the porous membrane. This will provide the bubble point, maximum pore size, mean flow pore size, minimum pore size, average pore size distribution (of uniform materials) and air permeability of the membrane under test.
  • the mean flow pore diameter is the pore size at which 50% of the total gas flow can be accounted. This
  • the porosity of the membrane under evaluation was determined from the apparent density (p a parent) and the real density of the membrane.
  • the p ap parent was measured in air by weighing the membrane and determining its volume from the dimensions of the membrane (length, width and thickness).
  • the real density of the membrane was determined from pycnometer measurements of the membrane with known weight under helium atmosphere. The Helium occupied the pores of the membrane with known weight, and therefore the volume of polymer could be determined. From this the porosity could be determined according to Formula (1):
  • the pycnometer used was the AccuPycTM II 1340 gas displacement pycnometry system from Micromeritics Instrument Corporation.
  • the thickness of the membranes was determined by contact mode measurement. The measurements were performed at five different positions of the membrane and the average thickness of these five measurements in pm was calculated.
  • the dry membrane was then allowed to stand in distilled water (100cm 3 ) for 16 hours to give a wet membrane.
  • the volume of the wet membrane was then determined by measuring the width and the thickness again in 2-3 locations. Also the average of the dimensions are taken and the volume is calculated according to the formula above.
  • the swelling % was then determined by performing the following calculation:
  • a cell containing a degassed sample of membrane under test was evacuated and then cooled using liquid nitrogen to a temperature of 77 Kelvin. Portions of nitrogen gas were then dosed into the cell and the nitrogen gas was partly adsorbed onto the surface of the membrane under test until an equilibrium was reached with the gas phase. In this way adsorption and desorption points were recorded at different pressures and an adsorption and desorption isotherm was constructed. Adsorbed nitrogen first formed a quasi-monolayer on the membrane surface whereas further increases in pressure resulted in the formation of multilayers. In the region where monolayer and multilayers were formed, the specific surface area (SBET) was determined according to the BET (Brunauer, Emmet and Teller) theory. This model is applicable to non-porous and meso- and macroporous materials and adsorption points in the relative pressure range between 0.05 and 0.25 were used.
  • SBET Brunauer, Emmet and Teller
  • L10 was characterised by 1 H NMR (62 MHz, CH3OD, S): 8.68-8.50 (m, 2H), 7.86-7.36 (m, 6H), 6.56-5.67 (m, 3H), 4.17 (s, 4H), 3.80-2.97 (m, 18H) and 2.81-2.56 (m, 2H).
  • the 2-aminomethyl-18-crown-6 (0.50mmol) was added to a mixture of 4- vinylbenzyl chloride (0.50mmol) in dry THF (42ml) at 0°C.
  • the reaction mixture was warmed to room temperature and stirring was continued for an additional 24 hours.
  • the THF was removed by concentration under reduced pressure and redissolved in CH2CI2 (100ml). Extraction was performed with NaOH (1.0 M aq., 25ml x3), water (25ml x2) and brine (25ml).
  • the organic phase was dried with Na 2 S0 4 and after filtration the solvent was removed and purified by flash chromatography (7% MeOH in CH2CI2).
  • compositions 1 to 31 were prepared by mixing the ingredients indicated in Table 1 below in the specified amounts.
  • component (ii) had the structure identified above in the description
  • component (i) was either N,N'- ethylenebis(acrylamide) (EBA) or M282
  • component (iii) was described in Table 1
  • component (iv) was IrgacureTM 1173 (a photoinitiator).
  • the compositions were each applied to a porous support (FO-2223-10) by the process described in more detail further in this specification.
  • compositions 32 to 46 were prepared by mixing the ingredients indicated in Table 2 below in the specified amounts.
  • component (ii) had the structure identified above in the description
  • component (i) was divinylbenzene (DVB)
  • component (iii) was as described in Table 2
  • component (iv) was IrgacureTM 1173 (a photoinitiator).
  • the compositions were each applied to a porous support (FO-2223- 10) by the process described in more detail below.
  • Table 2 Compositions
  • compositions present on the supports were cured by irradiation with UV using a Light Hammer LH6 UV exposure machine (manufactured by Fusion UV Systems, Inc.).
  • the Light Hammer machine was fitted with a Model H-bulb (100% strength).
  • the coated supports were passed through the Light Hammer machine at a speed of 10 m/min to expose the composition to the UV light from the H-bulb.
  • the curing time was 0.8 seconds.
  • the exposure time was 0.71 seconds.
  • the resultant membranes were removed from the glass plate and was stored in a polyolefin bag.
  • Comparative composition CEx1 to CEx4 were prepared by mixing the ingredients indicated in Table 4 below in the specified amounts.
  • component (ii) had the structure identified above in the description
  • component (i) consisted of the components specified in Table 4
  • component (iii) was IrgacureTM 1173 in the amounts indicated.
  • CEX3 and 4 become dense membranes and no flux could be obtained. Therefore no metal removal was observed.

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Abstract

L'invention concerne une membrane poreuse pouvant être obtenue par un procédé comprenant le durcissement d'une composition comprenant : (i) un ou plusieurs agents de réticulation ; (ii) un ou plusieurs monomères comprenant un groupe polymérisable et au moins un groupe ligand ; (iii) un ou plusieurs solvant inertes ; et (iv) un ou plusieurs initiateurs de polymérisation ; le pourcentage en poids du composant (i) présent dans la composition étant supérieur au pourcentage en poids du composant (ii) présent dans la composition.
PCT/EP2020/083128 2019-12-04 2020-11-24 Membranes d'affinité, composés, compositions et procédés pour leur préparation et leur utilisation WO2021110468A1 (fr)

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