WO2013005050A1 - Copolymères et membranes - Google Patents

Copolymères et membranes Download PDF

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Publication number
WO2013005050A1
WO2013005050A1 PCT/GB2012/051595 GB2012051595W WO2013005050A1 WO 2013005050 A1 WO2013005050 A1 WO 2013005050A1 GB 2012051595 W GB2012051595 W GB 2012051595W WO 2013005050 A1 WO2013005050 A1 WO 2013005050A1
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meth
monomer
addition copolymer
branched addition
acrylate
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PCT/GB2012/051595
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English (en)
Inventor
Paul Hugh Findlay
Brodyck James Lachlan Royles
Neil John Simpson
Roselyne Marie Andree Baudry
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Unilever Plc
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Publication of WO2013005050A1 publication Critical patent/WO2013005050A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/16—Halogens
    • C08F212/18—Chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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
    • B01D2323/32—Use of chain transfer agents or inhibitors
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2339/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2339/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2339/08—Homopolymers or copolymers of vinyl-pyridine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/20—Polymers characterized by their physical structure
    • C08J2400/202—Dendritic macromolecules, e.g. dendrimers or hyperbranched polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to soluble branched addition copolymers which may be cured post synthesis to form membranes. More specifically the present invention relates to the soluble branched addition copolymers which may be cured post synthesis to form ion-exchange membranes with improved properties, methods for their preparation, compositions comprising such soluble branched addition copolymers and their use in membrane preparation, most specifically ion-exchange membranes.
  • the present invention relates to novel soluble branched addition copolymers which may be cured via a cross-linking reaction and their use as membranes, most specifically ion-exchange membranes wherein the membranes exhibit improved hydrolytic stability.
  • branched addition copolymers may be successfully used to prepare ion-exchange membranes with high ion selectivity, low electrical resistance and low swelling. Additionally, as the polymers used to form the membranes are branched in nature they may be dissolved and cast at high concentration in organic solvents leading to reduced solvent usage.
  • novel branched addition copolymers may be used to form membranes with improved properties. These novel copolymers may be used to resolve or mitigate many of the problems associated with existing polymeric membranes. For example, there is a requirement in electrochemical desalination devices for the manufacture of membranes with suitably improved hydrolytic stability which may be used to withstand extremes of pH and which are particularly effective as ion-exchange membranes in such devices.
  • An ion-exchange membrane may be described as a charged, ion-selective barrier or component for use in devices where the removal or concentration of one ion species over another is required.
  • Such ion-exchange membranes have a net positive or negative charge and as such are selective for anions (Anion Exchange Membrane - AEM) or cations (Cation Exchange Membrane - CEM) respectively.
  • Ion-exchange membranes are typically polymeric in nature and may be prepared either from polymerising suitable monomers and or via post-functionalising or crosslinking of a pre-formed polymer or oligomer to achieve the desired membrane material.
  • an ion-selective membrane In order to provide charge discrimination an ion-selective membrane must possess a net positive or negative charge. These charged groups may be present in the monomer or pre-formed polymer structure or may be introduced via a post- modification step upon formation of the polymer or membrane. It is preferential to cast or fabricate an ion-exchange membrane from a polar or non-polar organic solvent, more preferably a polar organic solvent as casting charged ion-exchange membranes from water can lead to undesirable swollen membrane structures.
  • a particularly useful process involves the introduction of charged groups while crosslinking the polymer.
  • the membrane is formed by the reaction of a suitable pre-formed polymer with a functional co-reactant to achieve both crosslinking and introduction of the necessary charge in one step.
  • An example of such a process would be in the preparation of an anion exchange membrane (AEM) from a basic nitrogenous polymer which is then reacted with a dihalo alkane, such as in the reaction of a pyridine-functional polymer with a diiodo or dibromo alkane.
  • AEM anion exchange membrane
  • An alternative method involves reacting a polymer possessing a leaving group, such as a halogen atom, with a nucleophilic amine or polyamine molecule; such as the reaction between a polymer possessing benzyl chloride moieties with a tertiary diamine.
  • a leaving group such as a halogen atom
  • the charged species on the ion-exchange membrane is also important with regard to the selectivity and performance of the membrane.
  • the membrane must have a net positive or negative charge.
  • the charged species must be stable, advantageously permanent and accessible in order to have affinity for the appropriate ion.
  • the material In order for the membrane to be anion-selective (an AEM) the material must have a net positive charge and contain cationic species, preferred cationic groups tend to be formed from, for example, charged nitrogen or phosphorous species including quaternary ammonium, pyridinium, imidazolidinium, guanidinium or phosphonium moieties.
  • anionic groups tend to be strongly acidic species such as sulfonic or phosphoric acid moieties.
  • Weakly acidic groups such as carboxylic acid groups may also be used although in certain applications such groups may become irreversibly fouled with divalent cations such as magnesium or calcium. This is particularly true for example in the desalination or purification of seawater.
  • ion-exchange membranes can be prepared directly via polymerising suitable functional monomers, a particularly attractive route is through the preparation of a functional polymer or oligomer wherein the polymeric material is used to fabricate an ion-exchange membrane. It is usual to crosslink the polymer in order to obtain a stable, robust membrane. Crosslinking is obtained through the reaction of a first functional group on the polymer with a suitable second group. This crosslinking may be through an inter- or intra- molecular reaction. That is, the polymer can be designed to react with itself during a membrane casting or curing process or, the polymer may be designed to react with an additional molecule, wherein the additional molecule is either for example a polymer or a small molecule.
  • Suitable curing reactions include the polymerisation of, for example; a pendant alkene unit such as a vinyl or allyl unit; or alternatively, the reaction may be between two reactive units to form a covalent bond, such as the formation of an ester or amide link; the ring opening of an epoxide; formation of a urethane or urea bond; nucleophilic substitution or addition; electrophilic substitution or addition or via the formation of an ionic linkage, for example through the formation of a salt bridge.
  • a pendant alkene unit such as a vinyl or allyl unit
  • the reaction may be between two reactive units to form a covalent bond, such as the formation of an ester or amide link; the ring opening of an epoxide; formation of a urethane or urea bond; nucleophilic substitution or addition; electrophilic substitution or addition or via the formation of an ionic linkage, for example through the formation of a salt bridge.
  • Crosslinking reactions may take place at ambient temperature or through thermal means or via a photochemical reaction, typically via a UV source.
  • Additional initiators may also be used, for example a free radical initiator where the reactive species is an alkene unit.
  • Catalysts may also be used to accelerate the curing step such as, for example, a strong acid in the case of the preparation of an ester or amide linkage, or a metal compound in the case of urethane or urea formation.
  • Crosslinked membranes have the advantage of being more environmentally resilient than uncured materials due to the insoluble nature of the crosslinked network, that is, the curing mechanism renders the material essentially intractable, that is, insoluble, hence the requirement for pre-formation into the desired form of the end product prior to the crosslinking step.
  • the functional group may be incorporated into the polymer structure via the use of functional monomers or alternatively the reactive moiety may be introduced through a further reactive step onto a pre-formed polymer.
  • An unsaturated carbon-carbon unit in the form of for example an alkene bond may be essentially polymerised, usually via a free radical procedure.
  • the polymerisation occurs via the introduction of a free radical initiator which is then dissociated thermally, by the use of UV radiation or via a chemical means such as a redox reaction, to generate free radicals which react with the unsaturated units and provide a cured polymer, or alternatively via a transition metal catalyst "drier" in the case of alkyd systems.
  • Allyl, vinyl or alkyd-functional polymers are typically used in this type of curing.
  • the mutually reactive units described can be present within the same polymer structure or, on two or more polymers, or, on one polymer and one small molecule, wherein the complementary functionalities on each polymer or molecule may react. Ester or amide formation.
  • Alcohol or amine and carboxylic acid functionalities may be reacted to provide an ester or an amide linker unit respectively.
  • These linking reactions are typically thermally propagated in the presence of a strong acid catalyst.
  • Another route to these types of linkages is the reaction of an alcohol or amine with an anhydride an acid chloride or azlactone; or through the transesterification or transamidation of an activated ester such as that found in the monomer methyl acrylamidoglycolate methyl ether.
  • a compound possessing an epoxide ring is reacted with a nucleophilic material, usually a primary or secondary amine or alkoxide unit.
  • a nucleophilic material usually a primary or secondary amine or alkoxide unit.
  • the amine epoxy reaction may be catalysed by a hydroxylic species such as phenols and alcoholic solvents.
  • Epoxides may also react with other nucleophilic species such as thiols or carboxylic acids, in the presence of a tri- alkyl or aryl phosphine catalyst.
  • the epoxide may also be homopolymerised via the use of a Lewis or Bronsted acid such as boron tri-fluoride or tri-fluoromethane sulfonic acid.
  • an isocyanate group is reacted with a group possessing an active hydrogen such as a hydroxyl group, a thiol or an amine.
  • the polymer usually possesses the active hydrogen nucleophile and is reacted with a smaller molecular weight di- or poly-isocyanate, such as tolylenediisocyanate.
  • Blocked isocyanates, where the isocyanate unit has been reacted with a labile monofunctional active hydrogen compound may also be used, in which case, the isocyanate is rendered less reactive and the formulation may be stored as a stable one-pack formulation.
  • Nucleophilic substitution involve the substitution of a labile leaving group with a suitable nucleophile.
  • An example of such a reaction involves the substitution of an alkyl halide with an amine or alkoxide.
  • a charged species is formed which may be advantageous in the formation of a charged membrane.
  • an electrophile is reacted with a suitable electron-rich moiety.
  • An example of this crosslinking reaction is the reaction of an activated aryl unit with an electrophile such as an acid chloride, usually in the presence of a Lewis acid catalyst.
  • reaction of two thiol units to form a disulfide may be undertaken through oxidation, for example by the use of hydrogen peroxide.
  • siloxane linkages may be achieved through the reaction of an alkyloxysilane functionality where the curing proceeds via the elimination of a carboxylic acid, for example acetic acid in the case of an acetoxysilyl unit.
  • ion-exchange membranes take place in aqueous environments; the pH of the environment may vary from acidic to basic. This is particularly true where the ion-selective membranes are being used for metal ion concentration in acidic waste streams or where they are being used in the electrodialysis of water. In the latter case highly basic conditions may be generated at the cathode due to so- called water splitting, this is due to device inefficiency where water is electrolysed in addition to the potential difference between the two electrodes being used to separate ions.
  • the hydrolytic stability of the polymer membrane is important, as hydrolysis of the crosslinked membrane and/or polymer and/or functional units can reduce the performance or mechanical strength of the membrane. Additionally, if the crosslinking units are hydrolysed, the membrane may break-up or swell in-use which is highly undesirable.
  • hydrolytic stability in-use functional group stability where the membrane is utilised in an aqueous environment at extremes of low and high pH and is stable to hydrolysis for example via potential saponification or Hoffman elimination reactions.
  • the term 'hydrolytic stability' in the context of the present application relates to soluble branched copolymers which when used in the formation of a membrane, the permselectivity and electrical resistance of the membrane does not change by more than 50 % when subjected to hydrolysis at 25 °C for 48 hours and to extremes of pH such as greater than pH 12 and less than pH 3. More preferably the permselectivity and electrical resistance of the membrane does not change by more than 40 % when subjected to hydrolysis at 25 °C for 48 hours and extremes of pH above and below pH 12 and pH 3 respectively.
  • the permselectivity and electrical resistance of the membrane does not change by more than 25 % when subjected to hydrolysis at 25 °C for 48 hours and extremes of pH above and below pH 12 and pH 3 respectively. Most preferably the permselectivity and electrical resistance of the membrane does not change by more than 10 % when subjected to hydrolysis at 25 °C for 48 hours and extremes of pH such as greater than pH 12 and less than pH 3.
  • Membrane hydrolysis can be reduced by preparing the membrane or polymer from hydrolytically stable units.
  • hydrolytically stable units is meant stability in-use through potential membrane degradation reactions or reduction in functional groups via for example Hoffman elimination reactions or saponification reactions of the functional species.
  • Ion-selective membranes are used for a number of industrial applications. Essentially the membranes are used where ions are required to be separated, concentrated or detected from a solution. Ion-selective membranes can be simply utilised in place of conventional ion-exchange resins, for ion separation, removal or concentration applications whereby the laminar format of a membrane is preferable to a bead morphology. Ion-selective membranes also find uses in a number of electrically driven ion-separation devices, where the ion-selective membrane acts as a charged barrier in order for the device to operate or to improve performance.
  • Ion-exchange membranes can be used for electrodialysis which is a process whereby ions are removed from water or an aqueous solution via the use of a electrical potential difference. In this process, unlike pressure driven processes such as ultrafiltration or reverse osmosis, charged ions as opposed to water molecules pass through a membrane driven by an external electrical potential. Ion-selective membranes are used in these devices acting as a charge barrier and allowing only one ion species to traverse the membrane barrier, thereby enabling the device to act efficiently. Additional electro-purification devices are known in the art, and again ion- exchange membrane barriers are known to improve the efficiency when utilised in the device. For these applications, in order to be effective, the membranes require a high ion permselectivity, low electrical resistance, low swelling in water, high physical strength and resistance to hydrolysis.
  • Linear polymers are commonly used in many applications due to their high solubility and ease of preparation. Due to their architectures these polymers can give rise to high viscosity solutions or melts, in addition they can be extremely slow or difficult to dissolve or melt to give isotropic liquids. The high viscosity of these solutions can be problematic in membrane formulation where a large amount of solvent is required in order to provide a workable formulation. Where the solvent is organic in nature this can lead to a large amount of volatile organic compound (VOC) being necessary to use the linear polymer effectively. Increasing legislation to decrease the VOC levels of many formulations makes this undesirable. Linear addition polymers typically also have a functional group pendant to the main chain of the polymer. This situation may give rise to slow curing reactions due to the inaccessibility of functional groups within the interior of the polymer structure during the curing reaction. This in turn leads to longer cure times and higher cure temperatures in thermally mediated reactions.
  • VOC volatile organic compound
  • Linear polymers can also give rise to incomplete curing. Due to the architecture of these materials the membrane can also swell significantly in formulations leading to poor substrate adhesion and poor membrane properties. Swelling of a membrane during use is particularly problematic as it can lead to failure of the polymer membrane properties or the device itself.
  • linear polymers can also lead to poorly cross-linked or open networks when cured into a membrane. Where highly dense membranes are required, or where a high concentration of functionalities or charge is required in the finished membrane, this can be unfavourable. This can also lead to poorer mechanical strengths for membranes prepared using linear polymers.
  • the curing rate of a linear polymer system is proportional to the molecular weight of the macromolecule concerned. Ideally, high molecular weight materials are preferred. However due to the sharp increase in solution or melt viscosity of the formulation with increasing molecular weight a compromise in molecular weight must be achieved to avoid high amounts of solvent (typically a VOC) in the formulation, or temperature, in the case of melt processed systems.
  • solvent typically a VOC
  • Branched copolymers are polymer molecules of a finite size in which the backbone is branched. Branched copolymers differ from cross-linked polymer networks which tend towards an infinite size having interconnected molecules and which are generally not soluble. In some instances, branched polymers have advantageous properties when compared to analogous linear polymers. For instance, solutions of branched copolymers are normally less viscous than solutions of analogous linear polymers. Moreover, higher molecular weights of branched copolymers may be solubilised more easily than those of corresponding linear polymers. In addition, as branched polymers tend to have more end groups than a linear polymer they generally exhibit strong surface-modification properties.
  • branched polymers are useful components of many compositions and may be utilised in the formation of polymer membranes.
  • Branched and hyperbranched copolymers can also be used in curable systems. Unlike dendrimers branched copolymers typically show non-ideal branching in their structure and can possess polydisperse structures and molecular weights. The preparation of branched copolymers however is much easier than their dendrimer counterparts and although the final structure may not be perfect or monodisperse, branched copolymers are more suitable for a number of industrial applications.
  • Branched copolymers are usually prepared via a step-growth mechanism via the polycondensation of suitable monomers and are usually limited by the choice of monomers, the chemical functionality of the resulting polymer and the molecular weight.
  • a one-step process can be employed in which a multifunctional monomer is used to provide functionality in the polymer chain from which polymer branches may grow.
  • a limitation on the use of a conventional one-step process is that the amount of multifunctional monomer must be carefully controlled, usually to substantially less than 0.5% w/w in order to avoid extensive cross-linking of the polymer and the formation of insoluble gels. It is difficult to avoid cross-linking using this method, especially in the absence of a solvent as a diluent and/or at high conversion of monomer to polymer.
  • WO 99/46301 discloses a method of preparing a branched polymer comprising the steps of mixing together a monofunctional vinylic monomer with from 0.3 to 100% w/w (of the weight of the monofunctional monomer) of a multifunctional vinylic monomer and from 0.0001 to 50% w/w (of the weight of the monofunctional monomer) of a chain transfer agent and optionally a free-radical polymerisation initiator and thereafter reacting said mixture to form a copolymer.
  • the examples of WO 99/46301 describe the preparation of primarily hydrophobic polymers and, in particular, polymers wherein methyl methacrylate constitutes the monofunctional monomer. These polymers are useful as components in reducing the melt viscosity of linear poly(methyl methacrylate) in the production of moulding resins.
  • WO 99/46310 discloses a method of preparing a (meth)acrylate functionalised polymer comprising the steps of mixing together a monofunctional vinylic monomer with from 0.3 to 100 % w/w (based on monofunctional monomer) of a polyfunctional vinylic monomer and from 0.0001 to 50 % w/w of a chain transfer agent, reacting said mixture to form a polymer and terminating the polymerisation reaction before 99 % conversion.
  • the resulting polymers are useful as components of surface coatings and inks, as moulding resins or in curable compounds, for example curable moulding resins or photoresists.
  • WO 02/34793 discloses a rheology modifying copolymer composition containing a branched copolymer of an unsaturated carboxylic acid, a hydrophobic monomer, a hydrophobic chain transfer agent, a cross linking agent, and, optionally, a steric stabilizer.
  • the copolymer provides increased viscosity in aqueous electrolyte- containing environments at elevated pH.
  • the method for production is a solution polymerisation process.
  • the polymer is lightly cross-linked, less than 0.25%.
  • US 6,020,291 discloses aqueous metal working fluids used as lubricant in metal cutting operations.
  • the fluids contain a mist-suppressing branched copolymer, including hydrophobic and hydrophilic monomers, and optionally a monomer comprising two or more ethylenically unsaturated bonds.
  • the metal working fluid may be an oil-in-water emulsion.
  • the polymers are based on poly(acrylamides) containing sulfonate-containing and hydrophobically modified monomers. The polymers are cross-linked to a very small extent by using very low amount of bis-acrylamide, without using a chain transfer agent.
  • a hyperbranched polyester (Boltorn H40) to increase the gas permeability coefficients for polyimide membranes.
  • the hyperbranched material is cast together with the polyimide to give the corresponding hybrid membrane.
  • the Boltorn material is not covalently linked in any way in the membrane there is a marked increase in the permeability coefficients for nitrogen and oxygen with a modest (1 % w/w) incorporation of the hyperbranched polymer.
  • WO 03/104327A1 describes the formation of a highly gas impermeable film via the use of a functionalised hyperbranched polyester amide (HBPEA).
  • HBPEA functionalised hyperbranched polyester amide
  • the HBPEA is incorporated in a preferably post-cured film in conjunction with a quantity of poly(vinylalcohol) or derivative thereof.
  • the film is then post-cured by incorporation of a further reactive molecule capable of reacting covalently with hydroxyl groups.
  • the films were found to be effective barriers against oxygen.
  • soluble branched addition copolymers capable of crosslinking
  • the membranes could be cast or cured with ionic functionality and be used in ion-separation applications.
  • the inventors also showed that these materials could be cast from organic solvent where the ionic group was introduced during the crosslinking reaction to achieve an ion-exchange membrane.
  • the materials produced showed high ion permselectivities, low electrical resistances, high tensile strength and low swelling in aqueous solutions.
  • Polymers capable of undergoing a subsequent curing or cross-linking reaction are used in many everyday applications.
  • these polymers are of a linear architecture where the functional groups are either pendant to the polymer main chain or at the termini of the macromolecule.
  • the polymers can be natural, synthetic or hybrid in composition and can either react via an intra or intermolecular mechanism.
  • the functionality is usually either preformed within the polymer structure through choice of suitable reactive monomers or incorporated through a further chemical reaction. In these cases the functionality is placed along the carbon main-chain of the material.
  • the concentration and location of the functionality can be tuned through the ratios of functional monomers or by using a controlled technique respectively. Problems associated with using linear molecules to form membranes.
  • soluble curable branched copolymers in the formation of membrane has a number of advantages over linear systems.
  • the architecture of branched copolymers means that these polymers give rise to solutions or melts of lower viscosity enabling higher solids compositions to be formulated. This then enables less solvent to be used which can be problematic where volatile organic solvents (VOCs) are employed.
  • VOCs volatile organic solvents
  • curable systems there is a growing trend toward high solids formulations, the presence of organic solvents is something of a liability as they impart flammability, high cost and in many cases toxicity and are almost entirely lost in the final cured system. Since the solvent usually plays no part in the curing mechanism, and in many cases hinders it, the removal of the solvent is preferential.
  • Dendritic polymers are prepared via a multi-step synthetic route and are limited by chemical functionality and ultimate molecular weight, being prepared at a high end cost. Such molecules have therefore only limited high-end industrial applications. Branched copolymers are typically prepared via a step-growth procedure and again are limited by their chemical functionality and molecular weight. However, the reduced cost of manufacturing such polymers makes them more industrially attractive. Due to the chemical nature of both of these classes of macromolecules (that is, such molecules typically possess ester or amide linkages), problems arising from their miscibility with olefin-derived polymers have been observed. This may be circumvented by the use of hydrocarbon-based, star-shaped polymers prepared via anionic polymerisation or the post-functionalisation of pre-formed dendrimers or branched species although this again leads to an increased cost in the materials.
  • soluble branched copolymers of high molecular weight may be prepared via a one-step process using commodity monomers. Through specific monomer choices the chemical functionality of these polymers can be tuned depending on the specific application. These benefits therefore give advantages over dendritic or step-growth branched polymers. Since these polymers are prepared via an addition process from commodity monomers, they may be tuned to give good miscibility with equivalent linear addition polymers. Since branched copolymers comprise a carbon-carbon backbone they are not susceptible to thermal or hydrolytic instability unlike ester-backbone-based dendrimers or step-growth branched copolymers. It has been observed that these polymers also dissolve faster than equivalent linear polymers.
  • the branched soluble copolymers of the present invention are branched, non-cross- linked addition copolymers and include statistical, block, graft, gradient and alternating branched copolymers.
  • the copolymers of the present invention comprise at least two chains which are covalently linked by a bridge other than at their ends, that is, a sample of said copolymer comprises on average at least two chains which are covalently linked by a bridge other than at their ends.
  • the membrane composition may be tuned through a choice of the monomers and the curing of the material.
  • branched curable copolymers lead to; higher solids content formulations may be achieved; low viscosity formulations may be prepared; less volatile organic compounds (VOCs) are required in the final formulation; faster cure rates may be achieved leading to faster processing times; greater substrate adhesion may be obtained; higher density of functionalities or charge may be achieved; denser cross-linked structures may be obtained; greater mechanical strength may be achieved; thinner robust membranes may be prepared; higher permselectivities may be achieved; lower electrical resistances may be obtained and a lower swelling of the final polymer membrane with increased hydrolytic stability. That is, it has now been found that certain soluble branched copolymers with increased hydrolytic stability are able to withstand the demands of ion-selective membranes.
  • VOCs volatile organic compounds
  • the branched addition copolymers of the present invention are in contrast to insoluble polymer gels.
  • a gel is formed when a cross-linked non-soluble polymer is mixed with a solvent which would normally dissolve the polymer backbone if it were a linear and non crosslinked analogous polymer, that is, the same as those chains, which when linked together, form the cross-linked network.
  • the chains are compatible with the solvent but cannot form an isotropic homogenous solution because they are all linked together to form the network and are thus physically constrained. Hence the system is swollen to form a gel.
  • the rigidity or amount of swelling depends on the amount (or degree) of cross-linking present; the more cross-linking the more rigid and less swollen the gel will be.
  • a soluble branched addition copolymer will mix completely with a solvent to form a totally homogeneous isotropic solution.
  • Soluble branched addition copolymers are differ from microgels which are lightly cross-linked polymers, that is, small pieces of crosslinked networks that still appear soluble to the naked eye as when mixed with a good solvent they appear to form free flowing isotropic solutions.
  • a test for judging whether a polymer has dissolved to form a solution is to take a small amount of the polymer (around 0.2 g of greater than 50 weight % solution or dry material) and dilute with 10 g of a good solvent of the polymer. If this very dilute solution then passes through an in-line microdisc 0.2 micron pore size syringe filter then the polymer is truly soluble. A highly diluted micro gel will not pass though such a filter.
  • a soluble branched addition copolymer to form a cross-linked hydrolytically stable membrane wherein the soluble branched addition copolymer is cured after formation via an addition polymerisation process prior to formation of the cross- linked membrane;
  • the soluble branched addition copolymer is obtainable by an addition polymerisation process; and wherein the
  • branched addition polymer comprises a weight average molecular weight of 2,000 Da to 1 ,500,000 Da;
  • the branched addition copolymer comprises:
  • the at least two chains comprise at least one ethyleneically monounsatu rated monomer, and wherein
  • the bridge comprises at least one ethyleneically polyunsaturated monomer
  • the polymer comprises a residue of a chain transfer agent and optionally a residue of an initiator;
  • the mole ratio of polyunsaturated monomer(s) to monounsaturated monomer(s) is in a range of from 1 :100 to 1 :3 and wherein the branched copolymer is hydrolytically stable such that the permselectivity and electrical resistance of the membrane does not change by more than 50 % when subjected to hydrolysis at 25 °C for 48 hours and a pH of greater than 12.
  • a soluble branched addition copolymer according to the first aspect of the present invention wherein the soluble branched addition copolymer is obtainable by an addition polymerisation process; wherein the branched addition polymer comprises a weight average molecular weight of 2,000 Da to 1 ,500,000 Da; and wherein
  • the branched addition copolymer comprises:
  • the at least two chains comprise at least one ethylenically monounsatu rated monomer, and wherein
  • the bridge comprises at least one ethylenically polyunsaturated monomer
  • the polymer comprises a residue of a chain transfer agent and optionally a residue of an initiator;
  • the mole ratio of polyunsaturated monomer(s) to monounsaturated monomer(s) is in a range of from 1 :100 to 1 :3 and wherein the branched copolymer is hydrolytically stable such that the permselectivity and electrical resistance of the membrane does not change by more than 40 % when subjected to hydrolysis at 25 °C for 18 hours and a pH of greater than or equal to 12.
  • the branched addition copolymer When in use the branched addition copolymer may be cured by the addition of a reactive polymer, oligomer or small molecular weight reactive molecule and wherein the copolymer comprises at least 50 mole percent aromatic, heteroaromatic, amide, ether or urethane residues derived from the monofunctional monomer and/or the multifunctional monomer and/or the chain transfer agent.
  • the branched addition copolymer When in use the branched addition copolymer may be cured by the addition of a reactive polymer, oligomer or small molecular weight reactive molecule and the copolymer may comprise at least 50 mole percent aromatic or heteroaromatic residues derived from the monofunctional monomer and/or the multifunctional monomer and/or the chain transfer agent.
  • the branched addition copolymer When in use the branched addition copolymer may be cured by means of thermal, photolytic, oxidative, reductive reaction or nucleophilic or electrophilic substitutions or addition or by the addition of a catalyst or initiator.
  • the branched addition copolymer may be prepared from monomers comprising one or more of the following groups: hydroxyl, amino, carboxylic, epoxy, isocyanate, pyridinyl, imidazolyl, sulfonic acid, vinyl, allyl, (meth)acrylate and styrenyl.
  • the branched addition copolymer may be cured by means of the reaction of reactive functional groups provided by the monomers and the reactive functional groups may react via an inter or intra molecular process.
  • the soluble branched addition copolymer comprises less than 1 % monomer impurity.
  • the branched addition polymer preferably comprises a weight average molecular weight of 3,000 Da to 900,000 Da.
  • the soluble branched addition copolymer may be used in the membrane in the application areas selected from the group comprising:
  • the use of the soluble branched addition copolymer may be where the membrane comprises an anion exchange membrane and the branched addition copolymer comprises monomer residues selected from the groups consisting of:
  • a chain transfer agent (CTA); and wherein the copolymers formed from monofunctional monomers A or C are reacted with compounds selected from the groups B or D respectively below; and wherein A, C , B and D are selected from the groups comprising:
  • ⁇ , ⁇ -dihalodoalkanes such as ⁇ , ⁇ -diiodoalkanes such as 1 ,4-diiodobutane, 1 ,5-diiodopentane, 1 ,6-diiodohexane, 1 ,7-diiodoheptane, 1 ,8-diiodooctane, 1 ,9- diiodononane and 1 ,10-diiododecane; ⁇ , ⁇ -dibromoalkanes such as 1 ,4- dibromobutane, 1 ,5-dibromopentane, 1 ,6-dibromohexane, 1 ,7-dibromoheptane, 1 ,8- dibromooctane, 1 ,9-dibromononane and 1 ,10-dibromodecan
  • D ⁇ , ⁇ -tertiaryalkydiaminoalkanes such as: N,N,N'N'-tetramethyl-1 ,6- diaminohexane, N,N'-diisopropylethylenediamine, 4,4'- bis(dimethylamino)benzophenone and bis[2-(dimethylamino)ethyl]ether.
  • ⁇ , ⁇ -tertiaryalkydiaminoalkanes such as: N,N,N'N'-tetramethyl-1 ,6- diaminohexane, N,N'-diisopropylethylenediamine, 4,4'- bis(dimethylamino)benzophenone and bis[2-(dimethylamino)ethyl]ether.
  • soluble branched addition copolymer may be where the membrane comprises a cation exchange membrane and a negative charge is required the branched addition copolymer comprises monomer residues selected from the groups consisting of:
  • component S comprises a monomer with a permanently negative charge, selected from the group comprising: vinylsulfonic acid, styrene sulfonic acid or 2-acrylamido 2- methylpropanesulfonic acid;
  • CTA chain transfer agent
  • the neutral, hydrophilic monomers, (N) may be selected from the group comprising: hydroxyl-containing monomers such as hydroxyethyl(meth)acrylate, hydroxylpropyl(meth)acrylate, amides such as N-vinyl pyrollidine, (dimethyl)(meth)acrylamide, or ether-functional monomers such as poly or oligo(ethyleneglycol)(meth)acrylate and vinylacetate.
  • the monofunctional monomers A, C or S may be selected from the group comprising: 2-vinyl pyridine, 4-vinyl pyridine, N-vinyl imidazole, N-vinyl carbazole, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylamide, vinyl benzyl chloride, vinylsulfonic acid, styrene sulfonic acid or 2-acrylamido 2-methylpropanesulfonic acid;
  • the hydrophobic monomers (H) may be selected from the group comprising: styrene, vinyl naphthalene, alkl (meth)acrylates, such as methyl (meth)acrylate, ethyl methacrylate, propyl(meth)acrylate, isomers of butyl(meth)acrylate, 2-ethyl hexyl(methacrylate), lsobornyl(meth)acrylate, N-isopropyl(meth)acrylate, N- butyl(meth)acrylamide.
  • alkl (meth)acrylates such as methyl (meth)acrylate, ethyl methacrylate, propyl(meth)acrylate, isomers of butyl(meth)acrylate, 2-ethyl hexyl(methacrylate), lsobornyl(meth)acrylate, N-isopropyl(meth)acrylate, N- butyl(meth)acryl
  • the hydrophobic monomers (H) may be preferably selected from the group comprising: styrene, vinyl naphthalene, isomers of butyl(meth)acrylate and 2-ethyl hexyl(methacrylate).
  • the multifunctional monomers may be preferably selected from the group comprising: divinylbenzene, ethyleneglycol di(meth)acrylate, 1 ,4- butanediol(meth)acrylate, poly(ethyleneglycol)di(meth)acrylate, 1 ,3,5-triallyl-1 ,3,5- triazine-2,4,6(1 H,3H,5H)-trione.
  • the chain transfer agents are preferably selected from the group comprising: dodecane thiol, hexane thiol, 2-mercaptoethanol, 2-ethylhexyl thioglycolate and 2,4- diphenyl-4-methyl-1 -pentene.
  • an ion- exchange membrane comprising a cured branched addition copolymer as described in relation to the first aspect of the invention wherein the membrane further comprises a hardener selected from: ⁇ , ⁇ -diiodoalkanes such as 1 ,4-diiodobutane, 1 ,5-diiodopentane, 1 ,6-diiodo hexane, 1 ,7-diiodoheptane, 1 ,8-diiodooctane and 1 ,10-diiododecane; ⁇ , ⁇ - dibromoalkanes such as 1 ,4-dibromobutane, 1 ,5-dibromopentane, 1 ,6-dibromo hexane, 1 ,7-dibromoheptane, 1 ,8-d
  • the membrane may further comprise a support material.
  • the ion-exchange membrane may comprise a permselectivity of at least 80 %.
  • the ion-exchange membrane may comprise a permselectivity of at least 90 %.
  • the ion-exchange membrane may be in a film or membrane and may be comprised an electrical resistance of less than 5 ⁇ . ⁇ 2 .
  • a soluble branched addition copolymer for use in the formation of an ion exchange membrane or film as described in relation to aspects one or two of the present invention wherein the soluble branched addition copolymer is obtainable by an addition polymerisation process; wherein the
  • branched addition polymer comprises a weight average molecular weight of 2,000 Da to 1 ,500,000 Da;
  • the branched addition copolymer comprises:
  • the at least two chains comprise at least one ethylenically monounsatu rated monomer, and wherein
  • the bridge comprises at least one ethylenically polyunsaturated monomer
  • the polymer comprises a residue of a chain transfer agent and optionally a residue of an initiator; and wherein the mole ratio of polyunsaturated monomer(s) to monounsaturated monomer(s) is in a range of from 1 :100 to 1 :3 and wherein the branched copolymer is hydrolytically stable such that the permselectivity and electrical resistance of the membrane does not change by more than 50 % when subjected to hydrolysis at 25 °C for 48 hours and a pH of less than 3 and greater than 12.
  • the soluble branched addition copolymer may be a soluble branched addition copolymer obtainable by an addition polymerisation process; wherein the
  • branched addition polymer comprises a weight average molecular weight of 2,000 Da to 1 ,500,000 Da;
  • the branched addition copolymer comprises:
  • the at least two chains comprise at least one ethylenically monounsaturated monomer
  • the bridge comprises at least one ethylenically polyunsaturated monomer
  • the polymer comprises a residue of a chain transfer agent and optionally a residue of an initiator;
  • the mole ratio of polyunsaturated monomer(s) to monounsaturated monomer(s) is in a range of from 1 :100 to 1 :3 and wherein the branched copolymer is hydrolytically stable such that the permselectivity and electrical resistance of the membrane does not change by more than 40 % when subjected to hydrolysis at 25 °C for 18 hours and a pH of greater than or equal to 12.
  • At least 50 mole percent of the monofunctional monomers may comprise aromatic or heteroaromatic monofunctional monomers.
  • the aromatic monofunctional monomers may be selected from the group consisting of vinyl pyridine and styrene.
  • At least 10 mole percent of copolymer may comprise an aromatic chain transfer agent. At least 10 mole percent aromatic chain transfer agent may comprise 2,4-diphenyl-4- methyl-1 -pentene.
  • At least 5 mole percent of the copolymer may comprises aromatic multifunctional monomer.
  • the aromatic multifunctional monomer preferably comprises divinyl benzene.
  • At least 60% of the monofunctional monomers may comprise aromatic monofunctional monomers.
  • At least 70% of the monofunctional monomers comprise aromatic monofunctional monomers.
  • the chain transfer agent is a molecule which is known to reduce molecular weight during a free-radical polymerisation via a chain transfer mechanism.
  • These agents may be any thiol-containing molecule and can be either monofunctional or multifunctional.
  • the agent may be hydrophilic, hydrophobic, amphiphilic, anionic, cationic, neutral, zwitterionic or responsive.
  • the molecule may also be an oligomer or a pre-formed polymer containing a thiol moiety. (The agent may also be a hindered alcohol or similar free-radical stabiliser).
  • Catalytic chain transfer agents such as those based on transition metal complexes such as cobalt bis(borondifluorodimethyl-glyoximate) (CoBF) may also be used.
  • Suitable thiols include but are not limited to: C 2 to C-
  • Thiol-containing oligomers or polymers may also be used such as for example poly(cysteine) or an oligomer or polymer which has been post-functionalised to give a thiol group(s), such as poly(ethyleneglycol) (di)thio glycollate, or a pre-formed polymer functionalised with a thiol group.
  • a thiol group(s) such as poly(ethyleneglycol) (di)thio glycollate
  • a pre-formed polymer functionalised with a thiol group for example, the reaction of an end or side-functionalised alcohol such as polypropylene glycol) with thiobutyrolactone, to give the corresponding thiol- functionalised chain-extended polymer.
  • Multifunctional thiols may also be prepared by the reduction of a xanthate, dithioester or trithiocarbonate end-functionalised polymer prepared via a Reversible Addition Fragmentation Transfer (RAFT) or Macromolecular Design by the Interchange of Xanthates (MADIX) living radical method.
  • RAFT Reversible Addition Fragmentation Transfer
  • MADIX Macromolecular Design by the Interchange of Xanthates
  • Alternative chain transfer agents may be any species known to limit the molecular weight in a free-radical addition polymerisation including alkyl halides, ally-functional compounds and transition metal salts or complexes. More than one chain transfer agent may be used in combination.
  • Non-thiol chain transfer agents such as 2,4-diphenyl-4-methyl-1 -pentene may also be used.
  • Hydrophobic CTAs include but are not limited to: linear and branched alkyl and aryl (di)thiols such as dodecanethiol, octadecyl mercaptan, 2-methyl-1 -butanethiol and 1 ,9-nonanedithiol.
  • Hydrophobic macro-CTAs (where the molecular weight of the CTA is at least 1000 Daltons) may be prepared from hydrophobic polymers synthesised by RAFT (or MADIX) followed by reduction of the chain end, or alternatively the terminal hydroxyl group of a preformed hydrophobic polymer may be post functionalised with a compound such as thiobutyrolactone.
  • Hydrophilic CTAs typically contain hydrogen bonding and/or permanent or transient charges.
  • Hydrophilic CTAs include but are not limited to: thio-acids such as thioglycolic acid and cysteine, thioamines such as cysteamine and thio-alcohols such as 2-mercaptoethanol, thioglycerol and ethylene glycol mono- (and di-)thio glycollate.
  • Hydrophilic macro-CTAs (where the molecular weight of the CTA is at least 1000 Daltons) can be prepared from hydrophilic polymers synthesised by RAFT (or MADIX) followed by reduction of the chain end, or alternatively the terminal hydroxyl group of a preformed hydrophilic polymer can be post functionalised with a compound such as thiobutyrolactone.
  • Amphiphilic CTAs may also be incorporated in the polymerisation mixture, these materials are typically hydrophobic alkyl-containing thiols possessing a hydrophilic function such as but not limited to a carboxylic acid group. Molecules of this type include mercapto undecylenic acid.
  • Responsive macro-CTAs (where the molecular weight of the CTA is at least 1000 Daltons) may be prepared from responsive polymers synthesised by RAFT (or MADIX) followed by reduction of the chain end, or alternatively the terminal hydroxyl group of a preformed responsive polymer, such as polypropylene glycol), may be post functionalised with a compound such as thiobutyrolactone.
  • the residue of the chain transfer agent may comprise 0.05 to 80 mole % of the copolymer (based on the number of moles of monofunctional monomer). More preferably the residue of the chain transfer agent comprises 0.05 to 50 mole %, even more preferably 0.05 to 40 mole % of the copolymer (based on the number of moles of monofunctional monomer). However, most especially the chain transfer agent comprises 0.05 to 30 mole %, of the copolymer (based on the number of moles of monofunctional monomer).
  • the initiator is a free-radical initiator and may be any molecule known to initiate free-radical polymerisation such as for example azo-containing molecules, persulfates, redox initiators, peroxides, benzyl ketones. These may be activated via thermal, photolytic or chemical means.
  • Examples of these include but are not limited to: 2,2'-azobisisobutyronitrile (AIBN), azobis(4-cyanovaleric acid), benzoyl peroxide, diisopropyl peroxide, tert-butyl peroxybenzoate (Luperox® P, Trigonox C), di-tert- butyl peroxide (Luperox® Dl, Trigonox B), cumylperoxide, 1 -hydroxycyclohexyl phenyl ketone, hydrogenperoxide/ascorbic acid. Iniferters such as benzyl-N,N- diethyldithiocarbamate may also be used. In some cases, more than one initiator may be used. The initiator may be a macroinitiator having a molecular weight of at least 1000 Daltons. In this case, the macroinitiator may be hydrophilic, hydrophobic, or responsive in nature.
  • AIBN 2,2'-azobisisobutyronit
  • the residue of the initiator in a free-radical polymerisation may comprise from 0 to 10% w/w of the copolymer based on the total weight of the monomers.
  • the residue of the initiator in a free-radical polymerisation comprises from 0.001 to 15% w/w of the copolymer based on the total weight of the monomers.
  • the residue of the initiator in a free-radical polymerisation comprises from 0.001 to 10% w/w of the copolymer based on the total weight of the monomers.
  • the residue of the initiator in a free-radical polymerisation comprises from 0.001 to 8% w/w, of the copolymer based on the total weight of the monomers.
  • the use of a chain transfer agent and an initiator is preferred. However, some molecules can perform both functions.
  • Hydrophilic macroinitiators may be prepared from hydrophilic polymers synthesised by RAFT (or MADIX), or where a functional group of a preformed hydrophilic polymer, such as terminal hydroxyl group, may be post-functionalised with a functional halide compound, such as 2-bromoisobutyryl bromide, for use in Atom Transfer Radical Polymerisation (ATRP) with a suitable low valency transition metal catalyst, such as CuBr Bipyridyl.
  • RAFT or MADIX
  • a functional group of a preformed hydrophilic polymer such as terminal hydroxyl group
  • a functional halide compound such as 2-bromoisobutyryl bromide
  • Hydrophobic macroinitiators (where the molecular weight of the preformed polymer is at least 1000 Daltons) may be prepared from hydrophobic polymers synthesised by RAFT (or MADIX), or where a functional group of a preformed hydrophilic polymer, such as terminal hydroxyl group, may be post-functionalised with a functional halide compound, such as 2-bromoisobutyryl bromide, for use in Atom Transfer Radical Polymerisation (ATRP) with a suitable low valency transition metal catalyst, such as CuBr Bipyridyl.
  • RAFT or MADIX
  • a functional group of a preformed hydrophilic polymer such as terminal hydroxyl group
  • a functional halide compound such as 2-bromoisobutyryl bromide
  • Responsive macroinitiators may be prepared from responsive polymers synthesised by RAFT (or MADIX), or where a functional group of a preformed hydrophilic polymer, such as terminal hydroxyl group, may be post-functionalised with a functional halide compound, such as 2-bromoisobutyryl bromide, for use in Atom Transfer Radical Polymerisation (ATRP) with a suitable low valency transition metal catalyst, such as CuBr Bipyridyl.
  • RAFT or MADIX
  • a functional group of a preformed hydrophilic polymer such as terminal hydroxyl group
  • a functional halide compound such as 2-bromoisobutyryl bromide
  • the monofunctional monomer may comprise any carbon-carbon unsaturated compound which can be polymerised by an addition polymerisation mechanism, for example vinyl and allyl compounds.
  • the monofunctional monomer may be hydrophilic, hydrophobic, amphiphilic, anionic, cationic, neutral or zwitterionic in nature.
  • Preferably the monofunctional monomer is hydrolytically stable.
  • the monofunctional monomer may be selected from but not limited to monomers such as: vinyl acids, vinyl acid esters, vinyl aryl compounds, vinyl acid anhydrides, vinyl amides, vinyl ethers, vinyl amines, vinyl aryl amines, vinyl nitriles, vinyl ketones, and derivatives of the aforementioned compounds as well as corresponding allyl variants thereof.
  • Suitable monofunctional monomers include: hydroxyl-containing monomers and monomers which can be post-reacted to form hydroxyl groups, acid-containing or acid-functional monomers, zwitterionic monomers and quaternised amino monomers.
  • Oligomeric, polymeric and di- or multi-functionalised monomers may also be used, especially oligomeric or polymeric (meth)acrylic acid esters such as mono(alkyl/aryl) (meth)acrylic acid esters of polyalkyleneglycol or polydimethylsiloxane or any other mono-vinyl or allyl adduct of a low molecular weight oligomer.
  • Mixtures of more than one monomer may also be used to give statistical, graft, gradient or alternating copolymers.
  • Vinyl acids and derivatives thereof include: (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid vinyl sulfonic acid, vinyl phosphoric acid, 2-acrylamido 2- methylpropane sulfonic acid, and acid halides thereof such as (meth)acryloyl chloride.
  • Vinyl acid esters and derivatives thereof include: Ci to C 2 o alkyl(meth)acrylates (linear and branched) such as for example, methyl (meth)acrylate, stearyl (meth)acrylate and 2-ethyl hexyl (meth)acrylate; aryl(meth)acrylates such as for example benzyl (meth)acrylate; tri(alkyloxy)silylalkyl(meth)acrylates such as trimethoxysilylpropyl(meth)acrylate; and activated esters of (meth)acrylic acid such as N-hydroxysuccinamido (meth)acrylate.
  • Vinyl aryl compounds and derivatives thereof include: styrene, acetoxystyrene, styrene sulfonic acid, 2- and 4-vinyl pyridine, vinyl naphthalene, vinylbenzyl chloride and vinyl benzoic acid.
  • Vinyl acid anhydrides and derivatives thereof include: maleic anhydride.
  • Vinyl amides and derivatives thereof include: (meth)acrylamide, N-(2- hydroxypropyl)methacrylamide, N-vinyl pyrrolidone, N-vinyl formamide, (meth)acrylamidopropyl trimethyl ammonium chloride, [3-
  • (meth)acrylamidoglycolate methyl ether and N-isopropyl(meth)acrylamide vinyl ethers and derivatives thereof include: methyl vinyl ether.
  • Vinyl amines and derivatives thereof include: dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, mono-t-butylaminoethyl (meth)acrylate, morpholinoethyl(meth)acrylate and monomers which can be post- reacted to form amine groups, such as N-vinyl formamide.
  • Vinyl aryl amines and derivatives thereof include: vinyl aniline, 2- and 4-vinyl pyridine, N-vinyl carbazole and vinyl imidazole. Vinyl nitriles and derivatives thereof include: (meth)acrylonitrile. Vinyl ketones or aldehydes and derivatives thereof including acrolein.
  • Hydroxyl-containing monomers include: vinyl hydroxyl monomers such as hydroxyethyl (meth)acrylate, 1 - and 2-hydroxy propyl (meth)acrylate, glycerol mono(meth)acrylate and sugar mono(meth)acrylates such as glucose mono(meth)acrylate.
  • Monomers which may be post-reacted to form hydroxyl groups include: vinyl acetate, acetoxystyrene and glycidyl (meth)acrylate.
  • Acid-containing or acid functional monomers include: (meth)acrylic acid, styrene sulfonic acid, vinyl phosphonic acid, vinyl benzoic acid, maleic acid, fumaric acid, itaconic acid, 2- (meth)acrylamido 2-ethyl propanesulfonic acid, mono-2-((meth)acryloyloxy)ethyl succinate and ammonium sulfatoethyl (meth)acrylate.
  • Zwitterionic monomers include: (meth)acryloyl oxyethylphosphoryl choline and betaines, such as [2- ((meth)acryloyloxy)ethyl] dimethyl-(3-sulfopropyl)ammonium hydroxide.
  • Quaternised amino monomers include: (meth)acryloyloxyethyltri-(alkyl/aryl)ammonium halides such as (meth)acryloyloxyethyltrimethyl ammonium
  • Vinyl acetate and derivatives thereof may also be utilised.
  • Oligomeric and polymeric monomers include: oligomeric and polymeric (meth)acrylic acid esters such as mono(alk/aryl)oxypolyalkyleneglycol(meth)acrylates and mono(alk/aryl)oxypolydimethyl-siloxane(meth)acrylates.
  • esters include for example: monomethoxy oligo(ethyleneglycol) mono(meth)acrylate, monomethoxy oligo(propyleneglycol) mono(meth)acrylate, monohydroxy oligo(ethyleneglycol) mono(meth)acrylate, monohydroxy oligo(propyleneglycol) mono(meth)acrylate, monomethoxy poly(ethyleneglycol) mono(meth)acrylate, monomethoxy poly(propyleneglycol) mono(meth)acrylate, monohydroxy poly(ethyleneglycol) mono(meth)acrylate and monohydroxy poly(propyleneglycol) mono(meth)acrylate.
  • oligomers or polymers formed via ring-opening polymerisation such as oligo(caprolactam), oligo(caprolactone), poly(caprolactam) or poly(caprolactone), or oligomers or polymers formed via a living polymerisation technique such as poly(1 ,4- butadiene).
  • monofunctional monomers are:
  • Amide-containing monomers such as (meth)acrylamide, N-(2- hydroxypropyl)methacrylamide, N,N'-dimethyl(meth)acrylamide, N and/or N'-di(alkyl or aryl) (meth)acrylamide, N-vinyl pyrrolidone, [3-((meth)acrylamido)propyl] trimethyl ammonium chloride, 3-(dimethylamino)propyl(meth)acrylamide, 3-[N-(3- (meth)acrylamidopropyl)-N,N-dimethyl]aminopropane sulfonate, methyl
  • vinyl amines such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, mono-t- butylamino (meth)acrylate, morpholinoethyl(meth)acrylate; vinyl aryl amines such as vinyl aniline, vinyl pyridine, N-vinyl carbazole, N-vinyl imidazole, and monomers which may be post-reacted to form amine groups, such as N-vinyl formamide; vinyl aryl monomers such as styrene, vinyl benzyl chloride, vinyl toluene, cc-methyl styrene, styrene sulfonic acid, vinyl naphthalene and vinyl benzoic acid; vinyl hydroxyl monomers such as hydroxyethyl (meth)acrylate,
  • allyl monomer where applicable, may also be used in each case.
  • Functional monomers that is monomers with reactive pendant groups which can be pre or post-modified with another moiety following polymerisation may also be used such as for example glycidyl (meth)acrylate, tri(alkoxy)silylalkyl(meth)acrylates such as trimethoxysilylpropyl(meth)acrylate, (meth)acryloyl chloride, maleic anhydride, hydroxyalkyl (meth)acrylates, (meth)acrylic acid, vinylbenzyl chloride, activated esters of (meth)acrylic acid such as N-hydroxysuccinamido (meth)acrylate and acetoxystyrene.
  • Macromonomers are generally formed by linking a polymerisable moiety, such as a vinyl or allyl group, to a pre-formed monofunctional polymer via a suitable linking unit such as an ester, an amide or an ether.
  • suitable polymers include: monofunctional poly(alkylene oxides) such as monomethoxy[poly(ethyleneglycol)] or monomethoxy[poly(propyleneglycol)], silicones such as poly(dimethylsiloxane)s, polymers formed by ring-opening polymerisation such as poly(caprolactone) or poly(caprolactam) or mono-functional polymers formed via living polymerisation such as poly(1 ,4-butadiene).
  • monofunctional poly(alkylene oxides) such as monomethoxy[poly(ethyleneglycol)] or monomethoxy[poly(propyleneglycol)]
  • silicones such as poly(dimethylsiloxane)s
  • polymers formed by ring-opening polymerisation such as poly(caprolactone) or poly(caprolactam)
  • mono-functional polymers formed via living polymerisation such as poly(1 ,4-butadiene).
  • Preferred macromonomers include: monomethoxy[poly(ethyleneglycol)] mono(methacrylate), monomethoxy[poly(propyleneglycol)] mono(methacrylate) and mono(meth)acryloxypropyl-terminated poly(dimethylsiloxane).
  • Hydrophilic monofunctional monomers include: (meth)acryloyl chloride, N- hydroxysuccinamido (meth)acrylate, styrene sulfonic acid, maleic anhydride, (meth)acrylamide, N-(2-hydroxypropyl)methacrylamide, N-vinyl pyrrolidinone, N-vinyl formamide, quaternised amino monomers such as (meth)acrylamidopropyl trimethyl ammonium chloride, [3-((meth)acrylamido)propyl]trimethyl ammonium chloride and (meth)acryloyloxyethyltrimethyl ammonium chloride, 3-[N-(3-
  • (meth)acrylamidoglycolate methyl ether glycerol mono(meth)acrylate, monomethoxy and monohydroxy oligo(ethylene oxide) (meth)acrylate
  • sugar mono(meth)acrylates such as glucose mono(meth)acrylate, (meth)acrylic acid, vinyl phosphonic acid, fumaric acid, itaconic acid, 2-(meth)acrylamido 2-ethyl propanesulfonic acid, mono- 2-((meth)acryloyloxy)ethyl succinate, ammonium sulfatoethyl (meth)acrylate, (meth)acryloyl oxyethylphosphoryl choline and betaine-containing monomers such as [2-((meth)acryloyloxy)ethyl] dimethyl-(3-sulfopropyl)ammonium hydroxide.
  • Hydrophilic macromonomers may also be used and include: monomethoxy and monohydroxy poly(ethylene oxide) (meth)acrylate and other hydrophilic polymers with terminal functional groups which may be post-functionalised with a polymerisable moiety such as (meth)acrylate, (meth)acrylamide or styrenic groups.
  • Hydrophobic monofunctional monomers include: Ci to C 28 alkyl (meth)acrylates (linear and branched) and (meth)acrylamides, such as methyl (meth)acrylate and stearyl (meth)acrylate, aryl(meth)acrylates such as benzyl (meth)acrylate, tri(alkyloxy)silylalkyl(meth)acrylates such as trimethoxysilylpropyl(meth)acrylate, styrene, acetoxystyrene, vinylbenzyl chloride, methyl vinyl ether, vinyl formamide, (meth)acrylonitrile, acrolein, 1 - and 2-hydroxy propyl (meth)acrylate, vinyl acetate, 5- vinyl 2-norbornene, Isobornyl methacrylate and glycidyl (meth)acrylate.
  • Hydrophobic macromonomers may also be used and include: monomethoxy and monohydroxy poly(butylene oxide) (meth)acrylate and other hydrophobic polymers with terminal functional groups which may be post-functionalised with a polymerisable moiety such as (meth)acrylate, (meth)acrylamide or styrenic groups.
  • Responsive monofunctional monomers include: (meth)acrylic acid, 2- and 4-vinyl pyridine, vinyl benzoic acid, N-isopropyl(meth)acrylamide, tertiary amine (meth)acrylates and (meth)acrylamides such as 2-(dimethyl)aminoethyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, mono-t-butylaminoethyl (meth)acrylate and N-morpholinoethyl (meth)acrylate, vinyl aniline, 2- and 4-vinyl pyridine, N-vinyl carbazole, vinyl imidazole, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, maleic acid, fumaric acid, itaconic acid and vinyl benzoic acid.
  • Responsive macromonomers may also be used and include: monomethoxy and monohydroxy polypropylene oxide) (meth)acrylate and other responsive polymers with terminal functional groups which may be post-functionalised with a polymerisable moiety such as (meth)acrylate, (meth)acrylamide or styrenic groups.
  • Monomers based on styrene or those containing an aromatic functionality such as styrene, a-methyl styrene, vinyl benzyl chloride, vinyl naphthalene, vinyl benzoic acid, N-vinyl carbazole, 2-, 3- or 4- vinyl pyridine, vinyl aniline, acetoxy styrene, styrene sulfonic acid, vinyl imidazole or derivatives thereof may also be used.
  • the membrane may be formed from the reaction of a nitrogenous monomer (A) with a dihalo species (B).
  • the net positive charge may be formed by the reaction of a polymer comprising a halide (C), or equivalent, leaving group and a nucleophilic amino compound (D).
  • Examples of (A), (B), (C) and (D) are listed below:
  • Examples of (A) include: 2-vinyl pyridine, 4-vinyl pyridine, N-vinyl imidazole, N-vinyl carbazole, dimethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminopropyl (meth)acrylamide.
  • Preferred non-hydrolysable monomers are 2- vinyl pyridine, 4-vinyl pyridine, N-vinyl imidazole and N-vinyl carbazole. Most preferred is 4-vinyl pyridine.
  • Examples of (B) include: ⁇ , ⁇ -dihalodoalkanes such as ⁇ , ⁇ -diiodoalkanes such as 1 ,4-diiodobutane, 1 ,5-diiodopentane, 1 ,6-diiodohexane, 1 ,7-diiodoheptane, 1 ,8- diiodooctane, 1 ,9-diiodononane and 1 ,10-diiododecane; ⁇ , ⁇ -dibromoalkanes such as 1 ,4-dibromobutane, 1 ,5-dibromopentane, 1 ,6-dibromohexane, 1 ,7- dibromoheptane, 1 ,8-dibromooctane, 1 ,9-dibromononane and 1 ,10
  • dibromoalkanes such as 1 ,5-diiodopentane and diiodoalkanes such as 1 ,8-diiodooctane.
  • dibromoalkanes such as 1 ,5-diiodopentane and diiodoalkanes such as 1 ,8-diiodooctane.
  • (C) examples include: Vinyl benzyl chloride,
  • Examples of (D) include: ⁇ , ⁇ -Tertiarydiaminoalkanes such as:
  • CEMs cation-exchange membranes
  • CEMs are normally prepared by preparing a polymer with anionic functionality followed by membrane casting via a further crosslinking step.
  • the CEM may be prepared by the reaction of a diisocyanate with a hydroxyl functionality present in the polymer.
  • Crosslinking may also be achieved by crosslinking a sulfonic acid unit through the formation of for example, a sulfonamide.
  • Hydrophobic monomers can be used.
  • the multifunctional monomer may comprise a molecule containing at least two vinyl groups which may be polymerised via addition polymerisation.
  • the molecule may be hydrophilic, hydrophobic, amphiphilic, neutral, cationic, zwitterionic, oligomeric or polymeric.
  • Such molecules are often known as cross-linking agents in the art and may be prepared by reacting any di- or multifunctional molecule with a suitably reactive monomer.
  • the multifunctional monomer or brancher is hydrolytically stable, and as such avoids labile ester functionalities.
  • Examples include: di- or multivinyl esters, di- or multivinyl amides, di- or multivinyl aryl compounds, di- or multivinyl alk/aryl ethers.
  • a linking reaction is used to attach a polymerisable moiety to a di- or multifunctional oligomer or polymer.
  • the brancher may itself have more than one branching point, such as T- shaped divinylic oligomers or polymers. In some cases, more than one multifunctional monomer may be used.
  • Preferred multifunctional monomers or branchers include but are not limited to: divinyl aryl monomers such as divinyl benzene; (meth)acrylate diesters such as and 1 ,3-butylenedi(meth)acrylate; trimethylolpropane tri(meth)acrylate, 1 ,3,5-triallyl-1 ,3,5- triazine-2,4,6(1 H, 3H,5H)trione and bisacrylamide.
  • divinyl aryl monomers such as divinyl benzene
  • (meth)acrylate diesters such as and 1 ,3-butylenedi(meth)acrylate
  • trimethylolpropane tri(meth)acrylate 1 ,3,5-triallyl-1 ,3,5- triazine-2,4,6(1 H, 3H,5H)trione and bisacrylamide.
  • the polymers prepared and used comprise statistical copolymers. That is, a copolymer is a polymer derived from two (or more) monomeric monomers or residues. Since a copolymer comprises at least two types of monomer units / residues, copolymers may be classified according to how these monomers or residues are arranged in a polymer chain. These include: 1 . Alternating copolymers with regular alternating units of monomers A and B, that is, copolymers with A and B monomer units arranged in a repeating sequence for example, (A-B-A-B-B-A-A-A-A-B-B-B) n
  • Statistical copolymers are copolymers in which the sequence of monomer units or residues follows a statistical rule. That is, if the probability of finding a given type of monomer residue at a particular point in the chain is equal to the mole fraction of that monomer residue in the chain, then the polymer may be referred to as a truly random copolymer.
  • the statistical distribution depends upon the likelihood of whether a monomer residue will react with another monomer residue of the same type or one of a different type.
  • the statistical distribution of monomers in a copolymer is therefore a function of the reactivity ratios of the actual monomer residues and is described by the Mayo equation:
  • Equation 1 with the concentration of the components given in square brackets.
  • Equation 1 provides the copolymer composition at any instant during the polymerization.
  • Block copolymers comprise two or more homopolymer subunits linked by covalent bonds (4). The union of the homopolymer subunits may require an intermediate non-repeating subunit, known as a junction block. Block copolymers with two or three distinct blocks are called diblock copolymers and triblock copolymers, respectively.
  • the term hydrolytic stability means that the membrane has a low tendency to lose selectivity at alkaline pH as result of hydrolysis taking place.
  • cationic groups ammonium or pyridinium
  • the cationic groups may be lost from the polymer (as a result of nucleophilic substitution or elimination reactions) thus reducing the overall (cationic) charge on the membrane (that is, the ion exchange capacity, I EC mmol/g) and hence its selectivity toward anionic species.
  • a further measure of hydrolytic stability may be the assessment of the chemical stability (to hydrolysis) of the overall membrane structure to extremes of pH; that is, whether the membrane film itself is stable to exposure to such conditions or becomes mechanically weakened or disintegrates. This second indicator is relevant when the membrane already retains acceptable performance under such conditions.
  • the copolymers prepared and used in the membranes according to the present invention have a branched structure which is more compact. Therefore, when the copolymers are reacted to form a crosslinked membrane, the membrane comprises a dense and compact copolymer network with an increased concentration of functional groups. The nature of the functional groups ensures that the polymers have a reduced tendency to swelling and are therefore less susceptible to hydrolysis.
  • the degree of branching or branching level is denoted by I and d refers to the molar ratio of the chain transfer agent.
  • the molar ratio of chain transfer agent to multifunctional monomer is from 2 : 1 to 1 to 2. Most preferably the molar ratio of chain transfer agent to multifunctional monomer is from 1 .2 : 1 to 1 to 1 .2.
  • CTAs Chain Transfer Agents
  • BDMAE Bis[2-(N,N-dimethylamino)ethyl]ether
  • BDMAH 1 ,6-Bis(N.N-dimethylamino)hexane
  • THF was the mobile phase
  • the column oven temperature was set to 35 Q C
  • the flow rate was 1 mL.min "1 .
  • the samples were prepared for injection by dissolving 10 mg of polymer in 1 .5 ml_ of HPLC grade THF and filtered of with an Acrodisc® 0.2 ⁇ PTFE membrane. 0.1 ml_ of this mixture was then injected, and data collected for 30 minutes.
  • the Omnisec software package was used to collect and process the signals transmitted from the detectors to the computer and to calculate the molecular weight.
  • Example 1 4-Vinylpyridine-containing polymer for use as an AEM.
  • the Mark Houwink Equation relates to relationship between intrinsic viscosity and molecular weight and is specific to each polymer and solvent pairing.
  • [ ⁇ ] - is intrinsic viscosity
  • M - is molecular weight (viscosity average)
  • K and a are the Mark-Houwink constants, the values of which are dependent on the type of polymer and solvent used as well as temperature at which the viscosity measurements were made.
  • the Mark-Houwink constants are determined from a graph of log[r
  • the a value is a function of the polymer geometry and typical value ranges are as follows:
  • the solution of polymers 8 and 9 were concentrated (evaporation under vacuum) until solids content of the solution was 60.0 wt%.
  • the hardener crosslinker 0.45 molar equivalents (with respect to the total moles of chlorine groups in the copolymer; that is to say, sufficient to react with 90 mol% of the total chloromethyl groups).
  • the hardener was thoroughly mixed in to the polymer solution and a membrane or film of the mixture drawn over a piece of fabric mesh reinforcement (Sefar Petex 07/240-59) supported on a polished stainless steel plate.
  • the membrane films were cured in an oven at 60 °C for 14 hours then cooled and released from the stainless steel backing plates by immersion in a mixture of water and isopropanol (80:20 parts by volume) for one hour.
  • the reinforced membranes were robust enough to be handled wet or could be allowed to air dry.
  • the membrane under test was placed in a cell consisting of two measuring Haber- Lugin capillary electrodes placed adjacent to the membrane in order to measure the potential drop as a function of current density.
  • the outer chambers contained the working electrodes and were circulated with 0.5 M sodium sulfate (Na 2 S0 ) solution.
  • Both buffer chambers adjacent to the electrodes contained 0.5 M sodium chloride (NaCI) solution to protect the inner chambers from the acid produced at the electrodes.
  • the inner chambers were circulated with a different batch of 0.5 M NaCI. In these chambers, the two shielding and the two electrode compartments were paired to keep the concentration in the compartments constant.
  • limiting current density LCD
  • the selectivity of the membranes is an important feature with respect to the efficiency of the process to which the membrane is applied.
  • the permselectivity of the membrane can be determined via different methods like chronopotentiometry, Nernst potential and limiting current density (LCD) ratio.
  • the inventors employed the Nernst potential method in this application.
  • the permselectivity of the membranes was determined using a cell consisting of two compartments fitted with two Ag/AgCI reference electrodes separated by the membrane under test. Potassium chloride (KCI) 0.50 M was circulated through one chamber and potassium chloride (KCI) 0.10 M was circulated through the other chamber at 25 °C.
  • KCI potassium chloride
  • ⁇ TM is the apparent permselectivity and ⁇ and ⁇ ' are the measured and ideal electrical (Nernst) potential difference.
  • the membranes were cast using the same method as has been described for the VBC based membranes (M1 to M4).
  • Membranes M5, M6 and M7 were prepared from soluble copolymers comprising very similar molar quantities of nitrogen (amine) per gram (of dry copolymer), which are reacted with similar molar quantities of DIH crosslinker, therefore, it is assumed that the differences in permselectivity loss observed when the pH is increased must be due to the differences in the copolymer compositions themselves.
  • Membrane M5 was obtained from a copolymer comprising the ester-containing multifunctional monomer residue EGDMA; whereas M6 and M7 were obtained from copolymers which have DVB as the multifunctional monomer: the absence of ester linkages in DVB means that the copolymers derived from this multifunctional monomer are less susceptible to hydrolysis and thus the membranes made from such copolymers are more stable to alkaline conditions than those containing an ester derived multifunctional monomer residue such as M5. Hence membranes such as M6 and M7 have improved in-use stability at high pH.
  • the membrane resistance increases with pH which is due to a lower protonation of the amine groups and therefore lower polymer cationic character at high pH.
  • the branched addition copolymers of the present invention have been designed to contain non-hydrolysable units, that demonstrate an increased ⁇ -use stability' where the membrane is being used at extremes of pH in an aqueous environment.

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Abstract

L'invention concerne des copolymères d'addition ramifiés solubles qui peuvent être durcis après leur synthèse pour former des membranes, des procédés de préparation de ceux-ci, des compositions comprenant de tels copolymères et leur utilisation dans la préparation de membranes.
PCT/GB2012/051595 2011-07-06 2012-07-06 Copolymères et membranes WO2013005050A1 (fr)

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