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WO2019060433A1 - Poly(thioéthers) liés à un support solide pour la séquestration d'ions métalliques - Google Patents

Poly(thioéthers) liés à un support solide pour la séquestration d'ions métalliques Download PDF

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Publication number
WO2019060433A1
WO2019060433A1 PCT/US2018/051777 US2018051777W WO2019060433A1 WO 2019060433 A1 WO2019060433 A1 WO 2019060433A1 US 2018051777 W US2018051777 W US 2018051777W WO 2019060433 A1 WO2019060433 A1 WO 2019060433A1
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alkyl
hydroxy
formula
alkynyl
alkenyl
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Agostino PIETRANGELO
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Rutgers State University of New Jersey
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Rutgers State University of New Jersey
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1422—Side-chains containing oxygen containing OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1426—Side-chains containing oxygen containing carboxy groups (COOH) and/or -C(=O)O-moieties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/143—Side-chains containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/724—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00—Chemistry of inorganic compounds
    • Y10S423/09—Reaction techniques
    • Y10S423/14—Ion exchange; chelation or liquid/liquid ion extraction

Definitions

  • the present invention provides compounds that are useful to treat water contaminated with heavy metals. Accordingly, the invention provides a solid-support polymer of formula III-S or a salt thereof:
  • S is a solid support
  • X is a bond or a linker
  • p is two or more
  • each dash line is independently a single bond or a double bond
  • L is (Ci-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by -0-, - NH- or -S-, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C6)alkyl, (C 2 -C6)alkenyl, (C2-C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci-
  • Ce)alkyl -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 or -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • Q is (Ci-C6)alkyl, (C2-Ce)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-Ce)haloal
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C 6 )alkenyl, (C 2 -C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 -
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C 6 )alkenyl, (C 2 -C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci-
  • C 6 )alkyl -N0 2 , -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- Ce)alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • each R 3 is independently hydrogen or (Ci-Ce)alkyl
  • n 0, 1 or 2;
  • the invention also provides processes and intermediates disclosed herein that are useful for preparing a solid-support polymer of the invention.
  • the invention also provides a method for separating a metal from a solution that comprises the metal comprising contacting the solution with a solid-support polymer of the invention under conditions whereby the metal associates with the solid-support polymer to form a solid-support polymer-associated metal.
  • Figure 2 shows schematic representation of how poly-2b can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb from water.
  • Figure 3 shows AA spectroscopy results from control experiments.
  • An aqueous solution of lead ions [Pb 2+ ]o, ca. 10 ppm
  • the dot labeled by arrow represents [Pb 2+ ] in the filtrate.
  • Figure 4 shows AA spectroscopy results from poly-2b Pb 2+ -binding experiments.
  • the dot labeled by arrow represents [Pb 2+ ] in the filtrate.
  • Figures 6A-6B Figure 6A shows surface-modified polyacrylonitrile fiber for water treatment applications.
  • Figure 6B shows functionalized polyethylene graft copolymer fiber for water treatment applications.
  • Figures 7A-7B Figure 7A shows a plot of dispersities (Dm) versus monomer conversion
  • Figure 7B shows a plot of number-average molecular weight (Mn) versus monomer conversion.
  • Figure 8 shows IR spectra of poly-2, PTE-A and PTE-A/Pb 2+ mixtures at multiple Pb 2+ loadings. All spectra were obtained from samples in the sold state.
  • Figure 9 shows preparation of resin-bound macroinitiator by conversion of Merrifield chloromethyl polystyrene resin to vinyl polystyrene resin
  • FIGS 10A-10B 10A shows preparation of solid support-tethered poly(thioether), resin-bound PTE-A.
  • Resin-bound ruthenium macroinitiator reacts with norbornane compound 2 to form resin-bound poly-2 which is saponified to give resin-bound PTE-A.
  • Figure 10B shows preparation of solid support-tethered poly(thioether), resin-bound PTE-B.
  • Resin-bound ruthenium macroinitiator reacts with norbornyl nitrile compound 6 to form resin-bound poly-6 which is treated with aqueous hydroxylamine hydrochloride to give resin- bound PTE-B.
  • Figure 11 shows preparation of fiber-tethered poly(thioethers) where nitrile functionality of a PAN fiber is reduced with lithium aluminum hydride (L1AIH4) to PAN fiber-NHh which is alkylated with allylic bromide to give PAN fiber-vinyl.
  • Third generation Grubbs' catalyst (G3) converted the PAN fiber-vinyl to PAN-bound macroinitiator which undergoes SI-ROMP reaction with compound 2 or 6 to give solid support-tethered poly(thioethers) PAN-bound PTE- A or PTE-B, respectively.
  • Solid support is any material that absorbs or adsorbs liquids, such as water.
  • Halo is fluoro, chloro, bromo, or iodo.
  • alkyl by itself or as part of another substituent, means, unless otherwise stated, a straight or branched chain hydrocarbon radical, having the number of carbon atoms designated (i.e., Ci-6 means one to six carbons).
  • alkenyl refers to an unsaturated alkyl radical having one or more double bonds.
  • alkynyl refers to an unsaturated alkyl radical having one or more triple bonds.
  • haloalkyl or
  • hydroxyalkyl means an alkyl that is optionally substituted with halo or hydroxyl.
  • alkoxy refers to an alkyl groups attached to the remainder of the molecule via an oxygen atom (“oxy").
  • aryl refers to a single all carbon aromatic ring or a multiple condensed all carbon ring system wherein at least one of the rings is aromatic.
  • an aryl group has 6 to 20 carbon atoms, 6 to 14 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.
  • Aryl includes a phenyl radical.
  • Aryl also includes multiple condensed ring systems (e.g., ring systems comprising 2, 3 or 4 rings) having about 9 to 20 carbon atoms in which at least one ring is aromatic and wherein the other rings may be aromatic or not aromatic (i.e., cycloalkyl.
  • Such multiple condensed ring systems are optionally substituted with one or more (e.g., 1, 2 or 3) oxo groups on any carbocycle portion of the multiple condensed ring system.
  • the rings of the multiple condensed ring system can be connected to each other via fused, spiro and bridged bonds when allowed by valency requirements. It is to be understood that the point of attachment of a multiple condensed ring system, as defined above, can be at any position of the ring system including an aromatic or a carbocycle portion of the ring.
  • Non-limiting examples of aryl groups include, but are not limited to, phenyl, indenyl, indanyl, naphthyl, 1, 2, 3, 4-tetrahydronaphthyl, anthracenyl, and the like.
  • alkylene means a divalent radical derived from an alkane (including branched alkane), as exemplified by -CH2CH2CH2CH2- and -CH(CH 3 )CH 2 CH 2 -.
  • alkenylene and alkynylene refer to the unsaturated forms of “alkylene” having double or triple bonds, respectively.
  • arylene means a divalent radical derived from an arene, such as phenylene.
  • Alkylene, alkenylene”, “alkynylene” and “arylene” are also meant to include mono and poly-halogenated variants.
  • alkali metal means the chemical elements found in Group 1 of the periodic table, such as lithium, sodium, potassium, rubidium and cesium.
  • alkali earth metal means the chemical elements found in Group 2 of the periodic table, such as beryllium, magnesium, calcium, strontium, barium and radium.
  • Lawesson's reagent means 2,4-Bis(4-methoxyphenyl)-l, 3,2,4- dithiadiphosphetane-2,4-dithione, which is a mild and convenient thionating agent for ketones, esters, and amides that allows the preparation of thioketones, thionoesters and thioamides.
  • polymers of the invention having a chiral center may exist in and be isolated in optically active and racemic forms. Some compounds may exhibit polymorphism. It is to be understood that the present invention encompasses any racemic, optically-active, polymorphic, or stereoisomeric form, or mixtures thereof, of a compound of the invention, which possess the useful properties described herein, it being well known in the art how to prepare optically active forms (for example, by resolution of the racemic form by recrystallization techniques, by synthesis from optically-active starting materials, by chiral synthesis, or by chromatographic separation using a chiral stationary phase.
  • the atom to which the bond is attached includes all stereochemical possibilities.
  • a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge)
  • a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge)
  • the atom to which the stereochemical bond is attached is enriched in the relative stereoisomer depicted unless otherwise noted.
  • the compound may be at least 51% the relative stereoisomer depicted.
  • the compound may be at least 60% the relative stereoisomer depicted.
  • the compound may be at least 80% the relative stereoisomer depicted.
  • the compound may be at least 90% the relative stereoisomer depicted. In another embodiment, the compound may be at least 95 the relative stereoisomer depicted. In another embodiment, the compound may be at least 99% the relative stereoisomer depicted.
  • (Ci-Ce)alkyl can be methyl, ethyl, propyl, isopropyl, butyl, iso-butyl, sec- butyl, pentyl, 3-pentyl, or hexyl;
  • (Ci-C6)alkoxy can be methoxy, ethoxy, propoxy, isopropoxy, butoxy, iso-butoxy, sec-butoxy, pentoxy, 3-pentoxy, or hexyloxy;
  • (C2-Ce)alkenyl can be vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1, -pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1- hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl;
  • (C2-Cg)alkynyl can
  • the solid-support polymer of formula III-S comprises two or more residues of formula III or a salt thereof:
  • a residue of the solid su ort polymer has the following formula
  • X is -S-, -O- or -NH-;
  • Y is -S-, -0-, -NH- or -CH 2 -;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 -
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 - C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci-
  • C 6 )alkyl -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 .
  • a residue of the solid su ort polymer has formula V:
  • R 1 is hydrogen or (Ci-C6)alkyl. In one embodiment, R 1 is hydrogen or methyl.
  • R 2 is hydrogen or (Ci-C6)alkyl.
  • R 2 is hydrogen or methyl.
  • each dash line is a double bond.
  • R a is hydrogen
  • R b is hydrogen
  • R c is hydrogen
  • R d is hydrogen
  • each residue of the polymer is independently selected from the group consisting of:
  • each residue of the polymer is independently selected from the group consisting of:
  • one or more residues of the polymer are
  • An aspect of the invention is a solid-su ort ol mer of formula VI-S:
  • S is a solid support
  • X is a bond or a linker
  • p is two or more
  • each dash line is independently a single bond or a double bond
  • L is (Ci-C5)alkylene, (C2-Ce)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by -0-, - NH- or -S-, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-Ce)alkyl, (C2-C6)alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -
  • Q is (Ci-Ce)alkyl, (C 2 -C6)alkenyl, (C 2 -Ce)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C 6 )alkenyl, (C2-C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • each R 3 is independently hydrogen or (Ci-Ce)alkyl
  • n 0, 1 or 2;
  • An aspect of the invention is a polymer comprising two or more residues of formula VI or a salt thereof:
  • each dash line is independently a single bond or a double bond
  • L is (Ci-C6)alkylene, (C2-Ce)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by -0-, -NH- or -S-, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C6)alkyl, (C2-C6)alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci-
  • Ce)alkyl -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 or -N(R )-C(0)-N(R ) 2 ;
  • Q is (Ci-C6)alkyl, (C2-C6)alkenyl, (C2-C6)alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C 5 )alkyl, (C 2 -C 6 )alkenyl, (C2-C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy,
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 -C 6 )alkenyl, (C2-C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 -C 6 )alkenyl, (C 2 -Ce)alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 -C 5 )alkenyl, (C 2 -Ce)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 -C 6 )alkenyl, (C2-C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • each R 3 is independently hydrogen or (Ci-Ce)alkyl
  • n 0, 1 or 2.
  • the polymer of the invention further comprises a residue that is copolymerized from a monomer selected from the group consisting of:
  • An intermediate useful for preparing a polymer comprising two or more residues of formula III or a salt thereof, is a polymer com rising a residue of the following formula I:
  • L is (Ci-Ce)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms (e.g. 1, 2, or 3) in the alkylene, alkenylene and alkynylene is optionally replaced by -0-, -NH- or -S-, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C6)alkyl, (C 2 - Ce)alkenyl, (C2-C5)alkynyl, (Ci-C 6 )haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R
  • Q is (Ci-C 6 )alkyl, (C2-C6)alkenyl, (C2-C 6 )alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-Ce)alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R
  • R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C6)alkenyl, (C2-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2 C 6 )alkenyl, (C2-C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (Ci-Ce)alkyl
  • n 0, 1 or 2.
  • the invention provides a method to prepare a polymer comprising a resi of formula I or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula la:
  • L is (Ci-C6)alkylene, (C2-C6)alkenylene, (C2-C6)alkynylene or arylene, wherein one or more carbon atoms in the alkylene, alkenylene and alkynylene is optionally replaced by -0-, - NH- or -S-, and wherein the alkylene, alkenylene, alkynylene and arylene are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C6)alkyl, (C2-C6)alkenyl, (C2-C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3
  • Q is (Ci-C6)alkyl, (C2-C5)alkenyl, (C2-C 6 )alkynyl or aryl and wherein the alkyl, alkenyl, alkynyl and aryl are optionally substituted by one or more groups selected from halo, hydroxy, (Ci-C 6 )alkyl, (C 2 -C 6 )alkenyl, (C 2 -C 6 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-
  • Z is -0-R 3a , -S-R 3a or -N(R 3a ) 2
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C 6 )alkenyl, (C2-C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C 2 - C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C 2 - C6)alkenyl, (C 2 -C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- C 6 )alkyl, -N0 2 , -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • each R 3 is independently hydrogen or (Ci-Ce)alkyl
  • each R 3a is independently (Ci-Ce)alkyl
  • n 0, 1 or 2.
  • the polymer comprising a residue of formula I is a salt with an alkali metal or an alkali earth metal.
  • the method comprises saponifying the polymer comprising a residue of formula la by using MOH or M(OH) 2 to provide a corresponding polymer comprising a residue of formula Ig:
  • M is an alkali metal or an alkali earth metal.
  • the method further comprises preparing the polymer comprising a residue of formula la by converting a corres onding compound of formula lb:
  • the compound of formula lb is treated with a transition metal catalyst to provide the corresponding polymer comprising a residue of formula la.
  • the transition metal catalyst is 1 st , 2 nd or 3 rd Generation of Grubbs' catalyst.
  • the ratio of compound of formula lb to Grubbs' catalyst is about 100-800 to 1.
  • the method further comprises preparing the compound of formula lb by contacting a corresponding compound of formula Ic and a corresponding compound of formula Id:
  • a mixture of the compound of formula Ic and the compound of formula Id is heated to provide the corresponding compound of formula lb.
  • the method further comprises separating the corresponding product of formula lb by crystallization.
  • the method further preparing the compound of formula Ic by converting a corresponding compound of formula Ie:
  • the compound of formula le is treated with P4S10/
  • HMDO hexamethyldisiloxane
  • Lawesson's reagent to provide the corresponding compound of formula Ic.
  • the method further comprises converting the polymer comprising a residue of formula I or a salt thereof to a corresponding polymer comprising a residue of formula III:
  • each dash line is independently a single bond or a double bond; provided that at least one dash line is a single bond.
  • Another intermediate useful for preparing the polymer comprising two or more residues of formula IV or a salt thereof is a polymer comprising a residue of the following formula II:
  • X is S-, -O- or H-;
  • Y is -S-, -0-, -NH- or -CH2-;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 Ce)alkenyl, (C2-C5)alky
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C6)alkenyl, (C2-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C 6 )alkenyl, (C2-C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2 C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C6)alkenyl, (C2-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (Ci-C6)alkyl
  • n 0, 1 or 2.
  • the invention provides a method to prepare a polymer comprising a resi of formula II or a salt thereof, comprising converting a corresponding polymer comprising a residue of formula Ila:
  • X is -S-, -O- or -NH-;
  • Y is -S-, -0-, -NH- or -CH 2 -;
  • R 1 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2- Ce)alkenyl, (C2-C5)alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R ) 2 ;
  • R 2 is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2-
  • R a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C 6 )alkenyl, (C2-C 5 )alkynyl, (Ci-C 6 )haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci-
  • Ce)alkyl -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2- C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C 6 )alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C6)alkenyl, (C2-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C6)alkenyl, (C2-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-C6)alkoxy, hydroxy(Ci- C 6 )alkyl, -NO2, -N(R 3 ) 2 , -CN, -C(0)-N(R 3 ) 2 , -O-R 3 , -S-R 3 , -0-C(0)-R 3 , -C(0)-R 3 , -C(O)- OR 3 , -N(R 3 )-C(0)-R 3 and -N(R 3 )-C(0)-N(R 3 ) 2 ;
  • R 3 is independently hydrogen or (Ci-Ce)alkyl
  • n 0, 1 or 2.
  • the polymer comprising a residue of formula II is a salt with an alkali metal or an alkali earth metal.
  • the method comprises saponifying the polymer comprising a residue of formula Ila by using MOH or M(OH)2 to provide a corresponding polymer comprising a residue of formula Ilg:
  • M is an alkali metal or an alkali earth metal.
  • the compound of formula lib is treated with a transition metal catalyst to provide the corresponding compound of formula Ila.
  • the transition metal catalyst is 1 st , 2 nd or 3 rd Generation of Grubbs' catalyst.
  • the ratio of compound of formula lib to Grubbs' catalyst is about 100-800 to 1.
  • a mixture of the compound of formula IIc and the compound of formula lid is heated to provide the corresponding compound of formula lib.
  • the method further comprises separating the corresponding product of formula lib by crystallization.
  • the method further comprises preparing the compound of formula lie by converting a corresponding compound of formula He:
  • the compound of formula He is treated with P4S10/
  • HMDO hexamethyldisiloxane
  • Lawesson's reagent to provide the corresponding compound of formula lie.
  • the invention also provides a method of separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer under conditions whereby the metal associates with the polymer to form a polymer associated metal.
  • the polymer associates with the metal by chelation.
  • the polymer is a part of a membrane, coated on the surface of a bead or is form into a bead.
  • the membrane is part of a spiral wound module or present on the surface of porous hollow fibers.
  • the metal is lead, mercury, cadmium, chromium, arsenic, gold, manganese, selenium, silver, thallium or silver.
  • the method further comprises separating the polymer associated with the metal from the solution.
  • the method further comprises separating the polymer associated with the metal from the solution by filtration
  • the method further comprises releasing the metal from the polymer.
  • Poly(thioether) polymers of the invention may be covalently attached (tethered) via a linker or a direct bond to a solid support material.
  • Solid support materials include:
  • nanowires Alcaraz-Espinoza, J. J. et al, ACS Applied Materials & Interfaces, 2015, 7, 7231-7240; Tolani, S. et al, Journal of Applied Polymer Science, 2010, 1 16, 308-313
  • Polymer resins are among the most widely used platforms for wastewater treatment applications, serving both residential and municipal levels of society, as well as the textile, petroleum, pharmaceutical, automotive, mining, and refining industries.
  • Commercially available ion exchange resins comprise a cross-linked polymer matrix that is prepared by suspension polymerization using a monomer (e.g. styrene), a catalyst, and a cross-linker (e.g.
  • Fibers modified with coordinating ligands have also been used to capture metal ions from aqueous media, with notable success in the sorption of uranium from seawater (Chatterjee S. et al, Industrial & Engineering Chemistry Research, 2016, 55, 4161-4169; Sugasaka, K. et al, Separation Science Technology, 1981, 16, 971-985; Omichi, H. et al, Separation Science Technology, 1986, 21 :299-313).
  • ligand moieties are grafted directly onto the polymer fiber, as with surface-modified polyacrylonitrile bearing amidoxime, amine, and phosphonic acid groups (Figure 6A) (Alexandratos, S. D.
  • ligand moieties can be chemically modified onto polymers grown off a "trunk" polymer fiber.
  • 4-chlorostyrene is first polymerized off the surface of polyethylene fibers using radiation- induced graft polymerization (RIGP).
  • RIGP radiation- induced graft polymerization
  • the graft copolymer is then used as a macroinitiator for the subsequent atom transfer radical-polymerization (ATRP) of acrylonitrile and t-butylacrylate (Saito, T. et al, Jour, of Materials Chem. A. 2014, 2: 14674-14681).
  • ATRP atom transfer radical-polymerization
  • amidoximation (AO) followed by saponification completes the fabrication of the sorbent.
  • polymeric fiber metal -ion adsorbents include their light weight, shape/length flexibility, and proven deployability in seawater (Seko, N. et al, Nuclear
  • the present invention provides an olefin-metathesis chain-growth polymerization route to water-soluble and molecular-weight controlled polythioethers using ring-opening metathesis polymerization (Scheme 1), and covalent attachment (tethering) to a solid support.
  • ROMP offers several advantages over alternative methods such as RIGP and ATRP including applicability under mild reaction conditions, extremely high rates of polymerization, and high functional group tolerance. Moreover, the highly selective reactivity of the alkylidene catalyst negates the possibility of epimerization, a process that is detrimental to stereochemistry preservation.
  • the water-soluble polythioether PTE-A ( Figure 2) exhibits an extremely high affinity for extracting Pb2+ from water when used with an ultrafiltration membrane, a process known as liquid-phase polymer-based retention (LPR) (Spivakov, B. Y. et al, Nature, 1985, 315, 313-315; Geckeler, K. E.
  • Solid-state IR spectra of poly-2, PTE-A, and three PTE-A/Pb2+ mixtures are shown in Figure 5.
  • Polythioether PTE-B is prepare following Scheme 3. Bromoacetonitrile 4 is reacted with sodium thiosulfate (Na2S 2 03) to afford Bunte salt 5 (Kirby, G. W. et al, Journal of the Chemical Society., Chemical Communications 1984, 922-923). Next, endo and exo isomers of monomer 6 were synthesized by reacting 5 with cyclopentadiene. After isolating the kinetically favored endo isomer by column chromatography, the monomer is polymerized by ROMP to afford poly- 6, which is converted to PTE-B upon heating the polythioether with hydroxylamine
  • All polymers will be characterized by 1H NMR spectroscopy. Molecular weights will be measured by gel permeation chromatography (GPC) using a refractive index detector (with either THF or 0.1M LiBr in DMF as a mobile phase) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry. Thermal properties will be evaluated by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC).
  • GPC gel permeation chromatography
  • MALDI-TOF matrix-assisted laser desorption/ionization time-of-flight
  • silica column Silica column
  • Thia-Diels-Alder adduct 2 (20 mg, 0.0884 mmol) was added to 2 mL aq. NaOH solution (4 mg, 0.0972 mmol, 1.1 equiv) and stirred overnight at room temperature where it eventually dissolved. The solution was then filtered through a 0.2 ⁇ syringe filter and the solvent removed to afford a white solid.
  • a pressure vessel (equipped with a sidearm and stir bar) was charged with 2 (100 mg, 4.4 mmol) and the appropriate amount of Grubbs 2 nd generation catalyst (G2) in ca. 2 mL of anhydrous DCM.
  • the reaction was quenched with butyl vinyl ether (10 equiv. wrt (G2)) after consumption of the monomer was complete (as determined by 3 ⁇ 4 NMR spectroscopy).
  • Polythioether-modified resins are prepared using the surface-initiated ring-opening metathesis polymerization (SI-ROMP) method reported by Roberts and coworkers ( Figure 9) (Barrett, A. G. M. et al, Organic Letters, 1999, 1 : 1083-1086).
  • SI-ROMP surface-initiated ring-opening metathesis polymerization
  • Figure 9 Barrett, A. G. M. et al, Organic Letters, 1999, 1 : 1083-1086.
  • commercially available Merrifield resin 200-400 mesh, 1% cross-linked, 3.5-4.5 mmol/g CI- loading
  • THF tetrahydrofuran
  • the vinyl moieties will be identified by their IR absorption bands at 1628, 988, 903, and 837 cm-1 while the vinyl group loading (reported by Sylvain and coworkers to be quantitative) will be calculated from the bromine content measured by elemental analysis (after reacting the resin with 9-borabicyclo(3.3.1)nonane (9-BBN) followed by oxidative work-up and
  • ruthenium alkylidene groups will be immobilized onto the resin surface by reacting the (vinyl)polystyrene with Grubbs 3rd generation catalyst (G3, 8 mol% per 0.8 mmol of vinyl group/g of resin) in dichloromethane (CH2CI2) for 2 hours under an inert atmosphere. If G3 does not immobilize onto the surface, then generations G2 or Gl may be used (note that G2 and Gl have been used successfully for SI-ROMP). After filtration, the resin is dried to
  • the resin-bound macroinitiator that is reported to be stable under ambient conditions for several months without loss of catalytic activity.
  • the resin-bound macroinitiator is submerged into a monomer solution and shaken for 1 hour at 0 °C to minimize undesirable chain-transfer processes (Figure 9).
  • a 100: 1 weight ratio of 2/6:resin-bound macroinitiator may be used and adjusted if necessary to maximize polymer loading.
  • the resins After quenching the polymerization with ethyl vinyl ether, the resins will be filtered and washed to remove any remaining monomer and free polymer. Surface modification will be confirmed by IR spectroscopy while polymer loading will be calculated by the increase in weight of the resin.
  • Polythioether-functionalized polyacrylonitrile (PAN) fibers are prepared according to Figure 1 1.
  • solubility tests will be performed to identify solvents that solubilize the required reagents and not PAN.
  • vinyl groups will be added to the commercially available PAN fibers by reducing the surface cyano groups to amines (using lithium aluminum hydride, LiAlH4) (Martinez, C. et al, Angewandte Chemie, International Edition, 2015, 54, 8287-8291; Roman, M. et al, Jour, of the Amer. Chem. Soc, 2010, 132, 16818-16824) followed by treatment with 3 -bromo- 1 -propene (Porel, M.
  • Vinyl moieties will be identified by their IR absorption bands at 1628, 988, 903, and 837 cm-1 while the vinyl group loading can be calculated from the bromine content measured by elemental analysis (after reacting the resin with 9-borabicyclo(3.3.1)nonane (9-BBN) followed by oxidative work-up and esterification with 4-bromobenzoic acid).
  • ruthenium alkylidene groups will be immobilized onto the surface of the fibers followed by polymerization using SI-ROMP.
  • Polymer PTE-A (5) can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb 2+ from water.

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Abstract

L'invention concerne un polymère de support solide comprenant au moins deux résidus de formules III ou IV, ou des sels associés : (III) (IV), les résidus des formules III ou IV étant liés de manière covalente à un support solide. La ligne de pointillés, R1, R2, Ra, Rb, Rc and Rd adoptent une valeur quelconque parmi les valeurs définies dans la spécification. L'invention concerne également des intermédiaires de synthèse et des procédés de synthèse utiles pour la préparation desdits composés. Le polymère est utile pour le traitement de l'eau contaminée par chélation de métal.
PCT/US2018/051777 2017-09-20 2018-09-19 Poly(thioéthers) liés à un support solide pour la séquestration d'ions métalliques Ceased WO2019060433A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10669378B2 (en) 2016-04-22 2020-06-02 Rutgers, The State University Of New Jersey Poly(thioethers) for metal ion sequestration
CN111825236A (zh) * 2020-05-22 2020-10-27 西北矿冶研究院 一种富集回收冶炼硫酸废水中重金属的方法

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WO2000061288A1 (fr) * 1999-04-07 2000-10-19 Merck Patent Gmbh Vecteurs fonctionnalises obtenus par copolymerisation par greffage par metathese
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10669378B2 (en) 2016-04-22 2020-06-02 Rutgers, The State University Of New Jersey Poly(thioethers) for metal ion sequestration
CN111825236A (zh) * 2020-05-22 2020-10-27 西北矿冶研究院 一种富集回收冶炼硫酸废水中重金属的方法

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