WO2019060433A1

WO2019060433A1 - Solid support-tethered poly(thioethers) for metal ion sequestration

Info

Publication number: WO2019060433A1
Application number: PCT/US2018/051777
Authority: WO
Inventors: Agostino PIETRANGELO
Original assignee: Rutgers State University of New Jersey
Current assignee: Rutgers State University of New Jersey
Priority date: 2017-09-20
Filing date: 2018-09-19
Publication date: 2019-03-28
Anticipated expiration: 2020-03-20

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, R^a, R^b, R^c and R^d 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.The invention relates to a solid support polymer comprising at least two residues of formulas III or IV, or associated salts: (III) (IV), the residues of formulas III or IV being covalently bound to a solid support. The dotted line, R ¹ , R ² , R ^a , R ^b , R ^c and R ^d adopt any one of the values defined in the specification. The invention also relates to synthetic intermediates and synthetic methods useful for the preparation of said compounds. The polymer is useful for the treatment of contaminated water by metal chelation.

Description

SOLID SUPPORT-TETHERED POLY(THIOETHERS) FOR

METAL ION SEQUESTRATION BACKGROUND OF THE INVENTION

Polychelatogens (Spivakov, B. Y., et al., Nature 1985, 315:313-315; Geckeler, K. E., et al., Angew. Makromol. Chem. 1987, 155: 151-161; and TulU, M., et al., Appl. Polym. Sci. 2008, 109:2808-2814) and their heterogeneous (i.e. water-insoluble) alternatives (Alexandratos, S. D., et al., New. J. Chem. 2015, 39:5366-5373; Alexandratos, S. D., et al., Macromolecules 2001, 34:206-210; Bell, C. A., et al., Adv. Mater. 2006, 18:582-586; Rivas, B. L., et al., Inorg. Chem. Commun. 2007, 10: 151-154; Ramirez, E., et al., J. Hazard. Mater. 2011, 192:432-439; and Tomida, T., et al., Ind. Eng. Chem. Res. 2001, 40:3557-3562) form a broad set of polymer-based reagents that are designed to sequester heavy metal contaminants in water resources that pose a risk to human health (Jarup, L. Br. Med. Bull. 2003, 68: 167-182). In light of ongoing efforts to improve water quality in parts of the world where potable water is scarce (World Health

Organization. Guidelines for Drinking-water Quality, 4^th ed.; Gutenberg, Malta, 2011), there is a need for novel metal sequestration polymers (Elimelech, M., et al., A. Science 2011, 712-717; Shannon, M. A., et al., Nature 2008, 452:301-310; and Hartono, M. R, et al., Water Air Soil Pollut. 2015, 226: 1-11) that are chemically flexible for performance optimization in both the solid and/or solution state.

The synthesis of a bio-derived thionoester capable of thia-Diels-Alder cycloadduct formation with inexpensive and commercially available cyclopentadiene has been reported (Mangalum, A.; et al, RSC Advances, 2016, 6:74250-74253). Ring-opening metathesis polymerization (ROMP) of the norbornene-like monomer affords a polythioether with spirolactone pendent groups that are saponified to the corresponding hydroxy carboxylate derivative. This water-soluble polyanion exhibits high Pb2+-binding capacity (ca. 2481.9±158.4 mg Pb2+ /g of polymer), a feature that may be attributed to a coordination sphere that combines both thioether (Murray, S. G. et al, Chemical Rev., 1981, 81 :365-414; Masdeu-Bulto, A. M.; et al, Coordination Chemical Rev., 2003, 242: 159-201; Manceau, A. et al, Inorganic Chem., 2015, 54: 11776-11791) and hydroxy carboxylate (Paria, S.; Chatterjee, S.; Paine, T. K. Inorganic

Chem., 2014, 53 :2810-2821; Paine, T. K. et al, Chemical Comm., 2010, 46: 1830-1832; Cawich, C. M. et al, Inorganic Chem., 2003, 42:6458-6468; Codd, R. et al, Jour, of the. Amer. Chem. Soc, 1999, 121 :7864-7876; Saadeh, S. M. et al, Inorganic Chemistry, 1991, 30:8-15; Kipp, E. B. et al, Inorganic Chemistry, 1972, 11 :271-276; Haines, R. A. et al, Inorganic Chem., 1973, 12: 1426-1428; Cariati, F. et al, Inorganica Chimica Acta, 1977, 21 : 133-1440; Fishinger, A. et al, Canadian Jour, of Chem., 1969, 47:2629-2637; Zhang, Y. et al, Polyhedron, 2015, 87, 377-382) constituents into a single chelating species. Indeed, this remarkably simple architecture provides unprecedented performance by arranging common electron-donating moieties into a multi- dentate ligand environment that is integrated into the polymer backbone and pendent group, allowing for optimal ligand placement and density. Moreover, the monomer is amenable to surface-initiated ring-opening metathesis polymerization (SI-ROMP) and accordingly, can be used to form surface-modified platforms. This chemistry may enable new water purification technologies.

Poly(thioethers) polymers have been demonstrated as effective for metal ion

sequestration (Pietrangelo, A. and Mangalum, A., "POLY(THIOETHERS) FOR METAL ION SEQUESTRATION", PCT/US2017/029161, Intl. Filing date 24 April 2017).

SUMMARY OF THE INVENTION

In one aspect, 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:

wherein:

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, (C₂-C6)alkenyl, (C2-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)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-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-Ce)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

R^a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C₆)alkenyl, (C₂-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R^c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C₆)alkenyl, (C₂-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2;

or a salt thereof.

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.

BRIEF DESCRIPTION OF THE FIGURES

Figure 1 shows retention (%) of Pb²⁺ as a function of [Pb²⁺]o. Data is reported as a mean with standard deviation (n = 3). [5] = 0.033 mg/mL, pH = ca. 6.

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 ([Pb²⁺]o, ca. 10 ppm) was passed through the cellulose filter. The dot labeled by arrow represents [Pb²⁺] in the filtrate. Experiments performed in triplicate. Data suggests that the cellulose membrane does NOT participate in lead extraction to a significant extent.

Figure 4 shows AA spectroscopy results from poly-2b Pb²⁺-binding experiments. An aqueous solution of lead ions ([Pb²⁺]o, ca. 10 ppm) and poly-2b ([poly-2b] = 0.67 mg/mL) was passed through the cellulose filter. The dot labeled by arrow represents [Pb²⁺] in the filtrate. Experiments performed in triplicate. Data suggests that there is no detectable lead (according to the lower detection limit of our AA spectrometer) in the filtrate.

Figure 5 shows retention profile plotted against filtration factor Z where Z = VfVo^"1 (Vf = volume of filtrate and Vo = volume of cell. Data suggests that poly-2b holds onto Pb ⁺ even after several washes with pure deionized water.

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/Pb²⁺ mixtures at multiple Pb²⁺ 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 and

Figures 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.

DETAILED DESCRIPTION

The following definitions are used, unless otherwise described:

"Solid support" is any material that absorbs or adsorbs liquids, such as water.

"Halo" is fluoro, chloro, bromo, or iodo.

The term "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). The term "alkenyl" refers to an unsaturated alkyl radical having one or more double bonds. Similarly, the term "alkynyl" refers to an unsaturated alkyl radical having one or more triple bonds. The term "haloalkyl" or

hydroxyalkyl" means an alkyl that is optionally substituted with halo or hydroxyl. The term "alkoxy" refers to an alkyl groups attached to the remainder of the molecule via an oxygen atom ("oxy").

The term "aryl" as used herein 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. For example, in certain embodiments, 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.

The term "alkylene" means a divalent radical derived from an alkane (including branched alkane), as exemplified by -CH2CH2CH2CH2- and -CH(CH₃)CH₂CH₂-. "Alkenylene" and "alkynylene" refer to the unsaturated forms of "alkylene" having double or triple bonds, respectively. The term "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.

The term "alkali metal" means the chemical elements found in Group 1 of the periodic table, such as lithium, sodium, potassium, rubidium and cesium. The term "alkali earth metal" means the chemical elements found in Group 2 of the periodic table, such as beryllium, magnesium, calcium, strontium, barium and radium.

The term "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.

It will be appreciated by those skilled in the art that 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.

When a bond in a compound formula herein is drawn in a non-stereochemical manner (e.g. flat), the atom to which the bond is attached includes all stereochemical possibilities. When a bond in a compound formula herein is drawn in a defined stereochemical manner (e.g. bold, bold-wedge, dashed or dashed-wedge), it is to be understood that the atom to which the stereochemical bond is attached is enriched in the relative stereoisomer depicted unless otherwise noted. In one embodiment, the compound may be at least 51% the relative stereoisomer depicted. In another embodiment, the compound may be at least 60% the relative stereoisomer depicted. In another embodiment, the compound may be at least 80% the relative stereoisomer depicted. In another embodiment, 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.

Specific values listed below for radicals, substituents, and ranges, are for illustration only; they do not exclude other defined values or other values within defined ranges for the radicals and substituents

Specifically, (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 be ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 - hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, or 5-hexynyl; (Ci- Ce)haloalkyl can be iodomethyl, bromomethyl, chloromethyl, fluoromethyl, tnfluoromethyl, 2- chloroethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, or pentafluoroethyl; hydroxy(Ci-C6)alkyl can be hydroxym ethyl, 1 -hydroxyethyl, 2 -hydroxy ethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3- hydroxypropyl, 1 -hydroxybutyl, 4-hydroxybutyl, 1-hydroxypentyl, 5-hydroxypentyl, 1 - hydroxyhexyl, or 6-hydroxyhexyl; and aryl can be phenyl, indenyl, or naphthyl.

EMBODIMENTS OF THE INVENTION

The solid-support polymer of formula III-S comprises two or more residues of formula III or a salt thereof:

It is understood that when n is 0, the residue of formula III has the following formula

or a salt thereof.

It is understood that when n is i, the residue of formula III has the following formula

Illb

or a salt thereof. It is understood that when n is 2, the residue of formula III has the following formula

IIIc:

or a salt thereof.

In one embodiment, a residue of the solid su ort polymer has the following formula

or a salt thereof, wherein:

X is -S-, -O- or -NH-;

Y is -S-, -0-, -NH- or -CH₂-;

R¹ 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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂; and

R² 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-

C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂.

In one embodiment, a residue of the solid su ort polymer has formula V:

or a salt thereof.

In one embodiment, R¹ is hydrogen or (Ci-C6)alkyl. In one embodiment, R¹ is hydrogen or methyl.

In one embodiment, R² is hydrogen or (Ci-C6)alkyl.

In one embodiment, R² is hydrogen or methyl.

In one embodiment, each dash line is a double bond.

In one embodiment, R^a is hydrogen,

In one embodiment, R^b is hydrogen.

In one embodiment, R^c is hydrogen.

In one embodiment, R^d is hydrogen.

In one embodiment, each residue of the polymer is independently selected from the group consisting of:

and salts thereof.

In one embodiment, one or more residues of the polymer are

An aspect of the invention is a solid-su ort ol mer of formula VI-S:

wherein:

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, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

Q is (Ci-Ce)alkyl, (C₂-C6)alkenyl, (C₂-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-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

R^a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C6)alkenyl, (C₂-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R^c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C6)alkenyl, (C₂-C6)alkynyl, (Ci-Ce)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

each R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2;

or a salt thereof.

An aspect of the invention is a polymer comprising two or more residues of formula VI or a salt thereof:

VI wherein:

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, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ 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-C₅)alkyl, (C₂-C₆)alkenyl, (C2-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy,

hydroxy(Ci-C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -O-C(O)- R³, -C(0)-R³, -C(0)-OR³, -N(R )-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

R^a 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- Ce)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C₂-C₆)alkenyl, (C₂-Ce)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R^c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂-C₅)alkenyl, (C₂-Ce)alkynyl, (Ci-Ce)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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- Ce)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2.

In one embodiment, the polymer of the invention further comprises a residue that is copolymerized from a monomer selected from the group consisting of:

Processes for preparing a polymer comprising a residue of formula III are provided as further embodiments of the invention and are illustrated by the following procedures in which the meanings of the generic radicals are as given above unless otherwise qualified.

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, (C₂- Ce)alkenyl, (C2-C5)alkynyl, (Ci-C₆)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)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-Ce)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂; R^a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 Ce)alkenyl, (C2-C5)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2 C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2.

In one aspect, 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:

I la

to provide the polymer comprising a residue of formula I or a salt thereof, wherein:

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-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

Q is (Ci-C6)alkyl, (C2-C5)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-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R )-C(0)-N(R )₂;

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, (C₂- C6)alkenyl, (C₂-C6)alkynyl, (Ci-C6)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R^b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-Ce)alkyl;

each R^3a is independently (Ci-Ce)alkyl; and

n is 0, 1 or 2.

In one embodiment, the polymer comprising a residue of formula I is a salt with an alkali metal or an alkali earth metal.

In one embodiment, 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:

wherein M is an alkali metal or an alkali earth metal.

In one embodiment, the method further comprises preparing the polymer comprising a residue of formula la by converting a corres onding compound of formula lb:

to provide the polymer comprising a residue of formula la.

In one embodiment, the compound of formula lb is treated with a transition metal catalyst to provide the corresponding polymer comprising a residue of formula la.

In one embodiment, the transition metal catalyst is 1^st, 2^nd or 3^rd Generation of Grubbs' catalyst.

In one embodiment, the ratio of compound of formula lb to Grubbs' catalyst is about 100-800 to 1.

In one embodiment, 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:

Ic Id

to provide the compound of formula lb.

In one embodiment, a mixture of the compound of formula Ic and the compound of formula Id is heated to provide the corresponding compound of formula lb.

In one embodiment, the method further comprises separating the corresponding product of formula lb by crystallization.

In one embodiment, the method further preparing the compound of formula Ic by converting a corresponding compound of formula Ie:

le

to provide the compound of formula Ic.

In one embodiment, the compound of formula le is treated with P4S10/

hexamethyldisiloxane (HMDO) or Lawesson's reagent to provide the corresponding compound of formula Ic.

In another embodiment, 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:

in

or a salt thereof, wherein:

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:

wherein:

X is S-, -O- or H-;

Y is -S-, -0-, -NH- or -CH2-;

R¹ is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂; R² is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 Ce)alkenyl, (C2-C5)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2 C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R³ is independently hydrogen or (Ci-C6)alkyl; and

n is 0, 1 or 2.

In one aspect, 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:

to provide the polymer comprising a residue of formula II or a salt therof, wherein:

X is -S-, -O- or -NH-;

Y is -S-, -0-, -NH- or -CH₂-; R¹ is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C2- Ce)alkenyl, (C2-C5)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R² 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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

Ce)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2.

In one embodiment, the polymer comprising a residue of formula II is a salt with an alkali metal or an alkali earth metal.

In one embodiment, 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:

Ilg

wherein M is an alkali metal or an alkali earth metal.

In one embodiment the method further comprises preparing the polymer comprising a residue of formula Ila by converting a corres onding compound of formula lib:

lib

to provide the polymer comprising a residue of formula Ila.

In one embodiment, the compound of formula lib is treated with a transition metal catalyst to provide the corresponding compound of formula Ila.

In one embodiment the transition metal catalyst is 1^st, 2^nd or 3^rd Generation of Grubbs' catalyst.

In one embodiment the ratio of compound of formula lib to Grubbs' catalyst is about 100-800 to 1.

In one embodiment the method further comprises preparing the compound of formula lib by contacting a corresponding compound of formula IIc and a corresponding compound of formula lid:

lie lid

to provide the compound of formula lib.

In one embodiment, a mixture of the compound of formula IIc and the compound of formula lid is heated to provide the corresponding compound of formula lib. In one embodiment, the method further comprises separating the corresponding product of formula lib by crystallization.

In one embodiment, the method further comprises preparing the compound of formula lie by converting a corresponding compound of formula He:

He

to the compound of formula lie.

In one embodiment, the compound of formula He is treated with P4S10/

hexamethyldisiloxane (HMDO) or 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.

In one embodiment, the polymer associates with the metal by chelation.

In one embodiment, the polymer is a part of a membrane, coated on the surface of a bead or is form into a bead.

In one embodiment, the membrane is part of a spiral wound module or present on the surface of porous hollow fibers.

In one embodiment, the metal is lead, mercury, cadmium, chromium, arsenic, gold, manganese, selenium, silver, thallium or silver.

In one embodiment, the method further comprises separating the polymer associated with the metal from the solution.

In one embodiment, the method further comprises separating the polymer associated with the metal from the solution by filtration

In one embodiment, the method further comprises releasing the metal from the polymer.

SOLID SUPPORT FOR TETHERING TO POLY(THIOETHERS)

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:

1. polymer resins (Alexandratos, S. D. et al, Macromolecules, 1996, 29, 1021-1026;

Alexandratos, S. D. et al, New Journal of Chemistry, 2015, 39, 5366-5373;

Alexandratos, S. D. et al, Macromolecules, 2001, 34, 206-210; Alexandratos, S. D. et al, Macromolecules, 1998, 31, 3235-3238; Zhu, X. et al, Reactive & Functional Polymers, 2014, 81 :77-81),

2. fibers (Alexandratos, S. D. et al, Industrial & Engineering Research, 2016, 55, 4208- 4216; Seko, N. et al, Nippon Kaisui Gakkai-Shi, 2005, 59, 316-319; Seko, N. et al, Nuclear Instruments and Methods in Physics: Section B, 2005, 236, 21-29),

3. nanocomposites (Musico, Y. L. et al, ournal of Materials Chemistry A, 2013, 1, 3789- 3796; Rahman, M. L. et al RSC Advances, 2016, 745-757),

4. nanoparticles (Pezzato, C. et al, Chemical Comm., 2015, 15, 9922-9931 ; Bell, C. A. et al, Advanced Materials, 2006, 18, 582-586),

5. 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),

6. membranes (Bolisetty, S. et al, Nature nanotechnology, 2016, DOI:

10.1038/NNANO.2015.310), and hydrogels (Esser-Kahn, A. P. et al, Journal of the American Chemical Society, 2008, 130: 15820-15822; Ramirez, E. et al, Journal of Hazardous Materials, 2011, 192, 432-439.).

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.

divinylbenzene) (Miller, W. S.; Castagna, C. J., In Plant Engineering, Technical Publishing, A Division of Dun. Donnelley Publishing Corp. New York, 1981). Subsequent reactions such as aromatic sulfonation immobilize functional groups directly onto the resin lending them their ion- exchange capability, while reactions such as chloromethylation introduce intermediate groups that are required for post-polymerization modification. Advantages of resins over other water treatment platforms include functional group flexibility, recyclability, and high binding capacity, applied to the polythioether-modified resins of the invention. Moreover, the high chemical and physical stability of ion-exchange resins with strong and weak acidic/basic groups enable operation in marine conditions (Schenk, H. J. et al, Separation Science Technology, 1982, 17, 1293-1308; Separation Science Technology, 1983, 18, 307-339; "Cyclic Imide Dioximes:

Formation and Hydrolytic Stability", Industrial & Engineering Chemistry Research, 2012, 51, 6619-6624).

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). In these materials, 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. et al, Industrial & Engineering Research, 2016, 55, 4208-4216). Alternatively, ligand moieties can be chemically modified onto polymers grown off a "trunk" polymer fiber. In the representative example shown in Figure 6B, 4-chlorostyrene is first polymerized off the surface of polyethylene fibers using radiation- induced graft polymerization (RIGP). 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). In the final step,

amidoximation (AO) followed by saponification completes the fabrication of the sorbent.

Advantages of using polymeric fiber metal -ion adsorbents include their light weight, shape/length flexibility, and proven deployability in seawater (Seko, N. et al, Nuclear

Technology, 2003, 144:274-278).

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.

Scheme 1 :

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. et al, Angewandte Makromolekulare Chemie, 1987, 155: 151-161; Tulu, M. et al, Jour, of Applied Polymer Science, 2008, 109:2808-2814). The compounds of the invention provide useful option in water purification by efficient metal-sequestration.

Fabrication of polythioether-modified resins and fibers prepared by SI-ROMP (Specific Aim A) and the assessment of their sorbing capabilities under operationally relevant conditions (Specific Aim B). The structure of polythioether PTE-A was designed for treating heavy-metal toxicity with strategic use of hydroxyl, carboxylate and thioether functionalities that provide 'hard', 'borderline', and ' soft' electron-donor groups into a single multi-dentate ligand constructed from both the polymer backbone and pendent group, lending optimal ligand location and density to the system. Since stereochemistry may play a significant role PTE-A was designed to adopt two stereochemical microstructures that can be adjusted, lending a second synthetic handle to optimize metal ion coordination.

SYNTHESIS AND CHARACTERIZATION OF POLY(THIOETHERS)

The synthetic route to PTE-A is shown in Scheme 2 and Example 1. First, thionoester 1 is prepared by reacting biorenewable L-lactide (L-LA) with a reagent combination of phosphorous pentasulfide (P4S10) and hexamethyldisiloxane (HMDO) (Curphey, T. J. Jour, of Org. Chem., 2002, 67:6461-6473; Curphey, T. J. Tetrahedron Letters, 2002, 43, 371-373). Single-crystal X-ray diffraction (XRD) studies confirmed the proposed structure, revealing two independent molecules in the asymmetric unit (Z = 8) with C=S (ca. 1.617(2) and 1.621(2) A) and C=0 bond distances (ca. 1.193(3) and 1.196(3) A) that are in line with literature values (Allen, F. H.; Kennard, O ; Watson, D. G. Journal of the Chemical Society Perkin Transactions II, 1987, S 1-S19).

Scheme 2

0.25 equiv. P₄S ₀ 1.1 equiv. NaOH (aq) 1 M NaOH (aq)

1 .67 equiv. HMDO HC! (aq) RT / 24h: THF / RT / 48h

L-LA

PTE-A (5)

Characterization by chiral high performance liquid chromatography (HPLC) and polarimetry indicate that epimerization does not occur to a significant extent during the process of thionation, hence enantiomerically pure and racemic 1 can be prepared directly from the appropriate lactide stereoisomer(s).

Next, heating thionoester 1 with cyclopentadiene (Timoshenko, V. M. et al, Journal of Fluorine Chemistry, 2010, 131, 172-183) affords a mixture of thia-Diels-Alder products from which the major cycloadduct 2 can be separated via crystallization from hot hexanes. X-ray crystallographic data revealed that the sulfur atom is located over the least sterically encumbered face of the lactone ring, indicating a mechanism whereby the methyl groups of the dieneophile are positioned on the same side as the approaching diene. Despite the steric congestion about the lactone moiety, its conversion into the hydroxy carboxylate derivative was demonstrated as a proof-of-principle by saponifying 2 in aqueous NaOH (1.1 mol equiv. NaOH) until its complete dissolution. The identity of the PTE-A small molecule model 3 was unequivocally confirmed by NMR spectroscopy and high-resolution electrospray ionization mass spectrometry where peak masses of ca. 289.049, 555. I l l, and 821.172 are consistent with monomer (calcd for [3 + Na]+, 289.048), dimer (calcd for [(3)2 + Na]+, 555.107), and trimer adducts (calcd for [(3)3 + Na]+, 821.165) with an additional sodium ion.

Treatment of 3 with 1M aqueous HC1 regenerated 2 quantitatively suggesting that the coordination sites of PTE-A may be deactivated upon application of a pH stimulus. Monomer 2 is readily polymerized by ROMP at room temperature using 2nd generation Grubbs' catalyst (G2) (Scholl, M. et al, Organic Letters, 1999, 1 :953-965), however, polymers with controlled molecular weights and low dispersities (DM) could not be attained, likely due to the use of the G2 polymerization catalyst that is known for its slow initiation rates (Vougioukalakis, G. C; Grubbs, R. H. Chemical Reviews, 2010, 110: 1746-1787). On the contrary, polymerizations performed at 0 °C using 3rd generation Grubbs' catalyst (G3) exhibit a predominantly linear relationship between number average molecular weight Mn and monomer conversion (Figure 4), a hallmark of controlled polymerizations. Nonetheless, the thermal properties among these high molecular weight polymers are near identical with glass transition temperatures (Tgs) at ca. 142 °C and thermal decomposition temperatures Tdecs in the range of ca. 306-310 °C indicating high thermal stability and applicability at elevated temperatures. Finally, the synthesis of PTE-A (5) is completed by saponifying poly-2 (4) (Wathier, M. et al, Jour, of the Amer. Chem. Soc, 2013, 135:4930-4933; Wathier, M. et al, Jour, of the Amer. Chem. Soc, 2010, 132, 15887-15889) followed by dialysis against a 3.5 KDa MWCO bag in deionized water to remove excess hydroxide anion. Upon solvent removal, PTE-A is isolated as a highly water-soluble white powder. Importantly, near identical ¾ NMR spectra and gel permeation chromatographs (GPC) taken over a period of several months confirm the stability of this polymer when stored under ambient conditions.

Solid-state IR spectra of poly-2, PTE-A, and three PTE-A/Pb2+ mixtures are shown in Figure 5. The latter were prepared by stirring PTE-A in aqueous Pb2+ solutions of increasing lead concentration (i.e. polymer repeat unit: Pb2+ = 1 : 0.5, 1 : 0.75, and 1 : 1) followed by solvent removal under reduced pressure. The IR spectrum of poly-2 possesses a strong absorption band at 1745 cm-1 that is consistent with the C=0 stretching frequency of six- membered ring lactones (Lin-Vien, D. et al, The Handbook of Infrared and Raman

Characteristic Frequencies of Organic Molecules; Academic Press, San Diego, 1991, p 119). Upon saponification to PTE-A, the band is largely quenched and replaced with a strong band at 1577 cm-1 that is characteristic of the anti-symmetric C02 stretch of sodium carboxylate salts (Lin-Vien, D. et al, The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules; Academic Press, San Diego, 1991, p 1 19). As anticipated, a large symmetric CO2 stretching band at ca. 1347 cm-1 forms when PTE-A is exposed to lead, indicating metal ion coordination. Moreover, the ratio of the symmetric and anti-symmetric C02 stretch intensities increases as the Pb2+ loading increase. Taken together, the data confirm that IR spectroscopy will be ideal for characterizing the poly-2- and PTE-A-modified sorbants proposed herein, as well identifying metal ion uptake in a qualitative and potentially quantitative manner.

Polythioether PTE-B is prepare following Scheme 3. Bromoacetonitrile 4 is reacted with sodium thiosulfate (Na2S₂03) 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

hydrochloride (NH30H CI) in water at pH = ca. 6 (Alexandratos, S. D. et al, Industrial & Engineering Research, 2016, 55, 4208-4216).

Scheme 3

■OH ^PTE_B poiy-6

EXAMPLES

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). All data will be acquired using the following instrumentation: i) Bruker ASCEND 500 MHz NMR spectrometer (calibrated to the residual protonated solvent peaks at δ 7.24 for deuterated chloroform and δ 4.79 for deuterated water), ii) Bruker Ultraflex MALDI-TOF MS, iii) TA Instruments Discovery Series thermal gravimetric analyzer, and a iv) TA Instruments Discovery Series differential scanning calorimeter.

The invention will now be illustrated by the following non-limiting Examples.

Example 1. Preparation of polychelatogen 5

Step 1. Preparation of (3S,6S)-3,6-dimethyl-5-thioxo-l,4-dioxan-2-one (1)

A pressure vessel (equipped with a sidearm and stir bar) was charged with L-lactide (10.00 g, 69.40 mmol), P₄Sio (7.71 g, 17.35 mmol) and hexamethyldisiloxane (18.81 g, 115.87 mmol) in ca. 70 mL of anhydrous toluene (Scheme 2). After refluxing the contents for 24 h, the reaction was cooled to room temperature and the solvent removed under reduced pressure. The residue was taken up in DCM and passed through a silica column (Sorbtech silica gel; porosity, 60A; particle size, 40-60 μιη; column, 4 cm diameter, 15 cm length, Rf = 1.0) to remove sulfur impurities. The crude product was then passed through a second silica column (diameter, 4 cm; length, 15 cm) using a diethyl ether/hexane solvent mixture (25/75) as the eluent (¾ = 0.45). After solvent removal, the yellow solid was recrystallized thrice from cold diethyl ether (ca. -20 °C) and sublimed to afford analytically pure product (2.00 g, Yield: 18%). ¾ NMR (500 MHz, CDCh): δ 5.04 (q, ³JHH = 13.41, J_HH = 6.73, 1H), 4.96 (q, ³JHH = 12.77, J_HH = 6.41, 1H), 1.76 (d, ³JHH = 6.40, 3H), 1.73 (d, ³JHH = 6.68, 3H). ¹³C NMR (125 MHz, CDCh): δ 211.4, 167.5, 78.4, 75.1, 19.3, 15.5. IR: v = 2996, 1759, 1441, 1370, 1350, 1323, 1303, 1259, 1226, 1 147, 1080, 1063, 1035, 1010, 959, 833, 751, 727 cm^"1. [a]_D ²³ = -512.9 (c 0.59, CHC1₃). Melting point: 82-83 °C. Anal. Calc. for C₆H₈0₃S: C, 44.99; H, 5.03; N, 0.0. Found: C, 45.13; H, 4.99; N, 0.00.

Step 2. Preparation of (l S,2S,3'S,4R,6'S)-3',6'-dimethyl-3- thiaspiro[bicyclo[2.2.1]heptane-2,2'-[l,4]dioxan]-5-en-5'-one (2)

A pressure vessel (equipped with a sidearm and stir bar) was charged with 1 (1.40 g, 8.74 mmol) and freshly distilled cyclopentadiene (2.90 g, 43.72 mmol, 5 equiv) in 10 mL of anhydrous benzene and heated to 130 °C for 5 h. After cooling to room temperature, both solvent and excess cyclopentadiene were removed by reduced pressure and the residue passed through a silica gel column using a diethyl ether/hexane solvent mixture (5/95) as the eluent (Rf = 0.6). Compound 2 was isolated from its mixture of stereoisomers by recrystallization from boiling hexanes (thrice) to afford a white solid (0.50 g, Yield: 18%). ¾ NMR (500 MHz, CDCh): δ = 6.60 (q, ³JHH = 5.71, J_HH = 2.77, 1H), 5.93 (q, J_HH = 5.62, J_HH = 3.21, 1H), 4.71 (q, ³JHH = 13.99, J_HH = 7.01, 1H), 4.21 (m, 2H), 3.16 (d, ³JHH = 1.72, 1H), 2.23 (d, ³JHH = 9.42, 1H), 1.91 (m, 1H), 1.56 (m, 6H). ¹³C NMR (125 MHz, CDCh): δ 169.8, 143.2, 129.5, 102.1, 83.3, 71.9, 54.1, 52.7, 51.6, 19.7, 18.1. IR: v = 2990, 2935, 1737, 1441, 1375, 1332, 1269, 1228, 1182, 1 153, 1124, 1107, 1078, 1046, 1011, 980, 970, 958, 909, 884, 812, 798, 761, 733, 691 cm^" ^l. Melting point: 103-104 °C. Anal. Calc. for CiiH₁₄0₃S: C, 58.39; H, 6.24; N, 0.0. Found: C, 58.46; H, 6.11 ; N, 0.00. The stereochemistry of compound 2 was confirmed by X-ray crystal structure.

Step 3. Preparation of compound 3

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 μπι syringe filter and the solvent removed to afford a white solid. ¾ NMR (500 MHz, D₂0): δ = 6.53 (q, J_HH = 5.56, ³JHH = 2.65, 1H), 6.11 (q, ³J_HH = 5.50, ³J_HH = 3.33, 1H), 4.53 (q, J_HH = 13.89, ³J_HH = 6.95, 1H), 4.24 (s, 1H), 3.47 (0, ³JHH = 13.11, ³JHH = 6.56, 1H), 3.20 (s, 1H), 2.10 (d, JHH = 9.63, 1H), 1.86 (d, ³JHff = 9.68, 1H), 1.34 (m, 6H). ¹³C NMR (125 MHz, CDCh): δ 182.5, 141.2, 132.5, 1 10.7, 77.0, 75.0, 55.6, 53.3, 50.7, 19.4, 18.2.

Step 4. Preparation of compound poly-2 (4)

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 ¾ NMR spectroscopy).

Compound 4 was then precipitated upon dropwise addition of the reaction solution into cold {ca. 0 °C) methanol. After dissolving and precipitating the polymer in triplicate, the polymer was dried under vacuum for 24 h. Polymer poly-2 (4): ([2]₀/[G2]₀ = 100). ¾ NMR (500 MHz, CDCh): δ = 7.36 (br s, 5H), 5.81 - 5.65 (br m, 217H), 4.70 (br s, 105H), 4.53 - 4.11 (br m, 221H), 3.15 - 2.84 (br m, 219H), 1.75 (br s, 107H), 1.55 - 1.42 (br m, 640H).

Step 5. Preparation of PTE-A (5)

A solution of poly-2 (4) ([2]₀/[G2]₀ = 100, 50 mg in 5 mL THF) was added to 5 mL of 1 M NaOH (aq) and stirred for 48 h at room temperature. The solution was concentrated under reduced pressure and dialyzed against a 3500 M_w cutoff in deionized water for 48 h under sink conditions. The solvent was removed by reduced pressure and the white solid dried under vacuum for 24 h to give PTE-A (5) (52 mg). ¾ NMR (500 MHz, D₂0): δ = 5.77 - 5.66 (br m, 2H), 4.389 (br s, 1H), 4.13 - 4.09 (br m, 1H), 3.85 (br s, 1H), 3.34 (br, s, 1H), 3.02 (br s, 1H), 2.17 (br s, 1H), 1.92 (br s, 1H), 1.44 - 1.28 (br m, 5H). Example 2. Fabrication of Polythioether-Modified Sorbents

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). First, commercially available Merrifield resin (200-400 mesh, 1% cross-linked, 3.5-4.5 mmol/g CI- loading) will be converted to its (vinyl)polystyrene congener upon treatment with excess dimethyl sulfonium methylide at 0 °C for 24 hours in tetrahydrofuran (THF) (Sylvain, C. et al, Tetrahedron Letters 1998, 39:9679- 9680). 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

esterifi cation with 4- bromobenzoic acid). Next, 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

afford the resin-bound macroinitiator that is reported to be stable under ambient conditions for several months without loss of catalytic activity. To complete the synthesis of polythioether- modified resins, 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. 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. Prior to metal-ion uptake experiments, the resins will be activated by either stirring in aq. NaOH (Figure 10A) or heating with hydroxylamine hydrochloride (NH₂OH HCI/H2O) in water at pH = ca.

6 (Figure 10B) until maximum conversion (measured by IR spectroscopy) is obtained. Finally, sulfur and nitrogen contents will be measured by elemental analysis to calculate the percent loading of ligand moieties per gram of polymer resin.

Example 3. Fabrication of Polythioether-Modified Fibers

Polythioether-functionalized polyacrylonitrile (PAN) fibers are prepared according to Figure 1 1. First, solubility tests will be performed to identify solvents that solubilize the required reagents and not PAN. Next, 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. et al, Jour, of the Amer. Chem. Soc, 2014, 136: 13162-13165; Yamazaki, S. et al, Jour, of Org. Chem., 2013 , 78, 8405-8416). 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). In the same way that the resins were fabricated, ruthenium alkylidene groups will be immobilized onto the surface of the fibers followed by polymerization using SI-ROMP. Prior to metal-ion uptake experiments, the resins will be activated by either stirring in aq. NaOH or heating with hydroxylamine hydrochloride (NH2OH HC1, H20) in water at pH = ca. 6 until maximum conversion (measured by IR spectroscopy) is obtained.

Example 4. Heavy metal affinity test

Polymer PTE-A (5)can be used with a commercially available centrifuge tube equipped with a cellulose membrane to extract Pb²⁺ from water. To investigate the liquid-phase polymer- based retention (LPR) of Pb²⁺, aqueous solutions of PTE-A (5) (2 mL, [5] = ca. 1 mg/mL) and Pb²⁺ (1 mL, [Pb²⁺] = ca. 30 ppm) were combined ([5], ca. 0 67 mg/mL; [Pb²⁺]o, ca. 10 ppm) and stirred under ambient conditions for 90 min followed by centrifugation through an Amicon Ultra filter equipped with a regenerated cellulose membrane (3 kDa MWCO). Filtrate analysis by atomic absorption spectroscopy revealed no detectable Pb²⁺ in these solutions, even after several retentate washes (e.g., 5 x 3 mL) with deionized water. Indeed, filtrates from control experiments employing polymer-free solutions were found to possess Pb²⁺ concentrations of ca. 9.57 ± 0.08 ppm indicating that the cellulose membrane did not play a significant role in Pb²⁺ binding. As anticipated from earlier results, washing the membrane with three aliquots of 1 M HC1 (3 mL) afforded filtrates with [Pb²⁺] of 7.09, 1.63, and 0.21 ppm respectively indicating that Pb²⁺ can be released from the polymer upon treatment with aqueous acid.

To gain further insight into Pb²⁺ uptake by PTE-A (5), Pb²⁺ retention (%) was measured as a function of the initial Pb²⁺ concentration [Pb²⁺]o (Figure 1). Indeed, a near quantitative retention of Pb²⁺ by the polychelatogen ([5] = ca. 0.033 mg/mL). pH = ca. 6, n = 3) in solutions up to [Pb²⁺] ca. 50 ppm was observed, after which the Pb²⁺ retention drops considerably. Be that as it may, the binding capacity Pb²⁺ in milligrams per gram of compound 5 at [Pb²⁺]o = 100 ppm is ca. 1925.3 ± 148.9 mg (Pb )/g (5), a value that is considerably higher than many Pb binding systems reported to date (Spivakov, B. Y., et al., Nature 1985, 315, 313-3 15; Geckeler, K. E., et al., Angew. Makromol. Chem. 1987, 155, 151-161 ; Tulii, M., et al., Appl. Polym. Sci. 2008, 109, 2808-2814; and Alexandratos, S. D., et al., Macromolecules 2001, 34, 206-210) Moreover,

[5] concentrations could be increased to promote the near quantitative retention of Pb²⁺ from solutions of ca. [Pb²⁺]o = 100 ppm, indicating that the LPR system can be optimized to enhance performance. In solutions with [Pb²⁺]o = 150 and 200 ppm, the Pb²⁺ binding capacity was determined to be 2481.9 ± 158.4 and 2084.6 ± 255.5 mg (Pb²⁺)/g (5) respectively, indicating that the Langmuir adsorption model that predicts a plateau may not be applicable due to the homogenous nature of the binding process (Madadrang, C. J., et al., ACS Appl. Mater.

Interfaces 2012, 4: 1186-1193).

All publications, patents, and patent documents are incorporated by reference herein, as though individually incorporated by reference. The invention has been described with reference to various specific and preferred embodiments and techniques. However, it should be understood that many variations and modifications may be made while remaining within the spirit and scope of the invention.

Claims

What is claimed is

1. A solid-su ort polymer of formula III-S :

wherein:

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-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, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci-

C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R )-C(0)-N(R )₂;

Q is (Ci-C₆)alkyl, (C2-Cs)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-C₆)alkyl, (C₂-C₆)alkenyl, (C2-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

R^a is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- C6)alkenyl, (C2-Cs)alkynyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C2- Ce)alkenyl, (C2-C6)alkynyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^c is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-C6)alkyl, (C₂- C₆)alkenyl, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^d is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C₂- Ce)alkenyl, (C2-C6)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

each R³ is independently hydrogen or (Ci-C6)alkyl; and

n is 0, 1 or 2;

or a salt thereof.

2. The solid-support polymer of claim 1 comprising two or more residues of formula III or a salt thereof:

wherein:

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, (C₂-C6)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

Q is (Ci-Ce)alkyl, (C2-C6)alkenyl, (C2-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-C₆)alkyl, (C₂-C₆)alkenyl, (C2-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy,

hydroxy(Ci-C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -O-C(O)- R³, -C(0)-R³, -C(0)-OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂; 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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C₂-C₆)alkenyl, (C₂-Ce)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-C6)alkyl; and

n is 0, 1 or 2.

3. The solid-support polymer of claim 1, comprising two or more residues of formula Ilia:

or a salt thereof.

4. The solid-support polymer of claim 1, comprising two or more residues of formula Illb :

Illb or a salt thereof.

5. The solid-support polymer of claim 1, comprising two or more residues of formula IV:

or a salt thereof, wherein:

X is -S-, -O- or -NH-;

Y is -S-, -0-, -NH- or -CH₂-;

R¹ 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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂; and

R² 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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂ .

6. The solid-support polymer of claim 4, comprising two or more residues of formula V:

or a salt thereof.

The solid-support polymer of claim 5 or 6, wherein R¹ is hydrogen or (Ci-

C₆)alkyl.

The solid-support polymer of claim 5 or 6, wherein R¹ is hydrogen or methyl. The solid-support polymer of any one of claims 5-8, wherein R² is hydrogen or

(Ci-C₆)alkyl.

10. The solid-support polymer of any one of claims 5-8, wherein R² is hydrogen or methyl.

11. The solid-support polymer of any one of claims 1 -10, wherein each dash line is a double bond.

12. The solid-support polymer of any one of claims 1 -1 1, wherein R^a is hydrogen.

13. The solid-support polymer of any one of claims 1 -12, wherein R^¾ is hydrogen.

14. The solid-support polymer of any one of claims 1 -13, wherein R^c is hydrogen.

15. The solid-support polymer of any one of claims 1 -14, wherein R^d is hydrogen.

16. The solid-support polymer of claim 1, wherein each residue is independently selected from the rou consistin of:

and salts thereof.

17. The solid-support polymer of claim 1 wherein each residue is independently

18. A solid-support polymer of formula VI-S:

wherein:

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-Ce)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-Ce)alkyl, (C2-C6)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

Q is (Ci-C₆)alkyl, (C2-C5)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-Ce)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R^b is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C₂- C₆)alkenyl, (C₂-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-C6)alkyl; and

n is 0, 1 or 2;

or a salt thereof.

19. The solid-support polymer of claim 1 or 18, wherein solid support S is selected from a polymer resin, a fiber, a nanocomposite, a nanoparticle, a nanowire, and a membrane.

20. A polymer comprisin two or more residues of formula VI or a salt thereof:

vi

wherein:

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-Ce)alkyl, (C2-C6)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)₂;

Q is (Ci-C₆)alkyl, (C₂-C5)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-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy,

hydroxy(Ci-C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -O-C(O)- R³, -C(0)-R³, -C(0)-OR³, -N(R³)-C(0)-R³ or -N(R )-C(0)-N(R³)₂;

R^a 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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R is selected from the group consisting of hydrogen, halo, hydroxy, (Ci-Ce)alkyl, (C₂-C₅)alkenyl, (C₂-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-C6)alkyl; and

n is 0, 1 or 2.

21. The polymer in any one of claims 1-20 further comprising a residue that is copolymerized from a monomer selected from the group consisting of:

I la

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, (C2-C₅)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ or -N(R³)-C(0)-N(R³)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-C₆)alkyl, (C₂-C₆)alkenyl, (C₂-Ce)alkynyl, (Ci-Ce)haloalkyl, (Ci-Ce)alkoxy,

hydroxy(Ci-C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -O-C(O)- R³, -C(0)-R³, -C(0)-OR³, -N(R )-C(0)-R³ or -N(R )-C(0)-N(R³)₂;

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, (C₂-Ce)alkenyl, (C2-C₆)alkynyl, (Ci-C₆)haloalkyl, (Ci-C₆)alkoxy, hydroxy(Ci-

C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)-

OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

R 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- C₆)alkyl, -N0₂, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )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- C₆)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)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- Ce)alkyl, -N0₂, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂;

each R³ is independently hydrogen or (Ci-Ce)alkyl;

each R^3a is independently (Ci-C6)alkyl; and

n is 0, 1 or 2.

23. The method of claim 22, wherein the polymer comprising a residue of formula I is a salt with an alkali metal or an alkali earth metal.

24. The method of claim 22 comprising 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:

wherein M is an alkali metal or an alkali earth metal.

25. The method of any one of claims 22-24 further comprising preparing the polymer comprising a residue of formula la by converting a corresponding compound of formula lb:

to provide the polymer comprising a residue of formula la.

26. The method of claim 25, wherein the compound of formula lb is treated with a transition metal catalyst to provide the corresponding polymer comprising a residue of formula la.

27. The method of claim 26 wherein the transition catalyst is 1^st, 2^nd or 3^rd Generation of Grubbs' catalyst.

28. The method of claim 26 or 27 wherein the ratio of compound of formula lb to Grubbs' catalyst is about 100-800 to 1.

29. The method of any one of claims 25-28 further comprising preparing the compound of formula lb by contacting a corresponding compound of formula Ic and a corresponding compound of formula Id:

Ic Id

to provide the compound of formula lb.

30. The method of claim 29 wherein a mixture of the compound of formula Ic and the compound of formula Id is heated to provide the corresponding compound of formula lb.

31. The method of claim 29 or 30 further comprising separating the corresponding product of formula lb by crystallization.

32. The method of any one of claims 29-31 further comprising preparing the compound of formula Ic by converting a corresponding compound of formula le:

le

to provide the compound of formula Ic.

33. The method of claim 32 wherein the compound of formula Ie is treated with P4S10/ hexamethyldisiloxane (HMDO) or Lawesson' s reagent to provide the corresponding compound of formula Ic.

34. The method of any one of claims 22-33 further comprising converting the polymer comprising a residue of formula I or a salt thereof to a corresponding polymer comprising a residue of formula III:

or a salt thereof, wherein:

35. A method to prepare a polymer comprising a residue of formula II or a salt thereof, comprisin converting a corresponding polymer comprising a residue of formula Ila:

II Ila

X is -S-, -O- or -NH-;

Y is -S-, -0-, -NH- or -CH₂-;

R¹ 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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R² 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- C₆)alkyl, -NO2, -N(R³)₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R³)₂; 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-C₆)alkoxy, hydroxy(Ci- C₆)alkyl, -NO2, -N(R )₂, -CN, -C(0)-N(R³)₂, -O-R³, -S-R³, -0-C(0)-R³, -C(0)-R³, -C(O)- OR³, -N(R³)-C(0)-R³ and -N(R³)-C(0)-N(R )₂;

R³ is independently hydrogen or (Ci-Ce)alkyl; and

n is 0, 1 or 2.

36. The method of claim 35, wherein the polymer comprising a residue of formula II is a salt with an alkali metal or an alkali earth metal.

37. The method of claim 35 comprising 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 Ii :

wherein M is an alkali metal or an alkali earth metal.

38. The method of any one of claims 35-37 further comprising preparing the polymer comprising a residue of formula Ila by converting a corresponding compound of formula lib:

to provide the polymer comprising a residue of formula Ila.

39. The method of claim 38, wherein the compound of formula lib is treated with a transition metal catalyst to provide the corresponding compound of formula Ila.

40. The method of claim 39 wherein the transition metal catalyst is 1^st, 2^nd or 3^rd Generation of Grubbs' catalyst.

41. The method of claim 39 or 40 wherein the ratio of compound of formula lib to Grubbs' catalyst is about 100-800 to 1.

42. The method of any one of claims 38-41 further comprising preparing the compound of formula lib by contacting a corresponding compound of formula lie and a corresponding compound of formula Ild:

lie Ild

to provide the compound of formula lib.

43. The method of claim 42 wherein a mixture of the compound of formula lie and the compound of formula Ild is heated to provide the corresponding compound of formula lib.

44. The method of claim 42 or 43 further comprising separating the corresponding product of formula lib by crystallization.

45. The method of any one of claims 42-44 further comprising preparing the compound of formula lie by converting a corresponding compound of formula He:

to provide the compound of formula

46. The method of claim 45 wherein the compound of formula He is treated with P4S10/ hexamethyldisiloxane (HMDO) or Lawesson' s reagent to provide the corresponding compound of formula lie.

47. The method of any one of claims 35-46 further comprising converting the polymer comprising a residue of formula II or a salt thereof to a polymer comprising a residue formula IV:

or a salt thereof, wherein:

48. A method of separating a metal from a solution that comprises the metal comprising contacting the solution with a polymer as described in claims 1-20 under conditions whereby the metal associates with the polymer to form a polymer associated metal.

49. The method of claim 48, wherein the polymer associates with the metal by chelation.

50. The method of claim 48, wherein the polymer is part of a membrane.

51. The method of claim 50, wherein the membrane is part of a spiral wound module or present on the surface of porous hollow fibers.

52. The method of claim 48, wherein the polymer is coated on the surface of a bead or formed into a bead.

53. The method of any one of claims 48-52, wherein the metal is lead, mercury, cadmium, chromium, arsenic, gold, manganese, selenium, silver, thallium or silver.

54. The method of any one of claims 48-53 further comprising separating the polymer associated with the metal from the solution.

55. The method of claim 52 further comprising separating the polymer associated with the metal from the solution by filtration.

56. The method of claim 54 or 55 further comprising releasing the metal from the polymer.

57. The method of claim 48 wherein the solution contains one or more metals selected from lead, cadmium, copper, chromium, nickel, zinc, mercury, and uranium.