Synthesis of Cu^II‐complexed polymers and use as catalysts in the hydrolytic decontamination of Sarin nerve agent†

Abstract

A range of polymer-supported bidentate amine Cu II complexes have been synthesized based on linear polymers, crosslinked resins and hydrogels as precursor species. Linear styrene, acrylate and methacrylate structures have been examined along with reactive crosslinked resins derived from vinylbenzyl chloride, glycidyl methacrylate and methacrylic acid (Amberlite IRC-50). Hydrogels based on hydroxyethyl methacrylate, hydroxyethyl acrylate and hydroxypropyl acrylate, each copolymerized with a diamine containing monomer, have also been prepared.Each Cu II -complexed polymer has been assessed as a catalyst in the hydrolytic decomposition of the nerve agent, Sarin, as a possible strategy for developing selfdecontaminating materials and coatings for both personnel and equipment in the event of a nerve agent challenge in the field.Based on the measured half-lives for hydrolysis of Sarin all of the polymer Cu II complexes show remarkable catalytic activity relative to the rate of the uncatalyzed hydrolysis reaction. The linear polymethacrylate-based catalysts are the most active followed by the linear polystyrene-based species, the macroporous polymethacrylates and the polystyrene resins. The polymethacrylate hydrogels are the least effective. It seems therefore that the hydrophilic/hydrophobic balance is important in controlling Sarin access to the catalytic sites, and this seems to be optimal in the linear polymethacrylate-based catalysts. The results are discussed further in the context of the existing literature.

Ultrafine Selective Metal-Complexing Nanoparticles: Synthesis by Microemulsion Copolymerization, Binding Capacity, and Ligand Accessibility

“…9-11 Moreover, because of the well-defined structure of microemulsions, polymerization inside these systems allows one to control the structural properties of the resulting polymer and to synthesize special polymer materials, such as copolymers with high degrees of chemical functionalization, which are not accessible by other techniques. [9][10][11][12][13][14][15][16][17][18] On the other hand, resin beads or latex-supported ligands as well as soluble ligand-functionalized macromolecules and dendrimers have been used as metal ion complexing agents 2,[19][20][21][22][23][24][25][26][27][28][29][30][31] and proposed for an extensive variety of purposes as diverse as separation and recovery of metal ions, 2,[20][21][22][23][24]27 catalysis, 2,25,26,28,29 dioxygen transport, 30 or sensors. 31 In this field the use of microemulsions as polymerization media offers new prospect for the development of efficient colloidal supports with improved specific area and ligand accessibilty.…”

Micellar Interpolyelectrolyte Complexes with a Compartmentalized Shell

“…We were particularly interested in structural characteristics of micellar IPEC layers formed between PDAMAq and PMAA where we would expect a change in the IPEC compartment to a more dense structure due to the higher charge density in PDAMAq. The synthesis of PDAMA was first described by Sherrington et al by free radical polymerization and used as a chelating agent and polymeric support for copper complexes in the catalytic decomposition of the nerve agent Sarin . Homo- and copolymers of PDAMA have already been used as nonviral gene transfection agents. − …”

Synthetic Methods Applied to the Detection of Chemical Warfare Nerve Agents

“…DMMP detection limits as low as 10 -15 M were observed using this device with response times on the order of a few hundred seconds. Sherrington and coworkers advanced the application of Cu(II)-complexes imbedded in polymers for self-decontamination via catalytic degradation of the nerve agents [43]. A number of polymers based on the monomers, styrene, acrylate, and methacrylate were synthesized containing the Cu(II) complexes and may have eventual use in sensor development.…”