Reactive blending via metal‐ligand coordination

Abstract

d‐Block transition‐metal‐containing polymer blends which form coordination complexes are described in this treatise. The model compounds are zinc acetate dihydrate, copper acetate dihydrate, nickel acetate tetrahydrate, cobalt chloride hexahydrate, palladium chloride bis (acetonitrile), and the dimer of dichlorotricarbonylruthenium (II). Two classes of ligands are of interest. Poly (4‐vinylpyridine), P4VP, and copolymers that contain 4‐vinylpyridine repeat units form complexes with zinc, copper, nickel, cobalt, and ruthenium salts. Atactic 1,2‐polybutadiene contains olefinic sidegroups that displace weakly bound acetonitrile ligands and coordinate to palladium chloride. Thermal analysis via differential scanning calorimetry suggests that the glass transition temperature of the polymeric ligand is enhanced by these low‐molecular‐weight transition‐metal salts in binary and ternary blends. In some cases, d‐block salts function as transition‐metal compatibilizers for copolymers that would otherwise be immiscible. The isothermal ternary phase diagram for polybutadiene with palladium chloride highlights regions of gelation, precipitation, and transparent solutions during blend preparation in tetrahydrofuran. Fourier transform infrared spectroscopy provides molecular‐level data that support the concept of polymeric coordination complexes. High‐resolution carbon‐13 solid‐state NMR spectroscopy identifies (1) near‐neighbor interactions between polymeric pyridine ligands and the ruthenium salt, and (2) a considerable reduction in the molecular mobility of the polybutadiene chain backbone when it forms a coordination complex with palladium chloride. The elastic modulus of polybutadiene increases by three orders of magnitude when the palladium salt concentration is 4 mol % in a solid‐state glassy film. A thermodynamic interpretation of ligand field stabilization energies appropriate to tetrahedral cobalt and octahedral nickel complexes is employed to estimate the synergistic enhancement of the glass transition temperature, particularly when coordination crosslinks are present. ©1995 John Wiley & Sons, Inc.

Transition metal compatibilization of poly(vinylamine) and poly(ethylene imine)

“…Previous research in our laboratory 8,9,13,[17][18][19][20][21][22][23] has focused on divalent zinc, copper, nickel, cobalt, ruthenium and palladium complexes. Pyridine ligands in poly(4-vinylpyridine) and 4-vinylpyridine copolymers coordinate to zinc, copper, nickel, cobalt and ruthenium.…”

“…Under these conditions, T g increases by approximately 10 -30°C relative to the undiluted polymer. 13 Coordination crosslinks occur when the transition metal In memory of Olive M. Belfiore on the 88th anniversary of her birth.…”

Protective effect of poly(4-Vinylpyridine) containing surface films to the corrosion of copper

“…4 For instance, the conducting and thermal properties of poly(4-vinylpyridine) (P4VP) are significantly changed when the polymer is complexed with copper ions. 5 The technological applications of the P4VP/ copper system include reactive blending, 6 catalyst, [7][8][9] cation exchange resins and membranes designed to preconcentrate metals from dilute solutions 10 or remove them from wastewater, 11 solid-state electrochemical cells, 12 circuit manufacturing on microscopic smoothly polymeric surfaces 13 and anti-corrosion methods. 14 Poly(4-vinylpyridine)/cupric salts complexes can be synthesized by physical mixing methods, and their thermal and spectroscopic properties are already known.…”

Interaction of poly(4-vinylpyridine) with copper surfaces: electrochemical, thermal and spectroscopic studies

“…5 Additionally, it is known that in some cases, d-block salts may act as compatibilizers for copolymers that would be otherwise immiscible. 6 Our research group previously demonstrated the new properties of poly(vinylpyridine) when it forms a polymer-complex with Zn(II) ions. 7 The polymer poly(4-vinylpyridine) (P4VP) exhibited different thermal and conducting properties as a [P4VP]/copper iodide binary mixture; the electrical conductivity changes drastically with the increase in the amount of copper iodide in the blends.…”

“…7 The polymer poly(4-vinylpyridine) (P4VP) exhibited different thermal and conducting properties as a [P4VP]/copper iodide binary mixture; the electrical conductivity changes drastically with the increase in the amount of copper iodide in the blends. 8 Specifically, the couple P4VP/copper has been focused elsewhere 1,3,6,10-15 due its great potential for applications such as in reactive blending, 6 catalyst for determination and oxidation of ascorbic acid 9 and the technically important oxidative polymerization of 2,6-dimethylphenol 1 in addition to the selective conversion of 2,3,6-trimethylphenol and related compounds to p-benzoquinones, 10 cation exchange resins designed to remove or preconcentrate metals from dilute solutions by binding them to soluble polymers, 11 solid-state electrochemical cells, 12 anti-corrosion methods 13 and circuit manufacturing on microscopic smoothly polymeric surfaces or production of polymeric films on metallic surfaces. 14 Consequently, the importance in obtaining P4VP/copper films onto copper surfaces for technological development is clear.…”