The formation and characterization of the two binuclear copper(II) carboxylates Cu2(L)4·2CH3OH (1) and Cu(L)2·H2O·2pyridine (2) (L: methacrylate) are described which contain polymerizable groups. The dimeric Cu2(L)4·2CH3OH was prepared through reaction of methacrylic acid (LH) with basic copper carbonate in methanol solution. When 1 was dissolved in acetone and pyridine was added in excess to the solution, the binuclear complex turned into the mononuclear complex 2. 1 and 2 were characterized by UV−vis, IR, and elemental analysis, and the molecular structures were established by single-crystal X-ray diffraction studies. Both complexes were used in copolymerization with methyl methacrylate (MMA). Polymers containing the copper(II) carboxylates were prepared through radical copolymerization of 1 and 2 with MMA using azobis(isobutyronitrile) (AIBN) and benzoyl peroxide (BPO) as initiator. The obtained hybrid polymers were analyzed applying FT-IR, TGA, and size exclusion chromatography. All methods revealed an incorporation of both comonomers in the polymer backbone. Differences in the polymerization kinetics of the compounds can be explained by interactions of the primary initiating radicals with the copper complexes.
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