Copolymers of 4-Adamantylphenyl Methacrylate Derivatives with Methyl Methacrylate and Styrene

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Polymers and High Performance Materials


Three 4-(I-adamantyl)phenyl methacrylate monomers were synthesized from 4-(l-adamantyl)phenol derivatives which were obtained by Friedel-Crafts alkylation of phenol, 2-methylphenol and 2,6-dimethylphenol with 1-bromoadamantane. Characterization of the monomers by IR, H-1 and C-13 NMR, GC and elemental analysis confirmed structures and purities. Copolymers of these new monomers with styrene were synthesized using free radical techniques. One series of 4-(1-adamantyl)phenyl methacrylate was also prepared with methyl methacrylate (MMA). Copolymer compositions were evaluated by H-1 and C-13 solution NMR, and with FTIR. Reactivity ratios were estimated to have values of r(1) = 0.22 and r(2) = 1.51 for styrene and 4-(1-adamantyl)phenyl methacrylate copolymers; r(1) = 0.31 and r(2) = 2.44 for styrene and 2-methyl-4-(1-adamantyl)phenyl methacrylate; and r(1) = 0.97 and r(2) = 0 for styrene and 4-(1-adamantyl)-2,6-dimethylphenyl methacrylate copolymers (J Polym Sci A 3 (1965) 369-87, J Macromol Sci Rev C4 (1970) 281). All homo- and copolymers were characterized using DSC and TGA to determine copolymer composition effects on T-g and thermal stability. The estimated T-g for the homopolymer of 4-(l-adamantyl)phenyl methacrylate was 253 degreesC and the onset of decomposition was 250 degreesC in nitrogen. The homopolymer of 2-methyl-4-(1-adamantyl)phenyl methacrylate had a T-g of 250 degreesC which was at the onset of decomposition in nitrogen. The homopolymer of 4-(1-adamantyl)-2,6-dimethylphenyl methacrylate could not be obtained by free-radical polymerization. 4-(Adamantyl)phenyl methacrylate was incorporated into styrene copolymers at 1-30 mol% and gave T-g increases of cs. 5-60 degreesC over that of polystyrene, respectively. Incorporation of this monomer into MMA copolymers (0.75-35 mol%) resulted in T-g increases of ca. 6-70 degreesC over that of poly(methyl methacylate). (C) 2001 Elsevier Science Ltd. All rights reserved.

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