Copolymers of 4-adamantylphenyl methacrylate derivatives with methyl methacrylate and styrene

Lon J. Mathias, Jennifer Jensen, Kevin Thigpen, John McGowen, Demetrius McCormick, Louis Somlai

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Abstract

Three 4-(1-adamantyl)phenyl methacrylate monomers were synthesized from 4-(1-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, 1H and 13C 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 1H and 13C solution NMR, and with FTIR. Reactivity ratios were estimated to have values of r1 = 0.22 and r2 = 1.51 for styrene and 4-(1-adamantyl)phenyl methacrylate copolymers; r1 = 0.31 and r2 = 2.44 for styrene and 2-methyl-4-(1-adamantyl)phenyl methacrylate; and r1 = 0.97 and r2 = 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 Tg and thermal stability. The estimated Tg for the homopolymer of 4-(1-adamantyl) phenyl methacrylate was 253°C and the onset of decomposition was 250°C in nitrogen. The homopolymer of 2-methyl-4-(1-adamantyl) phenyl methacrylate had a Tg of 250°C 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 Tg increases of ca. 5-60°C over that of polystyrene, respectively. Incorporation of this monomer into MMA copolymers (0.75-35 mol%) resulted in Tg increases of ca. 6-70°C over that of poly(methyl methacylate).

Original languageEnglish (US)
Pages (from-to)6527-6537
Number of pages11
JournalPolymer
Volume42
Issue number15
DOIs
StatePublished - Jul 2001

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Keywords

  • 4-Adamantylphenyl methacrylate derivatives
  • Copolymers
  • Friedel-Crafts alkylation

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Materials Chemistry

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