Evaluation of the Spacer Effect on Adamantane-Containing Vinyl Polymer T_g's

Abstract

Two new adamantane-containing methacrylates having methylene and phenyl spacers between the adamantane and the methacrylate were synthesized: 1-adamantylmethyl methacrylate (AdMMA, 1) and 4-(1-adamantyl)phenyl methacrylate (AdPMA, 2). The homopolymer of 1 had a T g of 201 °C while 2 showed a Tg of 253 °C. Copolymers of both monomers with styrene (St) showed significant Tg increases over PSt. The incremental increase obtained with AdPMA per adamantane unit is the highest of all vinyl monomers reported to date, to the best of our knowledge, with a value of 2.2 °C/mol %. Both sets of copolymers showed higher incorporation of adamantane monomers in the copolymer than the feed, with reactivity ratios calculated to be r1(St) ) 0.22 and r2(AdPMA) ) 1.52 and r1(St) ) 0.94 and r2(AdMMA) ) 1.54.

Precise synthesis of poly(1-adamantyl methacrylate) by atom transfer radical polymerization

“…Various poly(meth)acrylates bearing bulky ester groups, such as bornyl, 1 isobornyl, 1-3 adamantyl [4][5][6][7] and its derivatives, [4][5][6][8][9][10][11] have been synthesized to improve the thermal properties, such as the glass transition temperature and the thermal degradation temperature, of poly(methyl methacrylate) (PMMA). For example, the incorporation of adamantyl groups into polymer structures generally produces not only a high thermal stability but also an improvement in other physical and chemical properties, such as transparency to ultraviolet light, low dielectric constant, hydrophobicity, high oxidation resistance, low surface energy and high density.…”

Anionic Polymerizations of 1‐Adamantyl Methacrylate and 3‐Methacryloyloxy‐1,1′‐biadamantane

“…[2] Among the above-mentioned substituents, adamantyl groups have been found to improve the thermal and physical properties of the polymers. [6,7] It is well known that the parent adamantane is a very unique molecule with a highly symmetrical tricyclic structure and various unusual physical and chemical properties such as high density, ease of Full Paper: Anionic polymerizations of 1-adamantyl methacrylate (1) and 3-methacryloyloxy-1,1 0 -biadamantane (2) were carried out in THF at À50 to À78 8C for 24 h. The initiator employed was either [1,1-bis(4 0 -trimethylsilylphenyl)-3-methylpentyl]lithium (3)/lithium chloride, or diphenylmethylpotassium. The polymerizations of 1 and 2 proceeded quantitatively to afford the polymers having the predicted molecular weights based on the molar ratios of monomers and initiators and the narrow molecular weight distributions (M w /M n ¼ 1.05-1.18), indicating the living character of the polymerization systems of 1 and 2.…”

Functional group transformation of perfluoroadamantane derivatives

“…Thus, several polymers containing adamantane skeletons have been synthesized, and some of them have showed good thermal stability and transparency [2][3][4][5][6][7][8]. Moreover, such the polymers are recently expected to use as highly functional materials for state-of-the-art industry.…”