Abstract: | Copolymers of 2-hydroxyethyl acrylate and 2-methoxyethyl acrylate with variable compositions were synthesized, fractionated, and characterized by 1H-NMR, IR, GPC, and viscometry. These copolymers were further modified via polymer analog esterification of copolymer hydroxy groups by a series of disulfide-containing carboxylic acids including lipoic acid and (n-pentyldithio) alkyl carboxylic acids (n-C5H11SS(CH2)m? COOH, m = 10, 15, 22) in the presence of 1,3-dicyclohexylcarbodiimide (DCC). Esterification reactions were quantitative for copolymers possessing hydroxy monomer contents ≤ 40% when excess acid and DCC were present for sufficiently long reaction times (2–4 days) at room temperature. Copolymer DSC analysis demonstrates a systematic variation of Tg with copolymer composition in good agreement with ideal mixing theory. These disulfide-bearing copolymers spontaneously yield two-dimensional ultrathin polymer films with side chain-dependent layer thicknesses of 20–45 Å by solution adsorption onto freshly deposited gold surfaces. Such ultrathin polymer films are expected to have diverse applications as bound polymeric surface modification reagents. © 1993 John Wiley & Sons, Inc. |