Synthesis and Characterization of Novel Complementary Multiple-Hydrogen Bonded (CMHB) Macromolecules via a Michael Addition

• Published in: Macromolecules Vol. 35; no. 23; pp. 8745 - 8750
• Main Authors: Yamauchi, Koji, Lizotte, Jeremy R, Long, Timothy E
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 05-11-2002
• Subjects: Applied sciences; Chemical modifications; Chemical reactions and properties; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Michael addition; End group; Association dissociation; Nitrogen heterocycle; Temperature effect; Experimental study; Oligomer; Monodispersed polymer; Chemical modification; Nucleic base; Preparation; Styrene polymer; Hydrogen bond
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma020961t

The synthesis and characterization of novel complementary multiple hydrogen-bonded poly(styrene) (CMHB-PS) oligomers possessing controlled molecular weights and narrow molecular distributions are described. Novel CMHB-PS oligomers comprising terminal heterocyclic base units were synthesized in a controlled fashion via derivatization of well-defined hydroxyl-terminated PS. The heterocyclic-terminated oligomers were synthesized via a Michael addition of the corresponding heterocyclic compounds such as adenine, thymine, and 2,6-purine with acrylated PS. The acrylated PS precursors were prepared in a quantitative fashion via reaction of hydroxyl-terminated PS with acryloyl chloride in the presence of triethylamine. Terminal heterocyclic bases were introduced via a Michael addition in the presence of potassium tert-butoxide (t-BuOK). Novel CMHB-PS aggregates were prepared via subsequent solution blending of PS with complementary heterocyclic base units. 1H NMR analysis confirmed that a 1:1 mixture of adenine-PS or purine-PS with thymine-PS formed complementary multiple hydrogen bonding and exhibited thermoreversibility. In addition, 1H NMR analysis confirmed that complementary hydrogen bonds dissociated at 95 °C in deuterated toluene.