Ureido cytosine and cytosine-containing acrylic copolymers

Keren Zhang, Mingtao Chen, Kevin J. Drummey, Samantha J. Talley, Lindsey J. Anderson, Robert B. Moore, Timothy Edward Long

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Regioselective Michael addition afforded a novel N1-substituted cytosine acrylate monomer for the synthesis of acrylic random copolymers with cytosine pendant groups. Quantitative post-functionalization converted cytosine to ureido-cytosine (UCy) with an increased self-association strength due to quadruple hydrogen bond formation. Thermogravimetric analysis (TGA) revealed a lower onset temperature of weight loss (∼200 °C) for UCy-containing copolymers, however, they proved to be more thermally stable at ≤130 °C than the cytosine-containing precursors during isothermal rheological experiments. The incorporation of UCy into random copolymers resulted in higher Tgs, enhanced mechanical performance, and better microphase-separation than the cytosine-containing precursors. Both dynamic mechanical analysis and rheological analysis revealed a plateau regime for each UCy-containing copolymer as well as a tan delta transition that corresponded to hydrogen bond dissociation. In contrast, the viscoelastic behavior of cytosine-containing random copolymers resembled entangled, non-associating polymers with increasing Tg as the cytosine content increased. A solution-cast UCy-containing copolymer film exhibited a more well-defined surface morphology with nano-fibrillar hard domains compared to the cytosine control. Variable temperature FTIR spectroscopy verified the presence of hydrogen bonding, and thermogravimetric sorption analysis (TGA-SA) compared the water uptake of UCy and cytosine-containing copolymers. UCy-containing random copolymers showed various advantages for applications as adhesives and thermoplastic elastomers compared to the cytosine copolymers, including superior cohesive strength, higher thermal stability, wider service temperature window, and lower moisture uptake. Free radical copolymerization of a quadruple hydrogen bond containing acrylic monomers provides a versatile avenue to supramolecular polymers with a tunable composition and improved scalability compared to earlier telechelic oligomers. This report describes the first synthesis of an acrylic monomer family and complementary evidence for tunable association in random copolymers.

Original languageEnglish
Pages (from-to)6671-6681
Number of pages11
JournalPolymer Chemistry
Volume7
Issue number43
DOIs
Publication statusPublished - 2016 Nov 21
Externally publishedYes

Fingerprint

Cytosine
Acrylics
Copolymers
Hydrogen bonds
Acrylic monomers
Hydrogen
Association reactions
Microphase separation
Thermoplastic elastomers
Temperature
Polymers
Dynamic mechanical analysis
Free radicals
Oligomers
Copolymerization
Surface morphology
Thermogravimetric analysis
Sorption
Scalability
Adhesives

ASJC Scopus subject areas

  • Bioengineering
  • Biochemistry
  • Polymers and Plastics
  • Organic Chemistry

Cite this

Zhang, K., Chen, M., Drummey, K. J., Talley, S. J., Anderson, L. J., Moore, R. B., & Long, T. E. (2016). Ureido cytosine and cytosine-containing acrylic copolymers. Polymer Chemistry, 7(43), 6671-6681. https://doi.org/10.1039/c6py01519k

Ureido cytosine and cytosine-containing acrylic copolymers. / Zhang, Keren; Chen, Mingtao; Drummey, Kevin J.; Talley, Samantha J.; Anderson, Lindsey J.; Moore, Robert B.; Long, Timothy Edward.

In: Polymer Chemistry, Vol. 7, No. 43, 21.11.2016, p. 6671-6681.

Research output: Contribution to journalArticle

Zhang, K, Chen, M, Drummey, KJ, Talley, SJ, Anderson, LJ, Moore, RB & Long, TE 2016, 'Ureido cytosine and cytosine-containing acrylic copolymers', Polymer Chemistry, vol. 7, no. 43, pp. 6671-6681. https://doi.org/10.1039/c6py01519k
Zhang K, Chen M, Drummey KJ, Talley SJ, Anderson LJ, Moore RB et al. Ureido cytosine and cytosine-containing acrylic copolymers. Polymer Chemistry. 2016 Nov 21;7(43):6671-6681. https://doi.org/10.1039/c6py01519k
Zhang, Keren ; Chen, Mingtao ; Drummey, Kevin J. ; Talley, Samantha J. ; Anderson, Lindsey J. ; Moore, Robert B. ; Long, Timothy Edward. / Ureido cytosine and cytosine-containing acrylic copolymers. In: Polymer Chemistry. 2016 ; Vol. 7, No. 43. pp. 6671-6681.
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