Condensation of DAMN with Conjugated Aldehydes and Polymerizations of the Corresponding Imines

• Published in: Macromolecules Vol. 38; no. 9; pp. 3615 - 3621
• Main Authors: Johnson, David M, Reybuck, Sarah E, Lawton, Richard G, Rasmussen, Paul G
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 03.05.2005
• Subjects: Applied sciences; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Polymerization; Preparation, kinetics, thermodynamics, mechanism and catalysts; Radiochemical polymerization; Branched polymer; Molecular structure; Schiff base polymer; Experimental study; Oligomer; Functional polymer; Solution polymerization; Thermal stability; Schiff base; Gamma radiation; Amine polymer; Thermal polymerization; Aminonitrile; Monomer; Chemical reactivity; Chemical synthesis; Dinitrile
• ISSN: 0024-9297; 1520-5835
• DOI: 10.1021/ma047918l

The reaction of diaminomaleonitrile (DAMN) with aldehydes such as acrolein, methacrolein, and crotonaldehyde in the presence of acid catalyst at low temperature yielded exclusively monoimine derivatives of DAMN. These compounds have very low loss of volatiles up to 1000 °C and form high char yields. The residual mass at 800 °C for the acrolein derivative was found to equal 70% of the starting material. Thermally induced step growth 1,4-conjugate addition polymerization on these compounds yields moderate molecular weight oligomeric materials (M n = 1376, M w = 2050). N-EthylDAMN was synthesized by reaction of DAMN with acetaldehyde followed by reduction with NaBH4. N-EthylDAMN reacted with acrolein, methacrolein, and crotonaldehyde to form N-ethyl-monoimine derivatives of DAMN. These analogues also undergo 1,4-conjugate addition polymerization to yield linear polymers. The dimethylamino derivative was found to undergo polymerization by a different mechanism, strengthening the proposed 1,4-conjugate addition mechanism.