Effect of solvent proton affinity on the kinetics of michael addition polymerization of n, n′‐bismaleimide‐4, 4′‐diphenylmethane with barbituric acid. Issue 3 (10th May 2013)

• Record Type: Journal Article
• Authors: Yu, Fu‐En; Hsu, Jung‐Mu; Pan, Jing‐Pin; Wang, Tsung‐Hsiung; Chiang, Yu‐Ching; Lin, Winnie; Jiang, Jyh‐Chiang; Chern, Chorng‐Shyan
• Is Part Of: Polymer engineering & science. Volume 54:Issue 3(2014:Mar.)
• Page Start: 559
• Page End: 568
• Publication Date: 2013-05-10
• Subjects: Polymer engineering -- Periodicals; Polymers -- Periodicals; 668.9
• DOI: 10.1002/pen.23587
• Languages: English
• ISSNs: 0032-3888

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The effect of solvent proton affinity on the kinetics of the Michael addition polymerizations of <italic>N</italic>, <italic>N</italic>′‐bismaleimide‐4, 4′‐diphenylmethane (BMI) and barbituric acid (BTA) in different solvents [<italic>N</italic>‐methyl‐2‐pyrrolidone (NMP), <italic>N</italic>, <italic>N</italic>′‐dimethylacetamide (DMAC), and <italic>N</italic>, <italic>N</italic>′‐dimethylformamide (DMF)] were investigated. This was achieved by the complete suppression of the competitive free radical polymerization via the addition of a sufficient amount of hydroquinone (HQ). A mechanistic model was developed to adequately predict the polymerization kinetics before a critical conversion, at which point the diffusion‐controlled polymerization become the predominant factor during the latter stage of polymerization, was achieved. The activation energy (<italic>E</italic><sub>a</sub>) of the Michael addition polymerization of BMI with BTA in the presence of HQ in increasing order was: NMP < DMAC < DMF, which was correlated quite well with the solvent proton affinity (NMP > DMAC > DMF). By contrast, the frequency factor (<italic>A</italic>) in increasing order is: NMP < DMAC < DMF. As a result of the compensation effect between <italic>E</italic><sub>a</sub> and <italic>A</italic>, at constant temperature, the Michael addition rate constant decreased with increasing solvent proton affinity. POLYM. ENG. SCI., 54:559–568, 2014. © 2013 Society of Plastics Engineers</p> </abstract>