The transamidation reaction converts the carbonate and amine into Naliphatic aromatic carbamate and urea, causing the equivalent of oxirane and amine nonstoichiometric in the primary cure stage. After postcure, the substitution reaction takes place and results in a more tightly crosslinked structure
The epoxy–polycarbonate blends cured with aliphatic amine—I. Mechanism and kinetics
✍ Scribed by Miaw-Ling Lin; Kuo-Hui Chang; Feng-Chih Chang; Ming-Shiu Li; Chen-Chi M. Ma
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 242 KB
- Volume
- 35
- Category
- Article
- ISSN
- 0887-6266
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✦ Synopsis
Reaction mechanism of the PC-epoxy blends cured by aliphatic amine has been investigated by varying PC contents in the blends. The transamidation reaction tends to convert nearly all the carbonates into N-aliphatic aromatic carbamates even at ambient temperature before normal curing. The remaining amine proceeds the normal curing with epoxy at a higher temperature (80ЊC). For the PC-epoxy/aliphatic amine blend containing 6 wt % PC, the yielded N-aliphatic aromatic carbamate further reacts with amine to produce the urea structure. The urea undergoes substitution reaction with the hydroxyl formed from the normal curing to give the N-aliphatic aliphatic carbamate. For the blend containing 12 wt % PC, the N-aliphatic aromatic carbamate converts into the N-aliphatic aliphatic carbamate via two different routes. For the blend containing lower molecular weight of the aliphatic amine, the N-aliphatic aromatic carbamate reacts with hydroxyl to form the N-aliphatic aliphatic carbamate directly. For the blend containing higher molecular weight of aliphatic amine, the N-aliphatic aromatic carbamate decomposes into the aliphatic isocyanate accelerated by the presence of the residual oxirane. The isocyanate formed then reacts with hydroxyl to yield the N-aliphatic aliphatic carbamate. The activation energy ( E a ) and preexponential factor (A) of the PC-epoxy/POPDA blends decrease with the increase of the PC content. Kinetic study by thermal analysis by the method of autocatalyzed model is able to correctly predict oxirane conversion vs. time relationship for the neat epoxy/aliphatic amine and the PC-epoxy/aromatic amine systems because the dominant reaction is the normal curing reaction between amine and oxirane. The model fails to predict the PC-epoxy/aliphatic amine system because the system is complicated by several other reactions besides the normal curing reaction.
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