Epoxy-amine cross-linking reaction

FIGURE 13.9 Epoxy-amine cross-linking reaction. Many other cross-linking reactions are used to achieve different properties, though most require high temperatures for curing. 

Fig. 3. Chemistry of Secondary and Primary Amine Cross-linking Reactions with Epoxies...

The cross-linking reactions of tetrafunctional epoxy resins with aromatic primary diamines were investigated by spectoscopy [141]. UV-Visible and fluorescence spectroscopies of the materials, after gelation, show signiflcant amounts of amines in the finished products. The infrared spectra also show that ether formation becomes significant only late in the cure. In addition, during the cure, especially in air, some oxidations and degradations occur [141]. This results in color formation. 

Discuss the chemistry of epoxy resins based on diglycidyl ethers of Bisphenol A, their preparations, and cross-linking reactions with amines, dianhydrides, and dicyanodiamide. 

Other possible reactions, such as homopolymerization (epoxide+epoxide) and epox-ide+hydroxyl group (in the latter stages of cure), can be neglected when the ratio of epoxide to amine is stoichiometric and in the absence of catalyst or accelerator [194], For TGDDM/DDS resins, the homopolymerization reaction may be neglected at cure temperature below 180°C [84], At temperatures between 177°C and 300°C, dehydration and/or network oxidation occur, which results in formation of ether cross-linkings with loss of water. Decomposition of the epoxy-OH cure reaction can also take place, which results in propenal... 

Photocationic initiators. Epoxy resins can be cross-linked by compounds containing active hydrogen, e.g., carboxylic acids, anhydrides, amines, phenols etc., or by the ionic polymerization process. Lewis acids such as BF3 and usually a crystalline complex of BF3 with amines, e.g., BF3 NH2C2H5, can be used for curing reaction at 80-100° C [124]. 

For the nonlinear step growth case above, eiTg, the crosslink density must be related to p. A relevant model, based on calculating the probabilities of finite chains being formed, has been published For the reaction of A -1- 2B2 (e.g., tetra-functional amine -b difunctional epoxy), A4 is considered to be an effective cross-linking site if three or more of its arms lead out to the infinite network. The probability of finding an effective crosslink is related to one minus the probability of a randomly chosen A leading to the start of a finite chain, which in turn is related to the extent of reaction. Application of this procedure to the system of Fig. 15 has been presented in detail The more complicated reaction of a tetrafunctional amine with a trifunctional epoxy was also considered. ... 

There are two options for the other component of an epoxy resin system. Use of mono- or di-anhydrides as curing agents, usually catalyzed by a tertiary amine, causes reactions with the residual secondary hydroxyls in the repeating unit of the prepolymer forming esters and free carboxylic acids. The carboxylic acids formed also react with the epoxide end groups forming cross-links and further free secondary hydroxyl groups. Maleic anhydride, phthalic anhydride, or pyromellitic dianhydride are suitable for this process (Eq. 21.27). 

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