Thermal and real-time FTIR spectroscopic analysis of the photopolymerization of diepoxide-vinyl ether mixtures

Both epoxides and vinyl ethers can be polymerized cationically albeit through different intermediates. However, in the case of epoxide-vinyl ether mixtures the exact mechanism of cationically initiated polymerization is unclear. Thus, although vinyl ethers can be used as reactive diluents for epoxides it is uncertain how they would affect their reactivity. Cationic photocuring of diepoxides has many industrial applications. Better understanding of the photopolymerization of epoxy-vinyl ether mixtures can lead to new applications of cationically photocured systems. In this work, photo-DSC and real-time Fourier Transform Infrared Spectroscopy (RT-FTIR) were used to study cationic photopolymerization of diepoxides and vinyl ethers. In the case of mixtures of aromatic epoxides with tri(ethylene glycol) divinyl ether, TEGDVE, photo-DSC measurements revealed a greatly reduced reactivity in comparison to the homopolymerizations and suggested the lack of copolymerization between aromatic epoxides and TEGDVE. On the other hand, for mixtures of 3,4-epoxycyclohexylmethyl-3', 4'-epoxycyclohexane carboxylate, ECH, with TEGDVE the results indicated high reactivity of the blends. The polymerization mechanism might include copolymerization. To examine this mechanism, mixtures of the ECH with a tri(ethylene glycol) mono-vinyl ether, TEGMVE, were studied by both photo-DSC and RT-FTIR. Principal component analysis (PCA) proved to be an efficient tool in analyzing a large matrix of the spectral data from the polymerization system. PCA was able to provide insight into the reasons for the differences among replicated experiments with the same composition ratio and supported the hypothesis of copolymerization in the ECH/TEGMVE system. Thus, blends of cycloaliphatic epoxides and vinyl ethers seem to have a great potential for applications in high-productivity industrial photopolymerization processes.