Novel diol Spiro orthocarbonates derived from glycerol as anti-shrinkage additives for the cationic photopolymerization of epoxy monomers

Shrinkage that takes place during polymerizations induces internal stress in polymeric materials generating a series of problems like poor adhesion to substrates and delamination in coatings or microcracks and microvoids in composites. Some additives like Spiro orthocarbonates can reduce or eliminate this shrinkage. This paper deals with the synthesis of novel diol spiro orthocarbonates (DIOL SOCs) and their effect as anti-shrinkage additives in the photopolymerization of the monomer 3,4-epoxycyclohexyl-3', 4'-epoxycyclohexanecarboxylate. It was found that increasing the concentration of the DIOL SOCs resulted in higher conversion of the monomer due to the presence of hydroxyl groups. The viscoelastic properties of the polymer products were also measured. It was observed that at 5 mol% of the mixture of DIOL SOCs there was an increase in the storage modulus due to the crosslinking produced by the bifunctional SOCs. However, at higher concentrations, a decrease in the storage modulus was observed. The level of shrinkage using the DIOL SOCs at 20 mol% was reduced by 45% when compared to the case without any additive. DIOL SOCs can be easily prepared by reacting glycerol with tetraethylorthocarbonate. These additives reduced significantly the level of shrinkage of the polyether derived from the diepoxycyclohexane monomer. (C) 2010 Society of Chemical Industry