Design and development of isocyanatoacrylates as dental adhesives

During the last 12 years, significant progress has been made in the development of dental adhesive systems. Some of the more promising systems are based on multifunctional structures that contain polymerizable vinyl double bonds and reactive isocyanate groups. The utility of compounds with such structures as adhesives arises in part because their isocyanate functionality is available for reaction independently, without compromising the reactivity of the vinyl groups. The hypotheses tested in this investigation were: (1) that the monomer reactivity ratios (r(1), r(2)) for the free-radical-initiated copolymerization of ethyl alpha-isocyanatoacrylate (alpha-EIA) and 2-isocyanatoethyl methacrylate (IEM) with selected vinyl monomers can be determined; (2) that these reactivity ratios can be used to establish Q (reactivity) and e (polarity) values for alpha-EIA and IEM; and (3) that these reactivity parameters can be useful in designing copolymers with controlled compositions for dental adhesive applications. The free-radical copolymerization characteristics of alpha-EIA and IEM were studied. The isocyanate monomers were copolymerized at seven comonomer ratios with n-butyl acrylate (NEA), methyl methacrylate (MMA), and styrene (STY). Reactivity ratios, r(1) and r(2), were calculated for each of the copolymer systems, giving: IEM (r(1)) = 0.38 and STY (r(2)) = 0.44; IEM (r(1)) = 1.19 and MMA (r(2)) = 0.84; IEM (r(1)) = 2.50 and NBA (r(2)) = 0.40; alpha-EIA (r(1)) = 2.20 and STY (r(2)) = 0.06; alpha-EIA (r(1)) = 7.00 and MMA (r(2)) = 0.10; and alpha-EIA (r(1)) = 23.50 and NBA (r(2)) = 0.04. The Q (reactivity) and e (polarity) values for IEM and alpha-EIA were calculated from r(1) and r(2) with use of the Alfrey-Price equations, giving, for IEM, Q = 0.89 and e = 0.60, and, for alpha-EIA, Q = 7.64 and e = 0.74. These reactivity parameters are useful for tailoring copolymers with controlled compositions and properties. Based on these calculated reactivity parameters, several copolymers of IEM [for example, IEM/2-hydroxyethyl methacrylate (HEMA)] are currently being prepared and evaluated as adhesives.