Spiromonomers with enhanced reactivity and ring-opening proficiency of the formulae: ##STR1## wherein R.sub.1 represents a C.sub.1 -C.sub.6 alkenyl, R.sub.2 represents hydrogen or C.sub.1 -C.sub.6 alkenyl, R.sub.3 represents a C.sub.1 -C.sub.6 alkyl or C.sub.3 -C.sub.8 cycloaliphatic unsubstituted, or substituted with halo, C.sub.1 -C.sub.6 alkyl, alkoxy, hydroxy, or one of one or more hetero atoms; and R.sub.4 represents a C.sub.1 -C.sub.6 alkyl or C.sub.3 -C.sub.8 cycloaliphatic unsubstituted, or substituted with halo, C.sub.1 -C.sub.6 alkyl, alkoxy, hydroxy, or one of one or more hetero atoms; formula (II) ##STR2## wherein R.sub.5 is a C.sub.1 -C.sub.6 alkenyl; R.sub.6 represents hydrogen or C.sub.1 -C.sub.6 alkenyl; R.sub.7 is a C.sub.1 -C.sub.6 alkenyl or C.sub.3 -C.sub.8 cycloaliphatic unsubstituted, or substituted with halo, C.sub.1 -C.sub.6 alkyl, alkoxy, hydroxy, or one of one or more hetero atoms; or aryl; and R.sub.8 is hydrogen or C.sub.1 -C.sub.6 alkyl or a C.sub.3 -C.sub.8 cycloaliphatic unsubstituted, or substituted with halo, C.sub.1 -C.sub.6 alkyl, alkoxy, hydroxy, or one of one or more hetero atoms; or aryl; and formula (III) ##STR3## wherein R.sub.9 is a C.sub.1 -C.sub.6 alkenyl and R.sub.10 is hydrogen or C.sub.1 -C.sub.6 alkyl; are used in compositions which, in the absence of the spiromonomers, normally undergo shrinkage, so that the resulting polymerizates exhibit substantially zero shrinkage or even slight positive expansion.
Photopolymerizable compositions are provided which are the reaction products of a vinyl ether, a photoinitiator system comprising an iodonium salt, a visible light sensitizer, and an electron donor compound. These monomeric/oligomeric compositions may also include epoxides, polyols, spiroorthocarbonates. One embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, a spiroorthocarbonate, and a photoinitiator system. Another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, and a photoinitiator system. Still another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, a spiroorthocarbonate, and a photoinitiator system. Still further, another embodiment of the present invention is certain novel spiroorthocarbonate compounds. Each of these novel spiroorthocarbonate compounds include at least one epoxy group as a substituent.
Photopolymerizable compositions are provided which are the reaction products of a vinyl ether, a photoinitiator system comprising an iodonium salt, a visible light sensitizer, and an electron donor compound. These monomeric/oligomeric compositions may also include epoxides, polyols, spiroorthocarbonates. One embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, a spiroorthocarbonate, and a photoinitiator system. Another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, and a photoinitiator system. Still another embodiment of the present invention is a polymerizable composition comprised of a vinyl ether, an epoxide, a polyol, a spiroorthocarbonate, and a photoinitiator system. Still further, another embodiment of the present invention is certain novel spiroorthocarbonate compounds. Each of these novel spiroorthocarbonate compounds include at least one epoxy group as a substituent.
An adhesive composition that includes a mixture of a cationically polymerizable component, an acidic component, and an initiator is provided. Preferably, the initiator comprises an iodonium salt, a visible light sensitizer, and an electron donor compound, wherein the initiator has a photoinduced potential greater than or equal to that of N,N-dimethylaniline in a standard solution of 2.9.times.10.sup.-5 moles/g diphenyl iodonium hexafluoroantimonate and 1.5.times.10.sup.-5 moles/g camphorquinone in 2-butanone. This adhesive composition is cationically polymerizable and is able to bond to hard tissue and cationic restorative materials upon curing.
