Properties of silorane-based dental resins and composites containing a stress-reducing monomer.

OBJECTIVE: To evaluate properties of silorane-based resins and composites containing a stress reducing monomer. METHODS: Resin mixtures and composites were formulated containing (a) a developmental stress reducing monomer [TOSU; Midwest Research Institute]; (b) Sil-Mix (3M-ESPE); (c) photo cationic initiator system. Standard BISGMA/TEGDMA resin (B/T) and composite (Filtek Z250) were used as controls. Polymerization volume change was measured using a NIST mercury dilatometer and polymerization stress using an Enduratec mechanical testing machine. Three point bend tests determined flexural elastic modulus, work of fracture, and ultimate strength (ADA 27; ISO 4049). Fracture toughness was measured using ASTM E399-90. Four groups of resins and composites were tested: Sil-Mix, methacrylate standard, and Sil-Mix with two addition levels of TOSU. An ANOVA was used and significant differences ranked using Student-Newman-Keuls test (alpha=0.05). RESULTS: Polymerization stress values for resins containing TOSU were significantly less than the other materials. Polymerization shrinkage values for Sil-Mix formulations were significantly less than for B/T, but were not different from each other. TOSU-containing formulations generally had somewhat lower mechanical properties values than Sil-Mix or B/T. Polymerization stress values for Sil-Mix-based composites were significantly less as compared to Z250. The 1wt.% TOSU composite had the lowest stress. No difference between composite groups was noted for fracture toughness or work of fracture. For ultimate strength, the 5wt.% TOSU formulation differed significantly from Z250. All Sil-Mix formulations had elastic modulus values significantly different from Z250. SIGNIFICANCE: The ability of TOSU to reduce polymerization stress without a proportional reduction in mechanical properties provides a basis for improvement of silorane-based composites.

Stability of silorane dental monomers in aqueous systems.

UNLABELLED: Siloranes (silicon-based monomers with oxirane functionality) are investigated as matrix resins for new low shrinkage/stress dental composites. Compounds containing oxirane groups are known to be reactive with water, which could impart instability to the composite. OBJECTIVE: To test the stability of siloranes by measuring changes in the chemical structure of the oxirane group in aqueous environments. METHODS: Two siloranes (PH-SIL and TET-SIL) and their 1:1 mixture (SIL-MIX) were evaluated (n=2-3). Siloranes were mixed in aqueous solutions with and without 1% tetrahydrofuran (THF) containing either liver esterase or epoxide hydrolase at pH 7.4, or dilute HCl at pH 1.4. The stability of conventional dioxiranes 3,4-epoxycyclohexyl-methyl-3,4-epoxycyclohexane carboxylate (ECHM-ECHC), and bisphenol A diglycidyl ether (BADGE) were also monitored under similar conditions. NMR was used to estimate the extent of reaction and give structural information about reaction products. RESULTS: Siloranes were found to be stable for 24h in all aqueous environments tested. In contrast, ECHM-ECHC reacted at pH 1.4 to form species containing oxirane, ester, hydroxyl and carboxylic acid groups. Water hydrolyzed the ester group of ECHM-ECHC in the presence of liver esterase. In the presence of epoxide hydrolase, BADGE oxirane groups were hydrolyzed to diols, hydrolysis ranged from 0 to 34% depending on the aqueous environment. CONCLUSION: The stability and insolubility of siloranes in biological fluid simulants suggests that these may be more suitable for use in the oral environment than conventional oxirane-functional monomers.

Photopolymerization of developmental monomers for dental cationically initiated matrix resins.

OBJECTIVES: The objectives were to investigate the structure and selected physical properties of products resulting from the photopolymerization of a binary mixture containing an aliphatic dioxirane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (ECHM-ECHC) and a potential expanding monomer, 3,9-bis(oxiranylcyclohexylmethyl)-1,5,7,11-tetraoxaspiro[5.5]undecane (BOCHM-TOSU). METHODS: Reaction mixtures were irradiated with a dental curing lamp at room temperature. Some reactions were quenched prior to gel point. Oligomeric products were separated from unreacted monomers by column chromatography, and analyzed by NMR. Physical properties of polymeric solids were measured using accepted standard methods. Protonation energies for monomers were calculated using semi-empirical quantum mechanical methods. RESULTS: Types of oligomers found included poly(ether)s and poly(carbonate)s. Quantum mechanical calculations indicated preferential attack at the more nucleophilic oxaspirocyclic ring sites. For cured solid polymer samples, the elastic modulus was 2.39 +/- 0.24 GPa and the fracture toughness was 0.73 +/- 0.10 MPa m(1/2). These values were similar to those measured for a cured conventional BISGMA/TEGDMA matrix resin. SIGNIFICANCE: The room-temperature photopolymerization of an aliphatic dioxirane and a potential expanding monomer demonstrates the possibility of making cross-linked copolymer resins with improved polymerization shrinkage characteristics for use in dental composites.