Photocuring 3D printing of materials exhibiting high fracture toughness and excellent mechanical properties (flexural strength/modulus) is challenging. Nowadays, most of the photocurable 3D printing resins are based on a mixture of multifunctional (meth)acrylates and provide therefore brittle materials. This article describes further developments of a toughening strategy based on the incorporation of block copolymers in low crosslink density methacrylate-based materials. Six dimethacrylates bearing a bisphenol A core and urethane groups are successfully synthesized. Various spacers between the bisphenol A core and the methacrylate groups are selected. Each monomer is combined with (octahydro-4,7-methano-1H-indenyl)methyl acrylate as a monofunctional monomer and a poly(epsilon-caprolactone)-polydimethylsiloxane-poly(epsilon-caprolactone) triblock copolymer is added as toughener. It is shown that the addition of the triblock copolymer results for all mixtures in a strong increase of the fracture toughness. Moreover, the higher the amount of monofunctional monomer, the stronger the increase. The nature of the urethane dimethacrylate is found to have a significant influence on the fracture toughness, flexural strength, and flexural modulus of cured materials. Two of the synthesized dimethacrylates are identified as promising candidates for the development of fracture-tough photocuring 3D printing materials. Innovative photocurable resins based on novel urethane macromonomers, a monofunctional acrylate, and a triblock copolymer, are evaluated for the preparation of fracture tough denture base materials. This article highlights the high efficiency of triblock copolymers as toughening agents in low crosslink density dimethacrylate networks. image

3D printing of fracture tough dental materials that additionally exhibit excellent mechanical properties is challenging. Nowadays, most of the 3D printing dental materials contain a mixture of highly reactive dimethacrylates. The corresponding printed materials exhibit a high crosslink density and are particularly brittle. They are therefore not suitable for additive manufacturing of fracture tough denture bases. Recently, an efficient technology based on the combination of a urethane dimethacrylate macromonomer with a monofunctional monomer and a poly(epsilon-caprolactone)-polydimethylsiloxane-poly(epsilon-caprolactone) triblock copolymer was developed. Materials exhibiting a low crosslink density, excellent mechanical properties, and high fracture toughness were obtained. In this article, further developments of this highly efficient technology are described. A wide range of monofunctional monomers (both methacrylates and acrylates) was evaluated in this system. It was shown that the structure of the selected monofunctional monomer has a strong influence on the mechanical properties (flexural strength and modulus) as well as on the fracture toughness of the light cured materials. Thanks to the formation of nanostructures, a strong increase of fracture toughness was obtained upon addition of the toughening agent (poly(epsilon-caprolactone)-polydimethylsiloxane-poly(epsilon-caprolactone) triblock copolymer). The most promising materials were the ones based on the following monofunctional monomers: 2-phenoxyethyl methacrylate, (octahydro-4,7-methano-1H-indenyl)methyl acrylate, isobornyl acrylate, tetrahydrofurfuryl methacrylate and 4-tert-butylcyclohexyl acrylate. Indeed, these materials exhibited excellent mechanical properties (90.0 +/- 3.8 MPa < flexural strength < 102.6 +/- 4.7 MPa; 2402 +/- 90 MPa < flexural modulus < 2714 +/- 68 MPa) combined with high fracture toughness (1.89 +/- 0.06 MPa m(1/2) <= maximum stress intensity factor (K-max) <= 2.18 +/- 0.08 MPa m(1/2); 418 +/- 14 J m(-2) <= work of fracture (W-f) <= 591 +/- 25 J m(-2)). The measured K-max and W-f were even significantly higher than the values reported for Probase Hot (K-max = 1.44 +/- 0.18 MPa m(1/2); W-f = 270 +/- 30 J m(-2)), a clinically proven and well-established PMMA based denture base material from Ivoclar. The successful DLP 3D printing of a monoblock denture using the most promising formulation confirmed the great potential of this technology for the development of 3D printing fracture tough denture bases.

One of the major drawbacks for restorative dentistry is the polymerization shrinkage and the consequential shrinkage stress in methacrylate-based dental composites. An efficient way to reduce shrinkage stress is the incorporation of addition fragmentation chain transfer agents (AFCT agents). In this contribution, five novel polymerizable allyl sulfones were synthesized in four to five steps. A photo-DSC study was carried out in order to evaluate the influence of the addition of each AFCT agent on the polymerization rate of a dimethacrylate-based monomer mixture. The glass transition temperature (Tg) of the resulting networks was measured using DMTA. Dental composites based on these new chain transfer agents (CTAs) were prepared. A combination of camphorquinone, ethyl 4-(dimethylamino)benzoate and bis-(4-t-butylphenyl)-iodonium hexafluorophosphate was selected as photoinitiator system. Low shrinkage force values, suitable ambient light working time and excellent mechanical properties were obtained for all CTA based materials. Composites based on three of the synthesized CTAs even exhibited higher flexural modulus than the corresponding CTA-free material. Furthermore, a significant reduction of unreacted CTA leaching was found if a polymerizable moiety was introduced in the CTA structure. Hence, the incorporation of polymerizable allyl sulfones in dental composites is a promising strategy to obtain low shrinkage materials exhibiting improved biocompatibility.

OBJECTIVE:To evaluate the potential of ethyl-2-(tosylmethyl)acrylate (ASEE) as chain transfer agent for the development of low-shrinkage photopolymerizable dental composites. METHODS:Composites containing 10, 20 and 30 mol% of ASEE in their organic matrix were formulated. Camphorquinone (CQ)/ethyl 4-(dimethylamino)benzoate (EDAB) (0.33 wt%/0.60 wt%), CQ/EDAB/Ivocerin® (0.33 wt%/0.60 wt%/0.10, 0.25 or 0.50 wt%), CQ/EDAB/SpeedCure 938 (SC-938) (0.33 wt%/0.60 wt%/0.30, 0.50 or 1.00 wt%) and Ivocerin® (0.50 wt%) were used as photoinitiator systems. The glass transition temperature (Tg) and the crosslink density were determined by DMTA measurements. The flexural strength/modulus and ambient light working time were assessed according to ISO 4049. The shrinkage force was evaluated using a universal testing machine. The double bond conversion (DBC) was determined by NIR spectroscopy. DBC, flexural strength and modulus were measured after the storage of the specimens in deionized water at 37 °C for 24 h. The DBC, flexural strength and modulus data were analyzed by one-way ANOVA with p = 0.05 as significance level. RESULTS:ASEE-based composites containing the classical initiator system CQ/EDAB exhibited low mechanical properties (flexural strength/modulus) and DBC. The screening of various photoinitiator systems showed that composites based on CQ/EDAB/Ivocerin® (0.33 wt%/0.60 wt%/0.50 wt%), Ivocerin® (0.50 wt%) or CQ/EDAB/SC-938 (0.33 wt%/0.60 wt%/1.00 wt%) were particularly attractive. Indeed, the use of these photoinitiator systems enabled the formulation of composites containing up to 30 mol% ASEE exhibiting excellent mechanical properties, high DBC, good network homogeneity and low shrinkage force values. Interestingly, the addition of SC-938 did not impair the ambient light working time of the uncured composites, whereas the incorporation of 0.50 wt% Ivocerin® resulted in a strong decrease of this value. SIGNIFICANCE:The addition of the allyl sulfone ASEE in combination with the initiator system CQ/EDAB/SC-938 (0.33 wt%/ 0.60 wt%/ 1.00 wt%) is a promising strategy to develop low-shrinkage dental composites which exhibit excellent mechanical properties, low shrinkage force, high DBC and suitable ambient light working time.

Objectives: Currently used thiourea-based two-component dental materials may release bitter compounds if they are not properly cured. To address this issue, the objective of this study was to evaluate the potential of acylthiourea oligomers as reducing agents for the development of self-cure composites. Methods: Acylthiourea oligomers ATUO1-3 were synthesized via cotelomerization of the acylthiourea methacrylate ATU1 with butyl methacrylate. They were characterized by 1H NMR spectroscopy and size exclusion chromatography. Self-cure composites based on the redox initiator system cumene hydroperoxide/acylthiourea oligomer/copper(II) acetylacetonate were formulated. The flexural strength and modulus were measured using a three-point bending setup. The double bond conversions were determined using NIR spectroscopy. The working time of each self-cure composite was measured using an oscillating rheometer. Leaching experiments using lightcure composites were performed in DMSO-d6. Results: Acylthiourea oligomers ATUO1-3 were successfully synthesized in good yields. Both the oligomer molecular weight and the amount of thiourea groups were varied. Self-cure composites containing ATUO1 or ATUO2 as reducing agents exhibited excellent mechanical properties and high double-bond conversions. The amounts of reducing agent, cumene hydroperoxide and copper(II) acetylacetonate were shown to have a significant impact on the working time. Moreover, a correlation between flexural modulus and the amount of metal salt was clearly established. Self-cure composites containing the oligomer ATUO1 exhibited a longer working time than materials containing ATU1 or acetylthiourea. Contrary to acetylthiourea, ATUO1 was not able to leach out of light-cured composites. Significance: Acylthiourea oligomers are promising reducing agents for the formulation of two-component dental materials that do not induce a bitter taste in mouth.

Polymerization shrinkage and the consequential shrinkage stress in methacrylate-based dental composites are crucial drawbacks for restorative dentistry. An effective way for the reduction of shrinkage stress is the incorporation of addition fragmentation chain transfer agents (AFCT agents). In this contribution, four novel polymerizable allyl sulfides were synthesized and evaluated in dental composites. Photo-DSC and DMTA measurements were performed to evaluate their influence on the polymerization rate and on the network homogeneity. Good to excellent shrinkage force values and mechanical properties were obtained for all AFCT based composites. Especially, the incorporation of AFCT agents containing multiple urethane and methacrylate moieties improved the mechanical properties. Hence, the incorporation of polymerizable and urethane-based allyl sulfides in dental composite is a promising strategy to obtain low shrinkage materials exhibiting high flexural strength and modulus.