Cole Megan A, Jankousky Katherine C, Bowman Christopher N
Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO 80309-0596, USA.
Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO 80309-0596, USA; Biomaterials Research Center, School of Dentistry, University of Colorado Health Sciences Center, Aurora, CO 80045, USA.
Dent Mater. 2014 Apr;30(4):449-55. doi: 10.1016/j.dental.2014.01.011. Epub 2014 Feb 16.
Thiol- and allyl-functionalized siloxane oligomers are synthesized and evaluated for use as a radical-mediated, rapid set elastomeric dental impression material. Thiol-ene siloxane formulations are crosslinked using a redox-initiated polymerization scheme, and the mechanical properties of the thiol-ene network are manipulated through the incorporation of varying degrees of plasticizer and kaolin filler. Formulations with medium and light body consistencies are further evaluated for their ability to accurately replicate features on both the gross and microscopic levels. We hypothesize that thiol-ene functionalized siloxane systems will exhibit faster setting times and greater detail reproduction than commercially available polyvinylsiloxane (PVS) materials of comparable consistencies.
Thiol-ene functionalized siloxane mixtures formulated with varying levels of redox initiators, plasticizer, and kaolin filler are made and evaluated for their polymerization speed (FTIR), consistency (ISO4823.9.2), and surface energy (goniometer). Feature replication is evaluated quantitatively by SEM. The Tg, storage modulus, and creep behavior are determined by DMA.
Increasing redox initiation rate increases the polymerization rate but at high levels also limits working time. Combining 0.86 wt% oxidizing agent with up to 5 wt% plasticizer gave a working time of 3 min and a setting time of 2 min. The selected medium and light body thiol-ene formulations also achieved greater qualitative detail reproduction than the commercial material and reproduced micrometer patterns with 98% accuracy.
Improving detail reproduction and setting speed is a primary focus of dental impression material design and synthesis. Radical-mediated polymerizations, particularly thiol-ene reactions, are recognized for their speed, reduced shrinkage, and 'click' nature.
合成并评估硫醇和烯丙基官能化的硅氧烷低聚物,用作自由基介导的快速固化弹性体牙科印模材料。硫醇-烯硅氧烷配方通过氧化还原引发的聚合方案进行交联,并通过加入不同程度的增塑剂和高岭土填料来控制硫醇-烯网络的机械性能。进一步评估具有中稠度和轻稠度的配方在宏观和微观层面准确复制特征的能力。我们假设,与具有可比稠度的市售聚乙烯基硅氧烷(PVS)材料相比,硫醇-烯官能化的硅氧烷体系将表现出更快的固化时间和更高的细节再现性。
制备含有不同水平氧化还原引发剂、增塑剂和高岭土填料的硫醇-烯官能化硅氧烷混合物,并评估其聚合速度(傅里叶变换红外光谱)、稠度(ISO4823.9.2)和表面能(测角仪)。通过扫描电子显微镜对特征复制进行定量评估。通过动态热机械分析确定玻璃化转变温度、储能模量和蠕变行为。
提高氧化还原引发速率会增加聚合速率,但在高水平时也会限制工作时间。将0.86 wt%的氧化剂与高达5 wt%的增塑剂混合,工作时间为3分钟,固化时间为2分钟。所选的中稠度和轻稠度硫醇-烯配方在细节再现性方面也比市售材料更好,并且以98%的准确度再现了微米级图案。
改善细节再现性和固化速度是牙科印模材料设计和合成的主要重点。自由基介导的聚合反应,特别是硫醇-烯反应,因其速度快、收缩率低和“点击”特性而受到认可。