A one-part free radical initiator system to enable visible light-activated polymerization with post-exposure dark cure and extensive, athermal shadow cure behavior

一种单组分自由基引发剂系统，可实现可见光活化聚合，并具有曝光后暗固化和广泛的无热阴影固化行为

• 批准号: 9903283
• 负责人: JEFFREY W. STANSBURY
• 金额: $ 18.77万
• 依托单位: UNIVERSITY OF COLORADO DENVER
• 依托单位国家: 美国
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-04-01 至 2022-03-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/9903283
• 关键词: Address; Adhesions; Adhesives; Amines; Amplifiers; Behavior; Clinical; Clinical Services; Composite Resins; Consumption; Coupled; Dental; Dental Cavity Preparation; Dental Materials; Dental caries; Dentistry; Dentists; Development; Dimensions; Exposure to; Failure; Fracture; Free Radicals; Goals; Hour; Lead; Life; Light; Link; Longevity; Maintenance; Measures; Methods; Orthodontic Brackets; Output; Oxidants; Oxidation-Reduction; Oxides; Pattern; Performance; Peroxides; Phase; Plant Resins; Polymers; Price; Process; Production; Property; Psychological reinforcement; Reaction; Reducing Agents; Sampling; Stress; Surface; Syringes; System; Techniques; Technology; Terminology; Thick; Time; Tooth structure; Visible Radiation; attenuation; base; clinically relevant; composite restoration; design; direct application; improved; irradiation; monomer; novel; novel strategies; photocuring; photolysis; photopolymerization; polymerization; polymerization stress; prevent; reaction rate; repaired; restoration; restoration placement; restorative composite; restorative material; restorative treatment; success

With a majority of the more than 160 million dental restorative treatments performed in the US each year involving the placement of resin-bonded composite materials, and the acknowledgement that a large portion of a dentist’s time is consumed with revising and replacing these restorations, there is a clear need for materials with improved clinical performance. The relatively short average clinical lifespan (~6 years), particularly for large restorations, is not just inefficient and expensive, but each revision escalates to more invasive treatment. The primary reasons for the failure rate of restorations are fracture or loss of the composite as well as secondary caries. These problems are all potentially linked to inadequate curing during placement of the restoration since polymer properties are correlated with degree of conversion while adhesion to the tooth and the associated reinforcement of a compromised tooth are also dependent on the extent of cure of the composite resin. Uncured monomer leaching from a restoration is known to promote more aggressive bacterial activity in the vicinity of a restoration, which further underscores the need for well cured composites. It is notable that there are significant discrepancies in the clinical service life of similar commercial composite materials, which indicates that the reliable placement of the materials is highly technique sensitive. The goal here is to design novel photoinitiating systems capable of delivering free radicals for reliable polymerization beyond the temporal and spatial footprint of a visible curing light. The intended clinically relevant application is for the direct placement of dimensionally thick, highly filled composite restorative materials in which substantial light attenuation and/or shadow patterning is encountered. These heavy-body materials cannot be accommodated in dual-cure auto-mixing syringes. The product of this proposal could alleviate all concern of incompletely photocured composite restorations by development of completely new photo-activated redox polymerization initiation systems that in one version can augment the initial cure in under-cured regions of a composite by engaging a dark curing process that continues beyond exposure to the curing light. Our early results demonstrate limited photopolymerizations reaching only 10% conversion during direct light exposure that can then progress to full conversion of colorless polymer in the ensuing dark phase. Alternatively, another version of the initiator is expected to produce full conversion following a brief activation by visible light even within regions that received no exposure from the curing light. If successful, this demonstration project will introduce a breakthrough in photocuring that would dramatically increase depth of cure and provide full assurance of complete conversion in dental composite and resin cement photopolymerizations. In addition to the obvious benefits of assured full conversion and optimized properties, other advantages such as reduced polymerization stress and improved adhesive bonding due to a more gradual polymerization process at the composite base may be realized. Success here would represent a tremendously important advance in photopolymerization that would undoubtedly extend beyond dentistry.

每年在美国进行的超过1.6亿牙牙还修复治疗中的大部分 涉及树脂键合复合材料的放置，并承认很大一部分 牙医的时间被修改和替换这些修复体所消耗，清楚地需要材料 随着临床表现的提高。相对短的平均临床寿命（约6年），尤其是大型 修复不仅效率低下且昂贵，而且每次修订都会升级为更具侵入性的治疗。 恢复失败率的主要原因是裂缝或复合材料的损失以及次要 携带。这些问题都可能与修复过程中的固化不足有关，因为 聚合物特性与转化程度相关，而粘合到牙齿和相关的 受损牙齿的增强也取决于复合树脂的治愈程度。未经意 已知恢复的单体浸出可以促进在A附近促进更具侵略性的细菌活性 恢复，这进一步强调了对固化复合材料的需求。值得注意的是 类似商业复合材料的临床服务寿命中的差异，这表明 可靠的材料放置对技术敏感。这里的目的是设计新颖的光电 能够提供自由基以在临时和空间足迹之外提供可靠的聚合的系统 可见的固化灯。预期的临床相关应用是直接放置尺寸 厚实，高度填充的复合修复材料，其中大量的光衰减和/或阴影 遇到图案。这些重型材料不能用于双固定自动混合 注射器。该提案的乘积可以减轻所有不完全光电复合材料的关注 通过开发全新的照片激活的氧化还原聚合计划系统的修复 一个版本可以通过参与深色固化过程来增强复合材料固化区域的初始治疗 这继续超出了固化光的暴露。我们的早期结果表明光聚合有限 在直接光线曝光期间仅达到10％的转换，然后可以进行无色的完全转换 在随之而来的黑阶段中聚合物。另外，预计发起者的另一个版本将产生完整 即使在没有接触过的区域内，可见光的短暂激活后，转换 固化光。如果成功的话，这个演示项目将引入光合的突破 急剧增加治疗深度，并提供牙科复合材料中完全转换的完全保证和 树脂水泥光聚合。除了假定的完全转换和优化的明显好处 特性，其他优势，例如减少聚合应力和由于A而改善的粘合键 可以实现复合基础的更多等级聚合过程。这里的成功将代表 毫无疑问将超越牙科的光聚合中非常重要的进步。

项目成果

Photo-polymerization kinetics of a dental resin at a high temporal resolution.

高时间分辨率下牙科树脂的光聚合动力学。

• DOI: 10.1016/j.jmbbm.2021.104884
• 发表时间: 2021
• 期刊: Journal of the mechanical behavior of biomedical materials
• 影响因子: 3.9
• 作者: Sullivan,Braden;Kalliecharan,David;Kostylev,Ivan;Earle,Guy;Stansbury,JeffreyW;Price,RichardB;Labrie,Daniel
• 通讯作者: Labrie,Daniel

Visible-Light Photoinitiation of (Meth)acrylate Polymerization with Autonomous Post-conversion.

• DOI: 10.1021/acs.macromol.1c00761
• 发表时间: 2021-09-14
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Kim, Kangmin;Sinha, Jasmine;Stansbury, Jeffrey W.;Musgrave, Charles B.
• 通讯作者: Musgrave, Charles B.