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Digital light processing 3D printing of modified liquid isoprene rubber using thiol-click chemistry

机译：数字光处理3D使用硫醇咔哒化学改性液体异戊二烯橡胶的3D印刷

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This study highlights the additive manufacturing of diene-rubbers with digital light processing (DLP). The network formation relies on the crosslinking of a methacrylate-functional liquid isoprene rubber via photo-induced thiol-click chemistry. Bi-functional divinyl ethers are added as reactive diluents, which benefit from a low potential for skin irradiation and skin sensitization. Along with significantly reducing the viscosity, the divinyl ethers accelerate the cure kinetics of the diene-rubber across the main chain CC bonds of the isoprene units. Photo-DSC measurements reveal that the length of the glycol-spacer and the chemical structure (glycol versus alkyl) of the divinyl ether influence the photo-reactivity of the rubber formulations in thiol–ene reactions. In the present study, the highest reactivity is observed for tri(ethylene glycol) divinylether comprising a spacer with three glycol units. To improve the storage stability of the rubber formulation, a radical scavenger is applied to reduce premature crosslinking reactions under dark conditions. With the stabilized liquid rubber formulations, precise 3D structures with features of 0.5 mm are successfully manufactured with bottom-up DLP 3D printing.
机译：本研究突出了具有数字光处理（DLP）二烯 - 橡胶的添加剂制造。网络形成依赖于通过光致硫醇咔哒化学的甲基丙烯酸酯官能液异戊二烯橡胶的交联。双官能二乙烯基醚作为反应性稀释剂加入，这受益于皮肤照射和皮肤敏化的低潜力。随着粘度显着降低，二乙烯基醚在异戊二烯单元的主链CC键上加速二烯 - 橡胶的固化动力学。 Photo-DSC测量表明，二醇 - 间隔物和二乙醚的化学结构（乙二醇与烷基）的长度会影响硫醇 - 烯反应中橡胶制剂的光反应性。在本研究中，对于三种二甘醇单元的间隔物，观察到三种（乙二醇）二乙醚的最高反应性。为了提高橡胶配方的储存稳定性，应用自由基清除剂以减少暗条件下的过早交联反应。通过稳定的液体橡胶配方，通过自下而上的DLP 3D打印成功地制造具有0.5毫米特性的精确3D结构。

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