用于前环开环易位聚合的亚磷酸烷基酯抑制剂可大幅延长适用期。
Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life.
作者信息
Robertson Ian D, Dean Leon M, Rudebusch Gabriel E, Sottos Nancy R, White Scott R, Moore Jeffrey S
机构信息
Departments of Chemistry, ‡Materials Science and Engineering, §Aerospace Engineering, and the ⊥Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
Departments of Chemistry, Materials Science and Engineering, §Aerospace Engineering, and the ⊥Beckman Institute for Advanced Science and Technology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, United States.
出版信息
ACS Macro Lett. 2017 Jun 20;6(6):609-612. doi: 10.1021/acsmacrolett.7b00270. Epub 2017 May 24.
Frontal ring-opening metathesis polymerization (FROMP) has potential for use in rapid fabrication of structural polymers. However, the high activity of the ruthenium catalyst used for FROMP has limited the working time to <1 h. We report the use of alkyl phosphites as inhibitors for Grubbs' type catalysts to substantially extend working time. Subtle changes in alkyl phosphite structure are shown to impact both pot life and frontal velocity. Specifically, by varying phosphite structure and concentration, we are able to control pot life between 0.25 and 30 h while still allowing FROMP to proceed at velocities between 1 and 8 cm/min to yield fully cured thermoset polymers. These results are of interest for conventional ROMP synthesis and may open the way to new FROMP-based manufacturing possibilities.
前沿开环易位聚合反应（FROMP）在快速制备结构聚合物方面具有应用潜力。然而，用于FROMP的钌催化剂活性很高，导致工作时间限制在1小时以内。我们报道了使用亚磷酸酯作为格拉布型催化剂的抑制剂，以大幅延长工作时间。结果表明，亚磷酸酯结构的细微变化会影响适用期和前沿速度。具体而言，通过改变亚磷酸酯的结构和浓度，我们能够将适用期控制在0.25至30小时之间，同时仍能使FROMP以1至8厘米/分钟的速度进行，从而得到完全固化的热固性聚合物。这些结果对于传统的开环易位聚合反应合成具有重要意义，可能为基于FROMP的新制造可能性开辟道路。
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