Page 101 - 《精细化工》2023年第5期

第 5 期 杨维成，等: Grubbs 三代催化剂的合成及其催化双环戊二烯可控成型 ·1021·

p-DCPD 板材主要失重在 450~550 ℃之间，这是由 p-DCPD 板材具有良好的热稳定性，274 ℃以下失
于 p-DCPD 网络结构崩溃造成的。由图 11 可见， 重率为 1.0%，良好的热性能可能是由 p-DCPD 交联
G3-5 催化所得 p-DCPD 板材显示了与文献报道类似 密度增加所致。
的奇异放热峰，但温度略有升高（在 150 ℃以后出
参考文献：
现)，这可能是由使用新型催化剂后 p-DCPD 交联密
度增加所致 [14-15] ，从而使材料具有了更加优异的耐 [1] OGBA O M, WARNER N C, O'LEARY D J, et al. Recent advances
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图 10 G-2（a）和 G3-5（b）催化所得 p-DCPD 板材的
polydicyclopentadiene nanoparticles into epoxy thermosets via ring
TGA 曲线 opening metathesis polymerization-induced self-assembly[J]. Polymer,
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by G-2 (a) and G3-5 (b)
[6] VALLONS K A M, DROZDZAK R, CHARRET M, et al.
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图 11 G3-5 催化所得 p-DCPD 板材的 DSC 曲线 41(21): 4035-4037.
Fig. 11 DSC curve of p-DCPD sheet material obtained by [10] SANFORD M S, LOVE J A, GRUBBS R H. A versatile precursor for
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通过配体设计，实现了 2 种新结构 G3-4、G3-5
[12] LOVE J A, SANFORD M S, DAY M W, et al. Synthesis, structure,
1
的制备， HNMR 结果表明，制备的催化剂结构与目 and activity of enhanced initiators for olefin metathesis[J]. Journal of
标结构一致。通过阻聚剂（三苯基膦）调控，可以 the American Chemical Society, 2003, 125: 10103-10109;
实现 G3 系列催化剂催化 DCPD 本体聚合，而通过 [13] ROBERTSON I D, DEAN L M, RUDEBUSCH G E, et al. Alkyl
phosphite inhibitors for frontal ring-opening metathesis polymerization
调控 G3 催化剂吡啶配体取代基给/吸电子能力，实
greatly increase pot life[J]. ACS Macro Letters, 2017, 6: 609-612.
现了对 DCPD 本体聚合的控制，500~600 s 为最佳聚 [14] HU F Y, DU J, OU T, et al. Preparation and properties of high
合时间，G2 和 G3 表现出相似的力学性能，其中 G3-5 performance phthalide-containing bismaleimide reinforced
在保持高效催化效率的同时，所得板材的性能与 G2 polydicyclopentadiene[J]. Journal of Applied Polymer Science, 2014,
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所得板材性能相当，甚至更优。当 G3-5 用量为 5.0%
[15] HU F Y, ZHENG Y B, FANG Y Y, et al. Preparation and properties of
时，拉伸强度为 48.5 MPa，弯曲强度为 65.4 MPa， cyclopentadiene-containingmonomer modified polydicyclopentadiene[J].
均优于其他催化剂。此外，由 G3-5 催化得到的 Polymer. 2014, 55(12): 1-8.