We investigated the ring-opening metathesis polymerization (ROMP) of readily preparable ester-functionalized tricyclo[4.2.2.0^2,5]deca-3,9-diene (TDD) monomers, 4-oxa-endo-tetracyclo[5.4.2.0^2,6.0^8,11]trideca-9,12-dien-3-one (1) and endo–endo-tricyclo[4.2.2.0^2,5]deca-3,9-diene-7,8-dicarboxylate (2), and disclose the thermal properties of the resulting polymers. The polymerizations of 1 and 2 proceed in a living fashion using Grubbs catalysts (first- and third-generation), and their ROMP rates were comparable with, or higher than, those of their norbornene (NB) derivatives. Poly1 and poly2 were amorphous in structure and found to be soluble in polar organic solvents. Owing to the bi- and tricyclic main chain polymer structures of poly1 and poly2, the glass transition temperatures of their copolymers with norbornene increased significantly, and linearly, with higher 1 and 2 content. Evolved gas analysis-gas chromatography/mass spectrometry studies suggested that the pyrolysis mechanism involves retro-Diels–Alder reactions.

中文翻译：

---

酯官能化内三环[4.2.2.02,5]deca-3,9-二烯的开环易位聚合和所得聚合物的热性能

我们研究了易于制备的酯官能化三环 [4.2.2.0 ^2,5 ]deca-3,9-二烯 (TDD) 单体、4-氧杂-内-四环[5.4.2.0 ^{2]的开环复分解聚合 (ROMP) ,6} .0 ^8,11 ]trideca-9,12-dien-3-one ( 1 ) 和endo – endo -tricyclo[4.2.2.0 ^2,5 ]deca-3,9-diene-7,8-dicarboxylate ( 2 ), 并公开了所得聚合物的热性能。1和2的聚合使用 Grubbs 催化剂（第一代和第三代）以活泼的方式进行，它们的 ROMP 率与降冰片烯 (NB) 衍生物相当或更高。Poly 1和 Poly 2在结构上是无定形的并且被发现可溶于极性有机溶剂。由于 poly 1和 poly 2的双环和三环主链聚合物结构，它们与降冰片烯的共聚物的玻璃化转变温度随着1和2含量的增加而显着增加，并且呈线性增加。逸出气体分析-气相色谱/质谱研究表明，热解机制涉及逆狄尔斯-奥尔德反应。