Hexacyclotetradecenes as polycyclic fused exo-norbornene monomers: synthesis of cyclic olefin copolymers via Ti-catalyzed controlled polymerization,Polymer Chemistry

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Hexacyclotetradecenes as polycyclic fused exo-norbornene monomers: synthesis of cyclic olefin copolymers via Ti-catalyzed controlled polymerization
Polymer Chemistry ( IF 4.1 ) Pub Date : 2024-07-04 , DOI: 10.1039/d4py00541d
Eri Funahashi ₁ , Yusuke Iwata ₁ , Shin-ichi Matsuoka ₁

Affiliation

Polycyclic fused norbornenes (NBs) are important monomers for producing thermally stable cyclic olefin polymers and copolymers (COCs). However, the difficult addition polymerization of sterically demanding endo-substituted NBs limits the range of accessible COCs. Here, we explored the synthesis and polymerization of an isomeric mixture of hexacyclotetradecenes (1a and 1b) as new polycyclic fused exo-NB-based monomers. These monomers were readily prepared via a two-step catalysis process: norbornadiene dimerization followed by protic-acid-catalyzed isomerization. While ring-opening metathesis polymerization using conventional Ru carbene catalysts was not viable, addition polymerization and copolymerization with 1-octene, using a constrained geometry Ti catalyst, successfully proceeded in a controlled manner. Monomer 1 was consumed faster than 1-octene to form gradient copolymers. ¹³C nuclear magnetic resonance spectra exhibited reasonable signals that indicated a 1,2-addition polymer structure. X-ray diffraction and thermogravimetry analysis confirmed the amorphous nature and thermal stability of poly1, which showed no weight loss below 400 °C. Thus, this study demonstrates the synthesis and polymerization of new promising polycyclic olefin monomers suitable for producing COC materials.

中文翻译：

六环十四烯作为多环稠合外降冰片烯单体：通过钛催化控制聚合合成环烯烃共聚物

多环稠合降冰片烯（NB）是生产热稳定环烯烃聚合物和共聚物（COC）的重要单体。然而，空间要求高的内取代NBs的加成聚合困难限制了可利用的COCs的范围。在这里，我们探索了六环十四烯（1a 和 1b）异构体混合物的合成和聚合，作为新型多环稠合外型-NB 基单体。这些单体很容易通过两步催化过程制备：降冰片二烯二聚，然后质子酸催化异构化。虽然使用传统Ru卡宾催化剂的开环复分解聚合不可行，但使用受限几何形状Ti催化剂的加成聚合和与1-辛烯的共聚以受控方式成功进行。单体 1 比 1-辛烯消耗得更快，形成梯度共聚物。 ¹³ 13C核磁共振谱显示出合理的信号，表明具有1,2-加成聚合物结构。 X 射线衍射和热重分析证实了 Poly1 的无定形性质和热稳定性，在 400 °C 以下没有失重。因此，本研究证明了适合生产 COC 材料的新型有前途的多环烯烃单体的合成和聚合。

更新日期：2024-07-09

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