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Spiro-Fluorene-Containing Cyclic Olefin Polymers
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2023-08-15 , DOI: 10.1021/acsapm.3c01543 Saki Ishii 1 , Yoshiya Ota 2 , Shin-ichi Matsuoka 1 , Masato Suzuki 1
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2023-08-15 , DOI: 10.1021/acsapm.3c01543 Saki Ishii 1 , Yoshiya Ota 2 , Shin-ichi Matsuoka 1 , Masato Suzuki 1
Affiliation
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For application to optical polymer materials with a high refractive index and low birefringence as well as high thermal stability and low hygroscopicity, we have performed the ring-opening metathesis (co)polymerization (ROMP, ROMCP) of fluorene-based norbornene (NB) monomers, spiro[fluorene-9,4′-tricyclo[5.2.1.02,6]dec-8-en] (endo-1 and exo-1) and subsequent hydrogenation to produce spiro-fluorene-containing cyclic olefin polymers. The living ROMP and the kinetics of the ROMCP with NB were investigated. A series of hydrogenated endo- and exo-isomeric polymers, H-poly(1) and H-poly(1-co-NB), with random, gradient, and block sequences, were synthesized and characterized. They are highly soluble in common organic solvents due to their large fractional free volume, as indicated by broad X-ray diffraction patterns. The glass-transition temperatures (Tg) of H-poly(1-co-NB) significantly increased with the content of 1 up to 273 °C [H-poly(endo-1)]. The endo-isomeric polymers exhibited significantly higher Tg values and slightly lower solubility than their exo-counterparts, probably because of the slightly smaller fractional free volume of the endo-isomers. The refractive indexes of H-poly(1)s are as high as 1.61, and the stress-optical coefficients in the rubbery state (CR) of H-poly(1-co-NB) are less than zero. These low birefringences and large fractional free volumes are derived from the bulky spiro-fluorene moiety oriented vertically to the polymer main chain.
中文翻译：
含螺环芴的环烯烃聚合物
针对高折射率、低双折射率、高热稳定性、低吸湿性的光学高分子材料的应用，我们进行了芴基降冰片烯（NB）单体的开环复分解（共）聚合（ROMP、ROMCP） 、螺[芴-9,4'-三环[5.2.1.0 2,6 ]dec-8-en]（endo - 1和exo - 1）并随后氢化以产生含螺芴的环状烯烃聚合物。研究了活性 ROMP 和带有 NB 的 ROMCP 的动力学。一系列氢化内型和外型异构聚合物，H-poly( 1 ) 和 H-poly( 1 - co-NB），具有随机、梯度和块序列，被合成和表征。正如宽 X 射线衍射图所示，由于其自由体积分数较大，它们在常见有机溶剂中的溶解度很高。H-poly( 1 - co -NB) 的玻璃化转变温度 ( T g ) 随着1的含量显着增加，最高可达 273 °C [H-poly( end- 1 ) ]。与外切聚合物相比，内切异构聚合物表现出显着更高的Tg值和略低的溶解度，这可能是因为内切异构体的自由体积分数稍小。-异构体。H-poly( 1 )s的折射率高达1.61，H-poly( 1 - co - NB )橡胶态下的应力光学系数( CR )小于0。这些低双折射率和大自由体积分数源自垂直于聚合物主链取向的大体积螺芴部分。
更新日期：2023-08-15
中文翻译：
含螺环芴的环烯烃聚合物
针对高折射率、低双折射率、高热稳定性、低吸湿性的光学高分子材料的应用，我们进行了芴基降冰片烯（NB）单体的开环复分解（共）聚合（ROMP、ROMCP） 、螺[芴-9,4'-三环[5.2.1.0 2,6 ]dec-8-en]（endo - 1和exo - 1）并随后氢化以产生含螺芴的环状烯烃聚合物。研究了活性 ROMP 和带有 NB 的 ROMCP 的动力学。一系列氢化内型和外型异构聚合物，H-poly( 1 ) 和 H-poly( 1 - co-NB），具有随机、梯度和块序列，被合成和表征。正如宽 X 射线衍射图所示，由于其自由体积分数较大，它们在常见有机溶剂中的溶解度很高。H-poly( 1 - co -NB) 的玻璃化转变温度 ( T g ) 随着1的含量显着增加，最高可达 273 °C [H-poly( end- 1 ) ]。与外切聚合物相比，内切异构聚合物表现出显着更高的Tg值和略低的溶解度，这可能是因为内切异构体的自由体积分数稍小。-异构体。H-poly( 1 )s的折射率高达1.61，H-poly( 1 - co - NB )橡胶态下的应力光学系数( CR )小于0。这些低双折射率和大自由体积分数源自垂直于聚合物主链取向的大体积螺芴部分。
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