9,9′‐spirobifluorene‐containing polycarbonates: Transparent polymers with high refractive index and low birefringence

Abstract

Syntheses of 2,2′‐bisalcoholic group‐substituted 9,9′‐spirobifluorene monomers 2 were performed by the reaction of 2,2′‐dihydroxy‐9,9′‐spirobifluorene 2a with haloalcohols. Polycarbonates consisting of 9,9′‐spirobifluorene skeleton in the main chain (PC 4) were synthesized by the polycondensation of 2,2′‐bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. PC 4 showed good thermal stability: the 5% weight loss temperature was over 330 °C under both nitrogen and air atmospheres. The glass transition temperature was in a range of 16–269 °C estimated by differential scanning calorimetry, depending on the flexibility of the alkylene or oxyethylene chains of 2. PC 4 showed high solubility toward ordinary organic solvents such as CHCl3, benzene, and THF, making possible the preparation of the flexible thin films. Very high refractive index in a range of 1.62–1.66 at 589 nm was observed although PC 4 consists only of C, H, and O atoms, whereas very low degree of birefringence was confirmed. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3658–3667, 2010

Synthesis, Chiral Resolution, and Absolute Configuration of C2‐Symmetric, Chiral 9,9′‐Spirobifluorenes

“…In 1988, Toda published a procedure for the resolution of 2,2′‐dihydroxy‐9,9′‐spirobifluorene through clathrate formation with ( R , R )‐(+)‐2,3‐dimethoxy‐ N , N , N′ , N′ ‐tetracyclohexylsuccindiamide,11 which was refined and improved by Thiemann in 2005 12. Although this approach has been applied successfully by us5e,5h and others6e,6h,13 it is quite tedious. This is not only due to the fact that the tartaric acid derivative must be synthesised in three steps and tends to racemise during the second step.…”

Facile synthesis and electro‐optic activities of new polycarbonates containing tricyanofuran‐based nonlinear optical chromophores

“…The literatures reported that high‐molecular‐weight polycarbonates can be obtained using convenient triphosgene on a laboratory scale, but usually limited in diphenolic monomers owing to the lower nucleophilicity of alcoholic moieties . In addition, the copolymerization of diphenolic monomers and dialcoholic monomers could not realize by neither interfacial polycondensation with triphosgene nor direct polycondensation with carbonyl sources such as diphenyl carbonate .…”

Dispirocycles: Platforms for the Construction of High‐Performance Host Materials for Phosphorescent Organic Light‐Emitting Diodes

“…[15a, 24] From as ynthetic point of view,t he functionalization of SBF can be accomplished after the SBFc ore is available or by decoration of the fluorene motif and the related precursors at an early stage. [25][26][27][28] For example, as ymmetrically 2,2',7,7'substituted SBF can be prepared with tetrahalogenated (bromide or iodide) SBFprecursors. [21,25,26] Recently,S BF derivatives are gaining increasingi nterestf or organic electronics, [14][15][16]29] and many spirocycles with various degrees of structural diversity have been developed in the pursuit of high-performance electronic devices.I na ddition, modern synthetic methodology allows the molecular fragmentsa nd functional groups to be manipulatedi nm any innovative ways, which promote the discovery of new materials.…”