Synthesis and properties of pendant fluorene moiety-tethered aliphatic polycarbonates

Abstract

A series of novel fluorene moiety-containing polycarbonates was synthesized by the anionic ring-opening polymerization of six-membered spirocyclic carbonates possessing 9,9-fluorene groups at the 5,5-position. The polymers could be considered cardo-type polymers because they had 9,9-fluorene groups as a loop-shaped side chain. Interestingly, the fluorene pendant polycarbonates were obtained in sufficiently high molecular weights and in good yields, although the monomers were structurally closely related to the 5,5-diphenyl-substituted cyclic carbonate that exhibited very low polymerizability. Furthermore, the polymerizations of substituted fluorene-based six-membered spirocyclic carbonates were investigated. All of the obtained polymers showed favorable properties, including good solubility, amorphous natures, favorable thermal stabilities, remarkably low birefringence values and high refractive indices despite consisting only of C, H and O atoms. The good potentiality in the application to optical materials was shown here.

Extending the Scope of “Living” Crystallization-Driven Self-Assembly: Well-Defined 1D Micelles and Block Comicelles from Crystallizable Polycarbonate Block Copolymers

“…The initial value for the SLD of the core was predicted using the literature value for the density of PFTMC. 72 Both models afforded good fits for the observed scattering pattern for 0.004 > Q < 0.1 and limiting the fitting to this range did not allow for a distinction to be made. AFM analysis of the micelles was therefore used to determine which model was most appropriate.…”

“…Determination of the core dimensions of the micelles (PFTMC 20 -b-PEG 220 , L n = 530 nm) using SAXS and TEM enabled us to gain further insight into the overall micelle structure. Using the density of PFTMC (ρ = 1.33 g/cm −3 ), 72 the volume of micelle core acquired from modeling the SAXS data, and the average mass of the PFTMC core-forming block, the number of polymer molecules comprising an average micelle was calculated to be ∼9300, which equates to a N agg,L of 17. For a full description of how N agg,L was calculated see the Supporting Information section.…”

Correlation of the Abbe Number, the Refractive Index, and Glass Transition Temperature to the Degree of Polymerization of Norbornane in Polycarbonate Polymers

“…Commercially available polymers with high refractive index include polycarbonates, polyesters, and polyester carbonate using bisphenol-A and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorine (BPEF) as monomers. These monomers consist of aromatic rings having high atomic refraction, which realize a high refractive index (n d 1.58-1.64) [2,[4][5][6][7][8]. On the other hand, commercially available polymers with low refractive index lens includes cyclo-olefin polymers (COP) and cyclo-olefin copolymers (COC) [9][10][11].…”

Synthesis and characterization of 9,9‐bis(4‐hydroxyphenyl and 4‐aminophenyl)dibenzofluorenes: Novel fluorene‐based monomers

“…In addition to various fluorene‐based polymers showing both high refractive index and low birefringence besides high solubility and thermal properties, we have developed a new monomer containing silicon atom at 9 position, 9,9‐bis(4‐hydroxyphenyl)‐9‐silafluorene, and its polymers, to emphasize the potentiality of the cardo 9,9‐difunctionalized fluorene function . Furthermore, six‐membered cyclic carbonate monomers derived from 9,9‐bis(hydroxymethyl)fluorenes have recently been prepared for the synthesis of controlled birefringence polymers …”

“…24 Furthermore, sixmembered cyclic carbonate monomers derived from 9,9-bis (hydroxymethyl)fluorenes have recently been prepared for the synthesis of controlled birefringence polymers. 26 In our continuing studies on the development of new 9,9-disubstituted fluorene moiety-containing monomers and their polymers, we have succeeded in synthesizing two novel fluorene monomers, 9,9-bis(4-hydroxyphenyl-and 4-aminophenyl)-2,3;6,7-dibenzofluorenes (1 and 2, Fig. 1).…”