Electroactive poly(arylene sulphide): electro-oxidative polymerization of 3,5-dimethylthiophenol

Designing Ultrahigh-Refractive-Index Amorphous Poly(phenylene sulfide)s Based on Dense Intermolecular Hydrogen-Bond Networks

“…Summarizing the above, as the polymer chains of OHPPS strongly interacted with each other in the bulk state through intermolecular H-bonds between the side chains (Figure c), the π–π interactions between the aromatic rings weakened and the average π–π spacing increased. The rigid and zig-zag PPS main chain suppressed excessive interactions between the hydroxy groups, leading to high solubility and transparency of the bulk OHPPS while maintaining an amorphous nature. Based on the above features, the simultaneous achievement of ultrahigh RI and high Abbe number for OHPPS was attributed to the following reasons: (1) the high [ R ] of the PPS scaffold in conjunction with the low V , (2) much lower atomic dispersion of hydroxy moiety ([Δ R ] −OH = 0.006) than other substituents (e.g., [Δ R ] −CH2– = 0.072 and [Δ R ] −O– = 0.012), and (3) the blue-shift of the peak top of refractive index (from 340 to 335 nm) (see the inset of Figure S18), which indicated the occurrence of anomalous dispersion in shorter wavelength and led to small RI dispersion.…”

Vanadyl-TrBR4 -Catalyzed Oxidative Polymerization of Diphenyl Disulfide

“…For example, TfOH (p K a = −5.5), CF 3 COOH (0.3), and CCl 3 COOH (0.8) with DDQ gave the polymer, but a weak acid such as acetic acid (AcOH) (4.8) was not effective . We suppose that the strong acid contributes to the stabilization of the bis(phenylthio)phenyl sulfonium cation as the active species of the polymerization which should decompose by nucleophilic attack under less acidic conditions . DDQ is reduced to a dianion form of 2,3‐dichloro‐5,6‐dicyano‐ para ‐hydroquinone (DDH), and finally to DDH by the protonation with the acid.…”

“…They noted nothing about the particular case of the oxidative polymerization. We previously examined the similar effects of anions using Bu 4 NClO 4 , Bu 4 NBF 4 , and Bu 4 NPF 6 as the supporting electrolytes of an electro‐oxidative polymerization, but the polymer yields remained low . It could be reasoned that these kinds of anions, ClO 4 − , BF 4 − , and PF 6 − , should form chemical bonds or interact with the sulfonium cation because of their moderate nucleophilicity.…”