Poly(arylene sulfide)s by nucleophilic aromatic substitution polymerization of 2,7‐difluorothianthrene

Abstract

Poly(thianthrene phenylene sulfide) and poly(thianthrene sulfide) have been prepared by nucleophilic aromatic substitution polymerization of the activated monomer 2,7-difluorothianthrene with bis thiophenoxide and sulfide nucleophiles, respectively. The resulting polymers are thermally stable, amorphous materials that have been characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), gel permeation chromatography (GPC), matrix-assisted laser desorption/ionization-time-of-flight (MALDI-TOF) mass spectrometry, UV-Vis spectroscopy, refractometry, and intrinsic viscosity (IV) measurements. The polymers produced exhibit 5% weight loss values approaching 500 C in inert and air atmospheres and glass transition temperatures that range from 149 to 210 C. Poly (thianthrene phenylene sulfide) with a number average molecular weight of 22,100 g/mol has been synthesized with an IV in DMPU of 0.62 dL/g at 30 C. Creasable films of this polymer have been prepared by solvent casting and melt pressing at 250 C. Films of poly(thianthrene phenylene sulfide) exhibit transparencies greater than 50% at wavelengths exceeding 400 nm and a high refractive index value of 1.692 at a wavelength of 633 nm, making the polymer interesting for optical applications.

Highly refractive and organo‐soluble poly(amide imide)s based on 5,5′‐thiobis(2‐amino‐4‐methyl‐thiazole): Synthesis and characterization

“…Among the various substituents, sulfur‐containing groups, such as linear thioether (–S–), cyclic thioether (thiophene and thianthrene), and sulfone (–SO 2 –), seem to be the most optimal candidates because of their combined advantages to develop high‐ n polymers 13–17. Consequently, various sulfur‐containing polymers, including poly(methacrylates),18 epoxy resins,19 polyurethanes,20 poly(arylene sulfide)s,21 and polyimides (PIs), have been well investigated as high‐ n optical materials 22, 23. Among them, PIs are well‐known for their excellent thermal stability, high chemical resistance, and good mechanical properties.…”

Synthesis and characterization of thianthrene-based poly(phenylene sulfide)s with high refractive index over 1.8

“…The TPPSs were prepared by the polycondensation of DFT with dithiols, such as TBBT, mBDT, and sodium sulfide nonahydrate under the similar condition reported before (Scheme 1). 18 However, all the TPPSs obtained were insoluble or partially soluble in organic solvents. Thus, we changed the polymerization condition to increase the solubility of the TPPSs.…”

“…Sulfur is the most commonly used atom for increasing the refractive index because of its high polarizability, stability, and facility to introduce to polymers. Various sulfur-containing polymers that exhibited high refractive indices were synthesized and characterized for optical applications, including polyimides, [9][10][11][12][13][14][15] poly(phenylene sulfide)s (PPSs), 17,18 and poly(phenylquinoxaline)s. 19 On the other hand, nanocomposites consisting of highly refractive inorganic nanoparticles and organic polymer matrices could easily achieve an n value higher than 1.8. 20 However, such polymer nanocomposites sometimes suffer from storage instability, higher optical loss, and poor processability.…”

“…However, TPPS 1 was poorly soluble and TPPS 3 was insoluble in organic solvents because of their rigid structures and lack of solubilizing groups. 18 In addition, the reported refractive index of TPPS 1 (1.692 at 633 nm, number average molecular weight: M n ¼ 22 100) was unexpectedly low despite its high sulfur content (see ESI †).…”

Highly refractive polymer resin derived from sulfur‐containing aromatic acrylate

“…Among the various substituents, the sulfur (S) atom is one of the most effective candidates because of its high‐atomic refraction. Recently, sulfur‐containing polymers with thioether linkages have been developed for optical applications 7–15. Although all of the polymers showed high‐refractive indices, high transparency and low birefringence, the polymer films were prepared by thermal conversion at high temperatures for a long time and solution processes using organic solvents were necessary, which led to deep colors and strong odors.…”