Poly(aryl ether ketone)s with (3‐methyl)phenyl and (3‐trifluoromethyl)phenyl side groups

Abstract

New bisphenol monomers, (3‐methyl)phenylhydroquinone and (3‐trifluoromethyl)phenylhydroquinone, were prepared in a two‐step synthesis. A series of poly(aryl ether ketone)s were derived from these bisphenols via a nucleophilic aromatic substitution polycondensation with various bisfluoro compounds. The polycondensation proceeded quantitatively in tetramethylene sulfone in the presence of anhydrous potassium carbonate and afforded the polymers with inherent viscosities of 0.63–0.91 dL/g. The fluorinated polymers showed lower glass‐transition temperatures and higher thermal‐decomposition temperatures than the corresponding nonfluorinated polymers. The solubility of the polymers was improved by the introduction of bulky pendant groups. All the polymers formed transparent, strong, and flexible films, with tensile strengths of 86.4–102.0 MPa, Young's moduli of 2.28–3.03 GPa, and elongations at break of 14–42%. All the polymers had low dielectric constants of 2.70–2.83 at 1 MHz. Compared with the methylated polymers, the trifluoromethylated polymers exhibited lower water sorption, which was attributed to the stronger hydrophobicity of the fluorine‐containing groups. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3392–3398, 2002

Methylated and Trifluoromethylated Poly(aryl ethers)

“…The 19 F NMR spectra of 14F-PAE and 11F-PAE showed three groups of peaks corresponding to the three kinds of distinguishable fluorines. However, only two groups of peaks centered at −138.5 and −153.8 ppm corresponding to the fluorines of biphenyls in the 19 F NMR spectrum of 8F-PAE. 10 As expected, due to the existence of asymmetric moieties in the backbones, the chemical shifts for fluorines of biphenyls exhibited a little difference.…”

“…The characteristic peaks of the methyl groups of m-TPEN and 8F-PAE appeared at 2.36 and 2.39 ppm, respectively. In the 19 F NMR spectra of 6F-PEN, 3F-PEN, 14F-PAE and 11F-PAE (Figure 1), the absorption peaks of the trifluoromethyl groups were observed at about −63 ppm. The 19 F NMR spectra of 14F-PAE and 11F-PAE showed three groups of peaks corresponding to the three kinds of distinguishable fluorines.…”

“…A possible explanation for the lower T g s of 3-trifluoromethylphenyl polymers is that the substitution of methyl with trifluoromethyl would lead to an internal plasticization in addition to the geometry and free-volume factors. 19,21 The poly(aryl ethers) showed good thermal stability based on their aromatic molecular structure. The temperatures at a 5% weight loss (TD 5 ) and at a 10% weight loss (TD 10 ) in air were above 443 • C and 496 • C, respectively.…”

Synthesis and characterization of novel cyanofunctionalized poly(aryl ether ketone)s

“…The resulting solution was filtered and added dropwise to a mixture of 1,4-benzoquinone (2.16 g, 0.02 mol), sodium bicarbonate (16.80 g, 0.2 mol), and water (100 mL). After that, the reaction mixture was stirred at [10][11][12][13][14][15] o C for about 2 h and then at room temperature for 2 h. Then the precipitate was collected by filtration and washed thoroughly with water and kept at 60 o C in a vacuum oven. Brown crystals were obtained after recrystallization from n- J=8.0Hz, 1H).…”

“…On the other hand, in the last few years more and more attention has been paid to their functionalization [9][10][11][12][13][14][15][16], which could be achieved either by chemical modification of the polymer or by direct synthesis using functional monomers. The cyano group on the aromatic ring (PEN) appears to promote adhesion of the polymer to many substrates [17][18], possibly through reaction or polar interaction with other functional groups [19][20].…”