Synthesis and characterization of highly fluorinated poly(phthalazinone ether)s based on AB‐type monomers

Abstract

Four different fluorinated methyl‐ and phenyl‐substituted 4‐(4‐hydroxyphenyl)‐2‐(pentafluorophenyl)‐phthalazin‐1(2H)‐ones, AB‐type phthalazinone monomers, have been successfully synthesized by nucleophilic addition–elimination reactions of methyl‐ and phenyl‐substituted 2‐((4‐hydroxy)benzoyl)benzoic acid with 1‐(pentafluorophenyl)hydrazine. Under mild reaction conditions, the AB‐type monomers underwent self‐condensation polymerization reactions successfully and gave fluorinated poly(phthalazinone ether)s with high molecular weights. Detailed structural characterization of the AB‐type monomers and fluorinated polymers was determined by 1H NMR, 19F NMR, FTIR, and GPC. The solubility, thermal properties, mechanical properties, water contact angles, and optical absorption of the polymers were evaluated. The polymers had high Tgs varying from 337 to 349 °C and decomposition temperatures (Td, 25 wt %) above 409 °C. Tough, flexible films were cast from THF and chloroform solutions. The films showed excellent tensile strengths ranging from 70 to 85 MPa with good hydrophobicities with water contact angles higher than 95.5 °C. The polymers had absorption edges below 340 nm and very low absorbance per cm at higher wavelengths 500–2500 nm. These results indicate that the polymers are promising as high performance materials, for example, membranes and hydrophobic materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1761–1770

Influence of donor-acceptor conjugation between thiophene-phthalazinone structures containing Sp3 CN bond on the frontier orbital levels and optic-electronic properties

“…As shown in Figure 7, due to the asymmetrical phthalazinone unit, the fluorine signal at 137 ppm split into two peaks in the 19 F-NMR spectra of these fluoropolymers (the similar results can be observed in ref. 27). 27 And the 19 F-NMR spectra of PDT2TF (different entries) indicate that the most appropriate polymerization temperature is 110 8C (entry 3).…”

“…17 Decafluorobiphenyl has been widely used in the CANDP as a halide monomer polymerized with various bisphenol monomer to achieve high molecular polymers. 27,43,44,50,51 This is the first time that di-NH monomer polymerized with decafluorobiphenyl. Thus, the polymerization conditions were optimized to avoid a great degree of cross-linking and branching side reactions and obtain high molecular polymers.…”

“…On the same principle as above, we introduced more rigid structure (decafluorobiphenyl) than that of di‐halogenated monomers containing ketone/di‐ketone/sulfone groups into the polymer main chains . Decafluorobiphenyl has been widely used in the CANDP as a halide monomer polymerized with various bisphenol monomer to achieve high molecular polymers . This is the first time that di‐NH monomer polymerized with decafluorobiphenyl.…”

“…[20][21][22][23][24][25][26] These high-performance phthalazinone-containing polymers have exhibited good solubility and rigidity, even excellent thermalstability and mechanical properties. [27][28][29][30] However, there has been seldom focusing on the optoelectronic properties of the phthalazinone structure. Thus, novel building D-A conjugated polymers with phthalazinone moiety is highly desirable for investigating its optoelectronic properties deeply.…”

Synthesis and properties of novel fluorinated poly(arylene ether)s

“…Fluorinated poly(arylene ether)s (FPAEs) or core‐fluorinated aromatic polyethers show various excellent properties such as high thermal stability and chemical resistance in combination with low dielectric constant and reduced friction coefficient, refractive index, optical losses and moisture absorption . FPAEs can be synthesized via nucleophilic substitution of fluorine atom(s) in a perfluorinated aromatic nucleus with a phenol‐type hydroxyl group in the presence of an alkali .…”