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Semi‐fluorinated polyarylenes: Microwave‐assisted synthesis and structure–property relationships
Author(s) -
Budy Stephen M.,
Khan Mansoor,
Chang Xu,
Iacono Scott T.,
Son David Y.
Publication year - 2020
Publication title -
journal of polymer science
Language(s) - English
Resource type - Journals
eISSN - 2642-4169
pISSN - 2642-4150
DOI - 10.1002/pol.20200386
Subject(s) - thermogravimetric analysis , differential scanning calorimetry , gel permeation chromatography , fluorine , fourier transform infrared spectroscopy , polymerization , chemistry , attenuated total reflection , polymer chemistry , polymer , char , thermal stability , dynamic mechanical analysis , thermal analysis , infrared spectroscopy , analytical chemistry (journal) , materials science , nuclear chemistry , chemical engineering , organic chemistry , pyrolysis , thermal , physics , meteorology , engineering , thermodynamics
A series of three fluorine containing and three non‐fluorinated Diels–Alder step‐growth polyarylene polymers and copolymers was synthesized via conventional oil bath heating (days/weeks). A drastic time reduction was realized with a microwave‐assisted polymerization (hours). The polymers were characterized by multinuclear ( 1 H, 13 C, and 19 F) NMR and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy, thermal analysis (thermogravimetric analysis [TGA], differential scanning calorimetry [DSC], and dynamic mechanical analysis [DMA]), gel permeation chromatography, X‐ray diffraction (XRD), water contact analysis, and refractive index (RI) measurements. The NMR spectra indicated a mixture of para and meta conformations through the polymer backbone increasing to more para with greater fluorine content. TGA revealed the fluorine‐containing polyarylenes possessed the highest char yields at almost 80% at 1000°C under nitrogen, and all the polyarylenes possessed onset of degradation temperatures above 550°C under nitrogen and air atmospheres. XRD analysis indicated more ordering for the fluorine‐containing polyarylenes which afforded the high char yields. DMA gave storage moduli values in the range of 1–10 GPa for the polyarylenes. Molecular weights for all samples were above 100 kg/mol. Water contact angles did not change with fluorine content due to the shielding effect of the pendant phenyl groups. However, the RI decreased to 1.6497 at 632.8 nm for the polyarylene with the highest fluorine content.