Abstract:Benzoxazine containing fluorinated aromatic ether nitrile linkage (FAEN-Bz) had been synthesized from 2,6-dichlorobenzonitrile, 4,4’-(hexafluoroisopropylidene)diphenol (bisphenol AF), 3-Aminophenol, formaldehyde, phenol by condensation polymerization and Mannich ring-forming reaction. Structures of the monomer were verified by Proton NMR spectrum (1H-NMR) and Fourier transform infrared spectroscopy (FTIR). Curing behaviors and curing kinetics of designed monomers were investigated and discussed. The activation… Show more
Due to their outstanding and versatile properties, polybenzoxazines have quickly occupied a great niche of applications. Developing the ability to polymerize benzoxazine resin at lower temperatures than the current capability is essential in taking advantage of these exceptional properties and remains to be most challenging subject in the field. The current review is classified into several parts to achieve this goal. In this review, fundamentals on the synthesis and evolution of structure, which led to classification of PBz in different generations, are discussed. Classifications of PBzs are defined depending on building block as well as how structure is evolved and property obtained. Progress on the utility of biobased feedstocks from various bio-/waste-mass is also discussed and compared, wherever possible. The second part of review discusses the probable polymerization mechanism proposed for the ring-opening reactions. This is complementary to the third section, where the effect of catalysts/initiators has on triggering polymerization at low temperature is discussed extensively. The role of additional functionalities in influencing the temperature of polymerization is also discussed. There has been a shift in paradigm beyond the lowering of ring-opening polymerization (ROP) temperature and other areas of interest, such as adaptation of molecular functionality with simultaneous improvement of properties.
Due to their outstanding and versatile properties, polybenzoxazines have quickly occupied a great niche of applications. Developing the ability to polymerize benzoxazine resin at lower temperatures than the current capability is essential in taking advantage of these exceptional properties and remains to be most challenging subject in the field. The current review is classified into several parts to achieve this goal. In this review, fundamentals on the synthesis and evolution of structure, which led to classification of PBz in different generations, are discussed. Classifications of PBzs are defined depending on building block as well as how structure is evolved and property obtained. Progress on the utility of biobased feedstocks from various bio-/waste-mass is also discussed and compared, wherever possible. The second part of review discusses the probable polymerization mechanism proposed for the ring-opening reactions. This is complementary to the third section, where the effect of catalysts/initiators has on triggering polymerization at low temperature is discussed extensively. The role of additional functionalities in influencing the temperature of polymerization is also discussed. There has been a shift in paradigm beyond the lowering of ring-opening polymerization (ROP) temperature and other areas of interest, such as adaptation of molecular functionality with simultaneous improvement of properties.
“…T 5% and char yield (%) of copolymers are shown in Table 3. This could be explained by the truth that there were a large number of benzene rings in polymer molecules, as well as the existence of a very strong polarity cyano-group 16 . The electron cloud density on the naphthalene ring was looser than that on benzene ring, 12 which endowed better thermal stability.Figure 6.The TGA test results of copolymers.…”
A novel series of polyarylene ether nitrile (PEN) random copolymers with a higher Tg and better mechanical and electrical properties were synthesized through nucleophilic substitution polycondensation. In the means of adjusting mole ratio of 4,4′-dihydroxybiphenyl (BP) to 2,7-naphthalenediol (ND), the performance of PEN random copolymer could be controlled. The FTIR, SEM, DSC, TGA, AR, intrinsic viscosity, and electrical and mechanical properties were performed on the samples. All the samples exhibited excellent thermal performance with Tg over 210°C, Td5% over 520°C, and heat conduction higher than 0.4 W/m·k. The PEN copolymers when the molar ratio of ND was 15% had the best comprehensive performances, whose Tg was 215°C, Td5% was up to 554.31°C, thermal conductivity was 0.4430 W/m·k, tensile strength was 113.27 MPa, and stable dielectric constant (at frequency from 103 Hz to 106 Hz) was lower than 4. As a result, this PEN copolymer obtained in this paper could provide practical value and possibility in further application in the filed including machine manufacture industry, electronic materials, and automotive industry.
“…S14). The slight solubility of DAB-A-1h and DAB-A-1O in DMAc, DMSO, and chloroform was accredited to the presence of nitrogen in the C = N group [9,11,46].…”
Section: Nucleophilic Aromatic Substitution (Nas) and Cross-linking F...mentioning
confidence: 99%
“…For example, the processability (e.g. solubility) of insoluble organic polymers such as poly(chains): ether, imine, azo-based, imide, ketone, sulfone, etc., in the non-polar media was improved through the incorporation of uorinated linkers that are known for their hydrophobicity nature (immiscibility in water) and very low dipole [4,5,9,11].…”
A new series of ether-linked, per-fluorinated organic polymers bearing azo- (-N = N-) and azomethane (-C = N-) organic linkers was reported. The synthetic methodology relied on applying the nucleophilic aromatic substitution reaction (NAS) to fluorinated linkers (e.g. decafluorobiphenyl and hexaflourobenzene) and diols of azo- and azomethane linkers. The successful formation of the new structures revealing ether-linkage substitution of selected fluorine sites was confirmed by 1H-, 13C-, 19F-NMR and FTIR. All polymers were thermally stable in the range of 350–500 °C due to the variation of fluorine and nitrogen contents. The extended conjugation of the polymers was confirmed by the changes in the UV-Vis spectra of the organic linkers and their corresponding polymers. A notable hypsochromic shift was observed in all cases, which was more pronounced with azo-based fluorinated chains due to the H-bonding on the nitrogen sites, chain conformations and planarity. The optical band gap (Eg) of the polymers was determined from the UV-Vis. The Eg values of azo-based fluorinated polymers were higher by 1eV compared to their corresponding linkers. The 19F-NMR analysis confirmed two types of NAS on both the ortho- and para- positions of the fluorinated linkers. These connections created the possibility of developing cross-linked frameworks beside the open-chain confirmation with tailored hydrophobic nature. The cross-linking formation was characterized by porosity measurements, including surface area (SA), pore size and pore volume. The highest measured values were recorded for the azo-based polymer (DAB-Z-1h), which reached 438 m2/g and a pore volume of 0.35 cm3/g. A surface area of 105 m2/g was the lowest for the open-chain azomethane-based polymer (DAB-A-1O) with a pore volume of 0.0872 cm3/g. The beneficial formation of porous structures with varied hydrophobic nature was investigated as adsorbents for separating water/benzene, water/phenol and the selective binding of methane/carbon dioxide gases from the air. The most hydrophobic polymers that contain the decafluorbiphenyl linker were suitable for benzene separation, and the superior methane uptake values were 6.14 and 3.46 mg/g, for DAB-Z-1O and DAB-A-1O, respectively. On the other hand, DAB-Z-1h, with the highest surface area (438 m2/g) and rich with nitrogen sites, has the highest CO2 uptake at 298 K (17.25 mg/g).
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