Preparation of Bio‐Based Polybenzoxazine/Pyrogallol/Polyhedral Oligomeric Silsesquioxane Nanocomposites: Low Dielectric Constant and Low Curing Temperature

Abstract

In this work, a bio-based benzoxazine monomer (C-s) is synthesized from cardanol, stearylamine, and paraformaldehyde through solvent-free method. Pyrogallol is used as a curing catalyst for the ring-opening polymerization of benzoxazine. Differential scanning calorimeter (DSC) results reveal that doping with pyrogallol reduces the exothermic peak temperature (T p ) of C-s from 256 to 174 °C. The polybenzoxazine/pyrogallol/polyhedral oligomeric silsesquioxane (PC-s/py/POSS) nanocomposites are prepared via thermal curing. The doping of aminopropyl isobutyl POSS (POSS-NH 2 ) can reduce the dielectric constant of polybenzoxazine. The dielectric constant of PC-s/py/POSS is 2.64 at 1 MHz when the doping amount of POSS-NH 2 is 10 wt%. The results of thermogravimetric analysis (TGA) and water absorption test indicate that the PC-s/py/POSS nanocomposites possess good thermal stability and water resistance. In summary, the PC-s/py/POSS nanocomposites with low curing temperature and low dielectric constant are expected to be applied to the low dielectric materials for microelectronic applications.

Highly Thermally Stable, Reversible, and Flexible Main Chain Type Benzoxazine Hybrid Incorporating Both Polydimethylsiloxane and Double‐Decker Shaped Polyhedral Silsesquioxane Units through Diels–Alder Reaction

“…[9] Attempts have been made to decrease chain mobility of BZ resin to improve its thermal and mechanical properties by incorporating unsaturated (such as allyl or alkynyl) groups, blending with high-performance polymers to form miscible blends, [10][11][12][13][14][15][16] and adding inorganic nanoparticles. [17][18][19][20][21][22] Many organic/inorganic polybenzoxazine (PBZ) hybrids (and other thermosetting resins) have been prepared by incorporating carbon-based materials (e.g., carbon nanotubes, [23][24][25] carbon black, [26] and graphene [27][28][29][30] ) and siliconbased materials [e.g., polydimethylsiloxane (PDMS), [5,[31][32][33] organic modified clay, [34,35] and polyhedral oligomeric silsesquioxane (POSS) [17][18][19][20][21][22][36][37][38][39][40] ]. For example, polymer/POSS hybrids have been obtained from mono-and multifunctionalized POSS derivatives through blending or copolymerization, initially forming organic/inorganic hybrids with only relatively lowmolecular-weight or insoluble cross-linked structures.…”

“…[ 9 ] Attempts have been made to decrease chain mobility of BZ resin to improve its thermal and mechanical properties by incorporating unsaturated (such as allyl or alkynyl) groups, blending with high‐performance polymers to form miscible blends, [ 10–16 ] and adding inorganic nanoparticles. [ 17–22 ]…”

“…Many organic/inorganic polybenzoxazine (PBZ) hybrids (and other thermosetting resins) have been prepared by incorporating carbon‐based materials (e.g., carbon nanotubes, [ 23–25 ] carbon black, [ 26 ] and graphene [ 27–30 ] ) and silicon‐based materials [e.g., polydimethylsiloxane (PDMS), [ 5,31–33 ] organic modified clay, [ 34,35 ] and polyhedral oligomeric silsesquioxane (POSS) [ 17–22,36–40 ] ]. For example, polymer/POSS hybrids have been obtained from mono‐ and multifunctionalized POSS derivatives through blending or copolymerization, initially forming organic/inorganic hybrids with only relatively low‐molecular‐weight or insoluble cross‐linked structures.…”

Synthesis of a Novel Bifunctional Epoxy Double-Decker Silsesquioxane: Improvement of the Thermal Stability and Dielectric Properties of Polybenzoxazine

“…The polymer/POSS nanocomposites formed by mixing POSS into thermosets have a significant impact on thermal stability, mechanical properties, dielectric properties and flame retardance of the resin, and their thermal stability and mechanical strength are better than pure resin [ 33 ]. The hollow structure of cage-type makes it an ideal low-dielectric nanometer filler [ 34 , 35 , 36 , 37 ]. In the past few years, there has been ample literature reported on the use of POSS to modify PBZ.…”

Metal Ion-Catalyzed Low-Temperature Curing of Urushiol-Based Polybenzoxazine

“…On the other hand, bio-based benzoxazines can be prepared by bio-based phenols and amines instead of petroleum-based ones. Until now, bio-based polybenzoxazine ( Salum et al, 2018 ; Zhan et al, 2019 ; Lu et al, 2020 ; Zhan et al, 2020 ; Cai et al, 2021 ; Machado et al, 2021 ; Zhang et al, 2022 ) resins have been successfully prepared by natural phenols (cardanol ( Appavoo et al, 2020 ), urushiol ( Chen et al, 2021b ), eugenol ( Zhu et al, 2019 ), resorcinol ( Arnebold et al, 2014 ), guaiacol ( Phalak et al, 2017 ), bisguaiacol F ( Periyasamy et al, 2016 ), phloretic acid ( Kirubakaran et al, 2020 ) ( Zhang et al, 2019a ), and resveratrol ( Zhang et al, 2019b )) and natural amines [( Zhu et al, 2020a ), stearyl amine ( Zhao et al, 2022 ), and rosin-based amines ( Liu et al, 2017 ) and ( Alhwaige et al, 2019) ].…”