Advanced Carbon Materials Derived from Polybenzoxazines: A Review

Abstract

This comprehensive review article summarizes the key properties and applications of advanced carbonaceous materials obtained from polybenzoxazines. Identification of several thermal degradation products that arose during carbonization allowed for several different mechanisms (both competitive ones and independent ones) of carbonization, while also confirming the thermal stability of benzoxazines. Electrochemical properties of polybenzoxazine-derived carbon materials were also examined, noting particularly high pseudocapacitance and charge stability that would make benzoxazines suitable as electrodes. Carbon materials from benzoxazines are also highly versatile and can be synthesized and prepared in a number of ways including as films, foams, nanofibers, nanospheres, and aerogels/xerogels, some of which provide unique properties. One example of the special properties is that materials can be porous not only as aerogels and xerogels, but as nanofibers with highly tailorable porosity, controlled through various preparation techniques including, but not limited to, the use of surfactants and silica nanoparticles. In addition to the high and tailorable porosity, benzoxazines have several properties that make them good for numerous applications of the carbonized forms, including electrodes, batteries, gas adsorbents, catalysts, shielding materials, and intumescent coatings, among others. Extreme thermal and electrical stability also allows benzoxazines to be used in harsher conditions, such as in aerospace applications.

Keywords: advanced carbon material; benzoxazine; polybenzoxazine.

Figure 1

(a) Benzoxazine monomer synthesis from a phenolic derivative with the open o-positions, a primary amine, and formaldehyde. (b) Cationic ring opening polymerization of benzoxazine monomer showing no production of reaction side products.

Figure 2

Comparison of polybenzoxazine aerogels prepared by (a) supercritical drying and (b) ambient drying showing the similarity of the microstructure. (Reproduced from the work in [36] with permission).

Figure 3

(a) Freeze-dried bisphenol A/tetraethylenepentamine (tepa) benzoxazine modified chitosan (1:1) (abbreviated as BA-tepa/CTS). (b) Freeze-dried BA-tepa/CTS reinforced with 5wt% of montmorillonite showing improved layer morphology. (Reproduced from the work in [37] with permission).

Figure 4

(a) A film made of PBA-ad6, and (b) electrospun nanowebs from 40% chloroform/DMF mixed solvent solution of PBA-ad6. (Reproduced from the work in [40] with permission).

Figure 5

Degradation of hydrogen bonded nitrogen in the Mannich base of aniline-based benzoxazines to produce (a) aniline or (b) conjugated Schiff bases [45].

Figure 6

Degradation of non-hydrogen bonded nitrogen in the Mannich base of aniline-based benzoxazines to produce aniline [45].

Figure 7

Deamination from C–N cleavage and deaminomethylation from C–C cleavage during char formation from BA-a. [46].

Figure 8

Effect of CuCl initiator concentration on char yield for 3-aminphenylacetylene based benzoxazines (Reproduced from [47] with permission).

Figure 9

Preparation process of nitrogen-doped carbonized benzoxazine. (Reproduced from the work in [57] with permission).

Figure 10

CV curves (a) and GCD plot (b) of nitrogen and sulfur co-doped benzoxazine at various scan rates (a) or current densities (b). (Reproduced from the work in [56] with permission).

Figure 11

TEM images of carbonized benzoxazine films that are (a) BA-a- or (b) PH-ddm-based and (c) carbonized PI film (reproduced from the work in [58] with permission).

Figure 12

Compression modulus effect with increasing foam density (reproduced from the work in [59] with permission).

Figure 13

Compressive stress–strain curve of benzoxazine foam at varying densities (reproduced from the work in [59] with permission).

Figure 14

Optical microscope images (with 5 times magnification) of benzoxazine foam at varying densities of (a) 407 kg/m³, (b) 378 kg/m³, (c) 339 kg/m³, (d) 306 kg/m³, and (e) 273 kg/m^3. (reproduced from the work in [59] with permission).

Figure 15

Compressive stress–strain curve of polybenzoxazine foam and carbon foam (reproduced from the work in [59] with permission).

Figure 16

Formation of A-Fe@CNF through BA-a polymerization, electrospinning, curing, activation, and carbonization (reproduced from the work in [39] with permission).

Figure 17

Formation process of GCAs through wrapping, interconnecting, and carbonization (reproduced from the work in [63] with permission).

Figure 18

Nanosphere size as it relates to IRT for nanospheres before (a) and after (b) carbonization (reproduced from the work in [64] with permission).

Figure 19

Catalyzed ring opening polymerization and carbonizations to form carbon nanospheres (reproduced from the work in [66] with permission).

Figure 20

SEM images of carbon aerogels at (a) 20 wt% monomer (cured), (b) 20 wt% monomer (uncured), (c) 40 wt% monomer (cured), and (d) 40 wt% monomer (uncured) (reproduced from the work in [33] with permission).

Figure 21

Phase separation of MCBP(BA-teta) solution to form secondary (a) and large primary (b) clusters and resulting scanning electron microscope (SEM) images of their morphology (reproduced from the work in [34] with permission).

Figure 22

Effects of silica loading on BET surface area (a) and pore volume (b) of PBZ carbon xerogels (reproduced from the work in [74] with permission).

Figure 23

SEM images with low magnification (1) or high magnification (2) of CTAB added at concentrations of (a) 0 M, (b) 0.003 M, (c) 0.009 M, (d) 0.030 M, (e) 0.090 M, and (f) 0.180 M (reproduced from the work in [36] with permission).

Figure 24

SEM images with low magnification (1) or high magnification (2) of Synperonic NP30 added at concentrations of (a) 0 M, (b) 0.003 M, (c) 0.009 M, (d) 0.030 M, (e) 0.090 M, and (f) and 0.180 M (reproduced from the work in [36] with permission).

Figure 25

Magnetic hysteresis loops of A-FeCNFs (a), dye adsorption over time of A-FeCNFs plotted as the ratio of dye concentration to initial concentration (b), and magnetic performance after MB dye adsorption (reproduced from the work in [61] with permission).

Figure 26

Schematic representation of flexibility of SnO₂ incorporated CNF membranes under bending (reproduced from the work in [78] with permission).

Figure 27

Photographs demonstrating (a) shape maintenance, (b) low density, and (c) and shape recovery capability of GCA (reproduced from the work in [63] with permission).

Figure 28

From biomass to supercapacitor (reproduced from the work in [77] with permission).

Figure 29

SEM electron photomicrographs of organic aerogel (a) and the carbon aerogel derived from it (b) (reproduced from the work in [89] with permission).

Figure 30

Cyclic voltammograms of CA(BA-teta) (a) and CA(BA-a) (b) with scan rates of 1, 5, 25, and 50 mV/s (reproduced from the work in [89] with permission).

Figure 31

Schematic illustration of L-lysine-assisted formation of cubic nitrogen-doped ordered mesoporous carbons (OMCs) (reproduced from the work in [96] with permission).

Figure 32

GO/NC nanocomposites prepared from a novel polybenzoxazine (reproduced from the work in [81] with permission).

Figure 33

Polybenzoxazine based hierarchically porous carbons (reproduced from the work in [83] with permission).

Figure 34

Synthesis principle of MHCN (a) negatively charged GO colloids; (b) the selected amino acid, asparagine (Asn) dispersed on GO platforms; (c) in situ reaction and condensation of pre-loading Asn, resorcinol and formaldehyde, forming poly(benzoxazine-co-resol) layer; and (d) formation of microporous hybrid carbon nanosheets during pyrolysis (reproduced from the work in [91] with permission).

Figure 35

Diagram for the formation process of coral-like carbon (reproduced from the work in [92] with permission).

Figure 36

Schematic synthesis of 3D core–shell UMCNs with regular ultra-micropores in the cores and abundant micropores in the shells (reproduced from the work in [79] with permission).

Figure 37

CV scan of UMCN-60 electrode at scan rate of 5 V/s (reproduced from the work in [79] with permission).

Figure 38

SEM images of (a) NPC-500, (b) NPC-600, (c) NPC-700, and (d) NPC-800 (reproduced from the work in [83] with permission).

Figure 39

Schematic representation of the skin-tissue-bone like structure (reproduced from the work in [85] with permission).

Figure 40

PSDs obtained from DFT method of all samples (reproduced from the work in [93] with permission).

Figure 41

CO₂ adsorption of MMT-CA-1 (highest micropore volume), MMT-CA-2 (highest BET surface area), and CA-1 benzoxazine samples with varying clay concentrations (reproduced from the work in [37] with permission).

Figure 42

CO₂ interactions with substrates (in the carbonized benzoxazine) containing (a) pyridonic nitrogen, (b) hydroxy groups, (c) carboxylic acids, (d) methoxyl, and (e) pyrrolic nitrogen, with the effect of hydrogen bonding shown in a–c (reproduced from the work in [108] with permission).

Figure 43

Breakthrough curves of MMT-CA-1 at increasing temperatures (reproduced from the work in [37] with permission).

Figure 44

CO₂ adsorption of N- and S-doped benzoxazines over 5 cycles (reproduced from the work in [109] with permission).

Figure 45

CO₂ and N₂ adsorption by benzoxazines at 25 °C (reproduced from the work in [109] with permission).

Figure 46

IAST selectivity factors of CO₂ adsorption from (a) N₂ and (b) CH₄ (reproduced from the work in [108] with permission).

Figure 47

Synthesis scheme for N,S functionalities in the porous carbons (reproduced from the work in [112] with permission).

Figure 48

Synthesis scheme of FeCo₂ crystals supported on N-doped hierarchical structured porous carbon fibers (reproduced from the work in [62] with permission).

Figure 49

Enhanced photocatalytic reaction at monolithic aerogel interface for stable water splitting reactions (reproduced from the work in [117] with permission).

Figure 50

Synthesis schematic of basophilic green fluorescent carbon nanoparticles derived from benzoxazine (reproduced from the work in [119] with permission).

Figure 51

Graphical representation of pH-controlled green luminescent carbon dots with fluorescence turn-on and turn-off detection (reproduced from the work in [41] with permission).

Figure 52

Benzoxazine-derived CD binding to the surface of virions, thus preventing entry of virions into the host cell; the first step of virus–cell interaction (reproduced from the work in [42] with permission).

Figure 53

Schematic of EMI shielding of polybenzoxazine/graphene nanocomposite samples PBA-a/G and PBA-a/GS (reproduced from the work in [121] with permission).

Figure 54

(a) Preparation process of novel biobased benzoxazine synthesized from DPA and furfurylamine with Fe₃CO₄ nanoparticles dispersed prepared by the solvothermal method with simultaneous polymerization and self-foaming reactions of benzoxazine monomer and thermal decomposition of Fe(acac)₂; (b) Synthesis of the benzoxazine monomer; (c) the structure of the dye used, and (d) the polymerization scheme of the benzoxazine monomer. Only idealized structure is shown. (reproduced from the work in [124] with permission).

Figure 55

Benzoxazine-co-resol based porous carbon monoliths for high-performance CO₂ capture (reproduced from the work in [125] with permission).

Figure 56

Optical photomicrographs of bonding layer cross sections derived from phenolic resin hot-pressed at 1 MPa during carbonization (a) and polybenzoxazine at 10 MPa (b) (reproduced from the work in [128] with permission).