There is, I think, something ethereal about i —the square root of minus one. I remember first hearing about it at school. It seemed an odd beast at that time—an intruder hovering on the edge of reality.

Usually familiarity dulls this sense of the bizarre, but in the case of i it was the reverse: over the years the sense of its surreal nature intensified. It seemed that it was impossible to write mathematics that described the real world in …

I and i

Five commercially available amines: m-phenylenediamine (A1), m-xylylenediamine (A2), isophorone diamine (A3), trimethylhexamethylenediamine (A4), and 4,4′-diaminodiphenyl sulfone (A5), were examined as nucleophilic hardeners for bis-benzoxazine monomers based on aniline paired with bisphenol-A (BA-a) or bisphenol-F (BF-a). The reactivities and reaction mechanisms of their mixtures with BA-a were investigated using FTIR and NMR spectroscopy, DSC, and HPLC techniques. It was found that BA-a rapidly cured with the amines upon heating at 120 °C or 150 °C. The cure rate was similar to the amine/epoxy curing process in practical uses, and significantly faster than the ring-opening polymerization of bulk BA-a. The possible reaction mechanism was supported by the experimental results and includes three successive steps: (i) nucleophilic substitution at the carbon atom (O–C–N) in the oxazine ring by the amine, (ii) thermal decomposition of the resulting aminomethanaminium structure, and (iii) electrophilic addition of the newly formed iminium ion with the aromatic ring to form stable aminomethylphenol structures. These findings are helpful to improve the thermosetting resins in terms of their chemical structure, material properties, and processability.

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A curing system of benzoxazine with amine: reactivity, reaction mechanism and material properties

Pyrene-functionalized tetraphenylethylene polybenzoxazine for dispersing single-walled carbon nanotubes and energy storage

A smart synthetic chemical design incorporating furfurylamine, a natural renewable amine, into a partially bio-based coumarin-containing benzoxazine is presented. The versatility of the synthetic approach is shown to be flexible and robust enough to be successful under more ecofriendly reaction conditions by replacing toluene with ethanol as the reaction solvent and even under solventless conditions. The chemical structure of this coumarin-furfurylamine-containing benzoxazine is characterized by FTIR, 1H NMR spectroscopy and two-dimensional 1H–1H nuclear Overhauser effect spectroscopy (2D 1H–1H NOESY). The thermal properties of the resin toward polymerization are characterized by differential scanning calorimetry (DSC) and the thermal stability of the resulting polymers by thermogravimetric analysis (TGA). The results reveal that the furanic moiety induces a co-operative activating effect, thus lowering the polymerization temperature and also contributes to a better thermal stability of the resulting polymers. These results, in addition to those of natural renewable benzoxazine resins reviewed herein, highlight the positive and beneficial implication of designing novel bio-based polybenzoxazine and possibly other thermosets with desirable and competitive properties.

Smart, Sustainable, and Ecofriendly Chemical Design of Fully Bio‐Based Thermally Stable Thermosets Based on Benzoxazine Chemistry

We have developed novel di-, tri-, and tetrafunctional benzoxazine monomers (BZ2, BZ3, and BZ4), solely containing benzoxazine moieties arranged one after the other on the backbone, to discover the role of additional oxazine moiety on thermal properties. A tandem reaction was adapted, at first a ring-closure and then subsequent Mannich condensation by reacting 2-((4-hydroxyphenyl)aminomethyl)phenol (HPAMP) and aniline/4-amino-2-((phenylamino)methyl)phenol/4-amino-2-(((4-hydroxy-3-((phenylamino)methyl)phenyl)amino)methyl)phenol in the presence of paraformaldehyde to obtain BZ2/BZ3/BZ4. Tetrafunctional benzoxazine monomers containing an intermediate group (R-BZ4) were also synthesized by reacting HPAMP and p-phenylenediamine/4,4′-diaminodiphenylmethane (PDA/DDM) to understand the differences in thermal properties due to the distance created by those between two benzoxazine moieties. The observations (in DSC and TGA analysis) with increase in number of oxazine rings include (i) reduction in curing temperatur...

Toward Elucidating the Role of Number of Oxazine Rings and Intermediates in the Benzoxazine Backbone on Their Thermal Characteristics

A novel furan-containing tetrafunctional fluorene-based benzoxazine monomer with bisphenol- and diamine-type oxazine rings was successfully prepared. The resulting polybenzoxazine exhibits extremely higher glass transition temperature (440 °C) and better thermal stability than difunctional furan-containing fluorene-based and traditional multifunctional benzoxazine resins.

Minjie Luan

Papers

Synthesis of novel furan-containing tetrafunctional fluorene-based benzoxazine monomer and its high performance thermoset