Synthesis and thermally induced structural transformation of phthalimide and nitrile-functionalized benzoxazine: toward smart <i>ortho</i>-benzoxazine chemistry for low flammability thermosets

Zhang, Kan; Liu, Yuqi; Han, Lu; Wang, Jin-Yun; Ishida, Hatsuo

doi:10.1039/c8ra10009h

Cited by 37 publications

(23 citation statements)

References 42 publications

(44 reference statements)

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“…The presence of ortho -nitrile group functionality in ortho -phthalimide-functionalized benzoxazine monomer revealed exceptionally high thermal stability ( T 5% = 550 °C) and high char yield value (70%). This is accounted to by the formation of highly crosslinked network, stemming from the occurrence of multiple polymerization reactions, namely, oxazine ROP, cyano cyclotrimerization and benzoxazole ring formation [ 199 ]. Benzoxazine monomers with atropisomerism [ 200 , 201 , 202 , 203 ] account for a more interesting set of properties than traditional benzoxazine structures.…”

Section: Classification Of Benzoxazine Monomersmentioning

confidence: 99%

Review on the Accelerated and Low-Temperature Polymerization of Benzoxazine Resins: Addition Polymerizable Sustainable Polymers

et al. 2021

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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.

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Section: Classification Of Benzoxazine Monomersmentioning

confidence: 99%

Review on the Accelerated and Low-Temperature Polymerization of Benzoxazine Resins: Addition Polymerizable Sustainable Polymers

et al. 2021

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“…Ring‐opened polymerization under heating or catalysis results in a network structure, which is called polybenzoxazine (PBO), similar to that of phenolic resin . Because of the different structural characteristics of phenolic resin, benzoxazine maintains the advantages such as excellent hardness, heat resistance, inner flame retardancy, electrical insulation, and low cost of traditional phenolic resin, but also has a certain degree of toughness, relatively high char yields and near‐zero shrinkage upon polymerization of the monomers . Therefore, PBO is the most desirable material for preparing high‐strength and flame‐retardant aerogel thermal insulating materials.…”

Section: Introductionmentioning

confidence: 99%

Thermal Insulation Characteristics of Polybenzoxazine Aerogels

Xiao

Zhang

et al. 2019

Macro Materials & Eng

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Polybenzoxazine (PBO) aerogels with low densities and low thermal conductivities are prepared from Bisphenol A (BPA) benzoxazine monomers by ring‐opened polymerisation using HCl as a catalyser at 10 °C. The obtained PBO aerogels have cross‐linked and 3D network structures with the densities ranging from 0.084 to 0.526 g cm−3. The thermal conductivities under different pressures (3–105 Pa, air) and different atmospheres (N2, Ar, and CO2, 105 Pa) are investigated. The thermal conductivities are in the range of 0.0335–0.0652 W m K−1 under ambient pressure and 0.0098–0.0571 W m K−1 at 3 Pa. The thermal transfer mechanism under different gas pressures is analyzed with increasing pressure. Under different atmospheres, the thermal conductivities decrease as the molecular weight of the gas increases. Compared with the traditional organic foam insulating materials of phenolic foam, polyurethane and polystyrene, which have similar apparent densities, PBO aerogels exhibit lower thermal conductivity of 0.0335 W m K−1 than that of traditional organic foam at room temperature.

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“…33 The existence of phthalonitrile group in o HMTI-pn is indicated by the bands centered at 2225 cm −1 , which is due to the cyanide stretching vibration. 34,35 Besides, the typical bands for the oxazine ring related mode are observed at 930 and 957 cm −1 for o HMTI-a and o HMTI-pn, respectively. 36 –38 Moreover, the presence of aromatic ether from the oxazine ring for o HMTI-a and o HMTI-pn is identified by bands centered at 1238 and 1243 cm −1 , respectively.…”

Section: Resultsmentioning

confidence: 94%

Synthesis ofortho-methyltetrahydrophthalimide functional benzoxazine containing phthalonitrile group: Thermally activated polymerization behaviors and properties of its polymer

Yang

Wang

Hao

et al. 2020

High Performance Polymers

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Two novel benzoxazine monomers, oHMTI-a and oHMTI-pn, have been obtained via the modified Mannich condensation from ortho-4-methyltetrahydrophalimide functional phenol, paraformaldehyde, and aniline/4-aminophthalonitrile, respectively. The chemical structures of both benzoxazine monomers have been studied by Fourier transform infrared (FT-IR) and 1H and 13C nuclear magnetic resonance (NMR) spectra. Their polymerization processes are investigated using in-situ FT-IR and different scanning calorimetry (DSC). Specifically, the phthalonitrile group in oHMTI-pn can react at a relatively lower temperature without adding any catalysts, which suggests the presence of the thermal synergistic polymerization effect in this benzoxazine monomer. In addition, the thermal and fire related properties of the resulting polybenzoxazines are evaluated by thermogravimetric analysis (TGA) and micro-scale combustion calorimetry (MCC). The polybenzoxazine derived from oHMTI-pn shows both high thermal stability and outstanding flame retardancy, with a T g of 350°C, a T d10 value of 417°C, a high char yield value of 65%, and a very low heat release capacity value of 35.2 J/(g·K).

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Synthesis and thermally induced structural transformation of phthalimide and nitrile-functionalized benzoxazine: toward smart ortho-benzoxazine chemistry for low flammability thermosets

Abstract: A novel ortho-phthalimide-functionalized benzoxazine monomer containing an ortho-nitrile group has been synthesized in order to develop high-performance thermosets with high thermal stability and low flammability.

Cited by 37 publications

References 42 publications

Review on the Accelerated and Low-Temperature Polymerization of Benzoxazine Resins: Addition Polymerizable Sustainable Polymers

Review on the Accelerated and Low-Temperature Polymerization of Benzoxazine Resins: Addition Polymerizable Sustainable Polymers

Thermal Insulation Characteristics of Polybenzoxazine Aerogels

Synthesis ofortho-methyltetrahydrophthalimide functional benzoxazine containing phthalonitrile group: Thermally activated polymerization behaviors and properties of its polymer

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