Synthesis of a triptycene-containing dioxazine benzoxazine monomer and a main-chain triptycene-polydimethysiloxane-benzoxazine copolymer with excellent comprehensive properties

Yang, Rui; Xie, Lin; Li, Nan; Froimowicz, Pablo; Zhang, Kan

doi:10.1039/d2py00244b

Cited by 19 publications

(14 citation statements)

References 62 publications

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“…2 So far, polybenzoxazines have been found to possess many advantages over most commercialized polymeric materials such as good mechanical performance, 5,6 high thermal resistance, 7−9 high T g , 10,11 high flame retardancy, 12,13 low dielectric constant (k), 14,15 and very low values of surface-free-energy. 9,16,17 The above discovered advantages make polybenzoxazine thermosets attractive candidates for a number of cutting-edge applications, including electronic materials, aerospace, and transit construction. 2 Utilizing naturally sourced chemicals to synthesize biobased polymers has been more and more important in order to satisfy the demand of sustainable development.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The flexible chemical structure and the existence of rich raw materials of benzoxazines allow researchers to obtain polybenzoxazine materials with many attractive properties . So far, polybenzoxazines have been found to possess many advantages over most commercialized polymeric materials such as good mechanical performance, , high thermal resistance, − high T g , , high flame retardancy, , low dielectric constant ( k ), , and very low values of surface-free-energy. ,, The above discovered advantages make polybenzoxazine thermosets attractive candidates for a number of cutting-edge applications, including electronic materials, aerospace, and transit construction …”

Section: Introductionmentioning

confidence: 99%

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Biobased Bisbenzoxazine Resins Derived from Natural Renewable Monophenols and Diamine: Synthesis and Property Investigations

Zhao

Chen

Zhang

2022

ACS Sustainable Chem. Eng.

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Synthesizing biobased thermosetting resins with unique performance from renewable resources has attracted increasing attention because of the sustainable development aspirations from human beings. However, diamine-derived bio-bisbenzoxazine resins have rarely been reported because of the lack of naturally sourced diamines in nature. Here, we report a series of biobased bisbenzoxazine resins via green synthetic methods using various monophenols (guaiacol/sesamol/peterostilbene) and a diamine (Priamine 1074) as natural renewable raw materials. Chemical structural details of these bisbenzoxazines were characterized by nuclear magnetic resonance, Fourier transform infrared spectroscopy, and size exclusion chromatography. Thermally activated polymerization behaviors were investigated by differential scanning calorimetry thermograms and in situ FT-IR analysis. Besides, surface properties of each resin were studied through the contact angle measurement, and surface-free-energy values without varying too much were achieved from this series of Priamine 1074-derived bioresin coatings before and after different polymerization cycles. Moreover, thermal stability of the fully polymerized bioresins was evaluated by dynamic mechanical analysis and thermogravimetry analyses. These bio-polybenzoxazines all showed good thermal properties with T d10 greater than 350 °C. Consequently, this new family of biobased bisbenzoxazine thermosetting resins and their corresponding polybenzoxazines exhibit outstanding surface and thermal performances, providing great potential applications for high-performance polymeric coating materials.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Biobased Bisbenzoxazine Resins Derived from Natural Renewable Monophenols and Diamine: Synthesis and Property Investigations

Zhao

Chen

Zhang

2022

ACS Sustainable Chem. Eng.

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“…Polybenzoxazine (PBa) is a phenolic-based thermoset resin with excellent thermo-oxidative stability and dielectric properties compared to epoxies due to their abundant hydrogen bonding (H-bonding) sites combined with crosslinked structures. − In addition, several features of PBa, including noncatalyst polymerization, near-zero cure shrinkage, low water absorption, good flame retardancy, and rich molecular design flexibility, make it attractive for a wide variety of applications. − However, PBa is intrinsically brittle due to its rigid and crosslinked structure, which limits its applications in the microelectronic and aerospace fields. , …”

Section: Introductionmentioning

confidence: 99%

Fracture Behavior of Polybenzoxazine Toughened by Polyrotaxane Molecules and Core–Shell Rubber

Zhu

Chen

Zhu

et al. 2023

ACS Appl. Eng. Mater.

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The inherent brittleness of polybenzoxazines (PBas) makes them difficult for high-performance microelectronics and composite applications. Conventional toughening approaches are either ineffective or cause a reduction in the glass transition temperature (T g ) of PBa. Polyrotaxane (PR), a mechanically interlocked supramolecular polymer, is an effective toughening agent to improve the tensile strength and fracture toughness of various polymers due to its unique topological structure. In this study, the effect of the molecular weight and functional groups of PRs on the morphology and mechanical properties of PR-modified PBa was investigated. PBa toughened by well-dispersed epoxide-functionalized PR (EPR) and benzoxazine-functionalized core−shell rubber (BCSR) was found to greatly enhance fracture toughness without compromising Young's modulus or T g . The fracture toughness is significantly improved from 0.82 MPa m 1/2 for neat PBa to 1.49 MPa m 1/2 for PBa/EPR/BCSR. The synergistic toughening effect is explained by the molecularly dispersed EPR in the PBa network, which results in higher network chain mobility, which promotes more cavitation of BCSR and triggers larger matrix plastic deformation. It is believed that the knowledge gained from the present study can help develop tougher polymers for vast engineering applications, especially in electronics, automotive, and aerospace applications.

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“…For instance, maleimide, , acetylene, thiazole, thioamide, and furan groups have been used to modify the chemical structure of benzoxazine monomers. Another efficient approach is to synthesize polymers and/or oligomers, placing the oxazine rings as constitutive parts of their main chains. − An extra advantage observed in the thermosets polymerized using main chain-type benzoxazines as precursors is that the resulting polybenzoxazines easily overcome the common shortcoming of brittleness normally present in polybenzoxazines prepared upon polymerization of conventional benzoxazine monomers. − …”

Section: Introductionmentioning

confidence: 99%

Competitive Study of Novel Triptycene-Containing Benzoxazine Monomers and a Thermoresponsive Linear Main Chain-Type Benzoxazine Copolymer: Synthesis, Polymerization, and Thermal Properties of Their Thermosets

Xie

Yang

et al. 2022

Macromolecules

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Two novel triptycene-based dioxazine benzoxazine monomers (TB-a and TB-fa) have been synthesized using triptycene-1,4-hydroquinone (TB), aniline/furfurylamine, and paraformaldehyde as raw materials. The chemical structures of both dioxazine benzoxazine monomers were elucidated by 1 H and 13 C NMR, Fourier transform infrared (FT-IR), high-resolution mass spectroscopy, and elemental analysis. By taking advantage of the furan groups present in TB-fa and the reversibility of the Diels−Alder reaction, 4,4′-bismaleimidodiphenylmethane (DDM-BMI) was used as a comonomer for synthesizing a thermoresponsive linear main chain-type benzoxazine copolymer (TB-fa-co-DDM-BMI). The polymerization processes of oxazine ring-containing monomers and the copolymer were studied by DSC and in situ FT-IR analyses, while the thermal stability and flammability of the resulting thermosets were studied by thermogravimetric analysis and microscale combustion calorimetry. Remarkably, the thermoset derived from the thermoresponsive TB-fa-co-DDM-BMI exhibits the best thermal stability as demonstrated by the T d10 and Yc values of 388 °C and 55% at 800 °C under a nitrogen atmosphere, respectively. Its low heat release capacity value of 31.9 J g −1 K −1 shows its great potential as a good flame retardant agent. The outstanding properties exhibited by the herein presented polybenzoxazines, compared to those of many other reported traditional polybenzoxazines, evidence their potential applications in the design of advanced materials.

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Synthesis of a triptycene-containing dioxazine benzoxazine monomer and a main-chain triptycene-polydimethysiloxane-benzoxazine copolymer with excellent comprehensive properties

Abstract: A novel triptycene-containing dioxazine benzoxazine monomer and a main-chain benzoxazine copolymer have been synthesized and their corresponding thermosets exhibit excellent thermal stability, low flammability and low dielectric constants.

Cited by 19 publications

References 62 publications

Biobased Bisbenzoxazine Resins Derived from Natural Renewable Monophenols and Diamine: Synthesis and Property Investigations

Biobased Bisbenzoxazine Resins Derived from Natural Renewable Monophenols and Diamine: Synthesis and Property Investigations

Fracture Behavior of Polybenzoxazine Toughened by Polyrotaxane Molecules and Core–Shell Rubber

Competitive Study of Novel Triptycene-Containing Benzoxazine Monomers and a Thermoresponsive Linear Main Chain-Type Benzoxazine Copolymer: Synthesis, Polymerization, and Thermal Properties of Their Thermosets

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