Heat-resistant and robust biobased benzoxazine resins developed with a green synthesis strategy

Sha, Xin-Long; Yuan, Li; Liang, Guozheng; Gu, Aijuan

doi:10.1039/d0py01529f

Cited by 37 publications

(25 citation statements)

References 65 publications

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“…As a new type of thermosetting resin, polybenzoxazine has attracted worldwide attention in the past 30 years owing to its prominent performances in terms of not only thermal and mechanical properties − but also flexibility of molecular design, − low dielectric constant, − very low surface free energy without using fluorine atoms, and excellent flame retardancy. − Unfortunately, applications of benzoxazine have encountered processing problems because most benzoxazine monomers are solid at room temperature and their melting temperatures are generally higher than 90 °C. − Until now, poor processability of benzoxazine monomers is still the key barrier that limits the development of polybenzoxazine resin.…”

Section: Introductionmentioning

confidence: 99%

Novel Combination of Vinyl Benzoxazine and Its Copolymerizable Diluent with Outstanding Processability for Preparing a Bio-Based Thermoset

Qian

Lou

et al. 2021

ACS Sustainable Chem. Eng.

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The application of polybenzoxazine resin still remains a puzzling problem in processability due to the high melting temperature of benzoxazine. Here, a bio-based reactive diluent, 4-vinyl guaiacol acetate (AC4VG), and a bio-based benzoxazine monomer, 4VG-fu, were synthesized using the diluent-based strategy for improving the poor processability of benzoxazine. 4VG-fu and AC4VG show good miscibility, and their mixture solutions exhibit a very low viscosity. When the mixtures are heated, free radical copolymerization of 4VG-fu and AC4VG takes place at a low temperature range (120−140 °C), and ringopening polymerization of the benzoxazine groups pendant to the copolymer chains occurs at a higher temperature range (140−220 °C). The last polymerization induces microphase separation in the cured resin, and the AC4VG/4VG-fu molar ratio exerts an important effect on the degree. The AC4VG/4VG-fu solutions also show good suitability with cotton fabrics for preparing composite materials, resulting in satisfactorily thermal and dynamic mechanical properties. These results suggest an effective strategy for improving the processability of benzoxazines, opening a way to develop fully bio-based polybenzoxazine resins with high performance.

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Section: Introductionmentioning

confidence: 99%

Novel Combination of Vinyl Benzoxazine and Its Copolymerizable Diluent with Outstanding Processability for Preparing a Bio-Based Thermoset

Qian

Lou

et al. 2021

ACS Sustainable Chem. Eng.

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“…115,116 Liang and Gu invented a vanillin-based benzoxazine bearing alkynyl by solvent-free method, the unique crosslinked network gives the resin high T g (304 C) and storage modulus (3.65 GPa), as shown in Scheme 11. 117 Eugenol contains both phenolic hydroxyl groups and carbon-carbon double bonds, which are potential coupling reaction sites. When the double bond acts as the potential crosslinking site, the resin showed increased crosslinking density which could be further adjusted by the addition of eugenol.…”

Section: High Performance Bio-based Benzoxazine Resinmentioning

confidence: 99%

“…The retention of aldehyde group was found to participate in the curing reaction of benzoxazine, of which the main process is oxidation and decarboxylation 115,116 . Liang and Gu invented a vanillin‐based benzoxazine bearing alkynyl by solvent‐free method, the unique crosslinked network gives the resin high T g (304°C) and storage modulus (3.65 GPa), as shown in Scheme 11 117 …”

Section: Bio‐based Benzoxazine Resinmentioning

confidence: 99%

Recent development on bio‐based thermosetting resins

Liu

Zhang

Shun

et al. 2021

Journal of Polymer Science

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Due to the rapid depletion of crude oil and serious environmental pollution, the synthesis of polymers from renewable resource is becoming more and more important. Up to now, a great variety of biomass and bio-based platform compounds have been taken to prepare the polymers. However, as two representative thermosetting resins, epoxy and benzoxazine resin derived from renewable feedstocks only obtain limited attention compared with the popular bio-based plastics, including PLA, PBAT and PHBV etc. The reason might be that the properties of previously reported thermosetting resins directly obtained from biomass are usually unsatisfied, and their application fields are limited. In this paper, the latest development on the synthesis of highperformance bio-based epoxy and polybenzoxazine resins are reviewed. In addition, to further broaden their applications, the functionalization strategies are also summarized. The objective of this work is to help us fully aware the present situation of bio-based thermosetting resins and then promote their faster development, especially practical application.

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“…Considering the great flexibility of molecular design, various bio-based phenols and primary amines have been directly applied to prepare benzoxazines. [15][16][17][18][19][20] Although considerable progress has been made in this field, there is still an extensive need to further broaden the sources of biomass and develop highperformance bio-based polybenzoxazines.…”

Section: Introductionmentioning

confidence: 99%

Bio‐basedbenzoxazine from renewableL‐tyrosine: Synthesis, polymerization, and properties

Ren

Tian

Zhang

et al. 2022

Journal of Polymer Science

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Developing thermosets derived from renewable sources is of great importance. In this work, a fully bio-based benzoxazine monomer, 3,6-bis ((3-(furan-2-ylmethyl)-3,4-dihydro-2H-benzo[e][1,3]oxazin-6-yl)methyl)piperazine-2,5-dione (TCDPF), is conveniently synthesized from L-tyrosine cyclic dipeptide (TCDP), furfurylamine and paraformaldehyde. The chemical structure of TCDPF is confirmed by nuclear magnetic resonance spectroscopy and Fourier transform infrared spectroscopy (FT-IR) techniques. The curing behavior of TCDPF is investigated by differential scanning calorimetry and in situ FT-IR techniques. After temperatureprogrammed curing, the thermomechanical property and thermal stability of the resulting TCDPF polymer (PTCDPF) are evaluated by dynamic mechanical analysis and thermogravimetric analysis techniques, respectively. It is found that PTCDPF have excellent comprehensive performance such as high glass transition temperature (T g = 322 C), high thermal degradation temperature (T 5% = 342 C, T 10% = 395 C in N 2 atmosphere), and high char yield (CY = 51.3% at 800 C in N 2 atmosphere). The results demonstrate that L-tyrosine is a promising bio-based raw material for preparing high performance polybenzoxazines.

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Heat-resistant and robust biobased benzoxazine resins developed with a green synthesis strategy

Abstract: Two high-performance biobased benzoxazine resins from mono-phenols are developed with a green synthesis strategy.

Cited by 37 publications

References 65 publications

Novel Combination of Vinyl Benzoxazine and Its Copolymerizable Diluent with Outstanding Processability for Preparing a Bio-Based Thermoset

Novel Combination of Vinyl Benzoxazine and Its Copolymerizable Diluent with Outstanding Processability for Preparing a Bio-Based Thermoset

Recent development on bio‐based thermosetting resins

Bio‐basedbenzoxazine from renewableL‐tyrosine: Synthesis, polymerization, and properties

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