Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines

Lyu, Ya; Rachita, Eric; Pogharian, Nicholas; Froimowicz, Pablo; Ishida, Hatsuo

doi:10.1039/c9py01641d

Cited by 30 publications

(23 citation statements)

References 54 publications

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“…Rather, multifunctional benzoxazines with possible multiple polymerization mechanisms often display a single exothermic peak. This seemingly a contradictory phenomenon was reported by Zhang et al [ 167 ] and recently by Lyu et al [ 139 ] Regio-isomers 5,5′-, 5,7′-, and 7,7′- based on 3-alkoxyphenol (methoxy, butoxy) and ddm, shown in Figure 12 a, were purified to form single crystals to study the effect of benzoxazines with different reactivity within the same molecule. The DSC thermograms of individual isomers are shown in Figure 12 b.…”

Section: Classification Of Benzoxazine Monomersmentioning

confidence: 89%

“…Of particular interest is the replacement of methyl to methoxy group at the meta -position with respect to the phenolic-OH led to a substantial reduction in T p [ 139 ].…”

Section: Classification Of Benzoxazine Monomersmentioning

confidence: 99%

“… ( a ) Synthesis of 3-methoxyphenol and ddm based benzoxazine isomers and ( b ) DSC thermograms of MOPH-ddm isomers showing only well-defined single exotherm for each isomer [ 139 ]. Copyright 2020.…”

Section: Figurementioning

confidence: 99%

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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: 89%

“…Of particular interest is the replacement of methyl to methoxy group at the meta -position with respect to the phenolic-OH led to a substantial reduction in T p [ 139 ].…”

Section: Classification Of Benzoxazine Monomersmentioning

confidence: 99%

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

et al. 2021

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“…This phenomenon can be ascribed to hydroxyl groups on the external surface of HNTs, which have a positive effect on the curing reaction. 26,27 Figure 8 shows the DSC curves of DGEBA/B-HNTs system after different curing stages. The exothermic peak disappeared after heating at 220°C for 2 h, which indicated the curing reaction was completed.…”

Section: Resultsmentioning

confidence: 99%

Preparation of benzoxazine-modified halloysite nanotubes and its application on epoxy/benzoxazine composites

Shen

Liu

et al. 2020

High Performance Polymers

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Benzoxazine monomer (named as B-aptes) was synthesized from 3-aminopropyltriethoxysilane (KH-550), bisphenol A (BPA), and paraformaldehyde. Subsequently, functionalized halloysite nanotubes were obtained by introducing B-aptes onto the surface of halloysite nanotubes (HNTs). Then, benzoxazine-modified halloysite nanotubes (B-HNTs) were used to combine with BPA epoxy resin to prepare the diglycidyl ether of bisphenol-A (DGEBA)/B-HNTs composites. The homogeneous dispersion state of modified HNTs in the cured composite matrix was observed by scanning electron microscopy. Differential scanning calorimetry was used to investigate polymerization behaviors of ternary composites. The results showed that the ternary composite possessed lower polymerization temperature compared with the neat DGEBA/benzoxazine. According to the results of thermogravimetric analysis, the thermal stability of DGEBA/benzoxazine copolymers was improved by the modified HNTs, the char yield increased with the increase of HNTs mass ratio. The results of mechanical tests and dynamic mechanical analysis displayed that the DGEBA/B-HNTs composites possessed promoted mechanical properties.

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“…However, due to the increase in environmental awareness and economic problems, the scientific community has focused on the employment of bio‐fillers, such as natural fibers. A variety of bio‐based materials were introduced as benzoxazine resin fillers such as basalt fibers, ramie fabric, chitosan, hemp fibers and sisal in order to further enhance its properties and reduce its various shortcomings …”

Section: Introductionmentioning

confidence: 99%

Non‐Isothermal Curing Kinetics of Alkali‐Treated Alfa Fibers/Polybenzoxazine Composites Using Differential Scanning Calorimetry

2020

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The exploration of curing process of benzoxazine resins, which possess outstanding features, is crucial for practical and advanced applications. In this study, bisphenol A-aniline based benzoxazine (BA-a) composites reinforced with alkali treated alfa fibers (TAF) were prepared. The influence of different loadings of the TAF on the curing kinetics of BA-a was investigated using non-isothermal differential scanning calorimetry (DSC) at different heating rates. Isoconversional integral methods or model free kinetics, namely, the iterative Kissinger-Akahira-Sunose (it-KAS), iterative Flynn-Wall-Ozawa (it-FWO), Sbirrazzuoli methodology (VYA/CE) and Trache-Abdelaziz-Siwa-ni (TAS) methods have been applied to the experimental data in order to evaluate the curing kinetic parameters. The study revealed that the presence of TAF improved the crosslinking reaction of benzoxazine and reduced the activation energy. The pre-exponential factor exhibited the same trend as the activation energy. The reaction model, examined for all composites, showed that all systems were accurately presented by an autocatalytic reaction model. The Avrami-Erofeev model was the most appropriate for describing the cure kinetics and revealed a good agreement with experimental data.

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Electronic effects of asymmetric and meta-alkoxy substituents on the polymerization behavior of bis-benzoxazines

Abstract: Three isomers of benzoxazine monomers based on m-alkoxyphenol and 4,4′-methylenedianiline were synthesized and successfully isolated by column chromatography.

Cited by 30 publications

References 54 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

Preparation of benzoxazine-modified halloysite nanotubes and its application on epoxy/benzoxazine composites

Non‐Isothermal Curing Kinetics of Alkali‐Treated Alfa Fibers/Polybenzoxazine Composites Using Differential Scanning Calorimetry

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