Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Ručigaj, Aleš; Alič, Branko; Krajnc, Matjaž; Šebenik, Urška

doi:10.3144/expresspolymlett.2015.60

Cited by 67 publications

(43 citation statements)

References 42 publications

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“…On the other hand there might be a reason, why there is not yet a known self-remendable benzoxazine polymer material with DA reaction based remendability. The reason being high curing temperature needed for polymerization of benzoxazines [31,32], usually quite above the temperature of rDA reaction (~100°C) of normally used diene and dienophile system (furan and maleimide) [5,6]. This means that DA connections are broken and starting compounds are formed.…”

Section: Introductionmentioning

confidence: 99%

Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

Štirn¹,

Ručigaj²,

Krajnc³

2016

Express Polym. Lett.

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Abstract. The Diels-Alder reaction between N-phenylmaleimide and benzoxazine bearing furan group was investigated for the purpose of successful appliance of self-healing in benzoxazine polymer networks. The reaction as a function of temperature/time was performed in molten state and in a solution, where also the kinetic study was performed. The Diels-Alder reaction leads to a mixture of two diastereomers: endo presented at lower cyclo-reversion temperature and exo at higher. Therefore, the conversion rates and exo/endo ratio were studied in detail for both systems. For instance, in molten state the Diels-Alder reaction was triggered by the temperature of the melting point at 60°C with exo/endo ratio preferable to the endo adduct. The study of the kinetics in a solution revealed that the Diels-Alder reaction followed typical bimolecular reversible second-order reaction. The activation energies were close to the previous literature data; 48.4 and 51.9 kJ·mol -1 for Diels-Alder reaction, and 91.0 and 102.3 kJ·mol -1 for retro-Diels-Alder reaction, in acetonitrile and chloroform, respectively. The reaction equilibrium in a solution is much more affected by the retro-Diels-Alder reaction than in a molten state. This study shows detailed investigation of DA reaction and provides beneficial knowledge for further use in self-healing polymer networks.

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Section: Introductionmentioning

confidence: 99%

Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

Štirn¹,

Ručigaj²,

Krajnc³

2016

Express Polym. Lett.

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“…The peak at 2.5 for all the three PBz precursors is due to the solvent peak (DMSO). 13 C-NMR spectra and SEC analysis are given as Supporting Information S1-S5.…”

Section: Structure Assignment Of Pbz Precursorsmentioning

confidence: 99%

“…Despite all these advantages (high mechanical strength, innate flame retardancy, excellent dimensional stability, low water retention, beneficial dielectric properties, and relatively high char yields) and applications (electronic materials, matrix resin for fiber‐reinforced plastics (FRP), high‐performance adhesives, composites, and non‐flammable materials), there are some disadvantages associated with them, including high polymerization temperature; lower crosslinking density because of intensive hydrogen bonding , which restricts their segmental mobility and hinders their network extension; brittleness; and outgassing during curing . Thus, focusing on reducing the polymerization temperature and increasing the crosslink density (CLD) (by tightening the PBz network structure) are expected to enhance their thermo‐mechanical performance .…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of main‐chain polybenzoxazines based on bisphenol‐S

Parveen

Kim

2017

Polymer Engineering & Sci

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Polybenzoxazines (PBzs) are novel thermosetting resins, having many prominent advantages, including high mechanical strength, innate flame retardancy, excellent dimensional stability, low water retention, beneficial dielectric, and relatively high char yields. In recent years, more attention has been paid to the synthesis of main‐chain PBz (MCPBz) precursors using difunctional amines and phenol. In this study, to enhance the rigidity and to improve the crosslink density of PBzs, novel high‐molecular‐weight PBz precursors were synthesized using bisphenol‐S, a diphenolic compound, and three different diamines (namely ethylene diamine, 1,4‐diaminobutane, and tetraethylenepentamine) through a Mannich‐type reaction. The onset of curing temperature for the three PBz precursors was much lower, in the range of 199–215°C, in comparison with bisphenol‐A and aniline‐based benzoxazine monomer [Tonset of BA‐a: 220°C]. The curing of PBz precursors proceeds via ring‐opening polymerization as monitored by FTIR analysis. Additionally, the polymer—PBz‐tepa possesses excellent thermal stability, showing 10% decomposition at 330°C with a char yield of 42.0%. Thus, the properties of PBz are greatly improved by preparing MCPBz and by incorporating sulfonyl group. POLYM. ENG. SCI., 58:1766–1773, 2018. © 2017 Society of Plastics Engineers

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“…The ROP, which is commonly thermally initiated, requires very high temperatures (usually higher than 180 °C), which may lead to thermal degradation of the monomer and in some cases of the corresponding resin. In order to respond to this issue, a considerable number of different accelerators have been tested and more or less successfully applied . Therefore, also difficulties in the molding process before curing and the curing process itself importantly contributed to the lack of benzoxazine utilization in the practice.…”

Section: Introductionmentioning

confidence: 99%

Main‐chain benzoxazine oligomers: Effects of molecular weight on the thermal, mechanical, and viscoelastic properties

Ručigaj

Štirn

Šebenik

et al. 2018

J of Applied Polymer Sci

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With the intent to study materials processing properties during the curing process, oligomeric benzoxazines of different molecular weight and distribution were obtained from 4‐tert‐butylphenol, bisphenol A, 4,4′‐diaminodiphenylmethane and paraformaldehyde by varying the amounts of phenolic compounds. Average molecular weight and distribution of prepared mixtures of polybenzoxazine precursors were determined by gel permeation chromatography analysis. By knowing the molecular weight distribution of prepared mixtures of polybenzoxazine precursors its effect on thermal, mechanical, and viscoelastic properties of the resin during processing and polymerization could be investigated. Mixtures of polybenzoxazine precursors of higher average molecular weight and broader molecular weight distribution displayed faster curing, lower curing conversions, and higher crosslinking densities of cured resins leading to polybenzoxazines with improved properties. This investigation was oriented towards the material processing aspects with the focus on the effect of molecular weights and viscoelastic properties of starting materials on the proceeding of the curing, including changes in material properties, and sample molding. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46659.

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Curing of bisphenol A-aniline based benzoxazine using phenolic, amino and mercapto accelerators

Cited by 67 publications

References 42 publications

Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

Characterization and kinetic study of Diels-Alder reaction: Detailed study on N-phenylmaleimide and furan based benzoxazine with potential self-healing application

Synthesis and properties of main‐chain polybenzoxazines based on bisphenol‐S

Main‐chain benzoxazine oligomers: Effects of molecular weight on the thermal, mechanical, and viscoelastic properties

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