Thermal Reactions of N-Phenylmaleimide and Mono- or Di-functional Allylphenols

Shibahara, Sumio; Yamamoto, Takahisa; Yamaji, Takashi; Motoyoshiya, Jiro; Hayashi, Sadao

doi:10.1295/polymj.30.404

Cited by 19 publications

(22 citation statements)

References 6 publications

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“…Regarding the reaction mechanism for DABA/BMIM, Enoki et al [23][24][25] and Reyx et al 26 reported that the thermal reaction of the monofunctional model compounds, 2-allylphenol and N-phenylmaleimide (PMI), produced the ene-adduct, which underwent the Diels-Alder reaction twice with two molars of PMI to form the 3:1 adduct ( Figure 5). In continued work, Shibahara et al 27 reported that the thermal reaction of DABA and PMI produced ene-adduct and chain-polymerized products, whereas the Diels-Alder adduct could not be detected. This difference in reactivity for 2-allylphenol/PMI and DABA/PMI was attributed to steric repulsion of DABA.…”

Section: Resultsmentioning

confidence: 99%

High-performance bio-based bismaleimide resins using succinic acid and eugenol

Shibata

Teramoto

Shimasaki

et al. 2011

Polym J

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Biseugenyl succinate (BEUS) and bis(4-maleimidephenyl) succinate (BMIS) were synthesized by the reaction of succinic acid (SA) with eugenol and the reaction of succinyl chloride with 4-hydroxyphenylmaleimide, respectively. A gelled mixture of BEUS and BMIS at a molar ratio of 1/1, 1/2 or 1/3 at 200 1C was compression-molded at 230 1C for 1 h to produce a cured BEUS/BMIS product. The properties of BEUS/BMIS were compared with the properties of 2,2¢-diallyl bisphenol A (DABA)/4,4¢-bismaleimidediphenylmethane (BMIM) cured at 230 1C for 1 h. The Fourier Transform Infrared (FTIR) analysis of the cured materials revealed that chain polymerization of allyl and maleimide groups occurred to produce BEUS/BMIS, whereas a stepwise ene reaction and subsequent chain polymerization in addition to an etherification reaction occurred to produce DABA/BMIM. The cured BEUS/BMIS (1/2, 1/3) showed a higher glass transition temperature and greater tensile strength than the corresponding DABA/BMIM.

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Section: Resultsmentioning

confidence: 99%

High-performance bio-based bismaleimide resins using succinic acid and eugenol

Shibata

Teramoto

Shimasaki

et al. 2011

Polym J

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“…6 At first, comparison between the liquid and solid state 13 C NMR spectra was made. Figure 1 shows their spectra for a reaction mixture of PMI and AP (molar ratio 2/1) treated at 175°C…”

Section: Resultsmentioning

confidence: 99%

“…6 At first, comparison between the liquid and solid state 13 C NMR spectra was made. Figure 1 shows their spectra for a reaction mixture of PMI and AP (molar ratio 2/1) treated at 175°C for 2 h. Solid-state 13 C NMR spectra were obtained by CPMAS and spinning sideband interference was eliminated by TOSS.…”

Section: Resultsmentioning

confidence: 99%

“…NMR spectra were obtained for samples dissolved in dimethyl-d6 sulfoxide (DMSO-d 6 ) or CDC1 3 at room temperature and were recorded on a JEOL JNM-GSX400 spectrometer.…”

Section: Liquid-state 13 C Nmr Measurementsmentioning

confidence: 99%

“…3 -5 The preceding paper showed that the thermal reaction of PMI and AP gave ene-and Diels-Alder adducts but PMI and DABA did not give the Diels-Alder adduct. 6 However, the practical curing reaction remains uncertain because the curing products are generally insoluble toward almost of organic solvents, which prevents to characterize the reaction products.…”

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Curing Reactions of Bismaleimidodiphenylmethane with Mono- or Di-functional Allylphenols. High Resolution Solid-State 13C NMR Study

Shibahara

Yamamoto²,

Motoyoshiya

et al. 1998

Polym J

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ABSTRACT:Analysis of the curing reactions of bismaleimidodiphenylmethane (BMI) with diallylbisphenol-A (DABA) or o-allylphenol (AP) with the high resolution solid-state 13 C NMR technique revealed that while cured products of BMI and AP are formed through ene-reaction and the sequential Diels-Alder reaction, no Diels-Alder reaction occurs in the case of DABA and only ene-reaction and polymerization proceed. This shows that the crosslinking of such widely used curing system proceeds via a different manner suggested previously.KEY WORDS Curing Reaction/ Diels-Alder Reaction/ ene-Reaction / Bismaleimide / Diallylbisphenol-A / Solid-State 13 C Nuclear Magnetic Resonance / The curing system of bismaleimide has been widely used as thermosetting polyimides, which provides excellent thermal stability but brittleness simultaneously because of the high crosslinking density of the network. In order to add toughness to bismaleimide resins, modification has been made by the addition of diallyl compounds such as diallylbisphenol-A (DABA). 1 • 2 The course of this reaction has been investigated and ene-and Diels-Alder reactions were suggested to be involved in this curing system based on the model reaction of Nphenylmaleimide (PMI) and o-allylphenol (AP). 3 -5 The preceding paper showed that the thermal reaction of PMI and AP gave ene-and Diels-Alder adducts but PMI and DABA did not give the Diels-Alder adduct. 6 However, the practical curing reaction remains uncertain because the curing products are generally insoluble toward almost of organic solvents, which prevents to characterize the reaction products.High resolution solid-state NMR with CPMAS (cross polarization magic angle spinning), developed by Schaefer, 7 has been applied to the analysis of insoluble polymer such as cured thermoset resins. 8 Our previous studies showed that the solid-state 13 C NMR is useful to investigate the curing reactions of bismaleimide resins. 9 -12 Although the solid-state 13 C NMR spectrum of the cured product of bismaleimidodiphenylmethane (BMI) with DABA has been illustrated by Carduner et al. 13 • 14 detailed descriptions are not available. On the basis of fundamental data of the model reactions, we report in this paper the direct measurements of the curing reactions of BMI and DABA with a high resolution solid-state 13 C NMR. EXPERIMENTAL MaterialsBMI, purchased from Wako Pure Chemical Industries, was recrystallized from chloroform-methanol. DABA 410 was obtained from Mitsui Toatsu Chemicals Inc. PMI and o-AP were purchased from Wako Pure Chemical Industries. Sample PreparationMono-or di-functional maleimides and mono-or di-functional allylphenols were mixed in a round bottom flask and heated by an oil bath at 150°C for 15 min. Continuous stirring led to a homogenous melt. This mixture was put in a closed aluminous vessel and heated at 175°C for 2 h, at 200°c for 1 h, and at 250°C for 1 h in an air oven. Each stage samples were analyzed by liquid-state and solid-state 13 C NMR. Liquid-State 13 C NMR MeasurementsNMR spectra were obtained...

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Morphology transition of bismaleimide‐modified novolac resin

Zhang

Yan

et al. 2006

J of Applied Polymer Sci

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ABSTRACT:The bismaleimide (BMI)-modified novolac resin was synthesized by allylation of the novolac resin and its "Ene" reaction with BMI. The reactions were monitored by Fourier transform infrared analysis (FTIR). The morphology of the BMI-modified novolac resin changed with degree of allylation (i.e., the amount of BMI used). On the basis of the studies done by dynamical mechanical analysis (DMA), differential scanning calorimetry (DSC), and field emission scanning electron microscopy (FE-SEM), it was found that when the degree of allylation increased from 48 to 59%, the resin changed from a single-phase structure to a two-phase structure. From the research by thermogravimetric analysis (TGA) and DMA, it was found that the higher allyl-content (when Ͼ 48%) caused a decrease of the thermal properties and mechanical properties of the resultant resin. The BMImodified allyl novolac resin with 48% degree of allylation has the best thermal properties and the highest dynamic modulus in the current research.

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Thermal Reactions of N-Phenylmaleimide and Mono- or Di-functional Allylphenols

Cited by 19 publications

References 6 publications

High-performance bio-based bismaleimide resins using succinic acid and eugenol

High-performance bio-based bismaleimide resins using succinic acid and eugenol

Curing Reactions of Bismaleimidodiphenylmethane with Mono- or Di-functional Allylphenols. High Resolution Solid-State 13C NMR Study

Morphology transition of bismaleimide‐modified novolac resin

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