Synthesis and Properties of Allyl-containing Trisphenol-based Benzoxazine†

doi:10.7503/cjcu20140204

Abstract

Abstract:

1,3,5-Tri(3-allyl-3,4-dihydro-2H-1,3-benzoxa-zinyl)benzene(tp-ala) was synthesized using allyl amine, para-formaldehyde and new synthesized 1,3,5-tri(p-hydroxyl-phenyl)benzene. The chemical structure of tp-ala was characterized by nuclear magnetic resonance spectroscopy(¹H NMR, ¹³C NMR), Fourier transform infrared spectroscopy(FTIR) and ultraviolet and visible absorption spectroscopy(UV-Vis). The curing behavior of tp-ala was studied by differential scanning calorimetry(DSC) analysis. The thermal and optical properties of cured tp-ala(P-tp-ala) were observed. The results showed that by introducing the allyl-group, the T_g of P-tp-ala was 322 ℃. 5% mass loss temperature was at 356 ℃ and the char yield at 800 ℃ was 61.4%, which were higher than those of the reported trisphenol-based polybenzoxazines. P-tp-ala also showed photoluminescent property. The fluorescence emission wavelength of P-tp-ala under an excitation at 233 nm was at 350 nm. In addition, due to the high aromatic content of P-tp-ala, P-tp-ala had a high refractive index of 1.6325. The high refractive-index characteristic makes P-tp-ala thermoset a potential candidate in antireflective coating.

Key words: Allyl-containing trisphend-based polybenzoxazine, Thermal property, Photoluminescent property

CLC Number:

O631

TrendMD:

ZHU Chunli, BAI Haijian, GENG Pengfei, WEI Yanze, LU Zaijun. Synthesis and Properties of Allyl-containing Trisphenol-based Benzoxazine^†[J]. Chem. J. Chinese Universities, 2014, 35(11): 2494.

Figures/Tables 11

Scheme 1 Synthetic routes of TP

Scheme 2 Synthetic route of tp-ala

Fig.1 1H NMR spectrum of tp-ala

Fig.2 13C NMR spectrum of tp-ala

Fig.3 FTIR spectrum of tp-ala

Fig.4 UV-Vis spectra of TP(a) and tp-ala(b) Solvent: CH2Cl2; cTP=1.0×10-6 mol/L, ctp-ala=1.0×10-6 mol/L.

Fig.5 DSC curve of tp-ala

Fig.6 DMA thermogram of P-tp-ala

Fig.7 TGA thermogram of P-tp-ala in N2

Table 1 Thermal properties of P-tp-ala

Polymer	G″_max/MPa	tanδ_max/℃	T_d,5%/℃	T_d,10%/℃	Char yield(%)
P-tp-pa^[18]	206	243	322	358	54.7
P-dp-ala^[16]	298	322	343	367	28.0
P-tp-ala	288	322	351	386	61.4

Fig.8 Photoluminescent spectra of TP(a), tp-ala(b), and P-tp-ala(c) under an excitation at 233 nm

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