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. 2022 Jan 23;14(3):449.
doi: 10.3390/polym14030449.

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

Guohu Zhang  1 , Ahmed F M El-Mahdy  1 , Lamiaa Reda Ahmed  1   2 , Babasaheb M Matsagar  3 , Sameerah Al-Saeedi  4 , Shiao-Wei Kuo  1   5 , Kevin C-W Wu  3   6
Affiliations

Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine

Guohu Zhang et al. Polymers (Basel). .

Abstract

New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on 1H and 13C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and salicylaldehyde and the subsequent reaction with CH2O. Thermal properties of the product formed through ring-opening polymerization (ROP) of Por-BZ were measured using DSC, TGA and FTIR spectroscopy. Because of the rigid structure of the porphyrin moiety appended to the benzoxazine unit, the temperature required for ROP (314 °C) was higher than the typical Pa-type benzoxazine monomer (ca. 260 °C); furthermore, poly(Por-BZ) possessed a high thermal decomposition temperature (Td10 = 478 °C) and char yield (66 wt%) after thermal polymerization at 240 °C. An investigation of the thermal and luminescence properties of metal-porphyrin complexes revealed that the insertion of Ni and Zn ions decreased the thermal ROP temperatures of the Por-BZ/Ni and Por-BZ/Zn complexes significantly, to 241 and 231 °C, respectively. The metal ions acted as the effective promoter and catalyst for the thermal polymerization of the Por-BZ monomer, and also improved the thermal stabilities after thermal polymerization.

Keywords: metal complex; polybenzoxazine; porphyrin; ring-opening polymerization; thermal stability.

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Conflict of interest statement

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

Figures

Scheme 1
Scheme 1
Synthesis of (f) Por-BZ monomer from (a) 4-nitrobenzaldehyde, (b) TNPP, (c) TAPP, (d) Por-Sa, and (e) Por-Hy.
Scheme 2
Scheme 2
Chemical structures of (a) Por-BZ and (b) the Por-BZ/metal complexes.
Scheme 3
Scheme 3
Thermal ring-opening polymerization of the Por-BZ, Por-BZ/Ni, and Por-BZ/Zn.
Figure 1
Figure 1
FTIR spectra of (a) 4-nitrobenzaldehyde, (b) TNPP, (c) TAPP, (d) Por-Sa, (e) Por-Hy, and (f) Por-BZ.
Figure 2
Figure 2
(A) 1H and (B) 13C NMR spectra of (a) TAPP, (b) Por-Sa, (c) Por-Hy, and (d) Por-BZ.
Figure 3
Figure 3
(A) DSC and (B) FTIR spectral analyses of the Por-BZ monomer after thermal ROP at various temperatures.
Figure 4
Figure 4
(A) TGA and (B) corresponding second-derivative curves based on TGA analyses of the Por-BZ monomer after thermal ROP at various temperatures.
Figure 5
Figure 5
(A) DSC and (B) FTIR spectral analyses of the (a) Por-BZ monomer, (b) Por-BZ/Ni complex, and (c) Por-BZ/Zn complex prior to thermal ROP.
Figure 6
Figure 6
XPS spectra of the (a) Por-BZ monomer, (b) Por-BZ/Ni complex, and (c) Por-BZ/Zn complex.
Figure 7
Figure 7
XPS spectra of the N1s species (a) Por-BZ monomer, (b) Por-BZ/Ni complex, and (c) Por-BZ/Zn complex. XPS spectra of (d) the Ni 2p, and Zn 2p species of Por-BZ monomer, (e) the Ni 2p species of Por-BZ/Ni complex, and (f) the Zn 2p species of Por-BZ/Zn complex.
Figure 8
Figure 8
UV–Vis absorption spectra of (a) TAPP, (b) Por-BZ, (c) the Por-BZ/Ni complex, and (d) the Por-BZ/Zn complex.
Figure 9
Figure 9
PL spectra of (a) TAPP, (b) Por-BZ, (c) the Por-BZ/Ni complex, and (d) the Por-BZ/Zn complex.
Figure 10
Figure 10
DSC and FTIR spectral analyses of (a,b) Por-BZ/Ni and (c,d) Por-BZ/Zn complexes after thermal ROP at various temperatures.
Figure 11
Figure 11
(a) TGA and (b) corresponding second-derivative curves based on TGA analyses of the Por-BZ monomer and the Por-BZ/Ni and Por-BZ/Zn complexes after thermal ROP at 210 °C.
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