Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine
New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on <sup>1</sup>H and <sup>13</sup>C NMR and FTIR spectroscopic analyses through the reduction of Schiff base formed from tetrakis(4-aminophenyl)porphyrin (TAPP) and...
| Main Authors: | , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-01-01
|
| Series: | Polymers |
| Subjects: | |
| Online Access: | https://www.mdpi.com/2073-4360/14/3/449 |
| _version_ | 1797485284545265664 |
|---|---|
| author | Guohu Zhang Ahmed F. M. EL-Mahdy Lamiaa Reda Ahmed Babasaheb M. Matsagar Sameerah Al-Saeedi Shiao-Wei Kuo Kevin C.-W. Wu |
| author_facet | Guohu Zhang Ahmed F. M. EL-Mahdy Lamiaa Reda Ahmed Babasaheb M. Matsagar Sameerah Al-Saeedi Shiao-Wei Kuo Kevin C.-W. Wu |
| author_sort | Guohu Zhang |
| collection | DOAJ |
| description | New porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on <sup>1</sup>H and <sup>13</sup>C 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 CH<sub>2</sub>O. 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 (<i>T</i><sub>d10</sub> = 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. |
| first_indexed | 2024-03-09T23:16:36Z |
| format | Article |
| id | doaj.art-65d5d55451384da38af011d12f8b362f |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-09T23:16:36Z |
| publishDate | 2022-01-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-65d5d55451384da38af011d12f8b362f2023-11-23T17:34:00ZengMDPI AGPolymers2073-43602022-01-0114344910.3390/polym14030449Metal Complexes of the Porphyrin-Functionalized PolybenzoxazineGuohu Zhang0Ahmed F. M. EL-Mahdy1Lamiaa Reda Ahmed2Babasaheb M. Matsagar3Sameerah Al-Saeedi4Shiao-Wei Kuo5Kevin C.-W. Wu6Center for Functional Polymers and Supramolecular Materials, Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 80424, TaiwanCenter for Functional Polymers and Supramolecular Materials, Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 80424, TaiwanCenter for Functional Polymers and Supramolecular Materials, Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 80424, TaiwanDepartment of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, TaiwanDepartment of Chemistry, College of Science, Princess Nourah Bint Abdulrahman University, Riyadh 11671, Saudi ArabiaCenter for Functional Polymers and Supramolecular Materials, Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung 80424, TaiwanDepartment of Chemical Engineering, National Taiwan University, No. 1, Sec. 4, Roosevelt Road, Taipei 10617, TaiwanNew porphyrin-functionalized benzoxazine (Por-BZ) in high purity and yield was synthesized in this study based on <sup>1</sup>H and <sup>13</sup>C 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 CH<sub>2</sub>O. 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 (<i>T</i><sub>d10</sub> = 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.https://www.mdpi.com/2073-4360/14/3/449polybenzoxazinering-opening polymerizationporphyrinmetal complexthermal stability |
| spellingShingle | Guohu Zhang Ahmed F. M. EL-Mahdy Lamiaa Reda Ahmed Babasaheb M. Matsagar Sameerah Al-Saeedi Shiao-Wei Kuo Kevin C.-W. Wu Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine Polymers polybenzoxazine ring-opening polymerization porphyrin metal complex thermal stability |
| title | Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine |
| title_full | Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine |
| title_fullStr | Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine |
| title_full_unstemmed | Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine |
| title_short | Metal Complexes of the Porphyrin-Functionalized Polybenzoxazine |
| title_sort | metal complexes of the porphyrin functionalized polybenzoxazine |
| topic | polybenzoxazine ring-opening polymerization porphyrin metal complex thermal stability |
| url | https://www.mdpi.com/2073-4360/14/3/449 |
| work_keys_str_mv | AT guohuzhang metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT ahmedfmelmahdy metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT lamiaaredaahmed metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT babasahebmmatsagar metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT sameerahalsaeedi metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT shiaoweikuo metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine AT kevincwwu metalcomplexesoftheporphyrinfunctionalizedpolybenzoxazine |