Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone
The bulk ring-opening polymerization (ROP) of ε-caprolactone using phosphazene-containing porous polymeric material (HPCP) has been studied at high reaction temperatures (130–150 °C). HPCP in conjunction with benzyl alcohol as an initiator induced the living ROP of ε-caprolactone, affording polyeste...
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MDPI AG
2023-03-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/5/1291 |
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| author | Yuliya A. Piskun Evgenii A. Ksendzov Anastasiya V. Resko Mikhail A. Soldatov Peter Timashev Hongzhi Liu Irina V. Vasilenko Sergei V. Kostjuk |
| author_facet | Yuliya A. Piskun Evgenii A. Ksendzov Anastasiya V. Resko Mikhail A. Soldatov Peter Timashev Hongzhi Liu Irina V. Vasilenko Sergei V. Kostjuk |
| author_sort | Yuliya A. Piskun |
| collection | DOAJ |
| description | The bulk ring-opening polymerization (ROP) of ε-caprolactone using phosphazene-containing porous polymeric material (HPCP) has been studied at high reaction temperatures (130–150 °C). HPCP in conjunction with benzyl alcohol as an initiator induced the living ROP of ε-caprolactone, affording polyesters with a controlled molecular weight up to 6000 g mol<sup>−1</sup> and moderate polydispersity (Ð~1.5) under optimized conditions ([BnOH]/[CL] = 50; HPCP: 0.63 mM; 150 °C). Poly(ε-caprolactone)s with higher molecular weight (up to M<sub>n</sub> = 14,000 g mol<sup>−1</sup>, Ð~1.9) were obtained at a lower temperature, at 130 °C. Due to its high thermal and chemical stability, HPCP can be reused for at least three consecutive cycles without a significant decrease in the catalyst efficiency. The tentative mechanism of the HPCP-catalyzed ROP of ε-caprolactone, the key stage of which consists of the activation of the initiator through the basic sites of the catalyst, was proposed. |
| first_indexed | 2024-03-11T07:13:01Z |
| format | Article |
| id | doaj.art-d2827fc05fc84c608c8525288cc74948 |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T07:13:01Z |
| publishDate | 2023-03-01 |
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| record_format | Article |
| series | Polymers |
| spelling | doaj.art-d2827fc05fc84c608c8525288cc749482023-11-17T08:28:48ZengMDPI AGPolymers2073-43602023-03-01155129110.3390/polym15051291Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-CaprolactoneYuliya A. Piskun0Evgenii A. Ksendzov1Anastasiya V. Resko2Mikhail A. Soldatov3Peter Timashev4Hongzhi Liu5Irina V. Vasilenko6Sergei V. Kostjuk7Research Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, BelarusResearch Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, BelarusResearch Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, BelarusDepartment of Science and Technology Projects, D. Mendeleev University of Chemical Technology of Russia, 9 Miusskaya Sq., 125047 Moscow, RussiaInstitute for Regenerative Medicine, Sechenov University, 8-2 Trubetskaya St., 119991 Moscow, RussiaKey Laboratory of Special Functional Aggregated Materials, Shandong University, 27 Shanda Nanlu, Jinan 250100, ChinaResearch Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, BelarusResearch Institute for Physical Chemical Problems of the Belarusian State University, 14 Leningradskaya St., 220006 Minsk, BelarusThe bulk ring-opening polymerization (ROP) of ε-caprolactone using phosphazene-containing porous polymeric material (HPCP) has been studied at high reaction temperatures (130–150 °C). HPCP in conjunction with benzyl alcohol as an initiator induced the living ROP of ε-caprolactone, affording polyesters with a controlled molecular weight up to 6000 g mol<sup>−1</sup> and moderate polydispersity (Ð~1.5) under optimized conditions ([BnOH]/[CL] = 50; HPCP: 0.63 mM; 150 °C). Poly(ε-caprolactone)s with higher molecular weight (up to M<sub>n</sub> = 14,000 g mol<sup>−1</sup>, Ð~1.9) were obtained at a lower temperature, at 130 °C. Due to its high thermal and chemical stability, HPCP can be reused for at least three consecutive cycles without a significant decrease in the catalyst efficiency. The tentative mechanism of the HPCP-catalyzed ROP of ε-caprolactone, the key stage of which consists of the activation of the initiator through the basic sites of the catalyst, was proposed.https://www.mdpi.com/2073-4360/15/5/1291ring-opening polymerizationphosphazene baseε-caprolactoneporous polymeric materialheterogeneous catalysis |
| spellingShingle | Yuliya A. Piskun Evgenii A. Ksendzov Anastasiya V. Resko Mikhail A. Soldatov Peter Timashev Hongzhi Liu Irina V. Vasilenko Sergei V. Kostjuk Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone Polymers ring-opening polymerization phosphazene base ε-caprolactone porous polymeric material heterogeneous catalysis |
| title | Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone |
| title_full | Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone |
| title_fullStr | Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone |
| title_full_unstemmed | Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone |
| title_short | Phosphazene Functionalized Silsesquioxane-Based Porous Polymer as Thermally Stable and Reusable Catalyst for Bulk Ring-Opening Polymerization of ε-Caprolactone |
| title_sort | phosphazene functionalized silsesquioxane based porous polymer as thermally stable and reusable catalyst for bulk ring opening polymerization of ε caprolactone |
| topic | ring-opening polymerization phosphazene base ε-caprolactone porous polymeric material heterogeneous catalysis |
| url | https://www.mdpi.com/2073-4360/15/5/1291 |
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