Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles
A facile and versatile approach for the synthesis of ultrahigh molecular weight poly(methyl methacrylate) (PMMA) at mild conditions was developed. Certain organic halides combined with a catalytical amount of palladium nanoparticles (Pd NPs) were found to be very effective in initiating polymerizati...
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MDPI AG
2020-11-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/12/11/2747 |
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| author | Ming Yuan Lili Xu Xuetao Cui Jiaxing Lv Panpan Zhang Huadong Tang |
| author_facet | Ming Yuan Lili Xu Xuetao Cui Jiaxing Lv Panpan Zhang Huadong Tang |
| author_sort | Ming Yuan |
| collection | DOAJ |
| description | A facile and versatile approach for the synthesis of ultrahigh molecular weight poly(methyl methacrylate) (PMMA) at mild conditions was developed. Certain organic halides combined with a catalytical amount of palladium nanoparticles (Pd NPs) were found to be very effective in initiating polymerizations of methyl methacrylate (MMA), methyl acrylate, vinyl acetate and other vinyl monomers. An ultrahigh molecular weight PMMA with a number-average molecular weight of 4.65 × 10<sup>6</sup> Da and a weight-average molecular weight of 8.08 × 10<sup>6</sup> Da was synthesized at 70 °C using 2-bromoisobutyric acid ethyl ester (EBiB) as an initiator in the presence of catalytical amount (10.1 ppm) of Pd NPs. A kinetic investigation found that the orders of polymerization with respect to EBiB, Pd NP and MMA were 0.23, 0.50, and 0.58, respectively. Proton nuclear magnetic resonance (<sup>1</sup>H NMR) combined with matrix-assisted laser desorption ionization time of flight mass spectroscopy (MALDI-TOF) and gel permeation chromatography (GPC) were used to prove that the macromolecular chain had an end-group of EBiB residue. The electron spin resonance (ESR), transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS) results reveal that the reaction of EBiB with Pd NPs caused a bromo atom (Br) transfer from EBiB to Pd NPs and resulted in the generation of EBiB residue radical to initiate the polymerization of MMA and the formation of Pd<sup>II</sup>Br<sub>2</sub> on the surface of Pd nanoparticles. |
| first_indexed | 2024-03-10T14:42:21Z |
| format | Article |
| id | doaj.art-cc8bcbfc4fa648ea8b77ffd985c418eb |
| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-10T14:42:21Z |
| publishDate | 2020-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Polymers |
| spelling | doaj.art-cc8bcbfc4fa648ea8b77ffd985c418eb2023-11-20T21:42:20ZengMDPI AGPolymers2073-43602020-11-011211274710.3390/polym12112747Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium NanoparticlesMing Yuan0Lili Xu1Xuetao Cui2Jiaxing Lv3Panpan Zhang4Huadong Tang5Institute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, ChinaInstitute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, ChinaInstitute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, ChinaInstitute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, ChinaState Key Laboratory of Modern Optical Instrumentation, Zhejiang University, Hangzhou 310027, ChinaInstitute of Industrial Catalysis, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, ChinaA facile and versatile approach for the synthesis of ultrahigh molecular weight poly(methyl methacrylate) (PMMA) at mild conditions was developed. Certain organic halides combined with a catalytical amount of palladium nanoparticles (Pd NPs) were found to be very effective in initiating polymerizations of methyl methacrylate (MMA), methyl acrylate, vinyl acetate and other vinyl monomers. An ultrahigh molecular weight PMMA with a number-average molecular weight of 4.65 × 10<sup>6</sup> Da and a weight-average molecular weight of 8.08 × 10<sup>6</sup> Da was synthesized at 70 °C using 2-bromoisobutyric acid ethyl ester (EBiB) as an initiator in the presence of catalytical amount (10.1 ppm) of Pd NPs. A kinetic investigation found that the orders of polymerization with respect to EBiB, Pd NP and MMA were 0.23, 0.50, and 0.58, respectively. Proton nuclear magnetic resonance (<sup>1</sup>H NMR) combined with matrix-assisted laser desorption ionization time of flight mass spectroscopy (MALDI-TOF) and gel permeation chromatography (GPC) were used to prove that the macromolecular chain had an end-group of EBiB residue. The electron spin resonance (ESR), transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS) results reveal that the reaction of EBiB with Pd NPs caused a bromo atom (Br) transfer from EBiB to Pd NPs and resulted in the generation of EBiB residue radical to initiate the polymerization of MMA and the formation of Pd<sup>II</sup>Br<sub>2</sub> on the surface of Pd nanoparticles.https://www.mdpi.com/2073-4360/12/11/2747ultrahigh molecular weightPMMAPd nanoparticlesorganic halidesmechanism |
| spellingShingle | Ming Yuan Lili Xu Xuetao Cui Jiaxing Lv Panpan Zhang Huadong Tang Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles Polymers ultrahigh molecular weight PMMA Pd nanoparticles organic halides mechanism |
| title | Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles |
| title_full | Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles |
| title_fullStr | Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles |
| title_full_unstemmed | Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles |
| title_short | Facile Synthesis of Ultrahigh Molecular Weight Poly(Methyl Methacrylate) by Organic Halides in the Presence of Palladium Nanoparticles |
| title_sort | facile synthesis of ultrahigh molecular weight poly methyl methacrylate by organic halides in the presence of palladium nanoparticles |
| topic | ultrahigh molecular weight PMMA Pd nanoparticles organic halides mechanism |
| url | https://www.mdpi.com/2073-4360/12/11/2747 |
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