Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides
Abstract In this study, organic halides, such as 2-bromobutane (C4H9Br), ethyl α-bromophenylacetate (BPA), ethyl 2-bromoisobutyrate (EBiB), and ethyl 2-bromopropionate (EBP) are utilized in conjunction with copper nanopowder (Nano-Cu) to initiate the polymerization of methyl methacrylate (MMA). Amon...
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2025-07-01
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| Online Access: | https://doi.org/10.1186/s13065-025-01597-w |
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| author | Ming Yuan Xiaofang Han Zekai Zhang Ruijia Wang Shengrong Guo |
| author_facet | Ming Yuan Xiaofang Han Zekai Zhang Ruijia Wang Shengrong Guo |
| author_sort | Ming Yuan |
| collection | DOAJ |
| description | Abstract In this study, organic halides, such as 2-bromobutane (C4H9Br), ethyl α-bromophenylacetate (BPA), ethyl 2-bromoisobutyrate (EBiB), and ethyl 2-bromopropionate (EBP) are utilized in conjunction with copper nanopowder (Nano-Cu) to initiate the polymerization of methyl methacrylate (MMA). Among these, BPA combined with nano-Cu exhibits the highest reactivity, resulting in the production of poly(methyl methacrylate) (PMMA) with a number-average molecular weight (M n) of 1.91 × 106 Da, a weight-average molecular weight (M w) of 3.46 × 106 Da, and a polydispersity index (PDI) of 1.81. A kinetic analysis of the polymerization reveals that the reaction orders for MMA, BPA, and nano-Cu concentration are 0.76, 0.49, and 0.77, respectively. The activation energy of the polymerization of MMA initiated by BPA is calculated to be 59.6 kJ/mol. The molecular weight of PMMA product is determined using gel permeation chromatography (GPC), while the structure of the synthesized PMMA is characterized through proton nuclear magnetic resonance (1H NMR). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) is employed to analyze the precise structure and molecular weight of PMMA. Additionally, the nano-Cu recovered after the polymerization is examined using X-ray photoelectron spectroscopy (XPS). An electron paramagnetic resonance (EPR) spectrometer is employed to detect the reaction intermediate formed during the polymerization. Results from MALDI-TOF, XPS and EPR reveal that the polymerization of MMA proceeds via a radical mechanism, with the combination of nano-Cu and BPA leading to the formation of BPA residual radicals that initiate the polymerization of MMA. |
| format | Article |
| id | doaj-art-bfa99f3366ee4c4a9dda97f02a81785d |
| institution | Kabale University |
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| language | English |
| publishDate | 2025-07-01 |
| publisher | BMC |
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| series | BMC Chemistry |
| spelling | doaj-art-bfa99f3366ee4c4a9dda97f02a81785d2025-08-20T03:42:29ZengBMCBMC Chemistry2661-801X2025-07-0119111110.1186/s13065-025-01597-wSynthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halidesMing Yuan0Xiaofang Han1Zekai Zhang2Ruijia Wang3Shengrong Guo4Department of Chemistry and Chemical Engineering, College of Ecology, Lishui UniversityDepartment of Chemistry and Chemical Engineering, College of Ecology, Lishui UniversityDepartment of Chemistry and Chemical Engineering, College of Ecology, Lishui UniversityDepartment of Chemistry and Chemical Engineering, College of Ecology, Lishui UniversityDepartment of Chemistry and Chemical Engineering, College of Ecology, Lishui UniversityAbstract In this study, organic halides, such as 2-bromobutane (C4H9Br), ethyl α-bromophenylacetate (BPA), ethyl 2-bromoisobutyrate (EBiB), and ethyl 2-bromopropionate (EBP) are utilized in conjunction with copper nanopowder (Nano-Cu) to initiate the polymerization of methyl methacrylate (MMA). Among these, BPA combined with nano-Cu exhibits the highest reactivity, resulting in the production of poly(methyl methacrylate) (PMMA) with a number-average molecular weight (M n) of 1.91 × 106 Da, a weight-average molecular weight (M w) of 3.46 × 106 Da, and a polydispersity index (PDI) of 1.81. A kinetic analysis of the polymerization reveals that the reaction orders for MMA, BPA, and nano-Cu concentration are 0.76, 0.49, and 0.77, respectively. The activation energy of the polymerization of MMA initiated by BPA is calculated to be 59.6 kJ/mol. The molecular weight of PMMA product is determined using gel permeation chromatography (GPC), while the structure of the synthesized PMMA is characterized through proton nuclear magnetic resonance (1H NMR). Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) is employed to analyze the precise structure and molecular weight of PMMA. Additionally, the nano-Cu recovered after the polymerization is examined using X-ray photoelectron spectroscopy (XPS). An electron paramagnetic resonance (EPR) spectrometer is employed to detect the reaction intermediate formed during the polymerization. Results from MALDI-TOF, XPS and EPR reveal that the polymerization of MMA proceeds via a radical mechanism, with the combination of nano-Cu and BPA leading to the formation of BPA residual radicals that initiate the polymerization of MMA.https://doi.org/10.1186/s13065-025-01597-wPoly(methyl methacrylate)Ultra-high molecular weightsOrganic halidesKineticsMechanism |
| spellingShingle | Ming Yuan Xiaofang Han Zekai Zhang Ruijia Wang Shengrong Guo Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides BMC Chemistry Poly(methyl methacrylate) Ultra-high molecular weights Organic halides Kinetics Mechanism |
| title | Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides |
| title_full | Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides |
| title_fullStr | Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides |
| title_full_unstemmed | Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides |
| title_short | Synthesis of ultra-high molecular weight poly(methyl methacrylate) initiated by the combination of copper nanopowder with organic halides |
| title_sort | synthesis of ultra high molecular weight poly methyl methacrylate initiated by the combination of copper nanopowder with organic halides |
| topic | Poly(methyl methacrylate) Ultra-high molecular weights Organic halides Kinetics Mechanism |
| url | https://doi.org/10.1186/s13065-025-01597-w |
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