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Activators regenerated by electron transfer in ATRP of methyl methacrylate with alcohol as reducing agent in the presence of a base

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Abstract

Poly(methyl methacrylate) (PMMA) was synthesized via activators regenerated by electron transfer (ARGET) in atom transfer radical polymerization (ATRP) (ARGET ATRP) of methyl methacrylate in N,N-dimethylformamide and using ethyl 2-bromoisobutyrate as initiator, CuCl2 as catalyst, N,N,N′,N′-tetramethylethylene-diamine as ligand and ethanol as a reducing agent. The polymerization temperature was kept at 70 °C. A well-defined PMMA with predetermined molecular weight and narrow molecular weight distribution was obtained. A linear relationship between ln([M]0/[M]) and polymerization time was found to show the living and controllable radical polymerization. The molecular weights of the obtained polymers increased linearly with monomer conversion and the data are in good agreement with the theoretical values with narrow molecular weight distribution (M w/M n). That is to say, alcohols were found to be a kind of highly efficient agents in the presence of Na2CO3 in this system. The effects of temperature, different types of alcohols and the amount of n-propanol on the polymerization were investigated. With increasing temperature (changed from 70 to 90 °C) and the amount of n-propanol (changed from 500:1:1:2:1:2 to 500:1:1:2:10:2), the conversion increased from 15.6 to 34.7 % and from 8.6 to 26.8 %, respectively. However, the value of M w/M n became broader when the molar ratio of [MMA]0/[EBiB]0/[CuCl2]0/[TMEDA]0/[n-propanol]0/[Na2CO3]0 was 500:1:1:2:1:2, indicating that the amount of n-propanol played an important role in ARGET ATRP of MMA. The activation energy was calculated to be 51.96 kJ/mol. The different types of alcohol were demonstrated to be an efficient reducing agent in this system except for tert-butyl alcohol. The “living” feature of the obtained polymer was further verified by a chain extension experiment. The obtained polymer was characterized by 1H NMR and GPC.

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Acknowledgments

The authors are grateful for the financial support by Scientific Research Fund of Hunan Provincial Education Department (Nos. 13A031 and 13C364), the Science and Technology Planning Project of Hunan Province, China (Nos. 2012FJ4272), and the Open Foundation of Fine Petrochemical Catalytic and Separating Key Laboratory of Hunan Province.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Hunan Institute of Science and Technology, Yueyang, 414006, People’s Republic of China

    Li-Chao Liu, Guo-Xiang Wang & Hu Wu

  2. School of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen, 333403, People’s Republic of China

    Mang Lu

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  1. Li-Chao Liu
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  2. Guo-Xiang Wang
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Correspondence to Guo-Xiang Wang.

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Liu, LC., Wang, GX., Lu, M. et al. Activators regenerated by electron transfer in ATRP of methyl methacrylate with alcohol as reducing agent in the presence of a base. Iran Polym J 22, 891–896 (2013). https://doi.org/10.1007/s13726-013-0188-5

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  • DOI: https://doi.org/10.1007/s13726-013-0188-5

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