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Chemcial Industry and Engineering 2016, Vol. 33 Issue (3) :25-30    DOI: 10.13353/j.issn.1004.9533.20141072
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Initiation Mechanism of 2, 2-Dihydroperoxybutane Accelerated by Cobalt Naphthenate to Initiate Styrene/Diethyl Fumarate
Huang Yifeng, Wang Congcai, Zhang Jianhua, Guo Ruiwei
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

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Abstract 

The initiation and competitive polymerization mechanism of 2, 2-dihydroperoxybutane (T4) accelerated by cobalt naphthenate to initiate styrene/diethyl fumarate was studied by radical trapping method and high pressure liquid chromatogram-electrospray ionization-mass spectrometry (HPLC-ESI/MS) with 4-benzyloxy-2, 2, 6, 6-tetramethyl-1-piperidinyloxy (T) as scavenger. The reaction pathways of T4-cobalt initiated polymerization were proposed based on this experiment. T4 can be accelerated by cobalt ion to generate alkoxyl radical, which majorly undergo β-scission to form ethyl radical and peroxyacetic acid, while peroxyacetic acid can decompose to produce methyl and hydroxyl radical. The generated methyl, ethyl, ethyl oxygen and hydroxyl radicals are the major source of initiating styrene and diethyl fumarate. As for the competitive initiation to styrene and diethyl fumarate, ethyl radical is more prone to initiate diethyl fumarate, methyl radical is easier to initiate styrene, and hydroxyl radical can only initiate styrene. Besides, there exists hydrogen abstraction and transfer in these highly active radicals.

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Articles by authors
Huang Yifeng
Wang Congcai
Zhang Jianhua
Guo Ruiwei
Keywordsinitiation mechanism of MEKP;   radical trapping method;   competitive initiation     
Received 2014-04-11;
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Huang Yifeng, Wang Congcai, Zhang Jianhua, Guo Ruiwei.Initiation Mechanism of 2, 2-Dihydroperoxybutane Accelerated by Cobalt Naphthenate to Initiate Styrene/Diethyl Fumarate[J]  Chemcial Industry and Engineering, 2016,V33(3): 25-30
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